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Sample records for intact molecular masses

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

    NARCIS (Netherlands)

    Dekker, MHA; Piersma, T; Damste, JSS; Dekker, Marlèn H.A.; Sinninghe Damsté, Jaap S.

    The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing

  2. Zooming into Molecular Biomarker Distribution through Spatially Resolved Mass Spectrometry on Intact Sediment Sections

    Science.gov (United States)

    Wörmer, L.; Fuchser, J.; Alfken, S.; Elvert, M.; Schimmelmann, A.; Hinrichs, K. U.

    2016-02-01

    Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. After sedimentation, and due to their persistence in the sedimentary record, the information archived in them remains available on geological time-scales. Thereby sedimentary lipid biomarkers become important informants of past environments. Conventional biomarker analysis is labor-intensive and requires cm-sized samples, temporal resolution is consequently low. We here present an approach, based on laser desorption ionization (LDI) coupled to ultra high resolution mass spectrometry, that avoids wet-chemical sample preparation and enables analysis directly on sediment sections at sub-mm spatial resolution. Our initial study targeted archaeal glycerol dialkyl glycerol tetraethers (GDGTs). GDGTS are ubiquitous and persistent components in marine sediments, and used in several, widely recognized paleoenvironmental proxies. Applied to an Eastern Mediterranean Sapropel layer, GDGT-profiles with previously unachieved temporal resolution were obtained, and pointed to a strong influence of high frequency cycles on sea-surface temperature and planktonic archaeal ecology. Spatial information furthermore revealed a new view on the fine-scale patchiness of lipid distribution. Following these pioneering studies, major developments are under way. A dedicated facility has been set up at MARUM/University of Bremen, which combines lipid biomarker and elemental analysis at sub-mm resolution (down to 50 µm). We present methods for other comprehensive lipid biomarkers (e.g. alkenones or sterols) that are currently being targeted; and the application of spatially resolved biomarker analysis to recent laminated sediments (Santa Barbara Basin), yielding informative profiles with subannual resolution. We also discuss criteria for analyte and sample selection, as well as the main potentialities and constraints of this new approach.

  3. Intact molecular characterization of cord factor (trehalose 6,6'-dimycolate) from nine species of mycobacteria by MALDI-TOF mass spectrometry.

    Science.gov (United States)

    Fujita, Yukiko; Naka, Takashi; McNeil, Michael R; Yano, Ikuya

    2005-10-01

    Cord factor (trehalose 6,6'-dimycolate, TDM) is an unique glycolipid with a trehalose and two molecules of mycolic acids in the mycobacterial cell envelope. Since TDM consists of two molecules of very long branched-chain 3-hydroxy fatty acids, the molecular mass ranges widely and in a complex manner. To characterize the molecular structure of TDM precisely and simply, an attempt was made to determine the mycolic acid subclasses of TDM and the molecular species composition of intact TDM by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry for the first time. The results showed that less than 1 microg mycolic acid methyl ester of TDM from nine representative species of mycobacteria and TDM from the same species was sufficient to obtain well-resolved mass spectra composed of pseudomolecular ions [M+Na]+. Although the mass ion distribution was extremely diverse, the molecular species of each TDM was identified clearly by constructing a molecular ion matrix consisting of the combination of two molecules of mycolic acids. The results showed a marked difference in the molecular structure of TDM among mycobacterial species and subspecies. TDM from Mycobacterium tuberculosis (H37Rv and Aoyama B) showed a distinctive mass pattern and consisted of over 60 molecular ions with alpha-, methoxy- and ketomycolate. TDM from Mycobacterium bovis BCG Tokyo 172 similarly showed over 35 molecular ions, but that from M. bovis BCG Connaught showed simpler molecular ion clusters consisting of less than 35 molecular species due to a complete lack of methoxymycolate. Mass ions due to TDM from M. bovis BCG Connaught and Mycobacterium kansasii showed a biphasic distribution, but the two major peaks of TDM from M. kansasii were shifted up two or three carbon units higher compared with M. bovis BCG Connaught. Within the rapid grower group, in TDM consisting of alpha-, keto- and wax ester mycolate from Mycobacterium phlei and Mycobacterium flavescens, the

  4. Intact glycopeptide characterization using mass spectrometry.

    Science.gov (United States)

    Cao, Li; Qu, Yi; Zhang, Zhaorui; Wang, Zhe; Prytkova, Iya; Wu, Si

    2016-05-01

    Glycosylation is one of the most prominent and extensively studied protein post-translational modifications. However, traditional proteomic studies at the peptide level (bottom-up) rarely characterize intact glycopeptides (glycosylated peptides without removing glycans), so no glycoprotein heterogeneity information is retained. Intact glycopeptide characterization, on the other hand, provides opportunities to simultaneously elucidate the glycan structure and the glycosylation site needed to reveal the actual biological function of protein glycosylation. Recently, significant improvements have been made in the characterization of intact glycopeptides, ranging from enrichment and separation, mass spectroscopy (MS) detection, to bioinformatics analysis. In this review, we recapitulated currently available intact glycopeptide characterization methods with respect to their advantages and limitations as well as their potential applications.

  5. Identification of intact high molecular weight glutenin subunits from the wheat proteome using combined liquid chromatography-electrospray ionization mass spectrometry.

    Science.gov (United States)

    Lagrain, Bert; Brunnbauer, Markus; Rombouts, Ine; Koehler, Peter

    2013-01-01

    The present paper describes a method for the identification of intact high molecular weight glutenin subunits (HMW-GS), the quality determining proteins from the wheat storage proteome. The method includes isolation of HMW-GS from wheat flour, further separation of HMW-GS by reversed-phase high-performance liquid chromatography (RP-HPLC), and their subsequent molecular identification with electrospray ionization mass spectrometry using a quadrupole-time-of-flight mass analyzer. For HMW-GS isolation, wheat proteins were reduced and extracted from flour with 50% 1-propanol containing 1% dithiothreitol. HMW-GS were then selectively precipitated from the protein mixture by adjusting the 1-propanol concentration to 60%. The composition of the precipitated proteins was first evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with Coomassie staining and RP-HPLC with ultraviolet detection. Besides HMW-GS (≥65%), the isolated proteins mainly contained ω5-gliadins. Secondly, the isolated protein fraction was analyzed by liquid chromatography-mass spectrometry. Optimal chromatographic separation of HMW-GS from the other proteins in the isolated fraction was obtained when the mobile phase contained 0.1% trifluoroacetic acid as ion-pairing agent. Individual HMW-GS were then identified by determining their molecular masses from the high-resolution mass spectra and comparing these with theoretical masses calculated from amino acid sequences. Using formic acid instead of trifluoroacetic acid in the mobile phase increased protein peak intensities in the base peak mass chromatogram. This allowed the detection of even traces of other wheat proteins than HMW-GS in the isolated fraction, but the chromatographic separation was inferior with a major overlap between the elution ranges of HMW-GS and ω-gliadins. Overall, the described method allows a rapid assessment of wheat quality through the direct determination of the HMW-GS composition and offers a basis for

  6. Identification of intact high molecular weight glutenin subunits from the wheat proteome using combined liquid chromatography-electrospray ionization mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Bert Lagrain

    Full Text Available The present paper describes a method for the identification of intact high molecular weight glutenin subunits (HMW-GS, the quality determining proteins from the wheat storage proteome. The method includes isolation of HMW-GS from wheat flour, further separation of HMW-GS by reversed-phase high-performance liquid chromatography (RP-HPLC, and their subsequent molecular identification with electrospray ionization mass spectrometry using a quadrupole-time-of-flight mass analyzer. For HMW-GS isolation, wheat proteins were reduced and extracted from flour with 50% 1-propanol containing 1% dithiothreitol. HMW-GS were then selectively precipitated from the protein mixture by adjusting the 1-propanol concentration to 60%. The composition of the precipitated proteins was first evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with Coomassie staining and RP-HPLC with ultraviolet detection. Besides HMW-GS (≥65%, the isolated proteins mainly contained ω5-gliadins. Secondly, the isolated protein fraction was analyzed by liquid chromatography-mass spectrometry. Optimal chromatographic separation of HMW-GS from the other proteins in the isolated fraction was obtained when the mobile phase contained 0.1% trifluoroacetic acid as ion-pairing agent. Individual HMW-GS were then identified by determining their molecular masses from the high-resolution mass spectra and comparing these with theoretical masses calculated from amino acid sequences. Using formic acid instead of trifluoroacetic acid in the mobile phase increased protein peak intensities in the base peak mass chromatogram. This allowed the detection of even traces of other wheat proteins than HMW-GS in the isolated fraction, but the chromatographic separation was inferior with a major overlap between the elution ranges of HMW-GS and ω-gliadins. Overall, the described method allows a rapid assessment of wheat quality through the direct determination of the HMW-GS composition and

  7. Oxidation of molecular tritium by intact soils

    International Nuclear Information System (INIS)

    Sweet, C.W.; Murphy, C.E. Jr.

    1980-01-01

    The effects of environmental factors on the rate of oxidation of molecular tritium (T 2 ) to tritiated water (HTO) were determined for intact soils during field exposures. Maximum deposition velocities of approximately 0.03 cm/sec were measured for T 2 at low wind speeds for a variety of soils over a wide range of conditions. Deposition velocities were slightly inhibited in wet soils and at 0 0 C. In dry soils, oxidation of T 2 to HTO occurred deeper in the soil profile, but deposition velocities were unaffected

  8. Intact glycopeptide characterization using mass spectrometry

    OpenAIRE

    Cao, Li; Qu, Yi; Zhang, Zhaorui; Wang, Zhe; Prykova, Iya; Wu, Si

    2016-01-01

    Glycosylation is one of the most prominent and extensively studied protein post-translational modifications. However, traditional proteomic studies at the peptide level (bottom-up) rarely characterize intact glycopeptides (glycosylated peptides without removing glycans), so no glycoprotein heterogeneity information is retained. Intact glycopeptide characterization, on the other hand, provides opportunities to simultaneously elucidate the glycan structure and the glycosylation site needed to r...

  9. Detection of intact megadalton protein assemblies of vanillyl-alcohol oxidase by mass spectrometry

    NARCIS (Netherlands)

    Berkel, van W.J.H.; Heuvel, van den R.H.H.; Versluis, C.; Heck, A.

    2000-01-01

    Well-resolved ion signals of intact large protein assemblies, with molecular masses extending above one million Dalton, have been detected and mass analyzed using electrospray ionization mass spectrometry, with an uncertainty in mass of <0.2&Eth;The mass spectral data seem to reflect known

  10. Capillary zone electrophoresis-mass spectromet of intact proteins

    NARCIS (Netherlands)

    Domínguez-Vega, Elena; Haselberg, Rob; Somsen, Govert W.

    2016-01-01

    Capillary electrophoresis (CE) coupled with mass spectrometry (MS) has proven to be a powerful analytical tool for the characterization of intact proteins. It combines the high separation efficiency, short analysis time, and versatility of CE with the mass selectivity and sensitivity offered by MS

  11. Structural determination of intact proteins using mass spectrometry

    Science.gov (United States)

    Kruppa, Gary [San Francisco, CA; Schoeniger, Joseph S [Oakland, CA; Young, Malin M [Livermore, CA

    2008-05-06

    The present invention relates to novel methods of determining the sequence and structure of proteins. Specifically, the present invention allows for the analysis of intact proteins within a mass spectrometer. Therefore, preparatory separations need not be performed prior to introducing a protein sample into the mass spectrometer. Also disclosed herein are new instrumental developments for enhancing the signal from the desired modified proteins, methods for producing controlled protein fragments in the mass spectrometer, eliminating complex microseparations, and protein preparatory chemical steps necessary for cross-linking based protein structure determination.Additionally, the preferred method of the present invention involves the determination of protein structures utilizing a top-down analysis of protein structures to search for covalent modifications. In the preferred method, intact proteins are ionized and fragmented within the mass spectrometer.

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

    NARCIS (Netherlands)

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

    2000-01-01

    The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing

  13. Two possible improvements for mass spectrometry analysis of intact biomolecules.

    Science.gov (United States)

    Raznikov, Valeriy V; Zelenov, Vladislav V; Aparina, Elena V; Pikhtelev, Alexander R; Sulimenkov, Ilia V; Raznikova, Marina O

    2017-08-01

    The goals of our study were to investigate abilities of two approaches to eliminate possible errors in electrospray mass spectrometry measurements of biomolecules. Passing of a relatively dense supersonic gas jet through ionization region followed by its hitting the spray of the analyzed solution in low vacuum may be effective to keep an initial biomolecule structure in solution. Provided that retention of charge carriers for some sites in the biomolecule cannot be changed noticeably in electrospray ion source, decomposition and separation of charge-state distributions of electrosprayed ions may give additional information about native structure of biomolecules in solution.

  14. Using Spores for Fusarium spp. Classification by MALDI-Based Intact Cell/Spore Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Wolfgang Winkler

    2012-01-01

    Full Text Available Fusarium is a widespread genus of filamentous fungi and a member of the soil microbial community. Certain subspecies are health threatening because of their mycotoxin production that affects the human and animal food chain. Thus, for early and effective pest control, species identification is of particular interest; however, differentiation on the subspecies level is challenging and time-consuming for this fungus. In the present study, we show the possibilities of intact cell mass spectrometry for spore analysis of 22 different Fusarium strains belonging to six Fusarium subspecies. We found that species differentiation is possible if mass spectrometric analyses are performed under well-defined conditions with fixed parameters. A critical point for analysis is a proper sample preparation of spores, which increases the quality of mass spectra with respect to signal intensity and m/z value variations. It was concluded that data acquistion has to be performed automatically; otherwise, user-specific variations are introduced generating data which cannot fit the existing datasets. Data that show clearly that matrix-assisted laser desorption ionization-based intact cell/intact spore mass spectrometry (IC/ISMS can be applied to differentiate closely related Fusarium spp. are presented. Results show a potential to build a database on Fusarium species for accurate species identification, for fast response in the case of infections in the cornfield. We furthermore demonstrate the high precision of our approach in classification of intact Fusarium species according to the location of their collection.

  15. Quantitative Analysis of Human Salivary Gland-Derived Intact Proteome Using Top-Down Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Si; Brown, Joseph N.; Tolic, Nikola; Meng, Da; Liu, Xiaowen; Zhang, Haizhen; Zhao, Rui; Moore, Ronald J.; Pevzner, Pavel A.; Smith, Richard D.; Pasa-Tolic, Ljiljana

    2014-05-31

    There are several notable challenges inherent to fully characterizing the entirety of the human saliva proteome using bottom-up approaches, including polymorphic isoforms, post-translational modifications, unique splice variants, deletions, and truncations. To address these challenges, we have developed a top-down based liquid chromatography-mass spectrometry (LC-MS) approach, which cataloged 20 major human salivary proteins with a total of 83 proteoforms, containing a broad range of post-translational modifications. Among these proteins, several previously reported disease biomarker proteins were identified at the intact protein level, such as beta-2 microglobulin (B2M). In addition, intact glycosylated proteoforms of several saliva proteins were also characterized, including intact N-glycosylated protein prolactin inducible protein (PIP) and O-glycosylated acidic protein rich protein (aPRP). These characterized proteoforms constitute an intact saliva proteoform database, which was used for quantitative comparison of intact salivary proteoforms among six healthy individuals. Human parotid (PS) and submandibular/sublingual gland (SMSL) secretion samples (2 μg of protein each) from six healthy individuals were compared using RPLC coupled with the 12T FTICR mass spectrometer. Significantly different protein and PTM patterns were resolved with high reproducibility between PS and SMSL glands. The results from this study provide further insight into the potential mechanisms of PTM pathways in oral glandular secretion, expanding our knowledge of this complex yet easily accessible fluid. Intact protein LC-MS approach presented herein can potentially be applied for rapid and accurate identification of biomarkers from only a few microliters of human glandular saliva.

  16. Mass Spectrometry of Intact Proteins Reveals +98 u Chemical Artifacts Following Precipitation in Acetone.

    Science.gov (United States)

    Güray, Melda Z; Zheng, Shi; Doucette, Alan A

    2017-02-03

    Protein precipitation in acetone is frequently employed ahead of mass spectrometry for sample preconcentration and purification. Unfortunately, acetone is not chemically inert; mass artifacts have previously been observed on glycine-containing peptides when exposed to acetone under acidic conditions. We herein report a distinct chemical modification occurring at the level of intact proteins when incubated in acetone. This artifact manifests as one or more satellite peaks in the MS spectrum of intact protein, spaced 98 u above the mass of the unmodified protein. Other artifacts (+84, +112 u) also appear upon incubation of proteins or peptides in acetone. The reaction is pH-sensitive, being suppressed when proteins are exposed to acetone under acidic conditions. The +98 u artifact is speculated to originate through an intermediate product of aldol condensation of acetone to form diacetone alcohol and mesityl oxide. A +98 u product could originate from nucleophilic attack on mesityl oxide or through condensation with diacetone alcohol. Given the extent of modification possible upon exposure of proteins to acetone, particularly following overnight solvent exposure or incubation at room temperature, an awareness of the variables influencing this novel modification is valued by proteomics researchers who employ acetone precipitation for protein purification.

  17. Novel molecular events associated with altered steroidogenesis induced by exposure to atrazine in the intact and castrate male rat

    Science.gov (United States)

    Toxicology is increasingly focused on molecular events comprising adverse outcome pathways. Atrazine activates the hypothalamic-pituitary adrenal axis, but relationships to gonadal alterations are unknown. We characterized hormone profiles and adrenal (intact and castrate) and te...

  18. A high-throughput mass spectrometry assay to simultaneously measure intact insulin and C-peptide.

    Science.gov (United States)

    Taylor, Steven W; Clarke, Nigel J; Chen, Zhaohui; McPhaul, Michael J

    2016-04-01

    Measurements of fasting levels of insulin and C-peptide are useful in documenting insulin resistance and may help predict development of diabetes mellitus. However, the specific insulin and C-peptide levels associated with specific degrees of insulin resistance have not been defined, owing to marked variability among immunoassays and lack of standardization. Herein, we describe a multiplexed liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay for intact insulin and C-peptide. Insulin and C-peptide were enriched from patient sera using monoclonal antibodies immobilized on magnetic beads and processed on a robotic liquid handler. Eluted peptides were analyzed by LC-MS/MS. Bovine insulin and a stable isotopically-labeled (13C/15N) C-peptide were utilized as internal standards. The assay had an analytical measurement range of 3 to 320 μIU/ml (18 to 1920 pmol/l) for insulin and 0.11 to 27.2 ng/ml (36 to 9006 pmol/l) for C-peptide. Intra- and inter-day assay variation was less than 11% for both peptides. Of the 5 insulin analogs commonly prescribed to treat diabetes, only the recombinant drug insulin lispro caused significant interference for the determination of endogenous insulin. There were no observed interferences for C-peptide. We developed and validated a high-throughput, quantitative, multiplexed LC-MS/MS assay for intact insulin and C-peptide. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Bioengineered human IAS reconstructs with functional and molecular properties similar to intact IAS

    Science.gov (United States)

    Singh, Jagmohan

    2012-01-01

    Because of its critical importance in rectoanal incontinence, we determined the feasibility to reconstruct internal anal sphincter (IAS) from human IAS smooth muscle cells (SMCs) with functional and molecular attributes similar to the intact sphincter. The reconstructs were developed using SMCs from the circular smooth muscle layer of the human IAS, grown in smooth muscle differentiation media under sterile conditions in Sylgard-coated tissue culture plates with central Sylgard posts. The basal tone in the reconstructs and its changes were recorded following 0 Ca2+, KCl, bethanechol, isoproterenol, protein kinase C (PKC) activator phorbol 12,13-dibutyrate, and Rho kinase (ROCK) and PKC inhibitors Y-27632 and Gö-6850, respectively. Western blot (WB), immunofluorescence (IF), and immunocytochemical (IC) analyses were also performed. The reconstructs developed spontaneous tone (0.68 ± 0.26 mN). Bethanechol (a muscarinic agonist) and K+ depolarization produced contraction, whereas isoproterenol (β-adrenoceptor agonist) and Y-27632 produced a concentration-dependent decrease in the tone. Maximal decrease in basal tone with Y-27632 and Gö-6850 (each 10−5 M) was 80.45 ± 3.29 and 17.76 ± 3.50%, respectively. WB data with the IAS constructs′ SMCs revealed higher levels of RhoA/ROCK, protein kinase C-potentiated inhibitor or inhibitory phosphoprotein for myosin phosphatase (CPI-17), phospho-CPI-17, MYPT1, and 20-kDa myosin light chain vs. rectal smooth muscle. WB, IF, and IC studies of original SMCs and redispersed from the reconstructs for the relative distribution of different signal transduction proteins confirmed the feasibility of reconstruction of IAS with functional properties similar to intact IAS and demonstrated the development of myogenic tone with critical dependence on RhoA/ROCK. We conclude that it is feasible to bioengineer IAS constructs using human IAS SMCs that behave like intact IAS. PMID:22790596

  20. MALDI FTICR IMS of Intact Proteins: Using Mass Accuracy to Link Protein Images with Proteomics Data

    Science.gov (United States)

    Spraggins, Jeffrey M.; Rizzo, David G.; Moore, Jessica L.; Rose, Kristie L.; Hammer, Neal D.; Skaar, Eric P.; Caprioli, Richard M.

    2015-06-01

    MALDI imaging mass spectrometry is a highly sensitive and selective tool used to visualize biomolecules in tissue. However, identification of detected proteins remains a difficult task. Indirect identification strategies have been limited by insufficient mass accuracy to confidently link ion images to proteomics data. Here, we demonstrate the capabilities of MALDI FTICR MS for imaging intact proteins. MALDI FTICR IMS provides an unprecedented combination of mass resolving power (~75,000 at m/z 5000) and accuracy (differentiate a series of oxidation products of S100A8 ( m/z 10,164.03, -2.1ppm), a subunit of the heterodimer calprotectin, in kidney tissue from mice infected with Staphylococcus aureus. S100A8 - M37O/C42O3 ( m/z 10228.00, -2.6ppm) was found to co-localize with bacterial microcolonies at the center of infectious foci. The ability of MALDI FTICR IMS to distinguish S100A8 modifications is critical to understanding calprotectin's roll in nutritional immunity.

  1. Nonreductive chemical release of intact N-glycans for subsequent labeling and analysis by mass spectrometry.

    Science.gov (United States)

    Yuan, Jiangbei; Wang, Chengjian; Sun, Yujiao; Huang, Linjuan; Wang, Zhongfu

    2014-10-01

    A novel strategy is proposed, using cost-saving chemical reactions to generate intact free reducing N-glycans and their fluorescent derivatives from glycoproteins for subsequent analysis. N-Glycans without core α-1,3-linked fucose are released in reducing form by selective hydrolysis of the N-type carbohydrate-peptide bond of glycoproteins under a set of optimized mild alkaline conditions and are comparable to those released by commonly used peptide-N-glycosidase (PNGase) F in terms of yield without any detectable side reaction (peeling or deacetylation). The obtained reducing glycans can be routinely derivatized with 2-aminobenzoic acid (2-AA), 1-phenyl-3-methyl-5-pyrazolone (PMP), and potentially some other fluorescent reagents for comprehensive analysis. Alternatively, the core α-1,3-fucosylated N-glycans are released in mild alkaline medium and derivatized with PMP in situ, and their yields are comparable to those obtained using commonly used PNGase A without conspicuous peeling reaction or any detectable deacetylation. Using this new technique, the N-glycans of a series of purified glycoproteins and complex biological samples were successfully released and analyzed by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS), demonstrating its general applicability to glycomic studies. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. The importance of the biomimetic composites components for recreating the optical properties and molecular composition of intact dental tissues.

    Science.gov (United States)

    Seredin, P. V.; Goloshchapov, D. L.; Gushchin, M. S.; Ippolitov, Y. A.; Prutskij, T.

    2017-11-01

    The objective of this paper was to investigate whether it is possible to obtain biomimetic materials recreating the luminescent properties and molecular composition of intact dental tissues. Biomimetic materials were produced and their properties compared with native dental tissues. In addition, the overall contribution of the organic and non-organic components in the photoluminescence band was investigated. The results showed that it is possible to develop biomimetic materials with similar molecular composition and optical properties to native dental tissues for the early identification of dental caries.

  3. Molecular and FISH analyses of a 53-kbp intact DNA fragment inserted by biolistics in wheat (Triticum aestivum L.) genome.

    Science.gov (United States)

    Partier, A; Gay, G; Tassy, C; Beckert, M; Feuillet, C; Barret, P

    2017-10-01

    A large, 53-kbp, intact DNA fragment was inserted into the wheat ( Triticum aestivum L.) genome. FISH analyses of individual transgenic events revealed multiple insertions of intact fragments. Transferring large intact DNA fragments containing clusters of resistance genes or complete metabolic pathways into the wheat genome remains a challenge. In a previous work, we showed that the use of dephosphorylated cassettes for wheat transformation enabled the production of simple integration patterns. Here, we used the same technology to produce a cassette containing a 44-kb Arabidopsis thaliana BAC, flanked by one selection gene and one reporter gene. This 53-kb linear cassette was integrated in the bread wheat (Triticum aestivum L.) genome by biolistic transformation. Our results showed that transgenic plants harboring the entire cassette were generated. The inheritability of the cassette was demonstrated in the T1 and T2 generation. Surprisingly, FISH analysis performed on T1 progeny of independent events identified double genomic insertions of intact fragments in non-homoeologous positions. Inheritability of these double insertions was demonstrated by FISH analysis of the T1 generation. Relative conclusions that can be drawn from molecular or FISH analysis are discussed along with future prospects of the engineering of large fragments for wheat transformation or genome editing.

  4. Differential isotope dansylation labeling combined with liquid chromatography mass spectrometry for quantification of intact and N-terminal truncated proteins

    International Nuclear Information System (INIS)

    Tang, Yanan; Li, Liang

    2013-01-01

    Graphical abstract: -- Highlights: •LC–MS was developed for quantifying protein mixtures containing both intact and N-terminal truncated proteins. • 12 C 2 -Dansylation of the N-terminal amino acid of proteins was done first, followed by microwave-assisted acid hydrolysis. •The released 12 C 2 -dansyl labeled N-terminal amino acid was quantified using 13 C 2 -dansyl labeled amino acid standards. •The method provided accurate and precise results for quantifying intact and N-terminal truncated proteins within 8 h. -- Abstract: The N-terminal amino acids of proteins are important structure units for maintaining the biological function, localization, and interaction networks of proteins. Under different biological conditions, one or several N-terminal amino acids could be cleaved from an intact protein due to processes, such as proteolysis, resulting in the change of protein properties. Thus, the ability to quantify the N-terminal truncated forms of proteins is of great importance, particularly in the area of development and production of protein-based drugs where the relative quantity of the intact protein and its truncated form needs to be monitored. In this work, we describe a rapid method for absolute quantification of protein mixtures containing intact and N-terminal truncated proteins. This method is based on dansylation labeling of the N-terminal amino acids of proteins, followed by microwave-assisted acid hydrolysis of the proteins into amino acids. It is shown that dansyl labeled amino acids are stable in acidic conditions and can be quantified by liquid chromatography mass spectrometry (LC–MS) with the use of isotope analog standards

  5. Differential isotope dansylation labeling combined with liquid chromatography mass spectrometry for quantification of intact and N-terminal truncated proteins

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Yanan; Li, Liang, E-mail: Liang.Li@ualberta.ca

    2013-08-20

    Graphical abstract: -- Highlights: •LC–MS was developed for quantifying protein mixtures containing both intact and N-terminal truncated proteins. •{sup 12}C{sub 2}-Dansylation of the N-terminal amino acid of proteins was done first, followed by microwave-assisted acid hydrolysis. •The released {sup 12}C{sub 2}-dansyl labeled N-terminal amino acid was quantified using {sup 13}C{sub 2}-dansyl labeled amino acid standards. •The method provided accurate and precise results for quantifying intact and N-terminal truncated proteins within 8 h. -- Abstract: The N-terminal amino acids of proteins are important structure units for maintaining the biological function, localization, and interaction networks of proteins. Under different biological conditions, one or several N-terminal amino acids could be cleaved from an intact protein due to processes, such as proteolysis, resulting in the change of protein properties. Thus, the ability to quantify the N-terminal truncated forms of proteins is of great importance, particularly in the area of development and production of protein-based drugs where the relative quantity of the intact protein and its truncated form needs to be monitored. In this work, we describe a rapid method for absolute quantification of protein mixtures containing intact and N-terminal truncated proteins. This method is based on dansylation labeling of the N-terminal amino acids of proteins, followed by microwave-assisted acid hydrolysis of the proteins into amino acids. It is shown that dansyl labeled amino acids are stable in acidic conditions and can be quantified by liquid chromatography mass spectrometry (LC–MS) with the use of isotope analog standards.

  6. Direct analysis of intact biological macromolecules by low-energy, fiber-based femtosecond laser vaporization at 1042 nm wavelength with nanospray postionization mass spectrometry.

    Science.gov (United States)

    Shi, Fengjian; Flanigan, Paul M; Archer, Jieutonne J; Levis, Robert J

    2015-03-17

    A fiber-based laser with a pulse duration of 435 fs and a wavelength of 1042 nm was used to vaporize biological macromolecules intact from the condensed phase into the gas phase for nanospray postionization and mass analysis. Laser vaporization of dried standard protein samples from a glass substrate by 10 Hz bursts of 20 pulses having 10 μs pulse separation and energy resulted in signal comparable to a metal substrate. The protein signal observed from an aqueous droplet on a glass substrate was negligible compared to either a droplet on metal or a thin film on glass. The mass spectra generated from dried and aqueous protein samples by the low-energy, fiber laser were similar to the results from high-energy (500 μJ), 45-fs, 800-nm Ti:sapphire-based femtosecond laser electrospray mass spectrometry (LEMS) experiments, suggesting that the fiber-based femtosecond laser desorption mechanism involves a nonresonant, multiphoton process, rather than thermal- or photoacoustic-induced desorption. Direct analysis of whole blood performed without any pretreatment resulted in features corresponding to hemoglobin subunit-heme complex ions. The observation of intact molecular ions with low charge states from protein, and the tentatively assigned hemoglobin α subunit-heme complex from blood suggests that fiber-based femtosecond laser vaporization is a "soft" desorption source at a laser intensity of 2.39 × 10(12) W/cm(2). The low-energy, turnkey fiber laser demonstrates the potential of a more robust and affordable laser for femtosecond laser vaporization to deliver biological macromolecules into the gas phase for mass analysis.

  7. Mass spectrometry imaging of surface lipids on intact Drosophila melanogaster flies

    Czech Academy of Sciences Publication Activity Database

    Kaftan, Filip; Vrkoslav, Vladimír; Kynast, P.; Kulkarni, P.; Böcker, S.; Cvačka, Josef; Knaden, M.; Svatoš, Aleš

    2014-01-01

    Roč. 49, č. 3 (2014), s. 223-232 ISSN 1076-5174 R&D Projects: GA ČR GA203/09/0139 Institutional support: RVO:61388963 Keywords : MALDI * laser desorption * mass spectrometric imaging * fruit flies * neutral lipids * sex pheromones * mass shift correction Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.379, year: 2014

  8. New Ionization and Detection Technologies for Mass Spectrometry Imaging. From Small Molecules to Intact Proteins

    NARCIS (Netherlands)

    Kiss, A.

    2014-01-01

    There is a constantly growing interest in biomedical research to visualize changes in the location of various biomolecules in tissue sections as a result of complex diseases. Mass spectrometry imaging is one of the techniques that enable the mapping of molecules on a 2D surface. However, the

  9. Performance of intact and partially degraded concrete barriers in limiting mass transport

    International Nuclear Information System (INIS)

    Walton, J.C.

    1992-06-01

    Mass transport through concrete barriers and release rate from concrete vaults are quantitatively evaluated. The thorny issue of appropriate diffusion coefficients for use in performance assessment calculations is covered, with no ultimate solution found. Release from monolithic concrete vaults composed of concrete waste forms is estimated with a semi-analytical solution. A parametric study illustrates the importance of different parameters on release. A second situation of importance is the role of a concrete shell or vault placed around typical waste forms in limiting mass transport. In both situations, the primary factor controlling concrete performance is cracks. The implications of leaching behavior on likely groundwater concentrations is examined. Frequently, lower groundwater concentrations can be expected in the absence of engineered covers that reduce infiltration

  10. Nuclear molecular structure in heavy mass systems

    International Nuclear Information System (INIS)

    Arctaedius, T.; Bargholtz, C.

    1989-04-01

    A study is made of nuclear molecular configurations involving one heavy mass partner. The stability of these configurations to mass flow and to fission is investigated as well as their population in fusion reactions. It is concluded that shell effects in combination with the effects of angular momentum may be important in stabilizing certain configurations. A possible relation of these configurations to the so called superdeformed states is pointed out. The spectrum of rotational and vibrational trasitions within molecular configurations is investigated. For sufficiently mass-asymmetric systems the engergies of vibrational transitions are comparable to the neutron separation energy. Gamma radiation from such transitions may then be observable above the background of statistical transitions. The gamma spectrum and the directional distribution of the radioation following fusion reactions with 12 C and 16 O are calculated. (authors)

  11. MCCREEP - a model to estimate creep produced by microcracking around a cavity in an intact rock mass

    International Nuclear Information System (INIS)

    Wilkins, B.J.S.; Rigby, G.L.

    1991-11-01

    AECL Research is examining the disposal of nuclear fuel waste in a vault in plutonic rock. Models (MCDIRC and MCROC) have been developed to predict the mechanical behaviour of the rock in response to excavation and heat from the waste. The dominant mechanism of deformation at temperatures below 150 degrees C is microcracking, which results in rock creep and a decrease in rock strength. MCDIRC has been constructed to consider the perturbation of the stress state of intact rock by long cylindrical cavities. Slow crack-growth data are used to estimate time-dependent changes in rock strength, from which possible movements (creep strain) in the rock mass are estimated. MCDIRC depends on analytical solutions for stress-state perturbations. MCCREEP has been developed from MCDIRC and relies on the use of finite-element methods to solve for stress states. It is more flexible than MCDIRC and can deal with non-homogeneous rock properties and non-symmetrical cavities

  12. Front-End Electron Transfer Dissociation Coupled to a 21 Tesla FT-ICR Mass Spectrometer for Intact Protein Sequence Analysis

    Science.gov (United States)

    Weisbrod, Chad R.; Kaiser, Nathan K.; Syka, John E. P.; Early, Lee; Mullen, Christopher; Dunyach, Jean-Jacques; English, A. Michelle; Anderson, Lissa C.; Blakney, Greg T.; Shabanowitz, Jeffrey; Hendrickson, Christopher L.; Marshall, Alan G.; Hunt, Donald F.

    2017-09-01

    High resolution mass spectrometry is a key technology for in-depth protein characterization. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enables high-level interrogation of intact proteins in the most detail to date. However, an appropriate complement of fragmentation technologies must be paired with FTMS to provide comprehensive sequence coverage, as well as characterization of sequence variants, and post-translational modifications. Here we describe the integration of front-end electron transfer dissociation (FETD) with a custom-built 21 tesla FT-ICR mass spectrometer, which yields unprecedented sequence coverage for proteins ranging from 2.8 to 29 kDa, without the need for extensive spectral averaging (e.g., 60% sequence coverage for apo-myoglobin with four averaged acquisitions). The system is equipped with a multipole storage device separate from the ETD reaction device, which allows accumulation of multiple ETD fragment ion fills. Consequently, an optimally large product ion population is accumulated prior to transfer to the ICR cell for mass analysis, which improves mass spectral signal-to-noise ratio, dynamic range, and scan rate. We find a linear relationship between protein molecular weight and minimum number of ETD reaction fills to achieve optimum sequence coverage, thereby enabling more efficient use of instrument data acquisition time. Finally, real-time scaling of the number of ETD reactions fills during method-based acquisition is shown, and the implications for LC-MS/MS top-down analysis are discussed. [Figure not available: see fulltext.

  13. A sulfuric-lactic acid process for efficient purification of fungal chitosan with intact molecular weight.

    Science.gov (United States)

    Naghdi, Mitra; Zamani, Akram; Karimi, Keikhosro

    2014-02-01

    The most recent method of fungal chitosan purification, i.e., two steps of dilute sulfuric acid treatment, pretreatment of cell wall at room temperature for phosphate removal and extraction of chitosan from the phosphate free cell wall at high temperature, significantly reduces the chitosan molecular weight. This study was aimed at improvement of this method. In the pretreatment step, to choose the best conditions, cell wall of Rhizopus oryzae, containing 9% phosphate, 10% glucosamine, and 21% N-acetyl glucosamine, was treated with sulfuric, lactic, acetic, nitric, or hydrochloric acid, at room temperature. Sulfuric acid showed the best performance in phosphate removal (90%) and cell wall recovery (89%). To avoid depolymerisation of chitosan, hot sulfuric acid extraction was replaced with lactic acid treatment at room temperature, and a pure fungal chitosan was obtained (0.12 g/g cell wall). Similar pretreatment and extraction processes were conducted on pure shrimp chitosan and resulted in a chitosan recovery of higher than 87% while the reduction of chitosan viscosity was less than 15%. Therefore, the sulfuric-lactic acid method purified the fungal chitosan without significant molecular weight manipulation. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. MALDI mass spectrometry based molecular phenotyping of CNS glial cells for prediction in mammalian brain tissue

    DEFF Research Database (Denmark)

    Hanrieder, Jørg; Wicher, Grzegorz; Bergquist, Jonas

    2011-01-01

    . Complementary proteomic experiments revealed the identity of these signature proteins that were predominantly expressed in the different glial cell types, including histone H4 for oligodendrocytes and S100-A10 for astrocytes. MALDI imaging MS was performed, and signature masses were employed as molecular...... tracers for prediction of oligodendroglial and astroglial localization in brain tissue. The different cell type specific protein distributions in tissue were validated using immunohistochemistry. ICMS of intact neuroglia is a simple and straightforward approach for characterization and discrimination...

  15. Definition of the mitochondrial proteome by measurement of molecular masses of membrane proteins

    Science.gov (United States)

    Carroll, Joe; Fearnley, Ian M.; Walker, John E.

    2006-01-01

    The covalent structure of a protein is incompletely defined by its gene sequence, and mass spectrometric analysis of the intact protein is needed to detect the presence of any posttranslational modifications. Because most membrane proteins are purified in detergents that are incompatible with mass spectrometric ionization techniques, this essential measurement has not been made on many hydrophobic proteins, and so proteomic data are incomplete. We have extracted membrane proteins from bovine mitochondria and detergent-purified NADH:ubiquinone oxidoreductase (complex I) with organic solvents, fractionated the mixtures by hydrophilic interaction chromatography, and measured the molecular masses of the intact membrane proteins, including those of six subunits of complex I that are encoded in mitochondrial DNA. These measurements resolve long-standing uncertainties about the interpretation of the mitochondrial genome, and they contribute significantly to the definition of the covalent composition of complex I. PMID:17060615

  16. RhoA/ROCK pathway is the major molecular determinant of basal tone in intact human internal anal sphincter.

    Science.gov (United States)

    Rattan, Satish; Singh, Jagmohan

    2012-04-01

    The knowledge of molecular control mechanisms underlying the basal tone in the intact human internal anal sphincter (IAS) is critical for the pathophysiology and rational therapy for a number of debilitating rectoanal motility disorders. We determined the role of RhoA/ROCK and PKC pathways by comparing the effects of ROCK- and PKC-selective inhibitors Y 27632 and Gö 6850 (10(-8) to 10(-4) M), respectively, on the basal tone in the IAS vs. the rectal smooth muscle (RSM). Western blot studies were performed to determine the levels of RhoA/ROCK II, PKC-α, MYPT1, CPI-17, and MLC(20) in the unphosphorylated and phosphorylated forms, in the IAS vs. RSM. Confocal microscopic studies validated the membrane distribution of ROCK II. Finally, to confirm a direct relationship, we examined the enzymatic activities and changes in the basal IAS tone and p-MYPT1, p-CPI-17, and p-MLC(20), before and after Y 27632 and Gö 6850. Data show higher levels of RhoA/ROCK II and related downstream signal transduction proteins in the IAS vs. RSM. In addition, data show a significant correlation between the active RhoA/ROCK levels, ROCK enzymatic activity, downstream proteins, and basal IAS tone, before and after ROCK inhibitor. From these data we conclude 1) RhoA/ROCK and downstream signaling are constitutively active in the IAS, and this pathway (in contrast with PKC) is the critical determinant of the basal tone in intact human IAS; and 2) RhoA and ROCK are potential therapeutic targets for a number of rectoanal motility disorders for which currently there is no satisfactory treatment.

  17. Capillary Isoelectric Focusing-Mass Spectrometry Method for the Separation and Online Characterization of Intact Monoclonal Antibody Charge Variants.

    Science.gov (United States)

    Dai, Jun; Lamp, Jared; Xia, Qiangwei; Zhang, Yingru

    2018-02-06

    We report a new online capillary isoelectric focusing-mass spectrometry (CIEF-MS) method for monoclonal antibody (mAb) charge variant analysis using an electrokinetically pumped sheath-flow nanospray ion source and a time-of-flight MS with pressure-assisted chemical mobilization. To develop a successful, reliable CIEF-MS method for mAb, we have selected and optimized many critical, interrelating reagents and parameters that include (1) MS-friendly anolyte and catholyte; (2) a glycerol enhanced sample mixture that reduced non-CIEF electrophoretic mobility and band broadening; (3) ampholyte selected for balancing resolution and MS sensitivity; (4) sheath liquid composition optimized for efficient focusing, mobilization, and electrospray ionization; (5) judiciously selected CIEF running parameters including injection amount, field strength, and applied pressure. The fundamental premise of CIEF was well maintained as verified by the linear correlation (R 2 = 0.99) between pI values and migration time using a mixture of pI markers. In addition, the charge variant profiles of trastuzumab, bevacizumab, infliximab, and cetuximab, obtained using this CIEF-MS method, were corroborated by imaged CIEF-UV (iCIEF-UV) analyses. The relative standard deviations (RSD) of absolute migration time of pI markers were all less than 5% (n = 4). Triplicate analyses of bevacizumab showed RSD less than 1% for relative migration time to an internal standard and RSD of 7% for absolute MS peak area. Moreover, the antibody charge variants were characterized using the online intact MS data. To the best of our knowledge, this is the first time that direct online MS detection and characterization were achieved for mAb charge variants resolved by CIEF as indicated by a well-established linear pH gradient and correlated CIEF-UV charge variant profiles.

  18. Direct molecular mass determination of trehalose monomycolate from 11 species of mycobacteria by MALDI-TOF mass spectrometry.

    Science.gov (United States)

    Fujita, Yukiko; Naka, Takashi; Doi, Takeshi; Yano, Ikuya

    2005-05-01

    Direct estimation of the molecular mass of single molecular species of trehalose 6-monomycolate (TMM), a ubiquitous cell-wall component of mycobacteria, was performed by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. When less than 1 microg TMM was analysed by MALDI-TOF mass spectrometry, quasimolecular ions [M+Na]+ of each molecular species were demonstrated and the numbers of carbons and double bonds (or cyclopropane rings) were determined. Since the introduction of oxygen atoms such as carbonyl, methoxy and ester groups yielded the appropriate shift of mass ions, the major subclasses of mycolic acid (alpha, methoxy, keto and wax ester) were identified without resorting to hydrolytic procedures. The results showed a marked difference in the molecular species composition of TMM among mycobacterial species. Unexpectedly, differing from other mycoloyl glycolipids, TMM from Mycobacterium tuberculosis showed a distinctive mass pattern, with abundant odd-carbon-numbered monocyclopropanoic (or monoenoic) alpha-mycolates besides dicyclopropanoic mycolate, ranging from C75 to C85, odd- and even-carbon-numbered methoxymycolates ranging from C83 to C94 and even- and odd-carbon-numbered ketomycolates ranging from C83 to C90. In contrast, TMM from Mycobacterium bovis (wild strain and BCG substrains) possessed even-carbon-numbered dicyclopropanoic alpha-mycolates. BCG Connaught strain lacked methoxymycolates almost completely. These results were confirmed by MALDI-TOF mass analysis of mycolic acid methyl esters liberated by alkaline hydrolysis and methylation of the original TMM. Wax ester-mycoloyl TMM molecular species were demonstrated for the first time as an intact form in the Mycobacterium avium-intracellulare group, M. phlei and M. flavescens. The M. avium-intracellulare group possessed predominantly C85 and C87 wax ester-mycoloyl TMM, while M. phlei and the rapid growers tested contained C80, C81, C82 and C83 wax ester

  19. MoFi: A Software Tool for Annotating Glycoprotein Mass Spectra by Integrating Hybrid Data from the Intact Protein and Glycopeptide Level.

    Science.gov (United States)

    Skala, Wolfgang; Wohlschlager, Therese; Senn, Stefan; Huber, Gabriel E; Huber, Christian G

    2018-04-18

    Hybrid mass spectrometry (MS) is an emerging technique for characterizing glycoproteins, which typically display pronounced microheterogeneity. Since hybrid MS combines information from different experimental levels, it crucially depends on computational methods. Here, we describe a novel software tool, MoFi, which integrates hybrid MS data to assign glycans and other post-translational modifications (PTMs) in deconvoluted mass spectra of intact proteins. Its two-stage search algorithm first assigns monosaccharide/PTM compositions to each peak and then compiles a hierarchical list of glycan combinations compatible with these compositions. Importantly, the program only includes those combinations which are supported by a glycan library as derived from glycopeptide or released glycan analysis. By applying MoFi to mass spectra of rituximab, ado-trastuzumab emtansine, and recombinant human erythropoietin, we demonstrate how integration of bottom-up data may be used to refine information collected at the intact protein level. Accordingly, our software reveals that a single mass frequently can be explained by a considerable number of glycoforms. Yet, it simultaneously ranks proteoforms according to their probability, based on a score which is calculated from relative glycan abundances. Notably, glycoforms that comprise identical glycans may nevertheless differ in score if those glycans occupy different sites. Hence, MoFi exposes different layers of complexity that are present in the annotation of a glycoprotein mass spectrum.

  20. Direct glycan structure determination of intact N-linked glycopeptides by low-energy collision-induced dissociation tandem mass spectrometry and predicted spectral library searching.

    Science.gov (United States)

    Pai, Pei-Jing; Hu, Yingwei; Lam, Henry

    2016-08-31

    Intact glycopeptide MS analysis to reveal site-specific protein glycosylation is an important frontier of proteomics. However, computational tools for analyzing MS/MS spectra of intact glycopeptides are still limited and not well-integrated into existing workflows. In this work, a new computational tool which combines the spectral library building/searching tool, SpectraST (Lam et al. Nat. Methods2008, 5, 873-875), and the glycopeptide fragmentation prediction tool, MassAnalyzer (Zhang et al. Anal. Chem.2010, 82, 10194-10202) for intact glycopeptide analysis has been developed. Specifically, this tool enables the determination of the glycan structure directly from low-energy collision-induced dissociation (CID) spectra of intact glycopeptides. Given a list of possible glycopeptide sequences as input, a sample-specific spectral library of MassAnalyzer-predicted spectra is built using SpectraST. Glycan identification from CID spectra is achieved by spectral library searching against this library, in which both m/z and intensity information of the possible fragmentation ions are taken into consideration for improved accuracy. We validated our method using a standard glycoprotein, human transferrin, and evaluated its potential to be used in site-specific glycosylation profiling of glycoprotein datasets from LC-MS/MS. In addition, we further applied our method to reveal, for the first time, the site-specific N-glycosylation profile of recombinant human acetylcholinesterase expressed in HEK293 cells. For maximum usability, SpectraST is developed as part of the Trans-Proteomic Pipeline (TPP), a freely available and open-source software suite for MS data analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Intact cell MALDI-TOF mass spectrometry on single bovine oocyte and follicular cells combined with top-down proteomics: A novel approach to characterise markers of oocyte maturation.

    Science.gov (United States)

    Labas, Valérie; Teixeira-Gomes, Ana-Paula; Bouguereau, Laura; Gargaros, Audrey; Spina, Lucie; Marestaing, Aurélie; Uzbekova, Svetlana

    2018-03-20

    Intact cell MALDI-TOF mass spectrometry (ICM-MS) was adapted to bovine follicular cells from individual ovarian follicles to obtain the protein/peptide signatures (top-down workflow using high resolution MS/MS (TD HR-MS) was performed on the protein extracts from oocytes, CC and GC. The TD HR-MS proteomic approach allowed for: (1) identification of 386 peptide/proteoforms encoded by 194 genes; and (2) characterisation of proteolysis products likely resulting from the action of kallikreins and caspases. In total, 136 peaks observed by ICM-MS were annotated by TD HR-MS (ProteomeXchange PXD004892). Among these, 16 markers of maturation were identified, including IGF2 binding protein 3 and hemoglobin B in the oocyte, thymosins beta-4 and beta-10, histone H2B and ubiquitin in CC. The combination of ICM-MS and TD HR-MS proved to be a suitable strategy to identify non-invasive markers of oocyte quality using limited biological samples. Intact cell MALDI-TOF mass spectrometry on single oocytes and their surrounding cumulus cells, coupled to an optimised top-down HR-MS proteomic approach on ovarian follicular cells, was used to identify specific markers of oocyte meiotic maturation represented by whole low molecular weight proteins or products of degradation by specific proteases. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. De novo quence analysis and intact mass measurements for characterization of phycocyanin subunit isoforms from the blue-green alga Aphanizomenon flos-aquae

    DEFF Research Database (Denmark)

    Rinalducci, Sara; Roepstorff, Peter; Zolla, Lello

    2009-01-01

    isothiocyanate (SPITC) and MALDI-TOF/TOF analyses, facilitated the acquisition of sequence information for AFA phycocyanin subunits. In fact, SPITC-derivatized peptides underwent facile fragmentation, predominantly resulting in y-series ions in the MS/MS spectra and often exhibiting uninterrupted sequences of 20...... of phycocyanin subunits was also revealed; subsequently Intact Mass Measurements (IMMs) by both MALDI- and ESI-MS supported the detection of these protein isoforms. Finally, we discuss the evolutionary importance of phycocyanin isoforms in cyanobacteria, suggesting the possible use of the phycocyanin operon...

  3. A rapid, simple method for the genetic discrimination of intact Arabidopsis thaliana mutant seeds using metabolic profiling by direct analysis in real-time mass spectrometry

    Directory of Open Access Journals (Sweden)

    Jang Young

    2011-06-01

    Full Text Available Abstract Background Efficient high throughput screening systems of useful mutants are prerequisite for study of plant functional genomics and lots of application fields. Advance in such screening tools, thanks to the development of analytic instruments. Direct analysis in real-time (DART-mass spectrometry (MS by ionization of complex materials at atmospheric pressure is a rapid, simple, high-resolution analytical technique. Here we describe a rapid, simple method for the genetic discrimination of intact Arabidopsis thaliana mutant seeds using metabolic profiling by DART-MS. Results To determine whether this DART-MS combined by multivariate analysis can perform genetic discrimination based on global metabolic profiling, intact Arabidopsis thaliana mutant seeds were subjected to DART-MS without any sample preparation. Partial least squares-discriminant analysis (PLS-DA of DART-MS spectral data from intact seeds classified 14 different lines of seeds into two distinct groups: Columbia (Col-0 and Landsberg erecta (Ler ecotype backgrounds. A hierarchical dendrogram based on partial least squares-discriminant analysis (PLS-DA subdivided the Col-0 ecotype into two groups: mutant lines harboring defects in the phenylpropanoid biosynthetic pathway and mutants without these defects. These results indicated that metabolic profiling with DART-MS could discriminate intact Arabidopsis seeds at least ecotype level and metabolic pathway level within same ecotype. Conclusion The described DART-MS combined by multivariate analysis allows for rapid screening and metabolic characterization of lots of Arabidopsis mutant seeds without complex metabolic preparation steps. Moreover, potential novel metabolic markers can be detected and used to clarify the genetic relationship between Arabidopsis cultivars. Furthermore this technique can be applied to predict the novel gene function of metabolic mutants regardless of morphological phenotypes.

  4. Subset of Kappa and Lambda Germline Sequences Result in Light Chains with a Higher Molecular Mass Phenotype.

    Science.gov (United States)

    Barnidge, David R; Lundström, Susanna L; Zhang, Bo; Dasari, Surendra; Murray, David L; Zubarev, Roman A

    2015-12-04

    In our previous work, we showed that electrospray ionization of intact polyclonal kappa and lambda light chains isolated from normal serum generates two distinct, Gaussian-shaped, molecular mass distributions representing the light-chain repertoire. During the analysis of a large (>100) patient sample set, we noticed a low-intensity molecular mass distribution with a mean of approximately 24 250 Da, roughly 800 Da higher than the mean of the typical kappa molecular-mass distribution mean of 23 450 Da. We also observed distinct clones in this region that did not appear to contain any typical post-translational modifications that would account for such a large mass shift. To determine the origin of the high molecular mass clones, we performed de novo bottom-up mass spectrometry on a purified IgM monoclonal light chain that had a calculated molecular mass of 24 275.03 Da. The entire sequence of the monoclonal light chain was determined using multienzyme digestion and de novo sequence-alignment software and was found to belong to the germline allele IGKV2-30. The alignment of kappa germline sequences revealed ten IGKV2 and one IGKV4 sequences that contained additional amino acids in their CDR1 region, creating the high-molecular-mass phenotype. We also performed an alignment of lambda germline sequences, which showed additional amino acids in the CDR2 region, and the FR3 region of functional germline sequences that result in a high-molecular-mass phenotype. The work presented here illustrates the ability of mass spectrometry to provide information on the diversity of light-chain molecular mass phenotypes in circulation, which reflects the germline sequences selected by the immunoglobulin-secreting B-cell population.

  5. Hemoglobin variants as models for investigation of dissociation of intact polypeptide chains by ESI tandem mass spectrometry

    International Nuclear Information System (INIS)

    Light, K.J.; Loo, J.A.; Edmonds, C.G.; Smith, R.D.

    1991-06-01

    Electrospray ionization mass spectroscopy (ESI-MS) is rapidly becoming a practical biochemical tool for peptide and protein sequence analysis. The utility of ESI-MS is through use of Collisionally Activated Dissociation (ESI-CAD-MS). Human hemoglobin (Hb, ∼62 kDa) consists of four polypeptide chains and a prosthetic heme group. There are over 400 Hb variants, characterized by amino acid substitutions in either the alpha or beta polypeptide chains. We investigated ESI-CAD-MS as a tool for rapidly analyzing amino acid substitutions, using eight Hb beta chain variants. The approximate location of the modification can be deduced from comparison of the CAD mass spectra and observance of the mass shifts of the fragment ion containing the substitution. Fragmentation occurs preferentially at the amino terminus of proline residues. For most substitutions, differences in CAD mass spectra were not seen. 2 figs

  6. The role of post-failure brittleness of soft rocks in the assessment of stability of intact masses: FDEM technique applications to ideal problems

    Science.gov (United States)

    Lollino, Piernicola; Andriani, Gioacchino Francesco; Fazio, Nunzio Luciano; Perrotti, Michele

    2016-04-01

    Strain-softening under low confinement stress, i.e. the drop of strength that occurs in the post-failure stage, represents a key factor of the stress-strain behavior of rocks. However, this feature of the rock behavior is generally underestimated or even neglected in the assessment of boundary value problems of intact soft rock masses. This is typically the case when the stability of intact rock masses is treated by means of limit equilibrium or finite element analyses, for which rigid-plastic or elastic perfectly-plastic constitutive models, generally implementing peak strength conditions of the rock, are respectively used. In fact, the aforementioned numerical techniques are characterized by intrinsic limitations that do not allow to account for material brittleness, either for the method assumptions or due to numerical stability problems, as for the case of the finite element method, unless sophisticated regularization techniques are implemented. However, for those problems that concern the stability of intact soft rock masses at low stress levels, as for example the stability of shallow underground caves or that of rock slopes, the brittle stress-strain response of rock in the post-failure stage cannot be disregarded due to the risk of overestimation of the stability factor. This work is aimed at highlighting the role of post-peak brittleness of soft rocks in the analysis of specific ideal problems by means of the use of a hybrid finite-discrete element technique (FDEM) that allows for the simulation of the rock stress-strain brittle behavior in a proper way. In particular, the stability of two ideal cases, represented by a shallow underground rectangular cave and a vertical cliff, has been analyzed by implementing a post-peak brittle behavior of the rock and the comparison with a non-brittle response of the rock mass is also explored. To this purpose, the mechanical behavior of a soft calcarenite belonging to the Calcarenite di Gravina formation, extensively

  7. Rapid Identification of Intact Staphylococcal Bacteriophages Using Matrix-Assisted Laser Desorption Ionization-Time-of-Flight Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Dana Štveráková

    2018-04-01

    Full Text Available Staphylococcus aureus is a major causative agent of infections associated with hospital environments, where antibiotic-resistant strains have emerged as a significant threat. Phage therapy could offer a safe and effective alternative to antibiotics. Phage preparations should comply with quality and safety requirements; therefore, it is important to develop efficient production control technologies. This study was conducted to develop and evaluate a rapid and reliable method for identifying staphylococcal bacteriophages, based on detecting their specific proteins using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS profiling that is among the suggested methods for meeting the regulations of pharmaceutical authorities. Five different phage purification techniques were tested in combination with two MALDI-TOF MS matrices. Phages, either purified by CsCl density gradient centrifugation or as resuspended phage pellets, yielded mass spectra with the highest information value if ferulic acid was used as the MALDI matrix. Phage tail and capsid proteins yielded the strongest signals whereas the culture conditions had no effect on mass spectral quality. Thirty-seven phages from Myoviridae, Siphoviridae or Podoviridae families were analysed, including 23 siphophages belonging to the International Typing Set for human strains of S. aureus, as well as phages in preparations produced by Microgen, Bohemia Pharmaceuticals and MB Pharma. The data obtained demonstrate that MALDI-TOF MS can be used to effectively distinguish between Staphylococcus-specific bacteriophages.

  8. High- and low-molecular-mass microbial surfactants.

    Science.gov (United States)

    Rosenberg, E; Ron, E Z

    1999-08-01

    Microorganisms synthesize a wide variety of high- and low-molecular-mass bioemulsifiers. The low-molecular-mass bioemulsifiers are generally glycolipids, such as trehalose lipids, sophorolipids and rhamnolipids, or lipopeptides, such as surfactin, gramicidin S and polymyxin. The high-molecular-mass bioemulsifiers are amphipathic polysaccharides, proteins, lipopolysaccharides, lipoproteins or complex mixtures of these biopolymers. The low-molecular-mass bioemulsifiers lower surface and interfacial tensions, whereas the higher-molecular-mass bioemulsifiers are more effective at stabilizing oil-in-water emulsions. Three natural roles for bioemulsifiers have been proposed: (i) increasing the surface area of hydrophobic water-insoluble growth substrates; (ii) increasing the bioavailability of hydrophobic substrates by increasing their apparent solubility or desorbing them from surfaces; (iii) regulating the attachment and detachment of microorganisms to and from surfaces. Bioemulsifiers have several important advantages over chemical surfactants, which should allow them to become prominent in industrial and environmental applications. The potential commercial applications of bioemulsifiers include bioremediation of oil-polluted soil and water, enhanced oil recovery, replacement of chlorinated solvents used in cleaning-up oil-contaminated pipes, vessels and machinery, use in the detergent industry, formulations of herbicides and pesticides and formation of stable oil-in-water emulsions for the food and cosmetic industries.

  9. Microwave-assisted acid and base hydrolysis of intact proteins containing disulfide bonds for protein sequence analysis by mass spectrometry.

    Science.gov (United States)

    Reiz, Bela; Li, Liang

    2010-09-01

    Controlled hydrolysis of proteins to generate peptide ladders combined with mass spectrometric analysis of the resultant peptides can be used for protein sequencing. In this paper, two methods of improving the microwave-assisted protein hydrolysis process are described to enable rapid sequencing of proteins containing disulfide bonds and increase sequence coverage, respectively. It was demonstrated that proteins containing disulfide bonds could be sequenced by MS analysis by first performing hydrolysis for less than 2 min, followed by 1 h of reduction to release the peptides originally linked by disulfide bonds. It was shown that a strong base could be used as a catalyst for microwave-assisted protein hydrolysis, producing complementary sequence information to that generated by microwave-assisted acid hydrolysis. However, using either acid or base hydrolysis, amide bond breakages in small regions of the polypeptide chains of the model proteins (e.g., cytochrome c and lysozyme) were not detected. Dynamic light scattering measurement of the proteins solubilized in an acid or base indicated that protein-protein interaction or aggregation was not the cause of the failure to hydrolyze certain amide bonds. It was speculated that there were some unknown local structures that might play a role in preventing an acid or base from reacting with the peptide bonds therein. 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  10. Use of a charge reducing agent to enable intact mass analysis of cysteine-linked antibody-drug-conjugates by native mass spectrometry

    Directory of Open Access Journals (Sweden)

    Kamila J. Pacholarz

    2016-06-01

    Full Text Available Antibody-drug-conjugates (ADC are a growing class of anticancer biopharmaceuticals. Conjugation of cysteine linked ADCs, requires initial reduction of mAb inter-chain disulfide bonds, as the drugs are attached via thiol chemistry. This results in the active mAb moiety being transformed from a covalently linked tetramer to non-covalently linked complexes, which hinders precise determination of drug load with LC–MS. Here, we show how the addition of the charge reducing agent triethylammonium acetate (TEAA preserves the intact mAb structure, is well suited to the study of cysteine linked conjugates and facilitates easy drug load determination by direct infusion native MS.

  11. Refinement of glucagon-like peptide 1 docking to its intact receptor using mid-region photolabile probes and molecular modeling.

    Science.gov (United States)

    Miller, Laurence J; Chen, Quan; Lam, Polo C-H; Pinon, Delia I; Sexton, Patrick M; Abagyan, Ruben; Dong, Maoqing

    2011-05-06

    The glucagon-like peptide 1 (GLP1) receptor is an important drug target within the B family of G protein-coupled receptors. Its natural agonist ligand, GLP1, has incretin-like actions and the receptor is a recognized target for management of type 2 diabetes mellitus. Despite recent solution of the structure of the amino terminus of the GLP1 receptor and several close family members, the molecular basis for GLP1 binding to and activation of the intact receptor remains unclear. We previously demonstrated molecular approximations between amino- and carboxyl-terminal residues of GLP1 and its receptor. In this work, we study spatial approximations with the mid-region of this peptide to gain insights into the orientation of the intact receptor and the ligand-receptor complex. We have prepared two new photolabile probes incorporating a p-benzoyl-l-phenylalanine into positions 16 and 20 of GLP1(7-36). Both probes bound to the GLP1 receptor specifically and with high affinity. These were each fully efficacious agonists, stimulating cAMP accumulation in receptor-bearing CHO cells in a concentration-dependent manner. Each probe specifically labeled a single receptor site. Protease cleavage and radiochemical sequencing identified receptor residue Leu(141) above transmembrane segment one as its site of labeling for the position 16 probe, whereas the position 20 probe labeled receptor residue Trp(297) within the second extracellular loop. Establishing ligand residue approximation with this loop region is unique among family members and may help to orient the receptor amino-terminal domain relative to its helical bundle region.

  12. Mass transport thermodynamics in nonisothermal molecular liquid mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Semenov, Semen N [Institute for Biochemical Physics, Russian Academy of Sciences, Moscow (Russian Federation); Schimpf, M E [Department of Chemistry and Biochemistry, Boise State University, Boise, ID (United States)

    2009-10-31

    Mass transport in a nonisothermal binary molecular mixture is systematically discussed in terms of nonequilibrium thermodynamics, which for the first time allows a consistent and unambiguous description of the process. The thermodynamic and hydrodynamic approaches are compared, revealing that nonequilibrium thermodynamics and physicochemical hydrodynamics yield essentially the same results for molecular systems. The applicability limits for the proposed version of the thermodynamic approach are determined for large particles. (methodological notes)

  13. Ejecting intact large molecular structures by C{sub 60} ion impact upon bio-organic solids; Ejection de tres grandes structures moleculaires intactes par impact de C{sub 60} sur des solides bioorganiques

    Energy Technology Data Exchange (ETDEWEB)

    Brunelle, A.; Della Negra, S.; Deprun, C.; Depauw, J.; Jacquet, D.; Le Beyec, Y.; Pautrat, N. [Experimental Research Division, Inst. de Physique Nucleaire, Paris-11 Univ., 91 - Orsay (France); Haakansson, P. [Division of Ion Physics, Angstrom Laboratory, Uppsala Univ. Uppsala (Sweden)

    1999-11-01

    C{sub 60} molecules accelerated to MeV energies (20 MeV) have been used to induce the desorption-ionization of large bio-molecules from solid samples. In the case of the trypsin molecules, the secondary molecular ion emission yield is about two orders of magnitude larger than with MeV atomic ions. This is a consequence of the very high energy density deposited in solids by 20 MeV C{sub 60} projectiles that gives rise to a large amount of matter ejected after each impact. Although time-of-flight mass spectra can be recorded within a few seconds, it is more the mechanistic aspects in comparison with other particle induced desorption methods, which are the objective of these first results with energetic fullerenes. (authors) 1 fig.

  14. Molecular mass spectrometry imaging in biomedical and life science research

    Czech Academy of Sciences Publication Activity Database

    Pól, Jaroslav; Strohalm, Martin; Havlíček, Vladimír; Volný, Michael

    2010-01-01

    Roč. 134, č. 5 (2010), s. 423-443 ISSN 0948-6143 R&D Projects: GA MŠk LC545; GA ČR GPP206/10/P018 Institutional research plan: CEZ:AV0Z50200510 Keywords : Mass spectrometry * Chemical imaging * Molecular imaging Subject RIV: EE - Microbiology, Virology Impact factor: 4.727, year: 2010

  15. Molecular characterization and expression analysis of fat mass and ...

    Indian Academy of Sciences (India)

    Keywords. fat mass and obesity-associated gene (FTO); rabbit; mRNA expression patterns; sequence analysis; Oryctolagus cuniculus. ... In this work, the molecular characterization and expression features of rabbit (Oryctolagus cuniculus) FTO cDNA were analysed. The rabbit FTO cDNA with a size of 2158 bp was cloned, ...

  16. Molecular engineering problems in heat and mass transfer

    International Nuclear Information System (INIS)

    Kotake, S.

    1991-01-01

    As for developing, manufacturing and applying new materials of advanced functions such as high-performance devices and high-temperature materials, fundamental understanding of the phenomena from the standpoint of molecular and atomic levels has been required. In these problems, the processes of heat and mass transfer play an important role, being one of the rate-controlling factors. But the energy levels associated with heat and mass transfer are of the orders much less than those of chemical reaction, and it is not easy to understand the thermal problems on the molecular and atomic basis. This paper views the processes of heat and mass transfer from the dynamical motions of atom and molecule for thermal engineering problems. Especially, problems are considered of heat conduction in fine-ceramics, sintered materials of high heat conductivity or high heat-insulation, phase change of condensation in vapor deposition processes such as CVD and PVD, and radiation in laser processing

  17. 1,8-Bis(dimethylamino)naphthalene/9-aminoacridine: A new binary matrix for lipid fingerprinting of intact bacteria by matrix assisted laser desorption ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Calvano, C.D., E-mail: cosimadamiana.calvano@uniba.it [Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, Via Orabona, 4, 70126 Bari (Italy); Monopoli, A.; Ditaranto, N. [Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, Via Orabona, 4, 70126 Bari (Italy); Palmisano, F. [Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, Via Orabona, 4, 70126 Bari (Italy); Centro Interdipartimentale di Ricerca S.M.A.R.T., Università degli Studi di Bari Aldo Moro, Via Orabona, 4, 70126 Bari (Italy)

    2013-10-10

    Graphical abstract: -- Highlights: •New binary matrix for less ionizable lipid analysis with no interfering peaks. •Combined MALDI and X-ray photoelectron spectroscopy (XPS) analyses. •Fast lipid fingerprint on Gram positive and Gram negative bacteria by MALDI MS. •Mapping of phospholipids by XPS imaging. •Very fast membrane lipid extraction procedure. -- Abstract: The effectiveness of a novel binary matrix composed of 1,8-bis(dimethylamino)naphthalene (DMAN; proton sponge) and 9-aminoacridine (9AA) for the direct lipid analysis of whole bacterial cells by matrix assisted laser desorption ionization mass spectrometry (MALDI MS) is demonstrated. Deprotonated analyte signals nearly free of matrix-related ions were observed in negative ion mode. The effect of the most important factors (laser energy, pulse voltage, DMAN/9AA ratio, analyte/matrix ratio) was investigated using a Box–Behnken response surface design followed by multi-response optimization in order to simultaneously maximize signal-to-noise (S/N) ratio and resolution. The chemical surface composition of single or mixed matrices was explored by X-ray photoelectron spectroscopy (XPS). Moreover, XPS imaging was used to map the spatial distribution of a model phospholipid in single or binary matrices. The DMAN/9AA binary matrix was then successfully applied to the analysis of intact Gram positive (Lactobacillus sanfranciscensis) or Gram negative (Escherichia coli) microorganisms. About fifty major membrane components (free fatty acids, mono-, di- and tri-glycerides, phospholipids, glycolipids and cardiolipins) were quickly and easily detected over a mass range spanning from ca. 200 to ca. 1600 m/z. Moreover, mass spectra with improved S/N ratio (compared to single matrices), reduced chemical noise and no formation of matrix-clusters were invariably obtained demonstrating the potential of this binary matrix to improve sensitivity.

  18. 1,8-Bis(dimethylamino)naphthalene/9-aminoacridine: A new binary matrix for lipid fingerprinting of intact bacteria by matrix assisted laser desorption ionization mass spectrometry

    International Nuclear Information System (INIS)

    Calvano, C.D.; Monopoli, A.; Ditaranto, N.; Palmisano, F.

    2013-01-01

    Graphical abstract: -- Highlights: •New binary matrix for less ionizable lipid analysis with no interfering peaks. •Combined MALDI and X-ray photoelectron spectroscopy (XPS) analyses. •Fast lipid fingerprint on Gram positive and Gram negative bacteria by MALDI MS. •Mapping of phospholipids by XPS imaging. •Very fast membrane lipid extraction procedure. -- Abstract: The effectiveness of a novel binary matrix composed of 1,8-bis(dimethylamino)naphthalene (DMAN; proton sponge) and 9-aminoacridine (9AA) for the direct lipid analysis of whole bacterial cells by matrix assisted laser desorption ionization mass spectrometry (MALDI MS) is demonstrated. Deprotonated analyte signals nearly free of matrix-related ions were observed in negative ion mode. The effect of the most important factors (laser energy, pulse voltage, DMAN/9AA ratio, analyte/matrix ratio) was investigated using a Box–Behnken response surface design followed by multi-response optimization in order to simultaneously maximize signal-to-noise (S/N) ratio and resolution. The chemical surface composition of single or mixed matrices was explored by X-ray photoelectron spectroscopy (XPS). Moreover, XPS imaging was used to map the spatial distribution of a model phospholipid in single or binary matrices. The DMAN/9AA binary matrix was then successfully applied to the analysis of intact Gram positive (Lactobacillus sanfranciscensis) or Gram negative (Escherichia coli) microorganisms. About fifty major membrane components (free fatty acids, mono-, di- and tri-glycerides, phospholipids, glycolipids and cardiolipins) were quickly and easily detected over a mass range spanning from ca. 200 to ca. 1600 m/z. Moreover, mass spectra with improved S/N ratio (compared to single matrices), reduced chemical noise and no formation of matrix-clusters were invariably obtained demonstrating the potential of this binary matrix to improve sensitivity

  19. (Photosynthesis in intact plants)

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    Progress in the two years since the last renewal application has been excellent. We have made substantial contributions on both main fronts of the projects, and are particularly happy with the progress of our research on intact plants. The approach of basing our field work on a sound foundation of laboratory studies has enabled is to use methods which provide unambiguous assays of well characterized reactions. We have also made excellent progress in several laboratory studies which will have direct applications in future field work, and have introduced to the laboratory a range of molecular genetics techniques which will allow us to explore new options in the attempt to understand function at the level of molecular structure.

  20. Piezoelectric sensors based on molecular imprinted polymers for detection of low molecular mass analytes.

    Science.gov (United States)

    Uludağ, Yildiz; Piletsky, Sergey A; Turner, Anthony P F; Cooper, Matthew A

    2007-11-01

    Biomimetic recognition elements employed for the detection of analytes are commonly based on proteinaceous affibodies, immunoglobulins, single-chain and single-domain antibody fragments or aptamers. The alternative supra-molecular approach using a molecularly imprinted polymer now has proven utility in numerous applications ranging from liquid chromatography to bioassays. Despite inherent advantages compared with biochemical/biological recognition (which include robustness, storage endurance and lower costs) there are few contributions that describe quantitative analytical applications of molecularly imprinted polymers for relevant small molecular mass compounds in real-world samples. There is, however, significant literature describing the use of low-power, portable piezoelectric transducers to detect analytes in environmental monitoring and other application areas. Here we review the combination of molecularly imprinted polymers as recognition elements with piezoelectric biosensors for quantitative detection of small molecules. Analytes are classified by type and sample matrix presentation and various molecularly imprinted polymer synthetic fabrication strategies are also reviewed.

  1. Atmospheric-pressure solution-cathode glow discharge: A versatile ion source for atomic and molecular mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Andrew J. [Department of Chemistry, Indiana University, Bloomington, IN, 47405 (United States); Williams, Kelsey L. [Department of Chemistry and Biochemistry, Kent State University, Kent, OH, 44242 (United States); Hieftje, Gary M. [Department of Chemistry, Indiana University, Bloomington, IN, 47405 (United States); Shelley, Jacob T., E-mail: shellj@rpi.edu [Department of Chemistry and Biochemistry, Kent State University, Kent, OH, 44242 (United States); Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY, 12180 (United States)

    2017-01-15

    An atmospheric-pressure solution-cathode glow discharge (SCGD) has been evaluated as an ion source for atomic, molecular, and ambient desorption/ionization mass spectrometry. The SCGD consists of a direct-current plasma, supported in the ambient air in the absence of gas flows, and sustained upon the surface of a flowing liquid cathode. Analytes introduced in the flowing liquid, as an ambient gas, or as a solid held near the plasma are vaporized and ionized by interactions within or near the discharge. Introduction of acidic solutions containing metal salts produced bare elemental ions as well as H{sub 2}O, OH{sup −} and NO{sub 3}{sup −} adducts. Detection limits for these elemental species ranged from 0.1 to 4 ppb, working curves spanned more than 4 orders of linear dynamic range, and precision varied between 5 and 16% relative standard deviation. Small organic molecules were also efficiently ionized from solution, and both the intact molecular ion and fragments were observed in the resulting SCGD mass spectra. Fragmentation of molecular species was found to be tunable; high discharge currents led to harder ionization, while low discharge currents produced stronger molecular-ion signals. Ambient gases and solids, desorbed by the plasma from a glass probe, were also readily ionized by the SCGD. Indeed, strong analyte signals were obtained from solid samples placed at least 2 cm from the plasma. These findings indicate that the SCGD might be useful also for ambient desorption/ionization mass spectrometry. Combined with earlier results that showed the SCGD is useful for ionization of labile biomolecules, the results here indicate that the SCGD is a highly versatile ion source capable of providing both elemental and molecular mass-spectral information. - Highlights: • Solution-cathode glow discharge used as an ionization source for mass spectrometry. • SCGD-MS can provide atomic as well as intact molecular mass spectra. • Atomic limits of detection range

  2. Molecular dynamics of nanodroplet impact: The effect of the projectile’s molecular mass on sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Saiz, Fernan [Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London, SW7 2A7 (United Kingdom); Gamero-Castaño, Manuel, E-mail: mgameroc@uci.edu [Department of Mechanical and Aerospace Engineering, University of California, Irvine, California, 92697 (United States)

    2016-06-15

    The impact of electrosprayed nanodroplets on ceramics at several km/s alters the atomic order of the target, causing sputtering, surface amorphization and cratering. The molecular mass of the projectile is known to have a strong effect on the impact phenomenology, and this article aims to rationalize this dependency using molecular dynamics. To achieve this goal, the article models the impact of four projectiles with molecular masses between 45 and 391 amu, and identical diameters and kinetic energies, 10 nm and 63 keV, striking a silicon target. In agreement with experiments, the simulations show that the number of sputtered atoms strongly increases with molecular mass. This is due to the increasing intensity of collision cascades with molecular mass: when the fixed kinetic energy of the projectile is distributed among fewer, more massive molecules, their collisions with the target produce knock-on atoms with higher energies, which in turn generate more energetic and larger numbers of secondary and tertiary knock-on atoms. The more energetic collision cascades intensify both knock-on sputtering and, upon thermalization, thermal sputtering. Besides enhancing sputtering, heavier molecules also increase the fraction of the projectile’s energy that is transferred to the target, as well as the fraction of this energy that is dissipated.

  3. Molecular dynamics of nanodroplet impact: The effect of the projectile’s molecular mass on sputtering

    International Nuclear Information System (INIS)

    Saiz, Fernan; Gamero-Castaño, Manuel

    2016-01-01

    The impact of electrosprayed nanodroplets on ceramics at several km/s alters the atomic order of the target, causing sputtering, surface amorphization and cratering. The molecular mass of the projectile is known to have a strong effect on the impact phenomenology, and this article aims to rationalize this dependency using molecular dynamics. To achieve this goal, the article models the impact of four projectiles with molecular masses between 45 and 391 amu, and identical diameters and kinetic energies, 10 nm and 63 keV, striking a silicon target. In agreement with experiments, the simulations show that the number of sputtered atoms strongly increases with molecular mass. This is due to the increasing intensity of collision cascades with molecular mass: when the fixed kinetic energy of the projectile is distributed among fewer, more massive molecules, their collisions with the target produce knock-on atoms with higher energies, which in turn generate more energetic and larger numbers of secondary and tertiary knock-on atoms. The more energetic collision cascades intensify both knock-on sputtering and, upon thermalization, thermal sputtering. Besides enhancing sputtering, heavier molecules also increase the fraction of the projectile’s energy that is transferred to the target, as well as the fraction of this energy that is dissipated.

  4. Phenotyping polyclonal kappa and lambda light chain molecular mass distributions in patient serum using mass spectrometry.

    Science.gov (United States)

    Barnidge, David R; Dasari, Surendra; Ramirez-Alvarado, Marina; Fontan, Adrian; Willrich, Maria A V; Tschumper, Renee C; Jelinek, Diane F; Snyder, Melissa R; Dispenzieri, Angela; Katzmann, Jerry A; Murray, David L

    2014-11-07

    We previously described a microLC-ESI-Q-TOF MS method for identifying monoclonal immunoglobulins in serum and then tracking them over time using their accurate molecular mass. Here we demonstrate how the same methodology can be used to identify and characterize polyclonal immunoglobulins in serum. We establish that two molecular mass distributions observed by microLC-ESI-Q-TOF MS are from polyclonal kappa and lambda light chains using a combination of theoretical molecular masses from gene sequence data and the analysis of commercially available purified polyclonal IgG kappa and IgG lambda from normal human serum. A linear regression comparison of kappa/lambda ratios for 74 serum samples (25 hypergammaglobulinemia, 24 hypogammaglobulinemia, 25 normal) determined by microflowLC-ESI-Q-TOF MS and immunonephelometry had a slope of 1.37 and a correlation coefficient of 0.639. In addition to providing kappa/lambda ratios, the same microLC-ESI-Q-TOF MS analysis can determine the molecular mass for oligoclonal light chains observed above the polyclonal background in patient samples. In 2 patients with immune disorders and hypergammaglobulinemia, we observed a skewed polyclonal molecular mass distribution which translated into biased kappa/lambda ratios. Mass spectrometry provides a rapid and simple way to combine the polyclonal kappa/lambda light chain abundance ratios with the identification of dominant monoclonal as well as oligoclonal light chain immunoglobulins. We anticipate that this approach to evaluating immunoglobulin light chains will lead to improved understanding of immune deficiencies, autoimmune diseases, and antibody responses.

  5. TRIMS: Validating T2 Molecular Effects for Neutrino Mass Experiments

    Science.gov (United States)

    Lin, Ying-Ting; Trims Collaboration

    2017-09-01

    The Tritium Recoil-Ion Mass Spectrometer (TRIMS) experiment examines the branching ratio of the molecular tritium (T2) beta decay to the bound state (3HeT+). Measuring this branching ratio helps to validate the current molecular final-state theory applied in neutrino mass experiments such as KATRIN and Project 8. TRIMS consists of a magnet-guided time-of-flight mass spectrometer with a detector located on each end. By measuring the kinetic energy and time-of-flight difference of the ions and beta particles reaching the detectors, we will be able to distinguish molecular ions from atomic ones and hence derive the ratio in question. We will give an update on the apparatus, simulation software, and analysis tools, including efforts to improve the resolution of our detectors and to characterize the stability and uniformity of our field sources. We will also share our commissioning results and prospects for physics data. The TRIMS experiment is supported by U.S. Department of Energy Office of Science, Office of Nuclear Physics, Award Number DE-FG02-97ER41020.

  6. Rapid method for direct identification of bacteria in urine and blood culture samples by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: intact cell vs. extraction method.

    Science.gov (United States)

    Ferreira, L; Sánchez-Juanes, F; Muñoz-Bellido, J L; González-Buitrago, J M

    2011-07-01

    Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) is a fast and reliable technology for the identification of microorganisms with proteomics approaches. Here, we compare an intact cell method and a protein extraction method before application on the MALDI plate for the direct identification of microorganisms in both urine and blood culture samples from clinical microbiology laboratories. The results show that the intact cell method provides excellent results for urine and is a good initial method for blood cultures. The extraction method complements the intact cell method, improving microorganism identification from blood culture. Thus, we consider that MALDI-TOF MS performed directly on urine and blood culture samples, with the protocols that we propose, is a suitable technique for microorganism identification, as compared with the routine methods used in the clinical microbiology laboratory. © 2010 The Authors. Clinical Microbiology and Infection © 2010 European Society of Clinical Microbiology and Infectious Diseases.

  7. Dietary flavonoid fisetin increases abundance of high-molecular-mass hyaluronan conferring resistance to prostate oncogenesis.

    Science.gov (United States)

    Lall, Rahul K; Syed, Deeba N; Khan, Mohammad Imran; Adhami, Vaqar M; Gong, Yuansheng; Lucey, John A; Mukhtar, Hasan

    2016-09-01

    We and others have shown previously that fisetin, a plant flavonoid, has therapeutic potential against many cancer types. Here, we examined the probable mechanism of its action in prostate cancer (PCa) using a global metabolomics approach. HPLC-ESI-MS analysis of tumor xenografts from fisetin-treated animals identified several metabolic targets with hyaluronan (HA) as the most affected. Efficacy of fisetin on HA was then evaluated in vitro and also in vivo in the transgenic TRAMP mouse model of PCa. Size exclusion chromatography-multiangle laser light scattering (SEC-MALS) was performed to analyze the molar mass (Mw) distribution of HA. Fisetin treatment downregulated intracellular and secreted HA levels both in vitro and in vivo Fisetin inhibited HA synthesis and degradation enzymes, which led to cessation of HA synthesis and also repressed the degradation of the available high-molecular-mass (HMM)-HA. SEC-MALS analysis of intact HA fragment size revealed that cells and animals have more abundance of HMM-HA and less of low-molecular-mass (LMM)-HA upon fisetin treatment. Elevated HA levels have been shown to be associated with disease progression in certain cancer types. Biological responses triggered by HA mainly depend on the HA polymer length where HMM-HA represses mitogenic signaling and has anti-inflammatory properties whereas LMM-HA promotes proliferation and inflammation. Similarly, Mw analysis of secreted HA fragment size revealed less HMM-HA is secreted that allowed more HMM-HA to be retained within the cells and tissues. Our findings establish that fisetin is an effective, non-toxic, potent HA synthesis inhibitor, which increases abundance of antiangiogenic HMM-HA and could be used for the management of PCa. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  8. pGlyco 2.0 enables precision N-glycoproteomics with comprehensive quality control and one-step mass spectrometry for intact glycopeptide identification.

    Science.gov (United States)

    Liu, Ming-Qi; Zeng, Wen-Feng; Fang, Pan; Cao, Wei-Qian; Liu, Chao; Yan, Guo-Quan; Zhang, Yang; Peng, Chao; Wu, Jian-Qiang; Zhang, Xiao-Jin; Tu, Hui-Jun; Chi, Hao; Sun, Rui-Xiang; Cao, Yong; Dong, Meng-Qiu; Jiang, Bi-Yun; Huang, Jiang-Ming; Shen, Hua-Li; Wong, Catherine C L; He, Si-Min; Yang, Peng-Yuan

    2017-09-05

    The precise and large-scale identification of intact glycopeptides is a critical step in glycoproteomics. Owing to the complexity of glycosylation, the current overall throughput, data quality and accessibility of intact glycopeptide identification lack behind those in routine proteomic analyses. Here, we propose a workflow for the precise high-throughput identification of intact N-glycopeptides at the proteome scale using stepped-energy fragmentation and a dedicated search engine. pGlyco 2.0 conducts comprehensive quality control including false discovery rate evaluation at all three levels of matches to glycans, peptides and glycopeptides, improving the current level of accuracy of intact glycopeptide identification. The N-glycoproteome of samples metabolically labeled with 15 N/ 13 C were analyzed quantitatively and utilized to validate the glycopeptide identification, which could be used as a novel benchmark pipeline to compare different search engines. Finally, we report a large-scale glycoproteome dataset consisting of 10,009 distinct site-specific N-glycans on 1988 glycosylation sites from 955 glycoproteins in five mouse tissues.Protein glycosylation is a heterogeneous post-translational modification that generates greater proteomic diversity that is difficult to analyze. Here the authors describe pGlyco 2.0, a workflow for the precise one step identification of intact N-glycopeptides at the proteome scale.

  9. Gas chromatography-mass spectrometry with supersonic molecular beams.

    Science.gov (United States)

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

    2008-02-01

    Gas chromatography-mass spectrometry (GC-MS) with supersonic molecular beams (SMBs) (also named Supersonic GC-MS) is based on GC and MS interface with SMBs and on the electron ionization (EI) of vibrationally cold analytes in the SMBs (cold EI) in a fly-through ion source. This ion source is inherently inert and further characterized by fast response and vacuum background filtration capability. The same ion source offers three modes of ionization including cold EI, classical EI and cluster chemical ionization (CI). Cold EI, as a main mode, provides enhanced molecular ions combined with an effective library sample identification, which is supplemented and complemented by a powerful isotope abundance analysis method and software. The range of low-volatility and thermally labile compounds amenable for analysis is significantly increased owing to the use of the contact-free, fly-through ion source and the ability to lower sample elution temperatures through the use of high column carrier gas flow rates. Effective, fast GC-MS is enabled particularly owing to the possible use of high column flow rates and improved system selectivity in view of the enhancement of the molecular ion. This fast GC-MS with SMB can be further improved via the added selectivity of MS-MS, which by itself benefits from the enhancement of the molecular ion, the most suitable parent ion for MS-MS. Supersonic GC-MS is characterized by low limits of detection (LOD), and its sensitivity is superior to that of standard GC-MS, particularly for samples that are hard for analysis. The GC separation of the Supersonic GC-MS can be improved with pulsed flow modulation (PFM) GC x GC-MS. Electron ionization LC-MS with SMB can also be combined with the Supersonic GC-MS, with fast and easy switching between these two modes of operation. (c) 2008 John Wiley & Sons, Ltd.

  10. Study of molecular iodine-epoxy paint mass transfer

    Energy Technology Data Exchange (ETDEWEB)

    Belval-Haltier, E [Inst. de Protection et Surete Nucleaire, IPSN, CEN Cadarache, St. Paul-lez-Durance (France)

    1996-12-01

    The mass transfer phenomena may have a significant influence on the quantity of I{sub 2} which could be released following a severe accident of a nuclear power plant and specially the mass transfer of iodine onto containment surfaces. So, the objective of the present work was to evaluate which phase limited the adsorption process of iodine onto gaseous epoxy paint under a range of conditions which may be relevant to a severe reactor accident. In this aim, a series of experiments was conducted in which the sorption kinetics of molecular iodine, labelled with {sup 131}I, was measured by monitoring continuously the accumulation of this species on the epoxy surface. For each test condition, the initial deposition velocity was determined and the corresponding gas phase mass transfer, kg, was estimated by using the heat transfer analogy for a laminar flow passing over a flat plate. Then, the surface reaction rate, Kr, was deduced from these two values. Experiments performed indicated that iodine adsorption onto epoxy paint is highly dependent on temperature, relative humidity of the carrier gas and moisture content of the painted coupon. In dry air flow conditions, the adsorption of iodine onto paint was found to increase with temperature and to be limited by the surface reaction rate, Kr. The I{sub 2} adsorption rate was found to increase with the humidity of carrier gas and in some studied conditions, the initial deposition velocity appeared to be controlled by gas phase mass transfer rather than surface interaction. The same phenomenon has been observed with an increase of the initial water content of the painted coupon. (author) 6 figs., 1 tab., 8 refs.

  11. Protein methylation reactions in intact pea chloroplasts

    International Nuclear Information System (INIS)

    Niemi, K.J.

    1989-01-01

    Post-translational protein methylation was investigated in Pisum sativum chloroplasts. Intact pea chloroplasts were incubated with ( 3 H-methyl)-S-adenosylmethionine under various conditions. The chloroplasts were then separated into stromal and thylakoid fractions and analyzed for radioactivity transferred to protein. Light enhanced the magnitude of labeling in both fractions. One thylakoid polypeptide with an apparent molecular mass of 43 kDa was labeled only in the light. Several other thylakoid and stromal proteins were labeled in both light and dark-labeling conditions. Both base-labile methylation, carboxy-methylesters and base-stable groups, N-methylations were found. Further characterization of the methyl-transfer reactions will be presented

  12. Valine pyrrolidide preserves intact glucose-dependent insulinotropic peptide and improves abnormal glucose tolerance in minipigs with reduced beta-cell mass

    DEFF Research Database (Denmark)

    Larsen, Marianne Olholm; Rolin, Bidda; Ribel, Ulla

    2003-01-01

    levels of intact GLP-1 but increased levels of intact GIP (from 4543 +/- 1880 to 9208 +/- 3267 pM x min; P glucose tolerance (area under the curve [AUC] for glucose reduced from 1904 +/- 480 to 1582 +/- 353 mM x min; P =.05). VP did not increase insulin levels during the oral......The incretin hormones glucagon-like peptide-1 (GLP-1) and glucose-dependent insulinotropic polypeptide (GIP) are important in blood glucose regulation. However, both incretin hormones are rapidly degraded by the enzyme dipeptidyl peptidase IV (DPPIV). The concept of DPPIV inhibition as a treatment...... glucose tolerance test (OGTT) but increased the insulinogenic index in normal animals (from 83 +/- 42 to 192 +/- 108; P

  13. Method for the elucidation of the elemental composition of low molecular mass chemicals using exact masses of product ions and neutral losses: application to environmental chemicals measured by liquid chromatography with hybrid quadrupole/time-of-flight mass spectrometry.

    Science.gov (United States)

    Suzuki, Shigeru; Ishii, Tetsuko; Yasuhara, Akio; Sakai, Shinichi

    2005-01-01

    A method for elucidating the elemental compositions of low molecular weight chemicals, based primarily on mass measurements made using liquid chromatography (LC) with time-of-flight mass spectrometry (TOFMS) and quadrupole/time-of-flight mass spectrometry (LC/QTOFMS), was developed and tested for 113 chemicals of environmental interest with molecular masses up to approximately 400 Da. As the algorithm incorporating the method is not affected by differences in the instrument used, or by the ionization method and other ionization conditions, the method is useful not only for LC/TOFMS, but also for all kinds of mass spectra measured with higher accuracy and precision (uncertainties of a few mDa) employing all ionization methods and on-line separation techniques. The method involves calculating candidate compositions for intact ionized molecules (ionized forms of the sample molecule that have lost or gained no more than a proton, i.e., [M+H](+) or [M-H](-)) as well as for fragment ions and corresponding neutral losses, and eliminating those atomic compositions for the molecules that are inconsistent with the corresponding candidate compositions of fragment ions and neutral losses. Candidate compositions were calculated for the measured masses of the intact ionized molecules and of the fragment ions and corresponding neutral losses, using mass uncertainties of 2 and 5 mDa, respectively. Compositions proposed for the ionized molecule that did not correspond to the sum of the compositions of a candidate fragment ion and its corresponding neutral loss were discarded. One, 2-5, 6-10, 11-20, and >20 candidate compositions were found for 65%, 39%, 1%, 1%, and 0%, respectively, for the 124 ionized molecules formed from the 113 chemicals tested (both positive and negative ions were obtained from 11 of the chemicals). However, no candidate composition was found for 2% of the test cases (i.e., 3 chemicals), for each of which the measured mass of one of the product ions was in

  14. Classical electron ionization mass spectra in gas chromatography/mass spectrometry with supersonic molecular beams.

    Science.gov (United States)

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

    2008-09-01

    A major benefit of gas chromatography/mass spectrometry (GC/MS) with a supersonic molecular beam (SMB) interface and its fly-through ion source is the ability to obtain electron ionization of vibrationally cold molecules (cold EI), which show enhanced molecular ions. However, GC/MS with an SMB also has the flexibility to perform 'classical EI' mode of operation which provides mass spectra to mimic those in commercial 70 eV electron ionization MS libraries. Classical EI in SMB is obtained through simple reduction of the helium make-up gas flow rate, which reduces the SMB cooling efficiency; hence the vibrational temperatures of the molecules are similar to those in traditional EI ion sources. In classical EI-SMB mode, the relative abundance of the molecular ion can be tuned and, as a result, excellent identification probabilities and very good matching factors to the NIST MS library are obtained. Classical EI-SMB with the fly-through dual cage ion source has analyte sensitivity similar to that of the standard EI ion source of a basic GC/MS system. The fly-through EI ion source in combination with the SMB interface can serve for cold EI, classical EI-SMB, and cluster chemical ionization (CCI) modes of operation, all easily exchangeable through a simple and quick change (not involving hardware). Furthermore, the fly-through ion source eliminates sample scattering from the walls of the ion source, and thus it offers full sample inertness, tailing-free operation, and no ion-molecule reaction interferences. It is also robust and enables increased column flow rate capability without affecting the sensitivity.

  15. High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Hourani, Nadim; Kuhnert, Nikolai

    2012-10-15

    High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

  16. Molecular Communication over Gas Stream Channels using Portable Mass Spectrometry.

    Science.gov (United States)

    Giannoukos, Stamatios; Marshall, Alan; Taylor, Stephen; Smith, Jeremy

    2017-11-01

    The synthetic generation/coding and transmission of olfactory information over a gas stream or an odor network is a new and unexplored field. Application areas vary from the entertainment or advertisement industry to security and telemedicine. However, current technological limitations frustrate the accurate reproduction of decoded and transmitted olfactory data. This study describes the development, testing, and characterization of a novel odor emitter (OE) that is used to investigate the generation-encoding of gaseous standards with odorous characteristics with a regulatable way, for scent transmission purposes. The calibration and the responses of a developed OE were examined using a portable quadrupole mass spectrometer (MS). Experiments were undertaken for a range of volatile organic compounds (VOCs) at different temperatures and flow rates. Individual compounds and mixtures were tested to investigate periodic and dynamic transmission characteristics within two different size tubular containers for distances up to 3 m. Olfactory information transmission is demonstrated using MS as the main molecular sensor for odor detection and monitoring and for the first time spatial encryption of olfactory information is shown. Graphical Abstract ᅟ.

  17. Molecular Communication over Gas Stream Channels using Portable Mass Spectrometry

    Science.gov (United States)

    Giannoukos, Stamatios; Marshall, Alan; Taylor, Stephen; Smith, Jeremy

    2017-07-01

    The synthetic generation/coding and transmission of olfactory information over a gas stream or an odor network is a new and unexplored field. Application areas vary from the entertainment or advertisement industry to security and telemedicine. However, current technological limitations frustrate the accurate reproduction of decoded and transmitted olfactory data. This study describes the development, testing, and characterization of a novel odor emitter (OE) that is used to investigate the generation-encoding of gaseous standards with odorous characteristics with a regulatable way, for scent transmission purposes. The calibration and the responses of a developed OE were examined using a portable quadrupole mass spectrometer (MS). Experiments were undertaken for a range of volatile organic compounds (VOCs) at different temperatures and flow rates. Individual compounds and mixtures were tested to investigate periodic and dynamic transmission characteristics within two different size tubular containers for distances up to 3 m. Olfactory information transmission is demonstrated using MS as the main molecular sensor for odor detection and monitoring and for the first time spatial encryption of olfactory information is shown.

  18. Dissecting plasmodesmata molecular composition by mass spectrometry-based proteomics.

    Directory of Open Access Journals (Sweden)

    Emmanuelle Maria Françoise Bayer

    2013-01-01

    Full Text Available In plants, the intercellular communication through the membranous channels called plasmodesmata (PD; singular plasmodesma plays pivotal roles in the orchestration of development, defence responses and viral propagation. PD are dynamic structures embedded in the plant cell wall that are defined by specialised domains of the endoplasmic reticulum and the plasma membrane. PD structure and unique functions are guaranteed by their particular molecular composition. Yet, up to recent years and despite numerous approaches such as mutant screens, immunolocalisation or screening of random cDNAs, only few PD proteins had been conclusively identified and characterised. A clear breakthrough in the search of PD constituents came from mass-spectrometry-based proteomic approaches coupled with subcellular fractionation strategies. Due to their position, firmly anchored in the extracellular matrix, PD are notoriously difficult to isolate for biochemical analysis. Proteomic-based approaches have therefore first relied on the use of cell wall fractions containing embedded PD then on free PD fractions whereby PD membranes were released from the walls by enzymatic degradation. To discriminate between likely contaminants and PD protein candidates, bioinformatics tools have often been used in combination with proteomic approaches. GFP fusion proteins of selected candidates have confirmed the PD association of several protein families. Here we review the accomplishments and limitations of the proteomic based strategies to unravel the functional and structural complexity of PD. We also discuss the role of the identified PD associated proteins.

  19. Dissecting plasmodesmata molecular composition by mass spectrometry-based proteomics.

    Science.gov (United States)

    Salmon, Magali S; Bayer, Emmanuelle M F

    2012-01-01

    In plants, the intercellular communication through the membranous channels called plasmodesmata (PD; singular plasmodesma) plays pivotal roles in the orchestration of development, defence responses, and viral propagation. PD are dynamic structures embedded in the plant cell wall that are defined by specialized domains of the endoplasmic reticulum (ER) and the plasma membrane (PM). PD structure and unique functions are guaranteed by their particular molecular composition. Yet, up to recent years and despite numerous approaches such as mutant screens, immunolocalization, or screening of random cDNAs, only few PD proteins had been conclusively identified and characterized. A clear breakthrough in the search of PD constituents came from mass-spectrometry-based proteomic approaches coupled with subcellular fractionation strategies. Due to their position, firmly anchored in the extracellular matrix, PD are notoriously difficult to isolate for biochemical analysis. Proteomic-based approaches have therefore first relied on the use of cell wall fractions containing embedded PD then on "free" PD fractions whereby PD membranes were released from the walls by enzymatic degradation. To discriminate between likely contaminants and PD protein candidates, bioinformatics tools have often been used in combination with proteomic approaches. GFP fusion proteins of selected candidates have confirmed the PD association of several protein families. Here we review the accomplishments and limitations of the proteomic-based strategies to unravel the functional and structural complexity of PD. We also discuss the role of the identified PD-associated proteins.

  20. The influence of extruded starch molecular mass on the properties of extruded thermoplastic starch

    NARCIS (Netherlands)

    Soest, van J.J.G.; Benes, K.; Wit, de D.; Vliegenthart, J.F.G.

    1996-01-01

    The mechanical properties of a low and a high molecular mass thermoplastic starch (TPS) were monitored at water contents in the range of 5-30% (w/w). The granular starches were plasticized by extrusion processing with glycerol and water. The low molecular mass starch was prepared by partial acid

  1. The influence of starch molecular mass on the properties of extruded thermoplastic starch

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Soest, J.J.G. van; Benes, K.; Wit, D. de

    1996-01-01

    The mechanical properties of a low and a high molecular mass thermoplastic starch (TPS) were monitored at water contents in the range of 5–30% (w/w). The granular starches were plasticized by extrusion processing with glycerol and water. The low molecular mass starch was prepared by partial acid

  2. Molecular mechanisms of induced mutagenesis. Replication in vivo of bacteriophage phiX174 single-stranded, ultraviolet light-irradiated DNA in intact and irradiated host cells

    Energy Technology Data Exchange (ETDEWEB)

    Caillet-Fauquet, P; Defais, M; Radman, M [Brussels Univ. (Belgium)

    1977-11-25

    Genetic analysis has revealed that radiation and many chemical mutagens induce in bacteria an error-prone DNA repair process which is responsible for their mutagenic effect. The biochemical mechanism of this inducible error-prone repair has been studied by analysis of the first round of DNA synthesis on ultraviolet light-irradiated phiX174 DNA in both intact and ultraviolet light-irradiated host cells. Intracellular phiX174 DNA was extracted, subjected to isopycnic CsCl density-gradient analysis, hydroxylapatite chromatography and digestion by single-strand-specific endonuclease S/sub 1/. Ultraviolet light-induced photolesions in viral DNA cause a permanent blockage of DNA synthesis in intact Escherichia coli cells. However, when host cells were irradiated and incubated to induce fully the error-prone repair system, a significant fraction of irradiated phiX174 DNA molecules can be fully replicated. Thus, inducible error-prone repair in E.coli is manifested by an increased capacity for DNA synthesis on damaged phiX174 DNA. Chloramphenicol (100 ..mu.. g/ml), which is an inhibitor of the inducible error-prone DNA repair, is also an inhibitor of this particular inducible DNA synthesis.

  3. The effect of the molecular mass on the sputtering by electrosprayed nanodroplets

    Energy Technology Data Exchange (ETDEWEB)

    Borrajo-Pelaez, Rafael; Gamero-Castaño, Manuel, E-mail: mgameroc@uci.edu

    2015-07-30

    Highlights: • We study the effect of the molecular mass on nanodroplet sputtering of silicon. • The impact phenomenology is a strong function of the projectile’s molecular mass. • Nanodroplet sputtering intrinsically is a molecular scale phenomenon. - Abstract: Energetic bombardment of covalently bonded materials by electrosprayed nanodroplets causes sputtering and topographic changes on the surface of the target. This work investigates the influence of the projectile's molecular mass on these phenomena by sputtering single-crystal silicon wafers with a variety of liquids (molecular masses between 45.0 and 773.3 amu), and acceleration voltages. The electrosprays are characterized via time of flight to determine the charge to mass ratio of the nanodroplets which, together with the acceleration voltage, yield the impact velocity, the stagnation pressure, and the molecular kinetic energy of the projectile. The estimated range of droplet diameters is 20–79 nm, while the impact velocity, the stagnation pressure and the molecular kinetic energy range between 2.9–10 km/s, 4.7–63 GPa, and 2.1–98 eV. We find that the damage on the surface of the targets strongly depends on the molecular mass of the projectile: liquids with low molecular mass sputter significantly less and produce nanometric indentations and low surface roughness, the latter increasing moderately with stagnation pressure; in contrast, the roughness and sputtering caused by the impacts of droplets with larger molecular mass reach significantly higher values, and exhibit non-monotonic behaviors. The maximum sputtering yields for formamide, EAN, EMI-BF{sub 4}, EMI-Im, TES, and TPP are 0.20, 0.75, 1.20, 2.80, 4.00 and 2.90 silicon atoms per molecule in the projectile. These trends indicate that despite their rather large diameters, the sputtering by electrosprayed nanodroplets is intrinsically a molecular scale phenomenon.

  4. Atmospheric pressure plasma analysis by modulated molecular beam mass spectrometry

    NARCIS (Netherlands)

    Aranda Gonzalvo, Y.; Whitmore, T.D.; Rees, J.A.; Seymour, D.L.; Stoffels - Adamowicz, E.

    2006-01-01

    Fractional no. d. measurements for a radiofrequency plasma needle operating at atm. pressure were obtained using a mol. beam mass spectrometer (MBMS) system designed for diagnostics of atm. plasmas. The MBMS system comprises three differentially pumped stages and a mass/energy analyzer and includes

  5. ESIprot: a universal tool for charge state determination and molecular weight calculation of proteins from electrospray ionization mass spectrometry data.

    Science.gov (United States)

    Winkler, Robert

    2010-02-01

    Electrospray ionization (ESI) ion trap mass spectrometers with relatively low resolution are frequently used for the analysis of natural products and peptides. Although ESI spectra of multiply charged protein molecules also can be measured on this type of devices, only average spectra are produced for the majority of naturally occurring proteins. Evaluating such ESI protein spectra would provide valuable information about the native state of investigated proteins. However, no suitable and freely available software could be found which allows the charge state determination and molecular weight calculation of single proteins from average ESI-MS data. Therefore, an algorithm based on standard deviation optimization (scatter minimization) was implemented for the analysis of protein ESI-MS data. The resulting software ESIprot was tested with ESI-MS data of six intact reference proteins between 12.4 and 66.7 kDa. In all cases, the correct charge states could be determined. The obtained absolute mass errors were in a range between -0.2 and 1.2 Da, the relative errors below 30 ppm. The possible mass accuracy allows for valid conclusions about the actual condition of proteins. Moreover, the ESIprot algorithm demonstrates an extraordinary robustness and allows spectral interpretation from as little as two peaks, given sufficient quality of the provided m/z data, without the necessity for peak intensity data. ESIprot is independent from the raw data format and the computer platform, making it a versatile tool for mass spectrometrists. The program code was released under the open-source GPLv3 license to support future developments of mass spectrometry software. Copyright 2010 John Wiley & Sons, Ltd.

  6. The Early Entry of Al into Cells of Intact Soybean Roots (A Comparison of Three Developmental Root Regions Using Secondary Ion Mass Spectrometry Imaging).

    Science.gov (United States)

    Lazof, D. B.; Goldsmith, J. G.; Rufty, T. W.; Linton, R. W.

    1996-11-01

    Al localization was compared in three developmental regions of primary root of an Al-sensitive soybean (Glycine max) genotype using secondary ion mass spectrometry. In cryosections obtained after a 4-h exposure to 38 [mu]M [Al3+], Al had penetrated across the root and into the stele in all three regions. Although the greatest localized Al concentration was consistently at the root periphery, the majority of the Al in each region had accumulated in cortical cells. It was apparent that the secondary ion mass spectrometry 27Al+ mass signal was spread throughout the intracellular area and was not particularly intense in the cell wall. Inclusion of some cell wall in determinations of the Al levels across the root radius necessitated that these serve as minimal estimates for intracellular Al. Total accumulation of intracellular Al for each region was 60, 73, and 210 nmol g-1 fresh weight after 4 h, increasing with root development. Early metabolic responses to external Al, including those that have been reported deep inside the root and in mature regions, might result directly from intracellular Al. These responses might include ion transport events at the endodermis of mature roots or events associated with lateral root emergence, as well as events within the root tip.

  7. Spatial and mass distributions of molecular clouds and spiral structure

    International Nuclear Information System (INIS)

    Kwan, J.; Valdes, F.; National Optical Astronomy Observatories, Tucson, AZ)

    1987-01-01

    The growth of molecular clouds resulting from cloud-cloud collisions and coalescence in the Galactic ring between 4 and 8 kpc are modeled, taking into account the presence of a spiral potential and the mutual cloud-cloud gravitational attraction. The mean lifetime of molecular clouds is determined to be about 200 million years. The clouds are present in both spiral arm and interarm regions, but a spiral pattern in their spatial distribution is clearly discernible, with the more massive clouds showing a stronger correlation with the spiral arms. As viewed from within the Galactic disk, however, it is very difficult to ascertain that the molecular cloud distribution in longitude-velocity space has a spiral pattern. 19 references

  8. Valine Pyrrolidide Preserves Intact Glucose-Dependent Insulinotropic Peptide and Improves Abnormal Glucose Tolerance in Minipigs With Reduced β-Cell Mass

    OpenAIRE

    Larsen, Marianne Olholm; Rolin, Bidda; Ribel, Ulla; Wilken, Michael; Deacon, Carolyn F.; Svendsen, Ove; Gotfredsen, Carsten F.; Carr, Richard David

    2003-01-01

    The incretin hormones glucagon-like peptide-1 (GLP-1) and glucose-dependent insulinotropic polypeptide (GIP) are important in blood glucose regulation.However, both incretin hormones are rapidly degraded by the enzyme dipeptidyl peptidase IV (DPPIV). The concept of DPPIV inhibition as a treatment for type 2 diabetes was evaluated in a new large animal model of insulin-deficient diabetes and reduced β-cell mass, the nicotinamide (NIA) (67 mg/kg) and streptozotocin (STZ) (125 mg/kg)–treated min...

  9. Photoionization mass spectrometric studies of selected compounds in a molecular beam

    Energy Technology Data Exchange (ETDEWEB)

    Trott, W.M.

    1979-03-01

    Photoionization efficiency curves have been measured at moderate to high resolution for several species produced in supersonic molecular beams of acetone, acetone-d/sub 6/ and CS/sub 2/. The molecular beam photoionization mass spectrometer which has been assembled for this work is described. The performance of this instrument has been characterized by a number of experiments and calculations.

  10. Photoionization mass spectrometric studies of selected compounds in a molecular beam

    International Nuclear Information System (INIS)

    Trott, W.M.

    1979-03-01

    Photoionization efficiency curves have been measured at moderate to high resolution for several species produced in supersonic molecular beams of acetone, acetone-d 6 and CS 2 . The molecular beam photoionization mass spectrometer which has been assembled for this work is described. The performance of this instrument has been characterized by a number of experiments and calculations

  11. Development of a New Reporter Gene System-dsRed/Xanthine Phosphoribosyltransferase-Xanthine for Molecular Imaging of Processes Behind the Intact Blood-Brain Barrier

    Directory of Open Access Journals (Sweden)

    Mikhail Doubrovin

    2003-04-01

    Full Text Available We report the development of a novel dual-modality fusion reporter gene system consisting of Escherichia coli xanthine phosphoribosyltransferase (XPRT for nuclear imaging with radiolabeled xanthine and Discosoma red fluorescent protein for optical fluorescent imaging applications. The dsRed/XPRT fusion gene was successfully created and stably transduced into RG2 glioma cells, and both reporters were shown to be functional. The level of dsRed fluorescence directly correlated with XPRT enzymatic activity as measured by ribophosphorylation of [14C]-xanthine was in vitro (Ki = 0.124 ± 0.008 vs. 0.00031 ± 0.00005 mL/min/g in parental cell line, and [*]-xanthine octanol/water partition coefficient was 0.20 at pH = 7.4 (logP = 0.69, meeting requirements for the blood-brain barrier (BBB penetrating tracer. In the in vivo experiment, the concentration of [* C]-xanthine in the normal brain varied from 0.20 to 0.16 + 0.05% dose/g under 0.87 + 0.24% dose/g plasma radiotracer concentration. The accumulation in vivo in the transfected flank tumor was to 2.4 ± 0.3% dose/g, compared to 0.78 ± 0.02% dose/g and 0.64 ± 0.05% dose/g in the control flank tumors and intact muscle, respectively. [14C]-Xanthine appeared to be capable of specific accumulation in the transfected infiltrative brain tumor (RG2-dsRed/XPRT, which corresponded to the 585 nm fluorescent signal obtained from the adjacent cryosections. The images of endogenous gene expression with the “sensory system” have to be normalized for the transfection efficiency based on the “beacon system” image data. Such an approach requires two different “reporter genes” and two different “reporter substrates.” Therefore, the novel dsRed/XPRT fusion gene can be used as a multimodality reporter system in the biological applications requiring two independent reporter genes, including the cells located behind the BBB.

  12. Molecular Isotopic Distribution Analysis (MIDAs) with adjustable mass accuracy.

    Science.gov (United States)

    Alves, Gelio; Ogurtsov, Aleksey Y; Yu, Yi-Kuo

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html.

  13. Cyclodextrin--piroxicam inclusion complexes: analyses by mass spectrometry and molecular modelling

    Science.gov (United States)

    Gallagher, Richard T.; Ball, Christopher P.; Gatehouse, Deborah R.; Gates, Paul J.; Lobell, Mario; Derrick, Peter J.

    1997-11-01

    Mass spectrometry has been used to investigate the natures of non-covalent complexes formed between the anti-inflammatory drug piroxicam and [alpha]-, [beta]- and [gamma]-cyclodextrins. Energies of these complexes have been calculated by means of molecular modelling. There is a correlation between peak intensities in the mass spectra and the calculated energies.

  14. Mass spectrometric identification of molecular species of phosphatidylcholine and lysophosphatidycholine extracted from shark liver

    NARCIS (Netherlands)

    Chen, S.; Li, K.W.

    2007-01-01

    The profile and structural characterization of molecular species of phosphatidylcholine (PC) and lysophosphatidylcholine (LysoPC) from shark liver using liquid chromatographic/electrospray ionization mass spectrometry (LC-ESI/MS) and tandem mass spectrometry (MS/MS) are described for the first time

  15. Newer methods for the characterization of higher molecular mass coal derivatives

    International Nuclear Information System (INIS)

    Bartle, K.D.

    1983-01-01

    Recent developments in a number of areas in the analytical chemistry of higher molecular mass coal derivatives are critically reviewed, viz. supercritical fluid chromatography, size-exclusion chromatography, charge-transfer fractionation, nmr spectroscopy, mass spectrometry and electrochemical analysis. (orig.) [de

  16. A Century of Progress in Molecular Mass Spectrometry

    Science.gov (United States)

    McLafferty, Fred W.

    2011-07-01

    The first mass spectrum of a molecule was measured by J.J. Thomson in 1910. Mass spectrometry (MS) soon became crucial to the study of isotopes and atomic weights and to the development of atomic weapons for World War II. Its notable applications to molecules began with the quantitative analysis of light hydrocarbons during World War II. When I joined the Dow Chemical Company in 1950, MS was not favored by organic chemists. This situation improved only with an increased understanding of gaseous ion chemistry, which was obtained through the use of extensive reference data. Gas chromatography-MS was developed in 1956, and tandem MS was first used a decade later. In neutralization-reionization MS, an unusual, unstable species is prepared by ion-beam neutralization and characterized by reionization. Electrospray ionization of a protein mixture produces its corresponding ionized molecules. In top-down proteomics, ions from an individual component can be mass separated and subjected to collision-activated and electron-capture dissociation to provide extensive sequence information.

  17. Electronic sputtering of large organic molecules and its application in bio molecular mass spectrometry

    International Nuclear Information System (INIS)

    Sundqvist, B.U.R.

    1992-01-01

    This is a review of research which has its origin in the discovery of Plasma Desorption Mass Spectrometry (PDMS). Two main fields of research have developed, namely fundamental studies of the ejection process at fast ion impact and studies of applications of the new mass spectrometric technique. In this review the emphasis will be on the process of electronic sputtering of organic solids but also applications of this process in bio molecular mass spectrometry will be discussed. (author)

  18. An algorithm for mass matrix calculation of internally constrained molecular geometries.

    Science.gov (United States)

    Aryanpour, Masoud; Dhanda, Abhishek; Pitsch, Heinz

    2008-01-28

    Dynamic models for molecular systems require the determination of corresponding mass matrix. For constrained geometries, these computations are often not trivial but need special considerations. Here, assembling the mass matrix of internally constrained molecular structures is formulated as an optimization problem. Analytical expressions are derived for the solution of the different possible cases depending on the rank of the constraint matrix. Geometrical interpretations are further used to enhance the solution concept. As an application, we evaluate the mass matrix for a constrained molecule undergoing an electron-transfer reaction. The preexponential factor for this reaction is computed based on the harmonic model.

  19. An algorithm for mass matrix calculation of internally constrained molecular geometries

    International Nuclear Information System (INIS)

    Aryanpour, Masoud; Dhanda, Abhishek; Pitsch, Heinz

    2008-01-01

    Dynamic models for molecular systems require the determination of corresponding mass matrix. For constrained geometries, these computations are often not trivial but need special considerations. Here, assembling the mass matrix of internally constrained molecular structures is formulated as an optimization problem. Analytical expressions are derived for the solution of the different possible cases depending on the rank of the constraint matrix. Geometrical interpretations are further used to enhance the solution concept. As an application, we evaluate the mass matrix for a constrained molecule undergoing an electron-transfer reaction. The preexponential factor for this reaction is computed based on the harmonic model

  20. The Anomalies of Hyaluronan Structures in Presence of Surface Active Phospholipids—Molecular Mass Dependence

    Directory of Open Access Journals (Sweden)

    Piotr Bełdowski

    2018-03-01

    Full Text Available Interactions between hyaluronan (A- and phospholipids play a key role in many systems in the human body. One example is the articular cartilage system, where the synergistic effect of such interactions supports nanoscale lubrication. A molecular dynamics simulation has been performed to understand the process of formation of hydrogen bonds inside the hyaluronan network, both in the presence and absence of phospholipids. Additionally, the effect of the molecular mass of (A- was analyzed. The main finding of this work is a robust demonstration of the optimal parameters (H-bond energy, molecular mass influencing the facilitated lubrication mechanism of the articular cartilage system. Simulation results show that the presence of phospholipids has the greatest influence on hyaluronan at low molecular mass. We also show the specific sites of H-bonding between chains. Simulation results can help to understand how hyaluronan and phospholipids interact at several levels of articular cartilage system functioning.

  1. Incorporating Biological Mass Spectrometry into Undergraduate Teaching Labs, Part 2: Peptide Identification via Molecular Mass Determination

    Science.gov (United States)

    Arnquist, Isaac J.; Beussman, Douglas J.

    2009-01-01

    Mass spectrometry has become a routine analytical tool in the undergraduate curriculum in the form of GC-MS. While relatively few undergraduate programs have incorporated biological mass spectrometry into their programs, the importance of these techniques, as demonstrated by their recognition with the 2002 Nobel Prize, will hopefully lead to…

  2. A new instrument of VUV laser desorption/ionization mass spectrometry imaging with micrometer spatial resolution and low level of molecular fragmentation.

    Science.gov (United States)

    Wang, Jia; Liu, Feng; Mo, Yuxiang; Wang, Zhaoying; Zhang, Sichun; Zhang, Xinrong

    2017-11-01

    Mass spectrometry imaging (MSI) has important applications in material research, biology, and medicine. The MSI method based on UV laser desorption/ionization (UVLDI) can obtain images of intact samples, but has a high level of molecular fragmentation. In this work, we report a new MSI instrument that uses a VUV laser (125.3 nm) as a desorption/ionization source to exploit its advantages of high single photon energy and small focus size. The new instrument was tested by the mass spectra of Nile red and FGB (Fibrinogen beta chain) samples and mass spectrometric images of a fly brain section. For the tested samples, the VUVDI method offers lower levels of molecular fragmentations and higher sensitivities than those of the UVLDI method and second ion mass spectrometry imaging method using a Bi 3 + beam. The ablation crater produced by the focused VUV laser on a quartz plate has an area of 10 μm 2 . The VUV laser is prepared based on the four-wave mixing method using three collimated laser beams and a heated Hg cell.

  3. A new instrument of VUV laser desorption/ionization mass spectrometry imaging with micrometer spatial resolution and low level of molecular fragmentation

    Science.gov (United States)

    Wang, Jia; Liu, Feng; Mo, Yuxiang; Wang, Zhaoying; Zhang, Sichun; Zhang, Xinrong

    2017-11-01

    Mass spectrometry imaging (MSI) has important applications in material research, biology, and medicine. The MSI method based on UV laser desorption/ionization (UVLDI) can obtain images of intact samples, but has a high level of molecular fragmentation. In this work, we report a new MSI instrument that uses a VUV laser (125.3 nm) as a desorption/ionization source to exploit its advantages of high single photon energy and small focus size. The new instrument was tested by the mass spectra of Nile red and FGB (Fibrinogen beta chain) samples and mass spectrometric images of a fly brain section. For the tested samples, the VUVDI method offers lower levels of molecular fragmentations and higher sensitivities than those of the UVLDI method and second ion mass spectrometry imaging method using a Bi3+ beam. The ablation crater produced by the focused VUV laser on a quartz plate has an area of 10 μm2. The VUV laser is prepared based on the four-wave mixing method using three collimated laser beams and a heated Hg cell.

  4. Determination of high molecular mass compounds from Amazonian plant's leaves

    International Nuclear Information System (INIS)

    Siqueira, Denilson Soares de; Pereira, Alberto dos Santos; Aquino Neto, Francisco Radler de; Simoneit, Bernd R.T.

    2003-01-01

    The fractions of dichloromethane extracts of leaves from andiroba (Carapa guianensis - Meliaceae), caapi (Banisteriopsis caapi - Malpighiaceae), cocoa (Theobroma cacao - Sterculiaceae), Brazil nut (Bertholletia excelsa - Lecytidaceae), cupuacu (Theobroma grandiflorum - Sterculiaceae), marupa (Simaruba amara - Simaroubaceae) and rubber tree (Hevea brasiliensis - Euphorbiaceae), were analyzed by HT-HRGC and HT-HRGC-MS. Esters of homologous series of fatty acids and long chain alcohols, phytol, amyrines and tocopherols were characterized. The characterization of the compounds was based mainly in mass spectra data and in addition by usual spectrometric data ( 1 H and 13 C NMR, IR). (author)

  5. Correct primary structure assessment and extensive glyco-profiling of cetuximab by a combination of intact, middle-up, middle-down and bottom-up ESI and MALDI mass spectrometry techniques.

    Science.gov (United States)

    Ayoub, Daniel; Jabs, Wolfgang; Resemann, Anja; Evers, Waltraud; Evans, Catherine; Main, Laura; Baessmann, Carsten; Wagner-Rousset, Elsa; Suckau, Detlev; Beck, Alain

    2013-01-01

    The European Medicines Agency received recently the first marketing authorization application for a biosimilar monoclonal antibody (mAb) and adopted the final guidelines on biosimilar mAbs and Fc-fusion proteins. The agency requires high similarity between biosimilar and reference products for approval. Specifically, the amino acid sequences must be identical. The glycosylation pattern of the antibody is also often considered to be a very important quality attribute due to its strong effect on quality, safety, immunogenicity, pharmacokinetics and potency. Here, we describe a case study of cetuximab, which has been marketed since 2004. Biosimilar versions of the product are now in the pipelines of numerous therapeutic antibody biosimilar developers. We applied a combination of intact, middle-down, middle-up and bottom-up electrospray ionization and matrix assisted laser desorption ionization mass spectrometry techniques to characterize the amino acid sequence and major post-translational modifications of the marketed cetuximab product, with special emphasis on glycosylation. Our results revealed a sequence error in the reported sequence of the light chain in databases and in publications, thus highlighting the potency of mass spectrometry to establish correct antibody sequences. We were also able to achieve a comprehensive identification of cetuximab's glycoforms and glycosylation profile assessment on both Fab and Fc domains. Taken together, the reported approaches and data form a solid framework for the comparability of antibodies and their biosimilar candidates that could be further applied to routine structural assessments of these and other antibody-based products.

  6. [Correlation of molecular weight and nanofiltration mass transfer coefficient of phenolic acid composition from Salvia miltiorrhiza].

    Science.gov (United States)

    Li, Cun-Yu; Wu, Xin; Gu, Jia-Mei; Li, Hong-Yang; Peng, Guo-Ping

    2018-04-01

    Based on the molecular sieving and solution-diffusion effect in nanofiltration separation, the correlation between initial concentration and mass transfer coefficient of three typical phenolic acids from Salvia miltiorrhiza was fitted to analyze the relationship among mass transfer coefficient, molecular weight and concentration. The experiment showed a linear relationship between operation pressure and membrane flux. Meanwhile, the membrane flux was gradually decayed with the increase of solute concentration. On the basis of the molecular sieving and solution-diffusion effect, the mass transfer coefficient and initial concentration of three phenolic acids showed a power function relationship, and the regression coefficients were all greater than 0.9. The mass transfer coefficient and molecular weight of three phenolic acids were negatively correlated with each other, and the order from high to low is protocatechualdehyde >rosmarinic acid> salvianolic acid B. The separation mechanism of nanofiltration for phenolic acids was further clarified through the analysis of the correlation of molecular weight and nanofiltration mass transfer coefficient. The findings provide references for nanofiltration separation, especially for traditional Chinese medicine with phenolic acids. Copyright© by the Chinese Pharmaceutical Association.

  7. Detection of irradiated food by the changes in protein molecular mass distribution

    International Nuclear Information System (INIS)

    Niciforovic, A.; Radojcic, M.; Milosavljevic, B.H.

    1998-01-01

    Complete text of publication follows. The present work deals with the radiation-induced damage of proteins, which is followed by the change in the molecular mass. The phenomenon was studied on protein rich samples, i.e., chicken meat and dehydrated egg white. The radiation dose applied was in the range of the ones used for food microbial control. Chicken drumstick and chicken white meat proteins were separated according to their molecular mass. The protein profile was compared to the meat samples irradiated in the frozen state with 5 kGy at 60 Co source. In the case of chicken white meat, irradiation produces both nonselective protein scission (e.g. the amount of proteins of molecular mass larger than 30 kDa decreases, while the amount of proteins of molecular mass smaller than 30 kDa increases), and selective protein scission (e.g. appearance of a protein fragment of molecular mass equal to 18 kDa). In the case of chicken drumstick proteins the irradiation induces both the protein scission and the aggregation. The changes are nonspecific as well as specific and the generation of Mm = 18 kDa protein fragment was observed again. Irradiation of aerated dehydrated egg white proteins produces only nonselective protein scission. The results are discussed in view of the routine application of SDS-PAGE method for the detection of irradiated foodstuff

  8. Synchrotron based mass spectrometry to investigate the molecular properties of mineral-organic associations

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Suet Yi; Kleber, Markus; Takahashi, Lynelle K.; Nico, Peter; Keiluweit, Marco; Ahmed, Musahid

    2013-04-01

    Soil organic matter (OM) is important because its decay drives life processes in the biosphere. Analysis of organic compounds in geological systems is difficult because of their intimate association with mineral surfaces. To date there is no procedure capable of quantitatively separating organic from mineral phases without creating artifacts or mass loss. Therefore, analytical techniques that can (a) generate information about both organic and mineral phases simultaneously and (b) allow the examination of predetermined high-interest regions of the sample as opposed to conventional bulk analytical techniques are valuable. Laser Desorption Synchrotron Postionization (synchrotron-LDPI) mass spectrometry is introduced as a novel analytical tool to characterize the molecular properties of organic compounds in mineral-organic samples from terrestrial systems, and it is demonstrated that when combined with Secondary Ion Mass Spectrometry (SIMS), can provide complementary information on mineral composition. Mass spectrometry along a decomposition gradient in density fractions, verifies the consistency of our results with bulk analytical techniques. We further demonstrate that by changing laser and photoionization energies, variations in molecular stability of organic compounds associated with mineral surfaces can be determined. The combination of synchrotron-LDPI and SIMS shows that the energetic conditions involved in desorption and ionization of organic matter may be a greater determinant of mass spectral signatures than the inherent molecular structure of the organic compounds investigated. The latter has implications for molecular models of natural organic matter that are based on mass spectrometric information.

  9. WISDOM Project - II. Molecular gas measurement of the supermassive black hole mass in NGC 4697

    Science.gov (United States)

    Davis, Timothy A.; Bureau, Martin; Onishi, Kyoko; Cappellari, Michele; Iguchi, Satoru; Sarzi, Marc

    2017-07-01

    As part of the mm-Wave Interferometric Survey of Dark Object Masses (WISDOM) project, we present an estimate of the mass of the supermassive black hole (SMBH) in the nearby fast-rotating early-type galaxy NGC 4697. This estimate is based on Atacama Large Millimeter/submillimeter Array (ALMA) cycle-3 observations of the 12CO(2-1) emission line with a linear resolution of 29 pc (0.53 arcsec). We find that NGC 4697 hosts a small relaxed central molecular gas disc with a mass of 1.6 × 107 M⊙, co-spatial with the obscuring dust disc visible in optical Hubble Space Telescope imaging. We also resolve thermal 1 mm continuum emission from the dust in this disc. NGC 4697 is found to have a very low molecular gas velocity dispersion, σgas = 1.65^{+0.68}_{-0.65} km s-1. This seems to be partially because the giant molecular cloud mass function is not fully sampled, but other mechanisms such as chemical differentiation in a hard radiation field or morphological quenching also seem to be required. We detect a Keplerian increase of the rotation of the molecular gas in the very centre of NGC 4697, and use forward modelling of the ALMA data cube in a Bayesian framework with the KINematic Molecular Simulation (kinms) code to estimate an SMBH mass of (1.3_{-0.17}^{+0.18}) × 108 M⊙ and an I-band mass-to-light ratio of 2.14_{-0.05}^{+0.04} M⊙/L⊙ (at the 99 per cent confidence level). Our estimate of the SMBH mass is entirely consistent with previous measurements from stellar kinematics. This increases confidence in the growing number of SMBH mass estimates being obtained in the ALMA era.

  10. Mass spectra of hidden-charm molecular pentaquarks states

    International Nuclear Information System (INIS)

    Patel, Smruti; Vinodkumar, P.C.

    2016-01-01

    Very recently, the LHCb Collaboration has reported two hidden-charmed resonances P_c(4380) and P_c(4450) consistent with pentaquark states in the Λ_b"0 → K"-J/Ψp process with masses (widths) (4380 ±8 ± 29) MeV ((205 ±18 ± 86) MeV) and (4449.8 ±1.7 ± 2.5) MeV ((39 ±5 ±19) MeV), respectively. The observation of the P_c states has aroused the theorist's strong interest in the hidden-charm pentaquark states. They have been studied in various frameworks, such as the molecule-like pentaquark states, the diquark-diquark-antiquark type pentaquark states, the diquark-triquark type pentaquark states, re-scattering effects, etc. An identification of pentaquark states as exotic hadron has been one of the long standing problems in the physics of strong interaction and quantum chromodynamics (QCD). A decade ago lots of discussion were made about pentaquarks states but due to lack of further experimental evidences the study of pentaquarks have been almost gone in the darkness. But, recent remarkable observation of two resonances i.e. P_c(4380) and P_c(4450) with hidden charm and the minimal quark content cc-baruud provided new impact for studies of pentaquark states and opens a new window to study the exotic hadronic matter

  11. Formation of truncated proteins and high-molecular-mass aggregates upon soft illumination of photosynthetic proteins

    DEFF Research Database (Denmark)

    Rinalducci, Sara; Campostrini, Natascia; Antonioli, Paolo

    2005-01-01

    Different spot profiles were observed in 2D gel electrophoresis of thylakoid membranes performed either under complete darkness or by leaving the sample for a short time to low visible light. In the latter case, a large number of new spots with lower molecular masses, ranging between 15,000 and 25......,000 Da, were observed, and high-molecular-mass aggregates, seen as a smearing in the upper part of the gel, appeared in the region around 250 kDa. Identification of protein(s) contained in these new spots by MS/MS revealed that most of them are simply truncated proteins deriving from native ones...

  12. Modulated molecular beam mass spectrometry: A generalized expression for the ''reaction product vector'' for linear systems

    International Nuclear Information System (INIS)

    Chang, H.; Weinberg, W.H.

    1977-01-01

    A generalized expression is developed that relates the ''reaction product vector'', epsilon exp(-iphi), to the kinetic parameters of a linear system. The formalism is appropriate for the analysis of modulated molecular beam mass spectrometry data and facilitates the correlation of experimental results to (proposed) linear models. A study of stability criteria appropriate for modulated molecular beam mass spectrometry experiments is also presented. This investigation has led to interesting inherent limitations which have not heretofore been emphasized, as well as a delineation of the conditions under which stable chemical oscillations may occur in the reacting system

  13. Extraction and analysis of intact glucosinolates--a validated pressurized liquid extraction/liquid chromatography-mass spectrometry protocol for Isatis tinctoria, and qualitative analysis of other cruciferous plants.

    Science.gov (United States)

    Mohn, Tobias; Cutting, Brian; Ernst, Beat; Hamburger, Matthias

    2007-09-28

    Glucosinolates have attracted significant interest due to the chemopreventive properties of some of their transformation products. Numerous protocols for the extraction and analysis of glucosinolates have been published, but limited effort has been devoted to optimize and validate crucial extraction parameters and sample preparation steps. We carried out a systematic optimization and validation of a quantitative assay for the direct analysis of intact glucosinolates in Isatis tinctoria leaves (woad, Brassicaceae). Various parameters such as solvent composition, particle size, temperature, and number of required extraction steps were optimized using pressurized liquid extraction (PLE). We observed thermal degradation of glucosinolates at temperatures above 50 degrees C, and loss of >60% within 10min at 100 degrees C, but no enzymatic degradation in the leaf samples at ambient temperature. Excellent peak shape and resolution was obtained by reversed-phase chromatography on a Phenomenex Aqua column using 10mM ammonium formate as ion-pair reagent. Detection was carried out by electrospray ionisation mass spectrometry in the negative ion mode. Analysis of cruciferous vegetables and spices such as broccoli (Brassica oleracea L. var. italica), garden cress (Lepidium sativum L.) and black mustard (Sinapis nigra L.) demonstrated the general applicability of the method.

  14. Molecular effects in the neutrino mass determination from beta-decay of the tritium molecule

    International Nuclear Information System (INIS)

    Fackler, O.; Jeziorski, B.; Kolos, W.; Szalewicz, K.; Monkhorst, H.J.; Mugge, M.

    1986-03-01

    Molecular final state energies and transition probabilities have been computed for beta-decay of the tritium molecule. The results are of sufficient accuracy to make a determination of the electron neutrino rest mass with an error not exceeding a few tenths of an electron volt. Effects of approximate models of tritium beta-decay on the neutrino mass determination are discussed. 14 refs., 3 figs., 1 tab

  15. Black hole mass measurement using molecular gas kinematics: what ALMA can do

    Science.gov (United States)

    Yoon, Ilsang

    2017-04-01

    We study the limits of the spatial and velocity resolution of radio interferometry to infer the mass of supermassive black holes (SMBHs) in galactic centres using the kinematics of circum-nuclear molecular gas, by considering the shapes of the galaxy surface brightness profile, signal-to-noise ratios (S/Ns) of the position-velocity diagram (PVD) and systematic errors due to the spatial and velocity structure of the molecular gas. We argue that for fixed galaxy stellar mass and SMBH mass, the spatial and velocity scales that need to be resolved increase and decrease, respectively, with decreasing Sérsic index of the galaxy surface brightness profile. We validate our arguments using simulated PVDs for varying beam size and velocity channel width. Furthermore, we consider the systematic effects on the inference of the SMBH mass by simulating PVDs including the spatial and velocity structure of the molecular gas, which demonstrates that their impacts are not significant for a PVD with good S/N unless the spatial and velocity scale associated with the systematic effects are comparable to or larger than the angular resolution and velocity channel width of the PVD from pure circular motion. Also, we caution that a bias in a galaxy surface brightness profile owing to the poor resolution of a galaxy photometric image can largely bias the SMBH mass by an order of magnitude. This study shows the promise and the limits of ALMA observations for measuring SMBH mass using molecular gas kinematics and provides a useful technical justification for an ALMA proposal with the science goal of measuring SMBH mass.

  16. Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments

    Energy Technology Data Exchange (ETDEWEB)

    Tonks, James P., E-mail: james.tonks@awe.co.uk [Department of Mechanical Engineering Sciences, University of Surrey, Guildford, Surrey GU2 7XH (United Kingdom); AWE Plc, Aldermaston, Reading, Berkshire RG7 4PR (United Kingdom); Galloway, Ewan C., E-mail: ewan.galloway@awe.co.uk; King, Martin O. [AWE Plc, Aldermaston, Reading, Berkshire RG7 4PR (United Kingdom); Kerherve, Gwilherm [VACGEN Ltd, St. Leonards-On-Sea, East Sussex TN38 9NN (United Kingdom); Watts, John F. [Department of Mechanical Engineering Sciences, University of Surrey, Guildford, Surrey GU2 7XH (United Kingdom)

    2016-08-15

    A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques.

  17. Molecular theory of mass transfer kinetics and dynamics at gas-water interface

    International Nuclear Information System (INIS)

    Morita, Akihiro; Garrett, Bruce C

    2008-01-01

    The mass transfer mechanism across gas-water interface is studied with molecular dynamics (MD) simulation. The MD results provide a robust and qualitatively consistent picture to previous studies about microscopic aspects of mass transfer, including interface structure, free energy profiles for the uptake, scattering dynamics and energy relaxation of impinging molecules. These MD results are quantitatively compared with experimental uptake measurements, and we find that the apparent inconsistency between MD and experiment could be partly resolved by precise decomposition of the observed kinetics into elemental steps. Remaining issues and future perspectives toward constructing a comprehensive multi-scale description of interfacial mass transfer are summarized.

  18. A High-Mass Cold Core in the Auriga-California Giant Molecular Cloud

    Science.gov (United States)

    Magnus McGehee, Peregrine; Paladini, Roberta; Pelkonen, Veli-Matti; Toth, Viktor; Sayers, Jack

    2015-08-01

    The Auriga-California Giant Molecular Cloud is noted for its relatively low star formation rate, especially at the high-mass end of the Initial Mass Function. We combine maps acquired by the Caltech Submillimeter Observatory's Multiwavelength Submillimeter Inductance Camera [MUSIC] in the wavelength range 0.86 to 2.00 millimeters with Planck and publicly-available Herschel PACS and SPIRE data in order to characterize the mass, dust properties, and environment of the bright core PGCC G163.32-8.41.

  19. Cocoa content influences chocolate molecular profile investigated by MALDI-TOF mass spectrometry.

    Science.gov (United States)

    Bonatto, Cínthia C; Silva, Luciano P

    2015-06-01

    Chocolate authentication is a key aspect of quality control and safety. Matrix-assisted laser desorption ionization time-of flight (MALDI-TOF) mass spectrometry (MS) has been demonstrated to be useful for molecular profiling of cells, tissues, and even food. The present study evaluated if MALDI-TOF MS analysis on low molecular mass profile may classify chocolate samples according to the cocoa content. The molecular profiles of seven processed commercial chocolate samples were compared by using MALDI-TOF MS. Some ions detected exclusively in chocolate samples corresponded to the metabolites of cocoa or other constituents. This method showed the presence of three distinct clusters according to confectionery and sensorial features of the chocolates and was used to establish a mass spectra database. Also, novel chocolate samples were evaluated in order to check the validity of the method and to challenge the database created with the mass spectra of the primary samples. Thus, the method was shown to be reliable for clustering unknown samples into the main chocolate categories. Simple sample preparation of the MALDI-TOF MS approach described will allow the surveillance and monitoring of constituents during the molecular profiling of chocolates. © 2014 Society of Chemical Industry.

  20. Heterogeneous chemical kinetics by modulated molecular beam mass spectrometry: limitations of technique

    International Nuclear Information System (INIS)

    Olander, D.R.

    1977-01-01

    The advantages and limitations of modulated molecular beam, mass spectrometry as applied to the study of heterogeneous chemical kinetics are reviewed. The process of deducing a model of the surface reaction from experimental data is illustrated by analysis of the hydrogen reduction of uranium dioxide

  1. ACYLTRANSFERASE ACTIVITIES OF THE HIGH-MOLECULAR-MASS ESSENTIAL PENICILLIN-BINDING PROTEINS

    NARCIS (Netherlands)

    ADAM, M; DAMBLON, C; JAMIN, M; ZORZI, W; DUSART, [No Value; GALLENI, M; ELKHARROUBI, A; PIRAS, G; SPRATT, BG; KECK, W; COYETTE, J; GHUYSEN, JM; NGUYENDISTECHE, M; FRERE, JM

    1991-01-01

    The high-molecular-mass penicillin-binding proteins (HMM-PBPs), present in the cytoplasmic membranes of all eubacteria, are involved in important physiological events such as cell elongation, septation or shape determination. Up to now it has, however, been very difficult or impossible to study the

  2. Molecular outflows driven by low-mass protostars. I. Correcting for underestimates when measuring outflow masses and dynamical properties

    Energy Technology Data Exchange (ETDEWEB)

    Dunham, Michael M. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, MS 78, Cambridge, MA 02138 (United States); Arce, Héctor G. [Department of Astronomy, Yale University, P.O. Box 208101, New Haven, CT 06520 (United States); Mardones, Diego [Departamento de Astronomía, Universidad de Chile, Casilla 36-D, Santiago (Chile); Lee, Jeong-Eun [Department of Astronomy and Space Science, Kyung Hee University, Yongin, Gyeonggi 446-701 (Korea, Republic of); Matthews, Brenda C. [National Research Council of Canada, Herzberg Astronomy and Astrophysics, 5071 W. Saanich Road, Victoria, BC V9E 2E7 (Canada); Stutz, Amelia M. [Max-Planck-Institut für Astronomie, Königstuhl 17, D-69117, Heidelberg (Germany); Williams, Jonathan P., E-mail: mdunham@cfa.harvard.edu [Institute for Astronomy, University of Hawaii, Honolulu, HI 96822 (United States)

    2014-03-01

    We present a survey of 28 molecular outflows driven by low-mass protostars, all of which are sufficiently isolated spatially and/or kinematically to fully separate into individual outflows. Using a combination of new and archival data from several single-dish telescopes, 17 outflows are mapped in {sup 12}CO (2-1) and 17 are mapped in {sup 12}CO (3-2), with 6 mapped in both transitions. For each outflow, we calculate and tabulate the mass (M {sub flow}), momentum (P {sub flow}), kinetic energy (E {sub flow}), mechanical luminosity (L {sub flow}), and force (F {sub flow}) assuming optically thin emission in LTE at an excitation temperature, T {sub ex}, of 50 K. We show that all of the calculated properties are underestimated when calculated under these assumptions. Taken together, the effects of opacity, outflow emission at low velocities confused with ambient cloud emission, and emission below the sensitivities of the observations increase outflow masses and dynamical properties by an order of magnitude, on average, and factors of 50-90 in the most extreme cases. Different (and non-uniform) excitation temperatures, inclination effects, and dissociation of molecular gas will all work to further increase outflow properties. Molecular outflows are thus almost certainly more massive and energetic than commonly reported. Additionally, outflow properties are lower, on average, by almost an order of magnitude when calculated from the {sup 12}CO (3-2) maps compared to the {sup 12}CO (2-1) maps, even after accounting for different opacities, map sensitivities, and possible excitation temperature variations. It has recently been argued in the literature that the {sup 12}CO (3-2) line is subthermally excited in outflows, and our results support this finding.

  3. Characterization of product-related low molecular weight impurities in therapeutic monoclonal antibodies using hydrophilic interaction chromatography coupled with mass spectrometry.

    Science.gov (United States)

    Wang, Shunhai; Liu, Anita P; Yan, Yuetian; Daly, Thomas J; Li, Ning

    2018-05-30

    Traditional SDS-PAGE method and its modern equivalent CE-SDS method are both widely applied to assess the purity of therapeutic monoclonal antibody (mAb) drug products. However, structural identification of low molecular weight (LMW) impurities using those methods has been challenging and largely based on empirical knowledges. In this paper, we present that hydrophilic interaction chromatography (HILIC) coupled with mass spectrometry analysis is a novel and orthogonal method to characterize such LMW impurities present within a purified mAb drug product sample. We show here that after removal of N-linked glycans, the HILIC method separates mAb-related LMW impurities with a size-based elution order. The subsequent mass measurement from a high-resolution accurate mass spectrometer provides direct and unambiguous identification of a variety of low-abundance LMW impurities within a single LC-MS analysis. Free light chain, half antibody, H2L species (antibody possessing a single light chain) and protein backbone-truncated species can all be confidently identified and elucidated in great detail, including the truncation sites and associated post-translational modifications. It is worth noting that this study provides the first example where the H2L species can be directly detected in a mAb drug product sample by intact mass analysis without prior enrichment. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

  4. Thermally modulated nano-trampoline material as smart skin for gas molecular mass detection

    Science.gov (United States)

    Xia, Hua

    2012-06-01

    Conventional multi-component gas analysis is based either on laser spectroscopy, laser and photoacoustic absorption at specific wavelengths, or on gas chromatography by separating the components of a gas mixture primarily due to boiling point (or vapor pressure) differences. This paper will present a new gas molecular mass detection method based on thermally modulated nano-trampoline material as smart skin for gas molecular mass detection by fiber Bragg grating-based gas sensors. Such a nanomaterial and fiber Bragg grating integrated sensing device has been designed to be operated either at high-energy level (highly thermal strained status) or at low-energy level (low thermal strained status). Thermal energy absorption of gas molecular trigs the sensing device transition from high-thermal-energy status to low-thermal- energy status. Experiment has shown that thermal energy variation due to gas molecular thermal energy absorption is dependent upon the gas molecular mass, and can be detected by fiber Bragg resonant wavelength shift with a linear function from 17 kg/kmol to 32 kg/kmol and a sensitivity of 0.025 kg/kmol for a 5 micron-thick nano-trampoline structure and fiber Bragg grating integrated gas sensing device. The laboratory and field validation data have further demonstrated its fast response characteristics and reliability to be online gas analysis instrument for measuring effective gas molecular mass from single-component gas, binary-component gas mixture, and multi-gas mixture. The potential industrial applications include fouling and surge control for gas charge centrifugal compressor ethylene production, gas purity for hydrogen-cooled generator, gasification for syngas production, gasoline/diesel and natural gas fuel quality monitoring for consumer market.

  5. The diverse and expanding role of mass spectrometry in structural and molecular biology.

    Science.gov (United States)

    Lössl, Philip; van de Waterbeemd, Michiel; Heck, Albert Jr

    2016-12-15

    The emergence of proteomics has led to major technological advances in mass spectrometry (MS). These advancements not only benefitted MS-based high-throughput proteomics but also increased the impact of mass spectrometry on the field of structural and molecular biology. Here, we review how state-of-the-art MS methods, including native MS, top-down protein sequencing, cross-linking-MS, and hydrogen-deuterium exchange-MS, nowadays enable the characterization of biomolecular structures, functions, and interactions. In particular, we focus on the role of mass spectrometry in integrated structural and molecular biology investigations of biological macromolecular complexes and cellular machineries, highlighting work on CRISPR-Cas systems and eukaryotic transcription complexes. © 2016 The Authors. Published under the terms of the CC BY NC ND 4.0 license.

  6. Molecular weight determination of bisbenzyl-isoquinoline alkaloids by 252Cf-plasma desorption mass spectrometer

    International Nuclear Information System (INIS)

    Kohno, Hiroyuki; Tatsunami, Shinobu; Hiroi, Tomoko; Kouyama, Hiroshi; Taniguchi, Masashi; Yago, Nagasumi; Nakamura, Iwao

    1995-01-01

    Bisbenzylisoquinoline alkaloids of Stephania cepharantha have been used for various clinical purposes and recently reevaluated as stimulators of interleukin secretion in tissues. We analyzed molecular stuctures of bisbenzylisoquinoline alkaloids by determining their molecular weights using the 252 Cf-plasma desorption mass spectrometry (PDMS). The spectra were accumulated for 500 000 fission events. The acceleration voltage used here was 15 kV. Samples were analyzed using nitrocellulose-coated sample targets. Of the 5 alkaloids studied here, cepharanthine gave a main peak of molecular weight of 606.1 for the theoretical molecular weight of 606.7. The other minor peaks were considered to be demethylated fragment ions. 252 Cf-PDMS should be quite useful in studying structure, metabolism and pharmacokinetics of various drugs with extremely low coefficients of variation. (author)

  7. A black-hole mass measurement from molecular gas kinematics in NGC4526.

    Science.gov (United States)

    Davis, Timothy A; Bureau, Martin; Cappellari, Michele; Sarzi, Marc; Blitz, Leo

    2013-02-21

    The masses of the supermassive black holes found in galaxy bulges are correlated with a multitude of galaxy properties, leading to suggestions that galaxies and black holes may evolve together. The number of reliably measured black-hole masses is small, and the number of methods for measuring them is limited, holding back attempts to understand this co-evolution. Directly measuring black-hole masses is currently possible with stellar kinematics (in early-type galaxies), ionized-gas kinematics (in some spiral and early-type galaxies) and in rare objects that have central maser emission. Here we report that by modelling the effect of a black hole on the kinematics of molecular gas it is possible to fit interferometric observations of CO emission and thereby accurately estimate black-hole masses. We study the dynamics of the gas in the early-type galaxy NGC 4526, and obtain a best fit that requires the presence of a central dark object of 4.5(+4.2)(-3.1) × 10(8) solar masses (3σ confidence limit). With the next-generation millimetre-wavelength interferometers these observations could be reproduced in galaxies out to 75 megaparsecs in less than 5 hours of observing time. The use of molecular gas as a kinematic tracer should thus allow one to estimate black-hole masses in hundreds of galaxies in the local Universe, many more than are accessible with current techniques.

  8. WISDOM project - I. Black hole mass measurement using molecular gas kinematics in NGC 3665

    Science.gov (United States)

    Onishi, Kyoko; Iguchi, Satoru; Davis, Timothy A.; Bureau, Martin; Cappellari, Michele; Sarzi, Marc; Blitz, Leo

    2017-07-01

    As a part of the mm-Wave Interferometric Survey of Dark Object Masses (WISDOM) project, we present an estimate of the mass of the supermassive black hole (SMBH) in the nearby fast-rotator early-type galaxy NGC 3665. We obtained the Combined Array for Research in Millimeter Astronomy (CARMA) B and C array observations of the 12CO(J = 2 - 1) emission line with a combined angular resolution of 0.59 arcsec. We analysed and modelled the three-dimensional molecular gas kinematics, obtaining a best-fitting SMBH mass M_BH=5.75^{+1.49}_{-1.18} × 108 M⊙, a mass-to-light ratio at H-band (M/L)H = 1.45 ± 0.04 (M/L)⊙,H and other parameters describing the geometry of the molecular gas disc (statistical errors, all at 3σ confidence). We estimate the systematic uncertainties on the stellar M/L to be ≈0.2 (M/L)⊙,H, and on the SMBH mass to be ≈0.4 × 108 M⊙. The measured SMBH mass is consistent with that estimated from the latest correlations with galaxy properties. Following our older works, we also analysed and modelled the kinematics using only the major-axis position-velocity diagram, and conclude that the two methods are consistent.

  9. A low thermal mass fast gas chromatograph and its implementation in fast gas chromatography mass spectrometry with supersonic molecular beams.

    Science.gov (United States)

    Fialkov, Alexander B; Moragn, Mati; Amirav, Aviv

    2011-12-30

    A new type of low thermal mass (LTM) fast gas chromatograph (GC) was designed and operated in combination with gas chromatography mass spectrometry (GC-MS) with supersonic molecular beams (SMB), including GC-MS-MS with SMB, thereby providing a novel combination with unique capabilities. The LTM fast GC is based on a short capillary column inserted inside a stainless steel tube that is resistively heated. It is located and mounted outside the standard GC oven on its available top detector port, while the capillary column is connected as usual to the standard GC injector and supersonic molecular beam interface transfer line. This new type of fast GC-MS with SMB enables less than 1 min full range temperature programming and cooling down analysis cycle time. The operation of the fast GC-MS with SMB was explored and 1 min full analysis cycle time of a mixture of 16 hydrocarbons in the C(10)H(22) up to C(44)H(90) range was achieved. The use of 35 mL/min high column flow rate enabled the elution of C(44)H(90) in less than 45 s while the SMB interface enabled splitless acceptance of this high flow rate and the provision of dominant molecular ions. A novel compound 9-benzylazidanthracene was analyzed for its purity and a synthetic chemistry process was monitored for the optimization of the chemical reaction yield. Biodiesel was analyzed in jet fuel (by both GC-MS and GC-MS-MS) in under 1 min as 5 ppm fatty acid methyl esters. Authentic iprodion and cypermethrin pesticides were analyzed in grapes extract in both full scan mode and fast GC-MS-MS mode in under 1 min cycle time and explosive mixture including TATP, TNT and RDX was analyzed in under 1 min combined with exhibiting dominant molecular ion for TATP. Fast GC-MS with SMB is based on trading GC separation for speed of analysis while enhancing the separation power of the MS via the enhancement of the molecular ion in the electron ionization of cold molecules in the SMB. This paper further discusses several features of

  10. Structural features of lipoarabinomannan from Mycobacterium bovis BCG. Determination of molecular mass by laser desorption mass spectrometry.

    Science.gov (United States)

    Venisse, A; Berjeaud, J M; Chaurand, P; Gilleron, M; Puzo, G

    1993-06-15

    It was recently shown that mycobacterial lipoarabinomannan (LAM) can be classified into two types (Chatterjee, D., Lowell, K., Rivoire B., McNeil M. R., and Brennan, P. J. (1992) J. Biol. Chem. 267, 6234-6239) according to the presence or absence of mannosyl residues (Manp) located at the nonreducing end of the oligoarabinosyl side chains. These two types of LAM were found in a pathogenic Mycobacterium tuberculosis strain and in an avirulent M. tuberculosis strain, respectively, suggesting that LAM with Manp characterizes virulent and "disease-inducing strains." We now report the structure of the LAM from Mycobacterium bovis Bacille Calmette-Guérin (BCG) strain Pasteur, largely used throughout the world as vaccine against tuberculosis. Using an up-to-date analytical approach, we found that the LAM of M. bovis BCG belongs to the class of LAMs capped with Manp. By means of two-dimensional homonuclear and heteronuclear scalar coupling NMR analysis and methylation data, the sugar spin system assignments were partially established, revealing that the LAM contained two types of terminal Manp and 2-O-linked Manp. From the following four-step process: (i) partial hydrolysis of deacylated LAM (dLAM), (ii) oligosaccharide derivatization with aminobenzoic ethyl ester, (iii) HPLC purification, (iv) FAB/MS-MS analysis; it was shown that the dimannosyl unit alpha-D-Manp-(1-->2)-alpha-D-Manp is the major residue capping the termini of the arabinan of the LAM. In this report, LAM molecular mass determination was established using matrix-assisted UV-laser desorption/ionization mass spectrometry which reveals that the LAM molecular mass is around 17.4 kDa. The similarity of the LAM structures between M. bovis BCG and M. tuberculosis H37Rv is discussed in regard to their function in the immunopathology of mycobacterial infection.

  11. Detailed molecular characterization of castor oil ethoxylates by liquid chromatography multistage mass spectrometry.

    Science.gov (United States)

    Nasioudis, Andreas; van Velde, Jan W; Heeren, Ron M A; van den Brink, Oscar F

    2011-10-07

    The molecular characterization of castor oil ethoxylates (CASEOs) was studied by reverse-phase liquid chromatography (RPLC) mass spectrometry (MS) and multistage mass spectrometry (MS(n)). The developed RPLC method allowed the separation of the various CASEO components, and especially, the baseline separation of multiple nominal isobars (same nominal mass) and isomers (same exact mass). MS and MS(n) were used for the determination and structure elucidation of various structures and for the discrimination of the isobars and isomers. Different ionization techniques and adduct ions were also tested for optimization of the MS detection and the MS(n) fragmentation. A unique fragmentation pathway of ricinoleic acid is proposed, which can be used as a marker of the polymerization process and the topology of ethoxylation in the CASEO. In addition, characteristic neutral losses of ricinoleic acid reveal its (terminal or internal) position in the molecule. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. THE PERILS OF CLUMPFIND: THE MASS SPECTRUM OF SUBSTRUCTURES IN MOLECULAR CLOUDS

    International Nuclear Information System (INIS)

    Pineda, Jaime E.; Goodman, Alyssa A.; Rosolowsky, Erik W.

    2009-01-01

    We study the mass spectrum of substructures in the Perseus Molecular Cloud Complex traced by 13 CO(1-0), finding that dN/dM ∝ M -2.4 for the standard Clumpfind parameters. This result does not agree with the classical dN/dM ∝ M -1.6 . To understand this discrepancy, we study the robustness of the mass spectrum derived using the Clumpfind algorithm. Both two- and three-dimensional Clumpfind versions are tested, using 850 μm dust emission and 13 CO spectral-line observations of Perseus, respectively. The effect of varying threshold is not important, but varying stepsize produces a different effect for two- and three-dimensional cases. In the two-dimensional case, where emission is relatively isolated (associated with only the densest peaks in the cloud), the mass spectrum variability is negligible compared to the mass function fit uncertainties. In the three-dimensional case, however, where the 13 CO emission traces the bulk of the molecular cloud (MC), the number of clumps and the derived mass spectrum are highly correlated with the stepsize used. The distinction between 'two dimension' and 'three dimension' here is more importantly also a distinction between 'sparse' and 'crowded' emission. In any 'crowded' case, Clumpfind should not be used blindly to derive mass functions. Clumpfind's output in the 'crowded' case can still offer a statistical description of emission useful in intercomparisons, but the clump-list should not be treated as a robust region decomposition suitable to generate a physically meaningful mass function. We conclude that the 13 CO mass spectrum depends on the observations resolution, due to the hierarchical structure of the MC.

  13. Analysis of sulfates on low molecular weight heparin using mass spectrometry: structural characterization of enoxaparin.

    Science.gov (United States)

    Gupta, Rohitesh; Ponnusamy, Moorthy P

    2018-05-21

    Structural characterization of Low Molecular Weight Heparin (LMWH) is critical to meet biosimilarity standards. In this context, the review focuses on structural analysis of labile sulfates attached to the side-groups of LMWH using mass spectrometry. A comprehensive review of this topic will help readers to identify key strategies for tackling the problem related to sulfate loss. At the same time, various mass spectrometry techniques are presented to facilitate compositional analysis of LMWH, mainly Enoxaparin. Areas covered: This review summarizes findings on mass spectrometry application for LMWH, including modulation of sulfates, using enzymology and sample preparation approaches. Furthermore, popular open-source software packages for automated spectral data interpretation are also discussed. Successful use of LC/MS can decipher structural composition for LMWH and help evaluate their sameness or biosimilarity with the innovator molecule. Overall, the literature has been searched using PubMed by typing various search queries such as "enoxaparin", "mass spectrometry", "low molecular weight heparin", "structural characterization", etc. Expert commentary: This section highlights clinically relevant areas that need improvement to achieve satisfactory commercialization of LMWHs. It also primarily emphasizes the advancements in instrumentation related to mass spectrometry, and discusses building automated software for data interpretation and analysis.

  14. Static secondary ion mass spectrometry for organic and inorganic molecular analysis in solids

    International Nuclear Information System (INIS)

    Ham, Rita van; Vaeck, Luc van; Adriaens, Annemie; Adams, Freddy

    2003-01-01

    The use of mass spectra in secondary ion mass spectrometry (S-SIMS) to characterise the molecular composition of inorganic and organic analytes at the surface of solid samples is investigated. Methodological aspects such as mass resolution, mass accuracy, precision and accuracy of isotope abundance measurements, influence of electron flooding and sample morphology are addressed to assess the possibilities and limitations that the methodology can offer to support the structural assignment of the detected ions. The in-sample and between-sample reproducibility of relative peak intensities under optimised conditions is within 10%, but experimental conditions and local hydration, oxidation or contamination can drastically affect the mass spectra. As a result, the use of fingerprinting for identification becomes compromised. Therefore, the preferred way of interpretation becomes the deductive structural approach, based on the use of the empirical desorption-ionisation model. This approach is shown to allow the molecular composition of inorganic and organic components at the surface of solids to be characterised. Examples of inorganic speciation and identification of organic additives with unknown composition in inorganic salt mixtures are given. The methodology is discussed in terms of foreseen developments with respect to the use of polyatomic primary ions

  15. Pathology interface for the molecular analysis of tissue by mass spectrometry

    Directory of Open Access Journals (Sweden)

    Jeremy L Norris

    2016-01-01

    Full Text Available Background: Imaging mass spectrometry (IMS generates molecular images directly from tissue sections to provide better diagnostic insights and expand the capabilities of clinical anatomic pathology. Although IMS technology has matured over recent years, the link between microscopy imaging currently used by pathologists and MS-based molecular imaging has not been established. Methods: We adapted the Vanderbilt University Tissue Core workflow for IMS into a web-based system that facilitates remote collaboration. The platform was designed to perform within acceptable web response times for viewing, annotating, and processing high resolution microscopy images. Results: We describe a microscopy-driven approach to tissue analysis by IMS. Conclusion: The Pathology Interface for Mass Spectrometry is designed to provide clinical access to IMS technology and deliver enhanced diagnostic value.

  16. Detection of high molecular weight proteins by MALDI imaging mass spectrometry.

    Science.gov (United States)

    Mainini, Veronica; Bovo, Giorgio; Chinello, Clizia; Gianazza, Erica; Grasso, Marco; Cattoretti, Giorgio; Magni, Fulvio

    2013-06-01

    MALDI imaging mass spectrometry (IMS) is a unique technology to explore the spatial distribution of biomolecules directly on tissues. It allows the in situ investigation of a large number of small proteins and peptides. Detection of high molecular weight proteins through MALDI IMS still represents an important challenge, as it would allow the direct investigation of the distribution of more proteins involved in biological processes, such as cytokines, enzymes, neuropeptide precursors and receptors. In this work we compare the traditional method performed with sinapinic acid with a comparable protocol using ferulic acid as the matrix. Data show a remarkable increase of signal acquisition in the mass range of 20k to 150k Th. Moreover, we report molecular images of biomolecules above 70k Th, demonstrating the possibility of expanding the application of this technology both in clinical investigations and basic science.

  17. Low molecular mass chitosan as carrier for hydrodynamically balanced system for sustained delivery of ciprofloxacin hydrochloride

    OpenAIRE

    VERMA, ANURAG; BANSAL, ASHOK K.; GHOSH, AMITAVA; PANDIT, JAYANTA K.

    2012-01-01

    Chitosan has become a focus of major interest in recent years due to its excellent biocompatibility, biodegradability and non-toxicity. Although this material has already been extensively investigated in the design of different types of drug delivery systems, it is still little explored for stomach specific drug delivery systems. The objective of the present investigation was to explore the potential of low molecular mass chitosan (LMCH) as carrier for a hydrodynamically balanced system (HBS)...

  18. Molecular mass distribution and epitopes of the beta lactoglobulin submitted to hydrolysis pre-transglutaminase treatment

    International Nuclear Information System (INIS)

    Villas-Boas, M.B.; Zollner, R.L.; Netto, F.M.; Paes Leme, A.F.; Benede, S.; Molina, E.

    2012-01-01

    Full text: The β-Lactoglobulin (β-Lg) is a whey protein with important nutritional proper ties but very resistant to pepsin digestion and consequently highly antigenic. This protein can be modified by transglutaminase (TG) although it is required a pretreatment to increase their susceptibility to the TG action. In the present study the hydrolysis pre-TG treatment was used to improve the TG accessibility on β-Lg and the MM distribution and antigenic fragments were evaluated. For pre-TG treatment, the β-Lg (Davisco Inc.) was hydrolyzed with bromelain (3% of β-Lg w/w in distilled water; 25 U enzyme g 1 of substrate, pH 7.5, 240 min) and then polymerized by TG (7% hydrolysate, 10U TG g 1 protein, 50 C/180 min). The samples were evaluated by SDS-PAGE/tricine and by RP-nanoUPLC (nanoAcquity UPLC, Waters) coupled with nano-electrospray tandem mass spectrometry on a Q-Tof Ultima API mass spectrometer (MicroMass/Waters) at LNBio. The products were also submitted to pepsin digestion and the peptide identification was performed by RP-HPLC-tandem mass spectrometry (RP-HPLC-MS/MS, Brucker) with support from CIAL. The β-Lg hydrolysed by bromelain and polymerized by TG had a broad MM distribution. The intact mass analysis indicated that the non modified βLg -A showed 18.362 Da and the non modified βLg -B 18.274 Da, which is in agreement with the theoretical corresponding masses. The use of bromelain pre-TG treatment resulted in polymers with MM from 61.052 to 67.654 Da, although some non modified protein was still present. In addition, the non modified β-Lg showed fragments that present high antigenicity (such as Leu 95 - Leu 104 , Asp 95 - Phe 105 , Tyr 42 - Leu 54 , lle 29 - Val 41 ), previously identified as IgE-binding epitopes. After hydrolysis following by TG treatment the fragment Tyr 42 - Leu 54 was still present, however the other fragments that were observed in the non modified β-Lg were not detected by LC-MS/MS, suggesting that structural change occurred in

  19. Molecular mass distribution and epitopes of the beta lactoglobulin submitted to hydrolysis pre-transglutaminase treatment

    Energy Technology Data Exchange (ETDEWEB)

    Villas-Boas, M.B.; Zollner, R.L.; Netto, F.M. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil); Paes Leme, A.F. [Laboratorio Nacional de Luz Sincrotron (LNLS), Campinas, SP (Brazil); Benede, S.; Molina, E. [Universidad Autonoma de Madrid (Spain)

    2012-07-01

    Full text: The {beta}-Lactoglobulin ({beta}-Lg) is a whey protein with important nutritional proper ties but very resistant to pepsin digestion and consequently highly antigenic. This protein can be modified by transglutaminase (TG) although it is required a pretreatment to increase their susceptibility to the TG action. In the present study the hydrolysis pre-TG treatment was used to improve the TG accessibility on {beta}-Lg and the MM distribution and antigenic fragments were evaluated. For pre-TG treatment, the {beta}-Lg (Davisco Inc.) was hydrolyzed with bromelain (3% of {beta}-Lg w/w in distilled water; 25 U enzyme g{sup 1} of substrate, pH 7.5, 240 min) and then polymerized by TG (7% hydrolysate, 10U TG g{sup 1} protein, 50 C/180 min). The samples were evaluated by SDS-PAGE/tricine and by RP-nanoUPLC (nanoAcquity UPLC, Waters) coupled with nano-electrospray tandem mass spectrometry on a Q-Tof Ultima API mass spectrometer (MicroMass/Waters) at LNBio. The products were also submitted to pepsin digestion and the peptide identification was performed by RP-HPLC-tandem mass spectrometry (RP-HPLC-MS/MS, Brucker) with support from CIAL. The {beta}-Lg hydrolysed by bromelain and polymerized by TG had a broad MM distribution. The intact mass analysis indicated that the non modified {beta}Lg -A showed 18.362 Da and the non modified {beta}Lg -B 18.274 Da, which is in agreement with the theoretical corresponding masses. The use of bromelain pre-TG treatment resulted in polymers with MM from 61.052 to 67.654 Da, although some non modified protein was still present. In addition, the non modified {beta}-Lg showed fragments that present high antigenicity (such as Leu{sub 95} - Leu{sub 104}, Asp{sub 95} - Phe{sub 105}, Tyr{sub 42} - Leu{sub 54}, lle{sub 29} - Val{sub 41}), previously identified as IgE-binding epitopes. After hydrolysis following by TG treatment the fragment Tyr{sub 42} - Leu{sub 54} was still present, however the other fragments that were observed in the non

  20. Mass transfer of SCWO processes: Molecular diffusion and mass transfer coefficients of inorganic nitrate species in sub- and supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Goemans, M.G.E.; Gloyna, E.F. [Univ. of Texas, Austin, TX (United States). Dept. of Civil Engineering; Buelow, S.J. [Los Alamos National Lab., NM (United States)

    1996-04-01

    Molecular diffusion coefficients of lithium-, sodium-, potassium-, cesium-, calcium-, and strontium nitrate in subcritical water were determined by analysis of Taylor dispersion profiles. Pressures ranged from 300 to 500 bar at temperatures ranging from 25{degrees}C to 300{degrees}C. The reported diffusion values were determined at infinite dilution. Molecular diffusion coefficients were 10 to 20 times faster in near-critical subcritical water than in water at ambient temperature and pressure (ATP). These findings implied that the diffusion rates were more liquid like than they were gas like, hence experimental results were correlated with diffusion models for liquids. The subcritical diffusion data presented in this work, and supercritical diffusion results published elsewhere were correlated with hydrodynamic diffusion equations. Both the Wilke-Chang correlation and the Stokes-Einstein equation yielded predictions within 10% of the experimental results if the structure of the diffusing species could be estimated. The effect of the increased diffusion rates on mass transfer rates in supercritical water oxidation applications was quantified, with emphasis on heterogeneous oxidation processes. This study and results published elsewhere showed that diffusion limited conditions are much more likely to be encountered in SCWO processes than commonly acknowledged.

  1. Direct molecular analysis of whole-body animal tissue sections by MALDI imaging mass spectrometry.

    Science.gov (United States)

    Reyzer, Michelle L; Chaurand, Pierre; Angel, Peggi M; Caprioli, Richard M

    2010-01-01

    The determination of the localization of various compounds in a whole animal is valuable for many applications, including pharmaceutical absorption, distribution, metabolism, and excretion (ADME) studies and biomarker discovery. Imaging mass spectrometry is a powerful tool for localizing compounds of biological interest with molecular specificity and relatively high resolution. Utilizing imaging mass spectrometry for whole-body animal sections offers considerable analytical advantages compared to traditional methods, such as whole-body autoradiography, but the experiment is not straightforward. This chapter addresses the advantages and unique challenges that the application of imaging mass spectrometry to whole-body animal sections entails, including discussions of sample preparation, matrix application, signal normalization, and image generation. Lipid and protein images obtained from whole-body tissue sections of mouse pups are presented along with detailed protocols for the experiments.

  2. High-molecular-mass hyaluronan mediates the cancer resistance of the naked mole rat.

    Science.gov (United States)

    Tian, Xiao; Azpurua, Jorge; Hine, Christopher; Vaidya, Amita; Myakishev-Rempel, Max; Ablaeva, Julia; Mao, Zhiyong; Nevo, Eviatar; Gorbunova, Vera; Seluanov, Andrei

    2013-07-18

    The naked mole rat (Heterocephalus glaber) displays exceptional longevity, with a maximum lifespan exceeding 30 years. This is the longest reported lifespan for a rodent species and is especially striking considering the small body mass of the naked mole rat. In comparison, a similarly sized house mouse has a maximum lifespan of 4 years. In addition to their longevity, naked mole rats show an unusual resistance to cancer. Multi-year observations of large naked mole-rat colonies did not detect a single incidence of cancer. Here we identify a mechanism responsible for the naked mole rat's cancer resistance. We found that naked mole-rat fibroblasts secrete extremely high-molecular-mass hyaluronan (HA), which is over five times larger than human or mouse HA. This high-molecular-mass HA accumulates abundantly in naked mole-rat tissues owing to the decreased activity of HA-degrading enzymes and a unique sequence of hyaluronan synthase 2 (HAS2). Furthermore, the naked mole-rat cells are more sensitive to HA signalling, as they have a higher affinity to HA compared with mouse or human cells. Perturbation of the signalling pathways sufficient for malignant transformation of mouse fibroblasts fails to transform naked mole-rat cells. However, once high-molecular-mass HA is removed by either knocking down HAS2 or overexpressing the HA-degrading enzyme, HYAL2, naked mole-rat cells become susceptible to malignant transformation and readily form tumours in mice. We speculate that naked mole rats have evolved a higher concentration of HA in the skin to provide skin elasticity needed for life in underground tunnels. This trait may have then been co-opted to provide cancer resistance and longevity to this species.

  3. Seven Golden Rules for heuristic filtering of molecular formulas obtained by accurate mass spectrometry

    Directory of Open Access Journals (Sweden)

    Fiehn Oliver

    2007-03-01

    Full Text Available Abstract Background Structure elucidation of unknown small molecules by mass spectrometry is a challenge despite advances in instrumentation. The first crucial step is to obtain correct elemental compositions. In order to automatically constrain the thousands of possible candidate structures, rules need to be developed to select the most likely and chemically correct molecular formulas. Results An algorithm for filtering molecular formulas is derived from seven heuristic rules: (1 restrictions for the number of elements, (2 LEWIS and SENIOR chemical rules, (3 isotopic patterns, (4 hydrogen/carbon ratios, (5 element ratio of nitrogen, oxygen, phosphor, and sulphur versus carbon, (6 element ratio probabilities and (7 presence of trimethylsilylated compounds. Formulas are ranked according to their isotopic patterns and subsequently constrained by presence in public chemical databases. The seven rules were developed on 68,237 existing molecular formulas and were validated in four experiments. First, 432,968 formulas covering five million PubChem database entries were checked for consistency. Only 0.6% of these compounds did not pass all rules. Next, the rules were shown to effectively reducing the complement all eight billion theoretically possible C, H, N, S, O, P-formulas up to 2000 Da to only 623 million most probable elemental compositions. Thirdly 6,000 pharmaceutical, toxic and natural compounds were selected from DrugBank, TSCA and DNP databases. The correct formulas were retrieved as top hit at 80–99% probability when assuming data acquisition with complete resolution of unique compounds and 5% absolute isotope ratio deviation and 3 ppm mass accuracy. Last, some exemplary compounds were analyzed by Fourier transform ion cyclotron resonance mass spectrometry and by gas chromatography-time of flight mass spectrometry. In each case, the correct formula was ranked as top hit when combining the seven rules with database queries. Conclusion The

  4. Determination of the neutrino mass from the beta decay of gaseous molecular tritium

    International Nuclear Information System (INIS)

    Decman, D.J.; Stoeffl, W.

    1992-06-01

    We set an upper limit of 8 eV for the mass of the electron antineutrino from studying the beta decay of tritium. We use a gaseous molecular tritium source, a high resolution magnetic spectrometer and a low background counting system to minimize the systematic errors encountered in these measurements. Our calibration data with radioactive 83m Kr enables us to measure our system response function and a good deal of atomic physics data. In addition to our end point results we have made the first measurement of the tritium beta decay spectrum below 200 keV. We find an excess of very low energy electrons which arise from molecular processes of the 3 He-T + ion

  5. Spring meeting of the scientific associations for atomic physics, high speed physics, mass spectrometry, molecular physics, plasma physics

    International Nuclear Information System (INIS)

    1996-01-01

    The volume contains the abstracts of the contributions to the Spring Meeting in Rostock with aspects of atomic physics, molecular physics, high speed physics, plasma physics and mass spectrometry. (MM)

  6. Chemistry of the High-mass Protostellar Molecular Clump IRAS 16562–3959

    Science.gov (United States)

    Guzmán, Andrés E.; Guzmán, Viviana V.; Garay, Guido; Bronfman, Leonardo; Hechenleitner, Federico

    2018-06-01

    We present molecular line observations of the high-mass molecular clump IRAS 16562‑3959 taken at 3 mm using the Atacama Large Millimeter/submillimeter Array at 1.″7 angular resolution (0.014 pc spatial resolution). This clump hosts the actively accreting high-mass young stellar object (HMYSO) G345.4938+01.4677, which is associated with a hypercompact H II region. We identify and analyze emission lines from 22 molecular species (encompassing 34 isomers) and classify them into two groups, depending on their spatial distribution within the clump. One of these groups gathers shock tracers (e.g., SiO, SO, HNCO) and species formed in dust grains like methanol (CH3OH), ethenone or ketene (H2CCO), and acetaldehyde (CH3CHO). The second group collects species closely resembling the dust continuum emission morphology and are formed mainly in the gas phase, like hydrocarbons (CCH, c-C3H2, CH3CCH), cyanopolyynes (HC3N and HC5N), and cyanides (HCN and CH3C3N). Emission from complex organic molecules (COMs) like CH3OH, propanenitrile (CH3CH2CN), and methoxymethane (CH3OCH3) arise from gas in the vicinity of a hot molecular core (T ≳ 100 K) associated with the HMYSO. Other COMs such as propyne (CH3CCH), acrylonitrile (CH2CHCN), and acetaldehyde seem to better trace warm (T ≲ 80 K) dense gas. In addition, deuterated ammonia (NH2D) is detected mostly in the outskirts of IRAS 16562‑3959 and associated with near-infrared dark globules, probably gaseous remnants of the clump’s prestellar phase. The spatial distribution of molecules in IRAS 16562‑3959 supports the view that in protostellar clumps, chemical tracers associated with different evolutionary stages—starless to hot cores/H II regions—exist coevally.

  7. Nanosecond and femtosecond mass spectroscopic analysis of a molecular beam produced by the spray-jet technique

    International Nuclear Information System (INIS)

    Yamada, Toshiki; Shinohara, Hidenori; Kamikado, Toshiya; Okuno, Yoshishige; Suzuki, Hitoshi; Mashiko, Shinro; Yokoyama, Shiyoshi

    2008-01-01

    The spray-jet molecular beam apparatus enabled us to produce a molecular beam of non-volatile molecules under high vacuum from a sprayed mist of sample solutions. The apparatus has been used in spectroscopic studies and as a means of molecular beam deposition. We analyzed the molecular beam, consisting of non-volatile, solvent, and carrier-gas molecules, by using femtosecond- and nanosecond- laser mass spectroscopy. The information thus obtained provided insight into the molecular beam produced by the spray-jet technique

  8. Pulsed glow discharge mass spectrometry for molecular depth profiling of polymers

    International Nuclear Information System (INIS)

    Lobo, L.; Pereiro, R.; Sanz-Medel, A.; Bordel, N.; Pisonero, J.; Licciardello, A.; Tuccitto, N.; Tempez, A.; Chapon, P.

    2009-01-01

    Full text: Nowadays thin films of polymeric materials involve a wide range of industrial applications, so techniques capable of providing in-depth profile information are required. Most of the techniques available for this purpose are based on the use of energetic particle beams which interact with polymers producing undesirable physicochemical modifications. Radiofrequency pulsed glow discharge (rf-pulsed-GD) coupled to time-of-flight mass spectrometry (TOFMS) could afford the possibility of acquiring both elemental and molecular information creating minimal damage to surfaces and thereby obtaining depth profiles. This work will evaluate rf-GDs coupled to an orthogonal TOFMS for direct analysis of polymers. (author)

  9. Mass spectrometric identification of Au68(SR)34 molecular gold nanoclusters with 34-electron shell closing.

    Science.gov (United States)

    Dass, Amala

    2009-08-26

    The molecular formula Au(68)(SCH(2)CH(2)Ph)(34) has been assigned to the 14 kDa nanocluster using MALDI-TOF mass spectrometry. The 34-electron shell closing in a macroscopically obtained thiolated gold nanocluster is demonstrated. The Au(68) nanocluster is predicted to have a 49 atom Marks decahedral core with 19 inner core atoms and 30 outer atoms chelating with the staple motifs. The nanoclusters' predicted formulation is [Au](19+30) [Au(SR)(2)](11) [Au(2)(SR)(3)](4).

  10. A molecular beam/quadrupole mass spectrometer system with synchronized beam modulation and digital waveform analysis

    Science.gov (United States)

    Pellett, G. L.; Adams, B. R.

    1983-01-01

    A performance evaluation is conducted for a molecular beam/mass spectrometer (MB/MS) system, as applied to a 1-30 torr microwave-discharge flow reactor (MWFR) used in the formation of the methylperoxy radical and a study of its subsequent destruction in the presence or absence of NO(x). The modulated MB/MS system is four-staged and differentially pumped. The results obtained by the MWFR study is illustrative of overall system performance, including digital waveform analysis; significant improvements over previous designs are noted in attainable S/N ratio, detection limit, and accuracy.

  11. Sharing and community curation of mass spectrometry data with Global Natural Products Social Molecular Networking

    DEFF Research Database (Denmark)

    Wang, Mingxun; Carver, Jeremy J.; Pevzner, Pavel

    2016-01-01

    are well-suited to high-throughput characterization of NP, there is a pressing need for an infrastructure to enable sharing and curation of data. We present Global Natural Products Social Molecular Networking (GNPS; http://gnps.ucsd.edu), an open-access knowledge base for community-wide organization...... and sharing of raw, processed or identified tandem mass (MS/MS) spectrometry data. In GNPS, crowdsourced curation of freely available community-wide reference MS libraries will underpin improved annotations. Data-driven social-networking should facilitate identification of spectra and foster collaborations...

  12. Mass spectral chemical fingerprints reveal the molecular dependence of exhaust particulate matters on engine speeds.

    Science.gov (United States)

    Li, Yi; Zhang, Hua; Zhao, Zongshan; Tian, Yong; Liu, Kun; Jie, Feifan; Zhu, Liang; Chen, Huanwen

    2018-05-01

    Particulate matters (PMs) emitted by automobile exhaust contribute to a significant fraction of the global PMs. Extractive atmospheric pressure chemical ionization mass spectrometry (EAPCI-MS) was developed to explore the molecular dependence of PMs collected from exhaust gases produced at different vehicle engine speeds. The mass spectral fingerprints of the organic compounds embedded in differentially sized PMs (e.g., 0.22-0.45, 0.45-1.00, 1.00-2.00, 2.00-3.00, 3.00-5.00, and 5.00-10.00μm) generated at different engine speeds (e.g., 1000, 1500, 2000, 2500, and 3000r/min) were chemically profiled in the mass range of mass to charge ratio (m/z) 50-800. Organic compounds, including alcohols, aldehydes, and esters, were detected in all the PMs tested, with varied concentration levels for each individual PM sample. At relatively low engine speeds (≤1500r/min), the total amount of organic species embedded in PMs of 0.22-1.00μm was greater than in PMs of other sizes, while more organic species were found in PMs of 5.00-10.00μm at high engine speeds (≥3000r/min), indicating that the organic compounds distributed in different sizes of PMs strongly correlated with the engine speed. The experimental data showed that the EAPCI-MS technique enables molecular characterization of PMs in exhaust, revealing the chemical dependence of PMs on the engine speeds (i.e., the combustion conditions) of automobiles. Copyright © 2017. Published by Elsevier B.V.

  13. Atmospheric Oxidation of Squalene: Molecular Study Using COBRA Modeling and High-Resolution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Fooshee, David R.; Aiona, Paige K.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey; Baldi, Pierre

    2015-10-22

    Squalene is a major component of skin and plant surface lipids, and is known to be present at high concentrations in indoor dust. Its high reactivity toward ozone makes it an important ozone sink and a natural protectant against atmospheric oxidizing agents. While the volatile products of squalene ozonolysis are known, the condensed-phase products have not been characterized. We present an analysis of condensed-phase products resulting from an extensive oxidation of squalene by ozone probed by electrospray ionization (ESI) high-resolution mass spectrometry (HR-MS). A complex distribution of nearly 1,300 peaks assignable to molecular formulas is observed in direct infusion positive ion mode ESI mass spectra. The distribution of peaks in the mass spectra suggests that there are extensive cross-coupling reactions between hydroxy-carbonyl products of squalene ozonolysis. To get additional insights into the mechanism, we apply a Computational Brewing Application (COBRA) to simulate the oxidation of squalene in the presence of ozone, and compare predicted results with those observed by the HR-MS experiments. The system predicts over one billion molecular structures between 0-1450 Da, which correspond to about 27,000 distinct elemental formulas. Over 83% of the squalene oxidation products inferred from the mass spectrometry data are matched by the simulation. Simulation indicates a prevalence of peroxy groups, with hydroxyl and ether groups being the second-most important O-containing functional groups formed during squalene oxidation. These highly oxidized products of squalene ozonolysis may accumulate on indoor dust and surfaces, and contribute to their redox capacity.

  14. Low molecular weight components in an aquatic humic substance as characterized by membrane dialysis and orbitrap mass spectrometry.

    Science.gov (United States)

    Remucal, Christina K; Cory, Rose M; Sander, Michael; McNeill, Kristopher

    2012-09-04

    Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses masses detected by Orbitrap MS were found in the 100-200 Da mass range. Many of these low molecular masses corresponded to molecular formulas of previously identified compounds in organic matter, lignin, and plants, and the use of the standard addition method provided an upper concentration estimate of selected target compounds in SRFA. Collectively, these results provide evidence that SRFA contains low molecular weight components that are present individually or in loosely bound assemblies.

  15. Low-mass molecular dynamics simulation: A simple and generic technique to enhance configurational sampling

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Yuan-Ping, E-mail: pang@mayo.edu

    2014-09-26

    Highlights: • Reducing atomic masses by 10-fold vastly improves sampling in MD simulations. • CLN025 folded in 4 of 10 × 0.5-μs MD simulations when masses were reduced by 10-fold. • CLN025 folded as early as 96.2 ns in 1 of the 4 simulations that captured folding. • CLN025 did not fold in 10 × 0.5-μs MD simulations when standard masses were used. • Low-mass MD simulation is a simple and generic sampling enhancement technique. - Abstract: CLN025 is one of the smallest fast-folding proteins. Until now it has not been reported that CLN025 can autonomously fold to its native conformation in a classical, all-atom, and isothermal–isobaric molecular dynamics (MD) simulation. This article reports the autonomous and repeated folding of CLN025 from a fully extended backbone conformation to its native conformation in explicit solvent in multiple 500-ns MD simulations at 277 K and 1 atm with the first folding event occurring as early as 66.1 ns. These simulations were accomplished by using AMBER forcefield derivatives with atomic masses reduced by 10-fold on Apple Mac Pros. By contrast, no folding event was observed when the simulations were repeated using the original AMBER forcefields of FF12SB and FF14SB. The results demonstrate that low-mass MD simulation is a simple and generic technique to enhance configurational sampling. This technique may propel autonomous folding of a wide range of miniature proteins in classical, all-atom, and isothermal–isobaric MD simulations performed on commodity computers—an important step forward in quantitative biology.

  16. Limit on the anti nu/sub e/ mass in free molecular tritium beta decay

    International Nuclear Information System (INIS)

    Bowles, T.J.; Wilkerson, J.F.; Browne, J.C.; Maley, M.P.; Robertson, R.G.H.; Knapp, D.A.; Helffrich, J.A.

    1986-01-01

    The question of a nonzero neutrino mass has received considerable attention since the claims of Lyubimov et al in 1980 were published which showed evidence for an electron antineutrino mass between 14 and 46 eV, with a best fit value of 35 eV. However, there are still considerable concerns about possible systematic problems in thier experiment. Many of these concerns revolve around the use of a tritiated valine source, in which the energy given up in final state excitations of the molecule following the veta decay of one of the tritium atoms is comparable to the size of the neutrino mass observed. The effect of these final state effects is difficult to calculate in a molecule as complex as valine. In addition, ionization energy loss and backscattering of the betas in traversing the solid source are appreciable and must be very accurately accounted for. These concerns have led us to carry out an experiment using free molecular tritium as the source material. The final state effects have been accurately calculated for the tritium molecule and the uncertainties in these calculations cannot generate a spurious neutrino mass greater than 1 eV. in addition, the energy loss in the source is small because the source consists of tritium only and there is no backscattering

  17. Mass transfer ranking of polylysine, poly-ornithine and poly-methylene-co-guanidine microcapsule membranes using a single low molecular mass marker

    Directory of Open Access Journals (Sweden)

    Rosinski Stefan

    2003-01-01

    Full Text Available On the long way to clinical transplantable hybrid systems, comprising of cells, acting as immuno-protected bioreactors microencapsulated in a polymeric matrix and delivering desired factors (proteins, hormones, enzymes etc to the patient's body, an important step is the optimization of the microcapsule. This topic includes the selection of a proper coating membrane which could fulfil, first of all, the mass transfer as well as biocompatibility, stability and durability requirements. Three different membranes from polymerised aminoacids, formed around exactly identical alginate gel cores, were considered, concerning their mass transport properties, as potential candidates in this task. The results of the evaluation of the mass ingress and mass transfer coefficient h for the selected low molecular mass marker, vitamin B12, in poly-L-lysine (HPLL poly-L-ornithine (HPLO and poly-methylene-co-guanidine hydrochloride (HPMCG membrane alginate microcapsules demonstrate the advantage of using the mass transfer approach to a preliminary screening of various microcapsule formulations. Applying a single marker and evaluating mass transfer coefficients can help to quickly rank the investigated membranes and microcapsules according to their permeability. It has been demonstrated that HPLL, HPLO and HPMCG microcapsules differ from each other by a factor of two concerning the rate of low molecular mass marker transport. Interesting differences in mass transfer through the membrane in both directions in-out was also found, which could possibly be related to the membrane asymmetry.

  18. Document authentication at molecular levels using desorption atmospheric pressure chemical ionization mass spectrometry imaging.

    Science.gov (United States)

    Li, Ming; Jia, Bin; Ding, Liying; Hong, Feng; Ouyang, Yongzhong; Chen, Rui; Zhou, Shumin; Chen, Huanwen; Fang, Xiang

    2013-09-01

    Molecular images of documents were obtained by sequentially scanning the surface of the document using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS), which was operated in either a gasless, solvent-free or methanol vapor-assisted mode. The decay process of the ink used for handwriting was monitored by following the signal intensities recorded by DAPCI-MS. Handwritings made using four types of inks on four kinds of paper surfaces were tested. By studying the dynamic decay of the inks, DAPCI-MS imaging differentiated a 10-min old from two 4 h old samples. Non-destructive forensic analysis of forged signatures either handwritten or computer-assisted was achieved according to the difference of the contour in DAPCI images, which was attributed to the strength personalized by different writers. Distinction of the order of writing/stamping on documents and detection of illegal printings were accomplished with a spatial resolution of about 140 µm. A Matlab® written program was developed to facilitate the visualization of the similarity between signature images obtained by DAPCI-MS. The experimental results show that DAPCI-MS imaging provides rich information at the molecular level and thus can be used for the reliable document analysis in forensic applications. © 2013 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.

  19. Applications of free-jet, molecular beam, mass spectrometric sampling: Proceedings

    Energy Technology Data Exchange (ETDEWEB)

    Milne, T. [ed.

    1995-03-01

    Over the past 35 years, the study of die behavior and uses of free-jet expansions for laboratory experiments has greatly expanded and matured. Not the least of these uses of free-jet expansions, is that of extractive sampling from high temperature, reactive systems. The conversion of the free-jet expanded gases to molecular flow for direct introduction into the ion source of a mass spectrometer offers several advantages, to be illustrated in these pages. Two meetings on this subject were held in 1965 and 1972 in Missouri, sponsored by the Office of Naval Research and Midwest Research Institute. At these meetings rarefied gas dynamicists came together with scientists using free-jet sampling for analytical purposes. After much too long a time, this workshop was convened to bring together modem practitioners of FJMBS (Free-jet, Molecular-beam, mass spectrometry) and long time students of the free-jet process itself, to assess the current state of the art and to forge a community that can foster the development of this novel analytical approach. This proceedings is comprised of 38 individually submitted papers. Individual papers are indexed separately on the Energy Data Base.

  20. The molecular mass of dextran used to modify magnetite nanoparticles affects insulin amyloid aggregation

    Energy Technology Data Exchange (ETDEWEB)

    Siposova, Katarina [Department of Biophysics, Institute of Experimental Physics, Slovak Academy of Sciences, Kosice (Slovakia); Pospiskova, Kristyna [Regional Centre of Advanced Technologies and Materials, Palacky University, Olomouc (Czech Republic); Bednarikova, Zuzana [Department of Biophysics, Institute of Experimental Physics, Slovak Academy of Sciences, Kosice (Slovakia); Department of Biochemistry, Faculty of Science, Safarik University, Kosice (Slovakia); Safarik, Ivo [Regional Centre of Advanced Technologies and Materials, Palacky University, Olomouc (Czech Republic); Department of Nanobiotechnology, Biology Centre, ISB, CAS, Ceske Budejovice (Czech Republic); Safarikova, Mirka [Department of Nanobiotechnology, Biology Centre, ISB, CAS, Ceske Budejovice (Czech Republic); Kubovcikova, Martina; Kopcansky, Peter [Department of Magnetism, Institute of Experimental Physics, Slovak Academy of Sciences, Kosice (Slovakia); Gazova, Zuzana, E-mail: gazova@saske.sk [Department of Biophysics, Institute of Experimental Physics, Slovak Academy of Sciences, Kosice (Slovakia)

    2017-04-01

    Protein transformation from its soluble state into amyloid aggregates is associated with amyloid-related diseases. Amyloid deposits of insulin fibrils have been found in the sites of subcutaneous insulin application in patients with prolonged diabetes. Using atomic force microscopy and ThT fluorescence assay we have investigated the interference of insulin amyloid aggregation with superparamagnetic Fe{sub 3}O{sub 4}-based nanoparticles (SPIONs) coated with dextran (DEX); molecular mass of dextran was equal to 15–20, 40 or 70 kDa. The obtained data indicate that all three types of dextran coated nanoparticles (NP-FeDEXs) are able to inhibit insulin fibrillization and to destroy amyloid fibrils. The extent of anti-amyloid activities depends on the properties of NP-FeDEXs, mainly on the size of nanoparticles which is determined by molecular mass of dextran molecules. The most effective inhibiting activity was observed for the smallest nanoparticles coated with 15–20 kDa dextran. Contrary, the highest destroying activity was observed for the largest NP-FeDEX (70 kDa dextran). - Highlights: • Interference of dextran- magnetite nanoparticles with insulin amyloid aggregation. • Nanoparticles inhibited insulin fibrillization and depolymerized insulin amyloid fibrils. • Size of nanoparticles significantly influences their anti-amyloid activities. • The most effective inhibition of insulin amyloid fibrillization was detected for the smallest nanoparticles. • Contrary, DC{sub 50} values decreased with increasing size of nanoparticles.

  1. Mass Spectrometry-based Approaches to Understand the Molecular Basis of Memory

    Directory of Open Access Journals (Sweden)

    Arthur Henriques Pontes

    2016-10-01

    Full Text Available The central nervous system is responsible for an array of cognitive functions such as memory, learning, language and attention. These processes tend to take place in distinct brain regions; yet, they need to be integrated to give rise to adaptive or meaningful behavior. Since cognitive processes result from underlying cellular and molecular changes, genomics and transcriptomics assays have been applied to human and animal models to understand such events. Nevertheless, genes and RNAs are not the end products of most biological functions. In order to gain further insights toward the understanding of brain processes, the field of proteomics has been of increasing importance in the past years. Advancements in liquid chromatography-tandem mass spectrometry (LC-MS/MS have enable the identification and quantification of thousand of proteins with high accuracy and sensitivity, fostering a revolution in the neurosciences. Herein, we review the molecular bases of explicit memory in the hippocampus. We outline the principles of mass spectrometry (MS-based proteomics, highlighting the use of this analytical tool to study memory formation. In addition, we discuss MS-based targeted approaches as the future of protein analysis.

  2. The molecular mass of dextran used to modify magnetite nanoparticles affects insulin amyloid aggregation

    Science.gov (United States)

    Siposova, Katarina; Pospiskova, Kristyna; Bednarikova, Zuzana; Safarik, Ivo; Safarikova, Mirka; Kubovcikova, Martina; Kopcansky, Peter; Gazova, Zuzana

    2017-04-01

    Protein transformation from its soluble state into amyloid aggregates is associated with amyloid-related diseases. Amyloid deposits of insulin fibrils have been found in the sites of subcutaneous insulin application in patients with prolonged diabetes. Using atomic force microscopy and ThT fluorescence assay we have investigated the interference of insulin amyloid aggregation with superparamagnetic Fe3O4-based nanoparticles (SPIONs) coated with dextran (DEX); molecular mass of dextran was equal to 15-20, 40 or 70 kDa. The obtained data indicate that all three types of dextran coated nanoparticles (NP-FeDEXs) are able to inhibit insulin fibrillization and to destroy amyloid fibrils. The extent of anti-amyloid activities depends on the properties of NP-FeDEXs, mainly on the size of nanoparticles which is determined by molecular mass of dextran molecules. The most effective inhibiting activity was observed for the smallest nanoparticles coated with 15-20 kDa dextran. Contrary, the highest destroying activity was observed for the largest NP-FeDEX (70 kDa dextran).

  3. The molecular mass of dextran used to modify magnetite nanoparticles affects insulin amyloid aggregation

    International Nuclear Information System (INIS)

    Siposova, Katarina; Pospiskova, Kristyna; Bednarikova, Zuzana; Safarik, Ivo; Safarikova, Mirka; Kubovcikova, Martina; Kopcansky, Peter; Gazova, Zuzana

    2017-01-01

    Protein transformation from its soluble state into amyloid aggregates is associated with amyloid-related diseases. Amyloid deposits of insulin fibrils have been found in the sites of subcutaneous insulin application in patients with prolonged diabetes. Using atomic force microscopy and ThT fluorescence assay we have investigated the interference of insulin amyloid aggregation with superparamagnetic Fe 3 O 4 -based nanoparticles (SPIONs) coated with dextran (DEX); molecular mass of dextran was equal to 15–20, 40 or 70 kDa. The obtained data indicate that all three types of dextran coated nanoparticles (NP-FeDEXs) are able to inhibit insulin fibrillization and to destroy amyloid fibrils. The extent of anti-amyloid activities depends on the properties of NP-FeDEXs, mainly on the size of nanoparticles which is determined by molecular mass of dextran molecules. The most effective inhibiting activity was observed for the smallest nanoparticles coated with 15–20 kDa dextran. Contrary, the highest destroying activity was observed for the largest NP-FeDEX (70 kDa dextran). - Highlights: • Interference of dextran- magnetite nanoparticles with insulin amyloid aggregation. • Nanoparticles inhibited insulin fibrillization and depolymerized insulin amyloid fibrils. • Size of nanoparticles significantly influences their anti-amyloid activities. • The most effective inhibition of insulin amyloid fibrillization was detected for the smallest nanoparticles. • Contrary, DC 50 values decreased with increasing size of nanoparticles.

  4. Detection of sputtered molecular doubly charged anions: a comparison of secondary-ion mass spectrometry (SIMS) and accelerator mass spectrometry (AMS)

    International Nuclear Information System (INIS)

    Gnaser, Hubert; Golser, Robin; Kutschera, Walter; Priller, Alfred; Steier, Peter; Vockenhuber, Christof

    2004-01-01

    The detection of small molecular dianions by secondary-ion mass spectrometry (SIMS) and by accelerator mass spectrometry (AMS) is compared. In SIMS, the existence of these dianions can be identified safely if the total mass number of the molecule is odd and the dianion is hence detected at a half-integral mass number. The occurrence of fragmentation processes which may interfere with this scheme, is illustrated by means of the energy spectra of singly and doubly charged negative cluster ions. As compared to SIMS, AMS can rely, in addition, on the break-up of molecular species in the stripping process: this allows to monitor the simultaneous arrival of several atomic constituents with a clear energetic pattern in coincidence at the detector. This feature is exemplified for the C 10 2- dianion

  5. Mass of 17O from Penning-trap mass spectrometry and molecular spectroscopy: A precision test of the Dunham-Watson model in carbon monoxide

    International Nuclear Information System (INIS)

    Mount, Brianna J.; Redshaw, Matthew; Myers, Edmund G.; Mueller, Holger S. P.

    2010-01-01

    By fitting the Dunham-Watson model to extensive rotational and vibrational spectroscopic data of isotopic variants of CO, and by using existing precise masses of 13 C, 16 O, and 18 O from Penning-trap mass spectrometry, we determine the atomic mass of 17 O to be M[ 17 O]=16.999 131 644(30) u, where the uncertainty is purely statistical. Using Penning-trap mass spectrometry, we have also directly determined the atomic mass of 17 O with the more precise result M[ 17 O]=16.999 131 756 6(9) u. The Dunham-Watson model applied to the molecular spectroscopic data hence predicts the mass of 17 O to better than 1 part in 10 8 .

  6. Total molecular gas masses of Planck - Herschel selected strongly lensed hyper luminous infrared galaxies

    Science.gov (United States)

    Harrington, K. C.; Yun, M. S.; Magnelli, B.; Frayer, D. T.; Karim, A.; Weiß, A.; Riechers, D.; Jiménez-Andrade, E. F.; Berman, D.; Lowenthal, J.; Bertoldi, F.

    2018-03-01

    We report the detection of CO(1-0) line emission from seven Planck and Herschel selected hyper luminous ({L_{IR (8-1000{μ m})} > 10^{13} L_{⊙}) infrared galaxies with the Green Bank Telescope (GBT). CO(1-0) measurements are a vital tool to trace the bulk molecular gas mass across all redshifts. Our results place tight constraints on the total gas content of these most apparently luminous high-z star-forming galaxies (apparent IR luminosities of LIR > 1013 - 14 L⊙), while we confirm their predetermined redshifts measured using the Large Millimeter Telescope, LMT (zCO = 1.33-3.26). The CO(1-0) lines show similar profiles as compared to Jup = 2-4 transitions previously observed with the LMT. We report enhanced infrared to CO line luminosity ratios of = 110 ± 22 L_{⊙} (K km s^{-1} pc^{-2})^{-1} compared to normal star-forming galaxies, yet similar to those of well-studied IR-luminous galaxies at high-z. We find average brightness temperature ratios of 〈 r21〉 = 0.93 (2 sources), 〈 r31〉 = 0.34 (5 sources), and 〈 r41〉 = 0.18 (1 source). The r31 and r41 values are roughly half the average values for SMGs. We estimate the total gas mass content as {μ M_{H2} = (0.9-27.2) × 10^{11} (α _CO/0.8) M_{⊙}, where μ is the magnification factor and αCO is the CO line luminosity to molecular hydrogen gas mass conversion factor. The rapid gas depletion times, = 80} Myr, reveal vigorous starburst activity, and contrast the Gyr depletion time-scales observed in local, normal star-forming galaxies.

  7. Chemical analysis and genotoxicity of high molecular mass PAH in sediment samples and biota

    International Nuclear Information System (INIS)

    McCarry, B.E.; Marvin, C.H.; Smith, R.W.; Bryant, D.W.

    1995-01-01

    A normal phase liquid chromatography (NPLC) method was used to fractionate the organic extracts of prepared from coal tar-contaminated sediments from hamilton Harbor in Ontario and from Sydney Harbor in Nova Scotia into molecular mass classes. Each PAH fraction up to 302 amu was analyzed by GC-MS and fractions containing PAH with molecular masses greater than 302 amu were analyzed by atmospheric pressure chemical ionization (APCI) LC-MS.Each fraction was also subjected to Ames bioassays using a TA100-like strain of Salmonella typhimurium (YG1025 + S9). The 300/302 amu, 326/328 and 350/352 amu PAH fractions accounted for 25% of the total genotoxic response of the extract; these PAH constitute a substantial genotoxic burden. A number of 300, 302, 326, 350, 374 and 400 amu PAH were identified using APCI LC-MS and comparison with authentic standards. The non-polar aromatic extracts of bottom sediments, suspended sediments and zebra mussels from Hamilton Harbor were also examined by GC-MS, APCI LC-MS and genotoxicity bioassays. The profiles of the priority and high mass PAH in these samples were identical showing that all PAH up to and exceeding 400 amu were readily bioavailable to biota such as Zebra mussels. In addition, the pseudo faeces of the Zebra mussels and amphipod detritivores which fed on the pseudo faeces had chemical profiles identical to the Zebra mussels. Since many sport fish prize amphipods as food, this observation demonstrates a pathway for organic contaminants adsorbed to suspended sediments to enter the food chain of non-bottom-feeding fish in areas infested by Zebra mussels

  8. Mass spectrometry-based serum proteome pattern analysis in molecular diagnostics of early stage breast cancer

    Directory of Open Access Journals (Sweden)

    Stobiecki Maciej

    2009-07-01

    Full Text Available Abstract Background Mass spectrometric analysis of the blood proteome is an emerging method of clinical proteomics. The approach exploiting multi-protein/peptide sets (fingerprints detected by mass spectrometry that reflect overall features of a specimen's proteome, termed proteome pattern analysis, have been already shown in several studies to have applicability in cancer diagnostics. We aimed to identify serum proteome patterns specific for early stage breast cancer patients using MALDI-ToF mass spectrometry. Methods Blood samples were collected before the start of therapy in a group of 92 patients diagnosed at stages I and II of the disease, and in a group of age-matched healthy controls (104 women. Serum specimens were purified and the low-molecular-weight proteome fraction was examined using MALDI-ToF mass spectrometry after removal of albumin and other high-molecular-weight serum proteins. Protein ions registered in a mass range between 2,000 and 10,000 Da were analyzed using a new bioinformatic tool created in our group, which included modeling spectra as a sum of Gaussian bell-shaped curves. Results We have identified features of serum proteome patterns that were significantly different between blood samples of healthy individuals and early stage breast cancer patients. The classifier built of three spectral components that differentiated controls and cancer patients had 83% sensitivity and 85% specificity. Spectral components (i.e., protein ions that were the most frequent in such classifiers had approximate m/z values of 2303, 2866 and 3579 Da (a biomarker built from these three components showed 88% sensitivity and 78% specificity. Of note, we did not find a significant correlation between features of serum proteome patterns and established prognostic or predictive factors like tumor size, nodal involvement, histopathological grade, estrogen and progesterone receptor expression. In addition, we observed a significantly (p = 0

  9. Application of molecular beam mass spectrometry to chemical vapor deposition studies

    International Nuclear Information System (INIS)

    Hsu, W.L.; Tung, D.M.

    1992-01-01

    A molecular beam mass spectrometer system has been designed and constructed for the specific purpose of measuring the gaseous composition of the vapor environment during chemical vapor deposition of diamond. By the intrinsic nature of mass analysis, this type of design is adaptable to a broad range of other applications that rely either on thermal- or plasma-induced chemical kinetics. When gas is sampled at a relatively high process pressure (∼2700 Pa for our case), supersonic gas expansion at the sampling orifice can cause the detected signals to have a complicated dependence on the operating conditions. A comprehensive discussion is given on the effect of gas expansion on mass discrimination and signal scaling with sampling pressure and temperature, and how these obstacles can be overcome. This paper demonstrates that radical species can be detected with a sensitivity better than 10 ppm by the use of threshold ionization. A detailed procedure is described whereby one can achieve quantitative analysis of the detected species with an accuracy of ±20%. This paper ends with an example on the detection of H, H 2 , CH 3 , CH 4 , and C 2 H 2 during diamond growth

  10. New simultaneous thermogravimetry and modulated molecular beam mass spectrometry apparatus for quantitative thermal decomposition studies

    International Nuclear Information System (INIS)

    Behrens, R. Jr.

    1987-01-01

    A new type of instrument has been designed and constructed to measure quantitatively the gas phase species evolving during thermal decompositions. These measurements can be used for understanding the kinetics of thermal decomposition, determining the heats of formation and vaporization of high-temperature materials, and analyzing sample contaminants. The new design allows measurements to be made on the same time scale as the rates of the reactions being studied, provides a universal detection technique to study a wide range of compounds, gives quantitative measurements of decomposition products, and minimizes interference from the instrument on the measurements. The instrument design is based on a unique combination of thermogravimetric analysis (TGA), differential thermal analysis (DTA), and modulated beam mass spectroscopy (MBMS) which are brought together into a symbiotic relationship through the use of differentially pumped vacuum systems, modulated molecular beam techniques, and computer control and data-acquisition systems. A data analysis technique that calculates partial pressures in the reaction cell from the simultaneous microbalance force measurements and the modulated mass spectrometry measurements has been developed. This eliminates the need to know the ionization cross section, the ion dissociation channels, the quadrupole transmission, and the ion detector sensitivity for each thermal decomposition product prior to quantifying the mass spectral data. The operation of the instrument and the data analysis technique are illustrated with the thermal decomposition of contaminants from a precipitated palladium powder

  11. Investigation of naproxen drug using mass spectrometry, thermal analyses and semi-empirical molecular orbital calculation

    Directory of Open Access Journals (Sweden)

    M.A. Zayed

    2017-03-01

    Full Text Available Naproxen (C14H14O3 is a non-steroidal anti-inflammatory drug (NSAID. It is important to investigate its structure to know the active groups and weak bonds responsible for medical activity. In the present study, naproxen was investigated by mass spectrometry (MS, thermal analysis (TA measurements (TG/DTG and DTA and confirmed by semi empirical molecular orbital (MO calculation, using PM3 procedure. These calculations included, bond length, bond order, bond strain, partial charge distribution, ionization energy and heat of formation (ΔHf. The mass spectra and thermal analysis fragmentation pathways were proposed and compared to select the most suitable scheme representing the correct fragmentation pathway of the drug in both techniques. The PM3 procedure reveals that the primary cleavage site of the charged molecule is the rupture of the COOH group (lowest bond order and high strain which followed by CH3 loss of the methoxy group. Thermal analysis of the neutral drug reveals a high response to the temperature variation with very fast rate. It decomposed in several sequential steps in the temperature range 80–400 °C. These mass losses appear as two endothermic and one exothermic peaks which required energy values of 255.42, 10.67 and 371.49 J g−1 respectively. The initial thermal ruptures are similar to that obtained by mass spectral fragmentation (COOH rupture. It was followed by the loss of the methyl group and finally by ethylene loss. Therefore, comparison between MS and TA helps in selection of the proper pathway representing its fragmentation. This comparison is successfully confirmed by MO-calculation.

  12. Low virial parameters in molecular clouds: Implications for high-mass star formation and magnetic fields

    Energy Technology Data Exchange (ETDEWEB)

    Kauffmann, Jens; Pillai, Thushara [Astronomy Department, California Institute of Technology, 1200 East California Boulevard, Pasadena, CA 91125 (United States); Goldsmith, Paul F., E-mail: jens.kauffmann@astro.caltech.edu, E-mail: tpillai@astro.caltech.edu [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Boulevard, Pasadena, CA 91109 (United States)

    2013-12-20

    Whether or not molecular clouds and embedded cloud fragments are stable against collapse is of utmost importance for the study of the star formation process. Only 'supercritical' cloud fragments are able to collapse and form stars. The virial parameter α = M {sub vir}/M, which compares the virial mass to the actual mass, provides one way to gauge stability against collapse. Supercritical cloud fragments are characterized by α ≲ 2, as indicated by a comprehensive stability analysis considering perturbations in pressure and density gradients. Past research has suggested that virial parameters α ≳ 2 prevail in clouds. This would suggest that collapse toward star formation is a gradual and relatively slow process and that magnetic fields are not needed to explain the observed cloud structure. Here, we review a range of very recent observational studies that derive virial parameters <<2 and compile a catalog of 1325 virial parameter estimates. Low values of α are in particular observed for regions of high-mass star formation (HMSF). These observations may argue for a more rapid and violent evolution during collapse. This would enable 'competitive accretion' in HMSF, constrain some models of 'monolithic collapse', and might explain the absence of high-mass starless cores. Alternatively, the data could point at the presence of significant magnetic fields ∼1 mG at high gas densities. We examine to what extent the derived observational properties might be biased by observational or theoretical uncertainties. For a wide range of reasonable parameters, our conclusions appear to be robust with respect to such biases.

  13. The atomic and molecular content of disks around very low-mass stars and brown dwarfs

    Energy Technology Data Exchange (ETDEWEB)

    Pascucci, I. [Lunar and Planetary Laboratory, The University of Arizona, Tucson, AZ 85721 (United States); Herczeg, G. [Kavli Institute for Astronomy and Astrophysics, Peking University, Beijing 100871 (China); Carr, J. S. [Naval Research Laboratory, Code 7211, Washington, DC 20375 (United States); Bruderer, S., E-mail: pascucci@lpl.arizona.edu [Max Planck Institute for Extraterrestrial Physics, Giessenbachstrasse 1, D-85748 Garching (Germany)

    2013-12-20

    There is growing observational evidence that disk evolution is stellar-mass-dependent. Here, we show that these dependencies extend to the atomic and molecular content of disk atmospheres. We analyze a unique dataset of high-resolution Spitzer/IRS spectra from eight very low mass star and brown dwarf disks. We report the first detections of Ne{sup +}, H{sub 2}, CO{sub 2}, and tentative detections of H{sub 2}O toward these faint and low-mass disks. Two of our [Ne II] 12.81 μm emission lines likely trace the hot (≥5000 K) disk surface irradiated by X-ray photons from the central stellar/sub-stellar object. The H{sub 2} S(2) and S(1) fluxes are consistent with arising below the fully or partially ionized surface traced by the [Ne II] emission in gas at ∼600 K. We confirm the higher C{sub 2}H{sub 2}/HCN flux and column density ratio in brown dwarf disks previously noted from low-resolution IRS spectra. Our high-resolution spectra also show that the HCN/H{sub 2}O fluxes of brown dwarf disks are on average higher than those of T Tauri disks. Our LTE modeling hints that this difference extends to column density ratios if H{sub 2}O lines trace warm ≥600 K disk gas. These trends suggest that the inner regions of brown dwarf disks have a lower O/C ratio than those of T Tauri disks, which may result from a more efficient formation of non-migrating icy planetesimals. An O/C = 1, as inferred from our analysis, would have profound implications on the bulk composition of rocky planets that can form around very low mass stars and brown dwarfs.

  14. Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Nils [Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551 (United States); Cool, Terrill A. [School of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853 (United States); Westmoreland, Phillip R. [Department of Chemical Engineering, University of Massachusetts, Amherst, MA 01003 (United States); Kohse-Hoeinghaus, Katharina [Department of Chemistry, Bielefeld University, D-33615 Bielefeld (Germany)

    2009-04-15

    Flame-sampling molecular-beam mass spectrometry of premixed, laminar, low-pressure flat flames has been demonstrated to be an efficient tool to study combustion chemistry. In this technique, flame gases are sampled through a small opening in a quartz probe, and after formation of a molecular beam, all flame species are separated using mass spectrometry. The present review focuses on critical aspects of the experimental approach including probe sampling effects, different ionization processes, and mass separation procedures. The capability for isomer-resolved flame species measurements, achievable by employing tunable vacuum-ultraviolet radiation for single-photon ionization, has greatly benefited flame-sampling molecular-beam mass spectrometry. This review also offers an overview of recent combustion chemistry studies of flames fueled by hydrocarbons and oxygenates. The identity of a variety of intermediates in hydrocarbon flames, including resonantly stabilized radicals and closed-shell intermediates, is described, thus establishing a more detailed understanding of the fundamentals of molecular-weight growth processes. Finally, molecular-beam mass-spectrometric studies of reaction paths in flames of alcohols, ethers, and esters, which have been performed to support the development and validation of kinetic models for bio-derived alternative fuels, are reviewed. (author)

  15. The role of carbohydrates in the radioimmunoassay of human low-molecular-mass kininogen

    International Nuclear Information System (INIS)

    Turpeinen, U.; Kaerkkaeinen, T.

    1985-01-01

    The immunoreactivity of human low-molecular-mass kininogen from Cohn plasma fraction IV was investigated after deglycosylations and carbohydrate modifications by radioimmunoassay using the conformation-specific antiserum. Removal of all sialic acids, 44% of amino sugars and 63% of neutral sugars did not alter the immunoreactivity of the protein but the periodate-treated concanavalin A fractions showed strikingly diminished immunoreactivity. A conformational change could account for the observed effect of periodate on the decreased reactivity of the protein in radioimmunoassay. Externally added carbohydrates had no effect on immunoreactivity. The results suggest that the carbohydrate part of kininogen is not involved in the immunoreactivity although it accounts for the observed lectin-binding heterogeneity. (Auth.)

  16. Ion-induced molecular emission of polymers: analytical potentialities of FTIR and mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Picq, V.; Balanzat, E. E-mail: balanzat@ganil.fr

    1999-05-02

    The release of small gaseous molecules is a general phenomenon of irradiated polymers. Polyethylene (PE), polypropylene (PP) and polybutene (PB) were irradiated with ions of different electronic stopping power. We show that the gas emission can provide important information on the damage process if a reliable chemical identification of the molecules released and accurate yield values are obtained. The outgassing products were analysed by two techniques: (1) by a novel set-up using a Fourier Transform Infrared (FTIR) analysis of the gas mixture released from the polymer film and (2) by residual gas analysis (RGA) with a quadrupole mass spectrometer. Comparing the analytical potentialities of both methods we come to the conclusion that the FTIR method gives a more straightforward and accurate determination of the chemical nature and of the yield of most of the released molecules. However, RGA provides complementary information on the gas release kinetics and also on the release of heavy hydrocarbon molecules and symmetric molecules like molecular hydrogen.

  17. Molecular identification of Mucorales in human tissues: contribution of PCR electrospray-ionization mass spectrometry.

    Science.gov (United States)

    Alanio, A; Garcia-Hermoso, D; Mercier-Delarue, S; Lanternier, F; Gits-Muselli, M; Menotti, J; Denis, B; Bergeron, A; Legrand, M; Lortholary, O; Bretagne, S

    2015-06-01

    Molecular methods are crucial for mucormycosis diagnosis because cultures are frequently negative, even if microscopy suggests the presence of hyphae in tissues. We assessed PCR/electrospray-ionization mass spectrometry (PCR/ESI-MS) for Mucorales identification in 19 unfixed tissue samples from 13 patients with proven or probable mucormycosis and compared the results with culture, quantitative real-time PCR, 16S-23S rRNA gene internal transcribed spacer region (ITS PCR) and 18S PCR sequencing. Concordance with culture identification to both genus and species levels was higher for PCR/ESI-MS than for the other techniques. Thus, PCR/ESI-MS is suitable for Mucorales identification, within 6 hours, for tissue samples for which microscopy results suggest the presence of hyphae. Copyright © 2015 European Society of Clinical Microbiology and Infectious Diseases. Published by Elsevier Ltd. All rights reserved.

  18. In vivo comparison of various polymeric and low molecular mass inhibitors of intestinal P-glycoprotein.

    Science.gov (United States)

    Föger, Florian; Hoyer, Herbert; Kafedjiiski, Krum; Thaurer, Michael; Bernkop-Schnürch, Andreas

    2006-12-01

    Several polymers have been reported to modulate drug absorption by inhibition of intestinal P-glycoprotein (P-gp). The aim of the present study was to provide a direct in vivo comparison of delivery systems based on Pluronic P85, Myrj 52 and chitosan-4-thiobutylamidine (Ch-TBA) in vivo in rats, using rhodamine-123 (Rho-123) as representative P-gp substrate. Furthermore, the postulated low molecular mass P-gp inhibitors 6-mercaptopurine and reduced glutathione (GSH) were evaluated in vitro and in vivo. In vitro, the permeation enhancing effect of 6-mercaptopurine, GSH, Pluronic P85, Myrj 52, and the combination of Ch-TBA with GSH was evaluated by using freshly excised rat intestinal mucosa mounted in Ussing-type diffusion chambers. In comparison to buffer only, Rho-123 transport in presence of 100 microm 6-mercaptopurine, 0.5% (w/v) GSH, 0.5% (w/v) Pluronic P85, 0.5% (w/v) Myrj 52 and the combination of 0.5% (w/v) Ch-TBA/ 0.5% (w/v) GSH, was 2.1, 1.6, 1.9, 1.8, 3.0-fold improved, respectively. In vivo in rat, enteric-coated tablets based on Pluronic P85, Myrj 52 or Ch-TBA/GSH increased the area under the plasma concentration time curve (AUC(0-12)) of Rho-123 1.6-fold, 2.4-fold, 4.3-fold, respectively, in comparison to control only. Contrariwise, the low molecular mass excipients 6-mercaptopurine and GSH showed no significant effect in vivo at all. This in vivo study showed that polymeric P-gp inhibitors and especially the delivery system based on thiolated chitosan significantly increased the oral bioavailability of P-gp substrate Rho-123.

  19. Sorption of cesium in intact rock

    International Nuclear Information System (INIS)

    Puukko, E.

    2014-04-01

    The mass distribution coefficient K d is used in performance assessment (PA) to describe sorption of a radionuclide on rock. The R d is determined using crushed rock which causes uncertainty in converting the R d values to K d values for intact rock. This work describes a method to determine the equilibrium of sorption on intact rock. The rock types of the planned Olkiluoto waste disposal site were T-series mica gneiss (T-MGN), T-series tonalite granodiorite granite gneiss (T-TGG), P-series tonalite granodiorite granite gneiss (P-TGG) and pegmatitic granite (PGR). These rocks contain different amount of biotite which is the main sorbing mineral. The sorption of cesium on intact rock slices was studied by applying an electrical field to speed up migration of cesium into the rock. Cesium is in the solution as a noncomplex cation Cs + and it is sorbed by ion exchange. The tracer used in the experiments was 134 Cs. The experimental sorption on the intact rock is compared with values calculated using the in house cation exchange sorption model (HYRL model) in PHREEQC program. The observed sorption on T-MGN and T-TGG rocks was close to the calculated values. Two PGR samples were from a depth of 70 m and three samples were from a depth of 150 m. Cesium sorbed more than predicted on the two 70 m PGR samples. The sorption of Cs on the three 150 m PGR samples was small which was consistent with the calculations. The pegmatitic granite PGR has the smallest content of biotite of the four rock types. In the case of P-TGG rock the observed values of sorption were only half of the calculated values. Two kind of slices were cut from P-TGG drill core. The slices were against and to the direction of the foliation of the biotite rims. The sorption of cesium on P-TGG rock was same in both cases. The results indicated that there was no effect of the directions of the electric field and the foliation of biotite in the P-TGG rock. (orig.)

  20. Peptide fragments induce a more rapid immune response than intact proteins in earthworms.

    Science.gov (United States)

    Hanusová, R; Tucková, L; Halada, P; Bezouska, K; Bilej, M

    1999-01-01

    The effect of in vivo proteolytic processing of protein antigen was studied in Eisenia foetida earthworms. Parenteral administration of the protein antigen induces elevated levels of an antigen-binding protein (ABP) which recognizes the protein used for stimulation. When the protein antigen is administered simultaneously with nontoxic serine proteinase inhibitor, ABP levels remain close to background. On the other hand, the in vivo adaptive response of earthworms to peptide fragments obtained by coelomic fluid digestion of the foreign antigen occurs even in the presence of proteinase inhibitor and, moreover, is significantly faster as compared to the response to intact antigen. These findings confirm the role of proteolytic processing in earthworms. MALDI mass spectrometric analysis of the fragments after coelomic fluid digestion has revealed the presence of the peptide fragments with molecular weights in the mass range 700-1100 Da.

  1. Comprehensive Analysis of Low-Molecular-Weight Human Plasma Proteome Using Top-Down Mass Spectrometry.

    Science.gov (United States)

    Cheon, Dong Huey; Nam, Eun Ji; Park, Kyu Hyung; Woo, Se Joon; Lee, Hye Jin; Kim, Hee Cheol; Yang, Eun Gyeong; Lee, Cheolju; Lee, Ji Eun

    2016-01-04

    While human plasma serves as a great source for disease diagnosis, low-molecular-weight (LMW) proteome (mass spectrometry to analyze the LMW proteoforms present in four types of human plasma samples pooled from three healthy controls (HCs) without immunoaffinity depletion and with depletion of the top two, six, and seven high-abundance proteins. The LMW proteoforms were first fractionated based on molecular weight using gel-eluted liquid fraction entrapment electrophoresis (GELFrEE). Then, the GELFrEE fractions containing up to 30 kDa were subjected to nanocapillary-LC-MS/MS, and the high-resolution MS and MS/MS data were processed using ProSightPC 3.0. As a result, a total of 442 LMW proteins and cleaved products, including those with post-translational modifications and single amino acid variations, were identified. From additional comparative analysis of plasma samples without immunoaffinity depletion between HCs and colorectal cancer (CRC) patients via top-down approach, tens of LMW proteoforms, including platelet factor 4, were found to show >1.5-fold changes between the plasma samples of HCs and CRC patients, and six of the LMW proteins were verified by Western blot analysis.

  2. The FADE mass-stat: A technique for inserting or deleting particles in molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Borg, Matthew K., E-mail: matthew.borg@strath.ac.uk [Department of Mechanical and Aerospace Engineering, University of Strathclyde, Glasgow G1 1XJ (United Kingdom); Lockerby, Duncan A., E-mail: duncan.lockerby@warwick.ac.uk [School of Engineering, University of Warwick, Coventry CV4 7AL (United Kingdom); Reese, Jason M., E-mail: jason.reese@ed.ac.uk [School of Engineering, University of Edinburgh, Edinburgh EH9 3JL (United Kingdom)

    2014-02-21

    The emergence of new applications of molecular dynamics (MD) simulation calls for the development of mass-statting procedures that insert or delete particles on-the-fly. In this paper we present a new mass-stat which we term FADE, because it gradually “fades-in” (inserts) or “fades-out” (deletes) molecules over a short relaxation period within a MD simulation. FADE applies a time-weighted relaxation to the intermolecular pair forces between the inserting/deleting molecule and any neighbouring molecules. The weighting function we propose in this paper is a piece-wise polynomial that can be described entirely by two parameters: the relaxation time scale and the order of the polynomial. FADE inherently conserves overall system momentum independent of the form of the weighting function. We demonstrate various simulations of insertions of atomic argon, polyatomic TIP4P water, polymer strands, and C{sub 60} Buckminsterfullerene molecules. We propose FADE parameters and a maximum density variation per insertion-instance that restricts spurious potential energy changes entering the system within desired tolerances. We also demonstrate in this paper that FADE compares very well to an existing insertion algorithm called USHER, in terms of accuracy, insertion rate (in dense fluids), and computational efficiency. The USHER algorithm is applicable to monatomic and water molecules only, but we demonstrate that FADE can be generally applied to various forms and sizes of molecules, such as polymeric molecules of long aspect ratio, and spherical carbon fullerenes with hollow interiors.

  3. The FADE mass-stat: A technique for inserting or deleting particles in molecular dynamics simulations

    International Nuclear Information System (INIS)

    Borg, Matthew K.; Lockerby, Duncan A.; Reese, Jason M.

    2014-01-01

    The emergence of new applications of molecular dynamics (MD) simulation calls for the development of mass-statting procedures that insert or delete particles on-the-fly. In this paper we present a new mass-stat which we term FADE, because it gradually “fades-in” (inserts) or “fades-out” (deletes) molecules over a short relaxation period within a MD simulation. FADE applies a time-weighted relaxation to the intermolecular pair forces between the inserting/deleting molecule and any neighbouring molecules. The weighting function we propose in this paper is a piece-wise polynomial that can be described entirely by two parameters: the relaxation time scale and the order of the polynomial. FADE inherently conserves overall system momentum independent of the form of the weighting function. We demonstrate various simulations of insertions of atomic argon, polyatomic TIP4P water, polymer strands, and C 60 Buckminsterfullerene molecules. We propose FADE parameters and a maximum density variation per insertion-instance that restricts spurious potential energy changes entering the system within desired tolerances. We also demonstrate in this paper that FADE compares very well to an existing insertion algorithm called USHER, in terms of accuracy, insertion rate (in dense fluids), and computational efficiency. The USHER algorithm is applicable to monatomic and water molecules only, but we demonstrate that FADE can be generally applied to various forms and sizes of molecules, such as polymeric molecules of long aspect ratio, and spherical carbon fullerenes with hollow interiors

  4. Detection of Low Molecular Weight Adulterants in Beverages by Direct Analysis in Real Time Mass Spectrometry.

    Science.gov (United States)

    Sisco, Edward; Dake, Jeffrey

    2016-04-14

    Direct Analysis in Real Time Mass Spectrometry (DART-MS) has been used to detect the presence of non-narcotic adulterants in beverages. The non-narcotic adulterants that were examined in this work incorporated a number low molecular weight alcohols, acetone, ammonium hydroxide, and sodium hypochlorite. Analysis of the adulterants was completed by pipetting 1 µL deposits onto glass microcapillaries along with an appropriate dopant species followed by introduction into the DART gas stream. It was found that detection of these compounds in the complex matrices of common beverages (soda, energy drinks, etc.) was simplified through the use of a dopant species to allow for adduct formation with the desired compound(s) of interest. Other parameters that were investigated included DART gas stream temperature, in source collision induced dissociation, ion polarity, and DART needle voltage. Sensitivities of the technique were found to range from 0.001 % volume fraction to 0.1 % volume fraction, comparable to traditional analyses completed using headspace gas chromatography mass spectrometry (HS-GC/MS). Once a method was established using aqueous solutions, , fifteen beverages were spiked with each of the nine adulterants, to simulate real world detection, and in nearly all cases the adulterant could be detected either in pure form, or complexed with the added dopant species. This technique provides a rapid way to directly analyze beverages believed to be contaminated with non-narcotic adulterants at sensitivities similar to or exceeding those of traditional confirmatory analyses.

  5. Origin of low-molecular mass aldehydes as disinfection by-products in beverages.

    Science.gov (United States)

    Serrano, María; Gallego, Mercedes; Silva, Manuel

    2017-09-01

    A novel, simple and automatic method based on static headspace-gas chromatography-mass spectrometry has been developed to determine 10 low-molecular mass aldehydes that can be found in beverages, coming from the treated water used in their production. These aldehydes are the most frequently found in treated water as water disinfection by-products, so they can be used as indicators of the addition of treated water to beverages. The study covered a large number of fruit juices and soft drinks. The presence of the whole array of analytes is related to the contact with treated water during beverage production, mainly by the addition of treated water as ingredient. In particular, propionaldehyde, valeraldehyde and benzaldehyde can be used as indicators of the addition of treated water in these kinds of beverages. Among the ten aldehydes, only formaldehyde and acetaldehyde are naturally present in all kinds of fruit, and their concentrations are related to stage of the ripening of the fruit.

  6. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography

    Science.gov (United States)

    Winter, Gregory T.; Wilhide, Joshua A.; LaCourse, William R.

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

  7. Probing the Composition, Assembly and Activity of Protein Molecular Machines using Native Mass Spectrometry

    NARCIS (Netherlands)

    van de Waterbeemd, M.J.

    2017-01-01

    Native mass spectrometry and mass spectrometry in general, are powerful analytical tools for studying proteins and protein complexes. Native mass spectrometry may provide accurate mass measurements of large macromolecular assemblies enabling the investigation of their composition and stoichiometry.

  8. Mass

    International Nuclear Information System (INIS)

    Quigg, Chris

    2007-01-01

    In the classical physics we inherited from Isaac Newton, mass does not arise, it simply is. The mass of a classical object is the sum of the masses of its parts. Albert Einstein showed that the mass of a body is a measure of its energy content, inviting us to consider the origins of mass. The protons we accelerate at Fermilab are prime examples of Einsteinian matter: nearly all of their mass arises from stored energy. Missing mass led to the discovery of the noble gases, and a new form of missing mass leads us to the notion of dark matter. Starting with a brief guided tour of the meanings of mass, the colloquium will explore the multiple origins of mass. We will see how far we have come toward understanding mass, and survey the issues that guide our research today.

  9. Position sensitive detection coupled to high-resolution time-of-flight mass spectrometry: Imaging for molecular beam deflection experiments

    International Nuclear Information System (INIS)

    Abd El Rahim, M.; Antoine, R.; Arnaud, L.; Barbaire, M.; Broyer, M.; Clavier, Ch.; Compagnon, I.; Dugourd, Ph.; Maurelli, J.; Rayane, D.

    2004-01-01

    We have developed and tested a high-resolution time-of-flight mass spectrometer coupled to a position sensitive detector for molecular beam deflection experiments. The major achievement of this new spectrometer is to provide a three-dimensional imaging (X and Y positions and time-of-flight) of the ion packet on the detector, with a high acquisition rate and a high resolution on both the mass and the position. The calibration of the experimental setup and its application to molecular beam deflection experiments are discussed

  10. Hybrid Imaging Labels: Providing the Link Between Mass Spectrometry-Based Molecular Pathology and Theranostics

    Science.gov (United States)

    Buckle, Tessa; van der Wal, Steffen; van Malderen, Stijn J.M.; Müller, Larissa; Kuil, Joeri; van Unen, Vincent; Peters, Ruud J.B.; van Bemmel, Margaretha E.M.; McDonnell, Liam A.; Velders, Aldrik H.; Koning, Frits; Vanhaeke, Frank; van Leeuwen, Fijs W. B.

    2017-01-01

    Background: Development of theranostic concepts that include inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) imaging can be hindered by the lack of a direct comparison to more standardly used methods for in vitro and in vivo evaluation; e.g. fluorescence or nuclear medicine. In this study a bimodal (or rather, hybrid) tracer that contains both a fluorescent dye and a chelate was used to evaluate the existence of a direct link between mass spectrometry (MS) and in vitro and in vivo molecular imaging findings using fluorescence and radioisotopes. At the same time, the hybrid label was used to determine whether the use of a single isotope label would allow for MS-based diagnostics. Methods: A hybrid label that contained both a DTPA chelate (that was coordinated with either 165Ho or 111In) and a Cy5 fluorescent dye was coupled to the chemokine receptor 4 (CXCR4) targeting peptide Ac-TZ14011 (hybrid-Cy5-Ac-TZ4011). This receptor targeting tracer was used to 1) validate the efficacy of (165Ho-based) mass-cytometry in determining the receptor affinity via comparison with fluorescence-based flow cytometry (Cy5), 2) evaluate the microscopic binding pattern of the tracer in tumor cells using both fluorescence confocal imaging (Cy5) and LA-ICP-MS-imaging (165Ho), 3) compare in vivo biodistribution patterns obtained with ICP-MS (165Ho) and radiodetection (111In) after intravenous administration of hybrid-Cy5-Ac-TZ4011 in tumor-bearing mice. Finally, LA-ICP-MS-imaging (165Ho) was linked to fluorescence-based analysis of excised tissue samples (Cy5). Results: Analysis with both mass-cytometry and flow cytometry revealed a similar receptor affinity, respectively 352 ± 141 nM and 245 ± 65 nM (p = 0.08), but with a much lower detection sensitivity for the first modality. In vitro LA-ICP-MS imaging (165Ho) enabled clear discrimination between CXCR4 positive and negative cells, but fluorescence microscopy was required to determine the

  11. Improved limit on the mass of ν/sub e/ from the beta decay of molecular tritium

    International Nuclear Information System (INIS)

    Bowles, T.J.; Friar, J.L.; Robertson, R.G.H.; Stephenson, G.J. Jr.; Wark, D.L.; Wilkerson, J.F.; Knapp, D.A.

    1989-01-01

    We report a new upper limit of 13.4 eV (95% confidence level) on the mass of the electron antineutrino from a study of the shape of the beta spectrum of free molecular tritium. This result appears to be inconsistent with a reported value for the mass of 26(5) eV. The electron neutrino is evidently not massive enough to close the universe by itself. 23 refs., 1 fig., 2 tabs

  12. Improved limit on the mass of bar νe from the beta decay of molecular tritium

    International Nuclear Information System (INIS)

    Bowles, T.J.; Robertson, R.G.H.; Wark, D.L.; Wilkerson, J.F.; Stephenson, G.J.; Friar, J.L.; Knapp, D.A.

    1990-01-01

    We report a new upper limit of 13.4 eV (95% confidence level) on the mass of the electron antineutrino from a study of the shape of the beta spectrum of free molecular tritium. This result appears to be inconsistent with a reported value for the mass of 26(5) eV. The electron neutrino is evidently not massive enough to close the universe by itself. 21 refs., 1 fig., 2 tabs

  13. Molecular diversity and body distribution of saponins in the sea star Asterias rubens by mass spectrometry.

    Science.gov (United States)

    Demeyer, Marie; De Winter, Julien; Caulier, Guillaume; Eeckhaut, Igor; Flammang, Patrick; Gerbaux, Pascal

    2014-02-01

    Saponins are natural molecules that the common sea star Asterias rubens produces in the form of steroid glycosides bearing a sulfate group attached on the aglycone part. In order to highlight the inter-organ and inter-individual variability, the saponin contents of five distinct body components, namely the aboral body wall, the oral body wall, the stomach, the pyloric caeca and the gonads, from different individuals were separately analyzed by mass spectrometry. MALDI-ToF experiments were selected as the primary tool for a rapid screening of the saponin mixtures, whereas LC-MS and LC-MS/MS techniques were used to achieve chromatographic separation of isomers. First of all, our analyses demonstrated that the diversity of saponins is higher than previously reported. Indeed, nine new congeners were observed in addition to the 17 saponins already described in this species. On the basis of all the collected MS/MS data, we also identified collision-induced key-fragmentations that could be used to reconstruct the molecular structure of both known and unknown saponin ions. Secondly, the comparison of the saponin contents from the five different body components revealed that each organ is characterized by a specific mixture of saponins and that between animals there are also qualitative and quantitative variability of the saponin contents which could be linked to the sex or to the collecting season. Therefore, the observed high variability unambiguously confirms that saponins probably fulfill several biological functions in A. rubens. The current results will pave the way for our future studies that will be devoted to the clarification of the biological roles of saponins in A. rubens at a molecular level. © 2013.

  14. Identification of proteins by combination of size-exclusion chromatography with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and comparison of some desalting procedures for both intact proteins and their tryptic digests

    Czech Academy of Sciences Publication Activity Database

    Šalplachta, Jiří; Řehulka, Pavel; Chmelík, Josef

    2004-01-01

    Roč. 39, č. 12 (2004), s. 1395-1401 ISSN 1076-5174. [Informal Meeting on Mass Spectrometry /22./. Tokaj, 02.05.2004-06.05.2004] R&D Projects: GA MZe QD1023 Institutional research plan: CEZ:AV0Z4031919 Keywords : MALDI-TOF mass spectrometry * sample cleanup * protein identification Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.056, year: 2004

  15. Substrate specificity of low-molecular mass bacterial DD-peptidases.

    Science.gov (United States)

    Nemmara, Venkatesh V; Dzhekieva, Liudmila; Sarkar, Kumar Subarno; Adediran, S A; Duez, Colette; Nicholas, Robert A; Pratt, R F

    2011-11-22

    The bacterial DD-peptidases or penicillin-binding proteins (PBPs) catalyze the formation and regulation of cross-links in peptidoglycan biosynthesis. They are classified into two groups, the high-molecular mass (HMM) and low-molecular mass (LMM) enzymes. The latter group, which is subdivided into classes A-C (LMMA, -B, and -C, respectively), is believed to catalyze DD-carboxypeptidase and endopeptidase reactions in vivo. To date, the specificity of their reactions with particular elements of peptidoglycan structure has not, in general, been defined. This paper describes the steady-state kinetics of hydrolysis of a series of specific peptidoglycan-mimetic peptides, representing various elements of stem peptide structure, catalyzed by a range of LMM PBPs (the LMMA enzymes, Escherichia coli PBP5, Neisseria gonorrhoeae PBP4, and Streptococcus pneumoniae PBP3, and the LMMC enzymes, the Actinomadura R39 dd-peptidase, Bacillus subtilis PBP4a, and N. gonorrhoeae PBP3). The R39 enzyme (LMMC), like the previously studied Streptomyces R61 DD-peptidase (LMMB), specifically and rapidly hydrolyzes stem peptide fragments with a free N-terminus. In accord with this result, the crystal structures of the R61 and R39 enzymes display a binding site specific to the stem peptide N-terminus. These are water-soluble enzymes, however, with no known specific function in vivo. On the other hand, soluble versions of the remaining enzymes of those noted above, all of which are likely to be membrane-bound and/or associated in vivo and have been assigned particular roles in cell wall biosynthesis and maintenance, show little or no specificity for peptides containing elements of peptidoglycan structure. Peptidoglycan-mimetic boronate transition-state analogues do inhibit these enzymes but display notable specificity only for the LMMC enzymes, where, unlike peptide substrates, they may be able to effectively induce a specific active site structure. The manner in which LMMA (and HMM) DD

  16. Design of a reflex time-of-flight mass spectrometer for the study of the desorption of molecular ions

    International Nuclear Information System (INIS)

    Riggi, F.

    1991-01-01

    A reflex time-of-flight mass spectrometer for the study of the desorption and dissociation of molecular ions has been designed. A general overview of the instrument is reported, together with the different experimental aspects of the technique. These include mechanical and vacuum solutions, secondary ion optics in the electrostatic mirror, electronics, data acquisition and analysis

  17. Reaction of low-molecular-mass organoselenium compounds (and their sulphur analogues) with inflammation-associated oxidants

    DEFF Research Database (Denmark)

    Carroll, L.; Davies, Michael J.; Pattison, D. I.

    2015-01-01

    Selenium is an essential trace element in mammals, with the majority specifically encoded as seleno-L-cysteine into a range of selenoproteins. Many of these proteins play a key role in modulating oxidative stress, via either direct detoxification of biological oxidants, or repair of oxidised...... the chemistry of low-molecular-mass organoselenium compounds (e.g. selenoethers, diselenides and selenols) with inflammatory oxidants, with a particular focus on the reaction kinetics and product studies, with the differences in reactivity between selenium and sulphur analogues described in the selected...... examples. These data provide insight into the therapeutic potential of low-molecular-mass selenium-containing compounds to modulate the activity of both radical and molecular oxidants and provide protection against inflammation-induced damage. Progress in their therapeutic development (including modulation...

  18. The characterisation of molecular boric acid by mass spectrometry and matrix isolation-infrared spectroscopy

    International Nuclear Information System (INIS)

    Ogden, J.S.; Young, N.A.; Bowsher, B.R.

    1987-10-01

    Boric acid (H 3 BO 3 ) is used as a soluble neutron absorber in the coolant of pressurised water reactors and will be an important species in defining the fission product chemistry of severe reactor accidents. Mass spectrometry and matrix isolation-infrared spectroscopy have been used to characterise boric acid in the vapour phase and hence assess the implications of any chemical interactions. Crystalline orthoboric acid vaporises to yield molecular H 3 BO 3 when heated in vacuum to approximately 40 0 C. The infrared spectrum of the vapour species isolated in low-temperature nitrogen matrices shows characteristic absorptions at 3668.5 (E'), 1426.2 (E'), 1009.9 (E'), 675.0 (A''), 513.8 (A'') and 448.9 (E') cm -1 , consistent with C 3h symmetry. These spectral assignments are supported by extensive isotope labelling, and by a partial normal co-ordinate analysis. These data will be used to quantify specific thermodynamic functions and hence assist in determining the magnitude of reactions such as boric acid with caesium iodide. (author)

  19. Quantification of low molecular weight compounds by MALDI imaging mass spectrometry - A tutorial review.

    Science.gov (United States)

    Rzagalinski, Ignacy; Volmer, Dietrich A

    2017-07-01

    Matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry imaging (MSI) permits label-free in situ analysis of chemical compounds directly from the surface of two-dimensional biological tissue slices. It links qualitative molecular information of compounds to their spatial coordinates and distribution within the investigated tissue. MALDI-MSI can also provide the quantitative amounts of target compounds in the tissue, if proper calibration techniques are performed. Obviously, as the target molecules are embedded within the biological tissue environment and analysis must be performed at their precise locations, there is no possibility for extensive sample clean-up routines or chromatographic separations as usually performed with homogenized biological materials; ion suppression phenomena therefore become a critical side effect of MALDI-MSI. Absolute quantification by MALDI-MSI should provide an accurate value of the concentration/amount of the compound of interest in relatively small, well-defined region of interest of the examined tissue, ideally in a single pixel. This goal is extremely challenging and will not only depend on the technical possibilities and limitations of the MSI instrument hardware, but equally on the chosen calibration/standardization strategy. These strategies are the main focus of this article and are discussed and contrasted in detail in this tutorial review. This article is part of a Special Issue entitled: MALDI Imaging, edited by Dr. Corinna Henkel and Prof. Peter Hoffmann. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Mapping of low molecular weight heparins using reversed phase ion pair liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Li, Daoyuan; Chi, Lequan; Jin, Lan; Xu, Xiaohui; Du, Xuzhao; Ji, Shengli; Chi, Lianli

    2014-01-01

    Low molecular weight heparins (LMWHs) are structurally complex, highly sulfated and negatively charged, linear carbohydrate polymers prepared by chemical or enzymatic depolymerization of heparin. They are widely used as anticoagulant drugs possessing better bioavailability, longer half-life, and lower side effects than heparin. Comprehensive structure characterization of LMWHs is important for drug quality assurance, generic drug application, and new drug research and development. However, fully characterization of all oligosaccharide chains in LMWHs is not feasible for current available analytical technologies due to their structure complexity and heterogeneity. Fingerprinting profiling is an efficient way for LMWHs' characterization and comparison. In this work, we present a simple, sensitive, and powerful analytical approach for structural characterization of LMWHs. Two different LMWHs, enoxaparin and nadroparin, were analyzed using reversed phase ion pair electrospray ionization mass spectrometry (RPIP-ESI-MS). More than 200 components were identified, including major structures, minor structures, and process related impurities. This approach is robust for high resolution and complementary fingerprinting analysis of LMWHs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Mass spectrometry imaging: Towards mapping the elemental and molecular composition of the rhizosphere

    Energy Technology Data Exchange (ETDEWEB)

    Veličković, Dušan; Anderton, Christopher R.

    2017-06-01

    This short review will discuss and provide perspective into the utilization of mass spectrometry imaging (MSI) in studying the rhizosphere. It also serves to compliment the multi-omic focused review by White et al. in this journal issue, as MSI is capable of elucidating chemical distributions within samples of interest in an in situ fashions, and thus can provide spatial context to MS omics data in complementary experimental endeavors. The majority of reported MSI-based studies of plant-microbe interactions have focused on the phyllosphere and ‘associated rhizosphere’ (e.g., material that is not removed during harvesting), as sample preparation for these in situ analyses tends to be a limiting factor. These studies have provided valuable insight into the spatial arrangement of proteins, peptides, lipids, and other metabolites within these systems. We intend for this short review to be a primer about the history of MSI and its role in plant-microbe analysis. Along the way we reference many comprehensive reviews for the interested reader. Lastly, we offer a perspective on the future of MSI and its use in understanding the molecular transformations beyond what we coined as the ‘associated rhizosphere’ to the rest of rhizosphere zone and into the bulk soil.

  2. Carbohydrate-rich high-molecular-mass antigens are strongly recognized during experimental Histoplasma capsulatum infection

    Directory of Open Access Journals (Sweden)

    Fabrine Sales Massafera Tristão

    2012-04-01

    Full Text Available INTRODUCTION: During histoplasmosis, Histoplasma capsulatum soluble antigens (CFAg can be naturally released by yeast cells. Because CFAg can be specifically targeted during infection, in the present study we investigated CFAg release in experimental murine histoplasmosis, and evaluated the host humoral immune response against high-molecular-mass antigens (hMMAg. >150 kDa, the more immunogenic CFAg fraction. METHODS: Mice were infected with 2.2x10(4 H. capsulatum IMT/HC128 yeast cells. The soluble CFAg, IgG anti-CFAg, IgG anti-hMMAg, and IgG-hMMAg circulating immune complexes (CIC levels were determined by enzymelinked immunosorbent assay, at days 0, 7, 14, and 28 post-infection. RESULTS: We observed a progressive increase in circulating levels of CFAg, IgG anti-CFAg, IgG anti-hMMAg, and IgG-hMMAg CIC after H. capsulatum infection. The hMMAg showed a high percentage of carbohydrates and at least two main immunogenic components. CONCLUSIONS: We verified for the first time that hMMAg from H. capsulatum IMT/HC128 strain induce humoral immune response and lead to CIC formation during experimental histoplasmosis.

  3. MOLECULAR OUTFLOWS IN THE SUBSTELLAR DOMAIN: MILLIMETER OBSERVATIONS OF YOUNG VERY LOW MASS OBJECTS IN TAURUS AND ρ OPHIUCHI

    International Nuclear Information System (INIS)

    Ngoc Phan-Bao; Lee, Chin-Fei; Ho, Paul T. P.; Tang, Ya-Wen

    2011-01-01

    We report here our search for molecular outflows from young very low mass stars and brown dwarfs in Taurus and ρ Ophiuchi. Using the Submillimeter Array and the Combined Array for Research in Millimeter-wave Astronomy, we have observed four targets at 1.3 mm wavelength (230 GHz) to search for CO J = 2 → 1 outflows. A young very low mass star MHO 5 (in Taurus) with an estimated mass of 90 M J , which is just above the hydrogen-burning limit, shows two gas lobes that are likely outflows. While the CO map of MHO 5 does not show a clear structure of outflow, possibly due to environment gas, its position-velocity diagram indicates two distinct blue- and redshifted components. We therefore conclude that they are components of a bipolar molecular outflow from MHO 5. We estimate an outflow mass of 7.0 x 10 -5 M sun and a mass-loss rate of 9.0 x 10 -10 M sun . These values are over two orders of magnitude smaller than the typical ones for T Tauri stars and somewhat weaker than those we have observed in the young brown dwarf ISO-Oph 102 of 60 M J in ρ Ophiuchi. This makes MHO 5 the first young very low mass star showing a bipolar molecular outflow in Taurus. The detection boosts the scenario that very low mass objects form like low-mass stars but in a version scaled down by a factor of over 100.

  4. Temperature modulates the cell wall mechanical properties of rice coleoptiles by altering the molecular mass of hemicellulosic polysaccharides

    Science.gov (United States)

    Nakamura, Yukiko; Wakabayashi, Kazuyuki; Hoson, Takayuki

    2003-01-01

    The present study was conducted to investigate the mechanism inducing the difference in the cell wall extensibility of rice (Oryza sativa L. cv. Koshihikari) coleoptiles grown under various temperature (10-50 degrees C) conditions. The growth rate and the cell wall extensibility of rice coleoptiles exhibited the maximum value at 30-40 degrees C, and became smaller as the growth temperature rose or dropped from this temperature range. The amounts of cell wall polysaccharides per unit length of coleoptile increased in coleoptiles grown at 40 degrees C, but not at other temperature conditions. On the other hand, the molecular size of hemicellulosic polysaccharides was small at temperatures where the cell wall extensibility was high (30-40 degrees C). The autolytic activities of cell walls obtained from coleoptiles grown at 30 and 40 degrees C were substantially higher than those grown at 10, 20 and 50 degrees C. Furthermore, the activities of (1-->3),(1-->4)-beta-glucanases extracted from coleoptile cell walls showed a similar tendency. When oat (1-->3),(1-->4)-beta-glucans with high molecular mass were incubated with the cell wall enzyme preparations from coleoptiles grown at various temperature conditions, the extensive molecular mass downshifts were brought about only by the cell wall enzymes obtained from coleoptiles grown at 30-40 degrees C. There were close correlations between the cell wall extensibility and the molecular mass of hemicellulosic polysaccharides or the activity of beta -glucanases. These results suggest that the environmental temperature regulates the cell wall extensibility of rice coleoptiles by modifying mainly the molecular mass of hemicellulosic polysaccharides. Modulation of the activity of beta-glucanases under various temperature conditions may be involved in the alteration of the molecular size of hemicellulosic polysaccharides.

  5. Comparison of LAMP and PCR for molecular mass screening of sand flies for Leishmania martiniquensis infection.

    Science.gov (United States)

    Tiwananthagorn, Saruda; Kato, Hirotomo; Yeewa, Ranchana; Muengpan, Amontip; Polseela, Raxsina; Leelayoova, Saovanee

    2017-02-01

    Leishmaniasis caused by Leishmania martiniquensis infection has been reported in human and domestic animals of Martinique Island, Germany, Switzerland, USA, Myanmar and Thailand. The peculiar clinical features of disseminated cutaneous and visceral forms co-existence render the urgent need of specific diagnostic tool to identify the natural sand fly vectors for effective prevention and control strategies. Loop-mediated isothermal amplification (LAMP) of 18S rRNA gene as well as polymerase chain reaction (PCR) of minicircle kinetoplast DNA gene (PCR-mkDNA) have never been applied to detect L. martiniquensis and L. siamensis in sand fly vectors. The present study was aimed to validate malachite green-LAMP (MG-LAMP) and PCR-mkDNA techniques to detect L. martiniquensis in sand fly vectors, compared with the conventional PCR of internal transcribed spacer 1 (PCR-ITS1). We compared the validity of LAMP of 18S rRNA gene and PCR-mkDNA, to PCR-ITS1 in simulation model of L. martiniquensis infection in Sergentomyia gemmea sand flies. Attributable to the sensitivity and specificity, PCR-mkDNA was consecutively applied to detect L. martiniquensis in 380 female sand fly individuals captured in the newly identified affected region of Lamphun Province, Thailand. Results showed that PCR-mkDNA could detect at least one promastigote per sand fly, which was 10-time superior to LAMP and PCR-ITS1. In addition, PCR-mkDNA was more specific, able to differentiate L. martiniquensis from other viscerotropic Leishmania species, such as L. siamensis, L. (L.) donovani, and L. (L.) infantum. Consecutively, mass screening of L. martiniquensis in 380 female sand fly individuals by PCR-mkDNA was implemented in a new affected area of Thailand where a patient with leishmaniasis/HIV co-infection resides; however Leishmania DNA was undetected. In conclusion, PCR-mkDNA is a promising tool for molecular mass screening of L. martiniquensis infection in outbreak areas where several species of Leishmania

  6. Comparison of LAMP and PCR for molecular mass screening of sand flies for Leishmania martiniquensis infection

    Science.gov (United States)

    Tiwananthagorn, Saruda; Kato, Hirotomo; Yeewa, Ranchana; Muengpan, Amontip; Polseela, Raxsina; Leelayoova, Saovanee

    2017-01-01

    BACKGROUND Leishmaniasis caused by Leishmania martiniquensis infection has been reported in human and domestic animals of Martinique Island, Germany, Switzerland, USA, Myanmar and Thailand. The peculiar clinical features of disseminated cutaneous and visceral forms co-existence render the urgent need of specific diagnostic tool to identify the natural sand fly vectors for effective prevention and control strategies. Loop-mediated isothermal amplification (LAMP) of 18S rRNA gene as well as polymerase chain reaction (PCR) of minicircle kinetoplast DNA gene (PCR-mkDNA) have never been applied to detect L. martiniquensis and L. siamensis in sand fly vectors. OBJECTIVE The present study was aimed to validate malachite green-LAMP (MG-LAMP) and PCR-mkDNA techniques to detect L. martiniquensis in sand fly vectors, compared with the conventional PCR of internal transcribed spacer 1 (PCR-ITS1). METHODS We compared the validity of LAMP of 18S rRNA gene and PCR-mkDNA, to PCR-ITS1 in simulation model of L. martiniquensis infection in Sergentomyia gemmea sand flies. Attributable to the sensitivity and specificity, PCR-mkDNA was consecutively applied to detect L. martiniquensis in 380 female sand fly individuals captured in the newly identified affected region of Lamphun Province, Thailand. FINDINGS AND MAIN CONCLUSIONS Results showed that PCR-mkDNA could detect at least one promastigote per sand fly, which was 10-time superior to LAMP and PCR-ITS1. In addition, PCR-mkDNA was more specific, able to differentiate L. martiniquensis from other viscerotropic Leishmania species, such as L. siamensis, L. (L.) donovani, and L. (L.) infantum. Consecutively, mass screening of L. martiniquensis in 380 female sand fly individuals by PCR-mkDNA was implemented in a new affected area of Thailand where a patient with leishmaniasis/HIV co-infection resides; however Leishmania DNA was undetected. In conclusion, PCR-mkDNA is a promising tool for molecular mass screening of L. martiniquensis

  7. Molecular cloning, structural analysis and mass spectrometric identification of native dioscorins of various yam species.

    Science.gov (United States)

    Tsai, Wei-Yi; Jheng, Yi-Jyun; Chen, Kuo-Hsuan; Lin, Kuo-Wei; Ho, Yen-Pen; Yang, Ching-Chi; Lin, Kuo-Chih

    2013-03-15

    Dioscorins are the major storage proteins of yam tubers. However, the molecular nature of their heterogeneity in tubers has not been fully elucidated. In this study the authors isolated the dioscorin gene families of Dioscorea japonica and Dioscorea pseudojaponica, performed matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) and elucidated which dioscorin isoforms are the major constituents in tubers. The dioscorin gene families of D. japonica (Dj-dioA1-Dj-dioA4, Dj-dioB1 and Dj-dioB2) and D. pseudojaponica (Dp-dioA1-Dp-dioA5 and Dp-dioB1) were cloned from cDNA libraries of yam tubers. The dioscorins isolated from Dioscorea alata (Da-dioscorins), D. japonica (Dj-dioscorins) and D. pseudojaponica (Dp-dioscorins) were mainly monomers, with a few dimers. The monomers contained one intramolecular disulfide bond (Cys(28)-Cys(187)) and belonged to Class A dioscorins with two cysteine residues. The dimers consisted of Class B dioscorins with one intermolecular disulfide bond (Cys(40)-Cys(40)). Results of MALDI-TOF-MS revealed that the Da-dioscorins were mainly encoded by Da-dioA2, Da-dioA3 and Da-dioA4. The majority of the Dj-dioscorins were encoded by Dj-dioA1, Dj-dioA2, Dj-dioA3 and Dj-dioB2. The Dp-dioscorins mainly comprised proteins encoded by Dp-dioA1, Dp-dioA3, Dp-dioA4, Dp-dioB1 and Dp-dioB2. Determination of the constituents of dioscorin isoforms in yam tubers provides a basis for future studies of their physiological and biomedical functions. © 2012 Society of Chemical Industry.

  8. Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study

    OpenAIRE

    Kourtchev, I; Godoi, RHM; Connors, S; Levine, JG; Archibald, AT; Godoi, AFL; Paralovo, SL; Barbosa, CGG; Souza, RAF; Manzi, AO; Seco, R; Sjostedt, S; Park, J-H; Guenther, A; Kim, S

    2016-01-01

    The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM$_{2.5}$ aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagr...

  9. TWO MASS DISTRIBUTIONS IN THE L 1641 MOLECULAR CLOUDS: THE HERSCHEL CONNECTION OF DENSE CORES AND FILAMENTS IN ORION A

    International Nuclear Information System (INIS)

    Polychroni, D.; Schisano, E.; Elia, D.; Molinari, S.; Turrini, D.; Rygl, K. L. J.; Benedettini, M.; Busquet, G.; Di Giorgio, A. M.; Pestalozzi, M.; Pezzuto, S.; Roy, A.; André, Ph.; Hennemann, M.; Hill, T.; Könyves, V.; Martin, P.; Di Francesco, J.; Arzoumanian, D.; Bontemps, S.

    2013-01-01

    We present Herschel survey maps of the L 1641 molecular clouds in Orion A. We extracted both the filaments and dense cores in the region. We identified which of the dense sources are proto- or pre-stellar, and studied their association with the identified filaments. We find that although most (71%) of the pre-stellar sources are located on filaments there, is still a significant fraction of sources not associated with such structures. We find that these two populations (on and off the identified filaments) have distinctly different mass distributions. The mass distribution of the sources on the filaments is found to peak at 4 M ☉ and drives the shape of the core mass function (CMF) at higher masses, which we fit with a power law of the form dN/dlogM∝M –1.4±0.4 . The mass distribution of the sources off the filaments, on the other hand, peaks at 0.8 M ☉ and leads to a flattening of the CMF at masses lower than ∼4 M ☉ . We postulate that this difference between the mass distributions is due to the higher proportion of gas that is available in the filaments, rather than in the diffuse cloud

  10. TWO MASS DISTRIBUTIONS IN THE L 1641 MOLECULAR CLOUDS: THE HERSCHEL CONNECTION OF DENSE CORES AND FILAMENTS IN ORION A

    Energy Technology Data Exchange (ETDEWEB)

    Polychroni, D. [Department of Astrophysics, University of Athens, Astronomy and Mechanics, Faculty of Physics, Panepistimiopolis, 15784 Zografos, Athens (Greece); Schisano, E.; Elia, D.; Molinari, S.; Turrini, D.; Rygl, K. L. J.; Benedettini, M.; Busquet, G.; Di Giorgio, A. M.; Pestalozzi, M.; Pezzuto, S. [Istituto di Astrofisica e Planetologia Spaziali (INAF-IAPS), via del Fosso del Cavaliere 100, I-00133 Roma (Italy); Roy, A.; André, Ph.; Hennemann, M.; Hill, T.; Könyves, V. [Laboratoire AIM, CEA/IRFU CNRS/INSU Université Paris Diderot, Paris-Saclay, F-91191 Gif-sur-Yvette (France); Martin, P. [Canadian Institute for Theoretical Astrophysics, University of Toronto, 60 St. George Street, Toronto, ON M5S 3H8 (Canada); Di Francesco, J. [National Research Council Canada, 5071 West Saanich Road, Victoria, BC V9E 2E7 (Canada); Arzoumanian, D. [IAS, CNRS (UMR 8617), Université Paris-Sud, Bâtiment 121, F-91400 Orsay (France); Bontemps, S., E-mail: dpolychroni@phys.uoa.gr [Université de Bordeaux, Laboratoire d' Astrophysique de Bordeaux, CNRS/INSU, UMR 5804, BP 89, F-33271, Floirac Cedex (France); and others

    2013-11-10

    We present Herschel survey maps of the L 1641 molecular clouds in Orion A. We extracted both the filaments and dense cores in the region. We identified which of the dense sources are proto- or pre-stellar, and studied their association with the identified filaments. We find that although most (71%) of the pre-stellar sources are located on filaments there, is still a significant fraction of sources not associated with such structures. We find that these two populations (on and off the identified filaments) have distinctly different mass distributions. The mass distribution of the sources on the filaments is found to peak at 4 M {sub ☉} and drives the shape of the core mass function (CMF) at higher masses, which we fit with a power law of the form dN/dlogM∝M {sup –1.4±0.4}. The mass distribution of the sources off the filaments, on the other hand, peaks at 0.8 M {sub ☉} and leads to a flattening of the CMF at masses lower than ∼4 M {sub ☉}. We postulate that this difference between the mass distributions is due to the higher proportion of gas that is available in the filaments, rather than in the diffuse cloud.

  11. Ion Mobility Mass Spectrometry for Extracting Spectra of N-Glycans Directly from Incubation Mixtures Following Glycan Release: Application to Glycans from Engineered Glycoforms of Intact, Folded HIV gp120

    Science.gov (United States)

    Harvey, David J.; Sobott, Frank; Crispin, Max; Wrobel, Antoni; Bonomelli, Camille; Vasiljevic, Snezana; Scanlan, Christopher N.; Scarff, Charlotte A.; Thalassinos, Konstantinos; Scrivens, James H.

    2011-03-01

    The analysis of glycosylation from native biological sources is often frustrated by the low abundances of available material. Here, ion mobility combined with electrospray ionization mass spectrometry have been used to extract the spectra of N-glycans released with PNGase F from a serial titration of recombinantly expressed envelope glycoprotein, gp120, from the human immunodeficiency virus (HIV). Analysis was also performed on gp120 expressed in the α-mannosidase inhibitor, and in a matched mammalian cell line deficient in GlcNAc transferase I. Without ion mobility separation, ESI spectra frequently contained no observable ions from the glycans whereas ions from other compounds such as detergents and residual buffer salts were abundant. After ion mobility separation on a Waters T-wave ion mobility mass spectrometer, the N-glycans fell into a unique region of the ion mobility/ m/z plot allowing their profiles to be extracted with good signal:noise ratios. This method allowed N-glycan profiles to be extracted from crude incubation mixtures with no clean-up even in the presence of surfactants such as NP40. Furthermore, this technique allowed clear profiles to be obtained from sub-microgram amounts of glycoprotein. Glycan profiles were similar to those generated by MALDI-TOF MS although they were more susceptible to double charging and fragmentation. Structural analysis could be accomplished by MS/MS experiments in either positive or negative ion mode but negative ion mode gave the most informative spectra and provided a reliable approach to the analysis of glycans from small amounts of glycoprotein.

  12. Strategies for Analyzing Data from Intact Groups.

    Science.gov (United States)

    Cross, Lawrence H.; Lane, Carolyn E.

    Action research often necessitates the use of intact groups for the comparison of educational treatments or programs. This paper considers several analytical methods that might be used for such situations when pretest scores indicate that these intact groups differ significantly initially. The methods considered include gain score analysis of…

  13. Exploratory investigations of hypervelocity intact capture spectroscopy

    Science.gov (United States)

    Tsou, P.; Griffiths, D. J.

    1993-01-01

    The ability to capture hypervelocity projectiles intact opens a new technique available for hypervelocity research. A determination of the reactions taking place between the projectile and the capture medium during the process of intact capture is extremely important to an understanding of the intact capture phenomenon, to improving the capture technique, and to developing a theory describing the phenomenon. The intact capture of hypervelocity projectiles by underdense media generates spectra, characteristic of the material species of projectile and capture medium involved. Initial exploratory results into real-time characterization of hypervelocity intact capture techniques by spectroscopy include ultra-violet and visible spectra obtained by use of reflecting gratings, transmitting gratings, and prisms, and recorded by photographic and electronic means. Spectrometry proved to be a valuable real-time diagnostic tool for hypervelocity intact capture events, offering understanding of the interactions of the projectile and the capture medium during the initial period and providing information not obtainable by other characterizations. Preliminary results and analyses of spectra produced by the intact capture of hypervelocity aluminum spheres in polyethylene (PE), polystyrene (PS), and polyurethane (PU) foams are presented. Included are tentative emission species identifications, as well as gray body temperatures produced in the intact capture process.

  14. Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

    Science.gov (United States)

    Koch, Boris P.; Witt, Matthias; Engbrodt, Ralph; Dittmar, Thorsten; Kattner, Gerhard

    2005-07-01

    The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

  15. Chemometric Analysis of High Molecular Mass Glutenin Subunits and Image Data of Bread Crumb Structure from Croatian Wheat Cultivars

    OpenAIRE

    Zorica Jurković; Rezica Sudar; Damir Magdić; Daniela Horvat; Želimir Kurtanjek

    2002-01-01

    The aim of this work is to investigate functional relationships among wheat properties, high molecular mass (weight) (HMW) glutenin subunits and bread quality produced from eleven Croatian wheat cultivars by chemometric analysis. HMW glutenin subunits were fractionated by sodium dodecylsulfate polyacrylamid gel electrophoresis (SDS-PAGE) and subsequently analysed by scanning densitometry in order to quantify HMW glutenin fractions. Wheat properties are characterised by four variables: protein...

  16. Comparison of molecular species of various transphosphatidylated phosphatidylserine (PS) with bovine cortex PS by mass spectrometry

    NARCIS (Netherlands)

    Chen, S.; Li, K.W.

    2008-01-01

    The exogenous introduction of a molecular species mixture of bovine cortex phosphatidylserine (BC-PS) has been claimed to improve memory function in subjects suffering from age-associated memory impairment and dementia. However, it has been also reported that oral administration of another molecular

  17. Evaporation of liquid droplets of nano- and micro-meter size as a function of molecular mass and intermolecular interactions: experiments and molecular dynamics simulations.

    Science.gov (United States)

    Hołyst, Robert; Litniewski, Marek; Jakubczyk, Daniel

    2017-09-13

    Transport of heat to the surface of a liquid is a limiting step in the evaporation of liquids into an inert gas. Molecular dynamics (MD) simulations of a two component Lennard-Jones (LJ) fluid revealed two modes of energy transport from a vapour to an interface of an evaporating droplet of liquid. Heat is transported according to the equation of temperature diffusion, far from the droplet of radius R. The heat flux, in this region, is proportional to temperature gradient and heat conductivity in the vapour. However at some distance from the interface, Aλ, (where λ is the mean free path in the gas), the temperature has a discontinuity and heat is transported ballistically i.e. by direct individual collisions of gas molecules with the interface. This ballistic transport reduces the heat flux (and consequently the mass flux) by the factor R/(R + Aλ) in comparison to the flux obtained from temperature diffusion. Thus it slows down the evaporation of droplets of sizes R ∼ Aλ and smaller (practically for sizes from 10 3 nm down to 1 nm). We analyzed parameter A as a function of interactions between molecules and their masses. The rescaled parameter, A(k B T b /ε 11 ) 1/2 , is a linear function of the ratio of the molecular mass of the liquid molecules to the molecular mass of the gas molecules, m 1 /m 2 (for a series of chemically similar compounds). Here ε 11 is the interaction parameter between molecules in the liquid (proportional to the enthalpy of evaporation) and T b is the temperature of the gas in the bulk. We tested the predictions of MD simulations in experiments performed on droplets of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. They were suspended in an electrodynamic trap and evaporated into dry nitrogen gas. A changes from ∼1 (for ethylene glycol) to approximately 10 (for tetraethylene glycol) and has the same dependence on molecular parameters as obtained for the LJ fluid in MD simulations. The value of x = A

  18. Toward best practices in data processing and analysis for intact biotherapeutics by MS in quantitative bioanalysis.

    Science.gov (United States)

    Kellie, John F; Kehler, Jonathan R; Karlinsey, Molly Z; Summerfield, Scott G

    2017-12-01

    Typically, quantitation of biotherapeutics from biological matrices by LC-MS is based on a surrogate peptide approach to determine molecule concentration. Recent efforts have focused on quantitation of the intact protein molecules or larger mass subunits of monoclonal antibodies. To date, there has been limited guidance for large or intact protein mass quantitation for quantitative bioanalysis. Intact- and subunit-level analyses of biotherapeutics from biological matrices are performed at 12-25 kDa mass range with quantitation data presented. Linearity, bias and other metrics are presented along with recommendations made on the viability of existing quantitation approaches. This communication is intended to start a discussion around intact protein data analysis and processing, recognizing that other published contributions will be required.

  19. THE MASS-SIZE RELATION FROM CLOUDS TO CORES. I. A NEW PROBE OF STRUCTURE IN MOLECULAR CLOUDS

    International Nuclear Information System (INIS)

    Kauffmann, J.; Shetty, R.; Goodman, A. A.; Pillai, T.; Myers, P. C.

    2010-01-01

    We use a new contour-based map analysis technique to measure the mass and size of molecular cloud fragments continuously over a wide range of spatial scales (0.05 ≤ r/pc ≤ 10), i.e., from the scale of dense cores to those of entire clouds. The present paper presents the method via a detailed exploration of the Perseus molecular cloud. Dust extinction and emission data are combined to yield reliable scale-dependent measurements of mass. This scale-independent analysis approach is useful for several reasons. First, it provides a more comprehensive characterization of a map (i.e., not biased toward a particular spatial scale). Such a lack of bias is extremely useful for the joint analysis of many data sets taken with different spatial resolution. This includes comparisons between different cloud complexes. Second, the multi-scale mass-size data constitute a unique resource to derive slopes of mass-size laws (via power-law fits). Such slopes provide singular constraints on large-scale density gradients in clouds.

  20. Linking the formation of molecular clouds and high-mass stars: a multi-tracer and multi-scale study

    International Nuclear Information System (INIS)

    Nguyen-Luong, Quang

    2012-01-01

    Star formation is a complex process involving many physical processes acting from the very large scales of the galaxy to the very small scales of individual stars. Among the highly debated topics, the gas to star-formation-rate (SFR) relation is an interesting topic for both the galactic and extragalactic communities. Although it is studied extensively for external galaxies, how this relation behaves with respect to the molecular clouds of the Milky Way is still unclear. The detailed mechanisms of the formation of molecular clouds and stars, especially high-mass stars, are still not clear. To tackle these two questions, we investigate the molecular cloud formation and the star formation activities in the W43 molecular cloud complex and the G035.39-00.33 filament. The first goal is to infer the connections of the gas-SFR relations of these two objects to those of other galactic molecular clouds and to extragalactic ones. The second goal is to look for indications that the converging flows theory has formed the W43 molecular cloud since it is the first theory to explain star formation self-consistently, from the onset of molecular clouds to the formation of seeds of (high-mass) stars. We use a large dataset of continuum tracers at 3.6--870 μm extracted from Galaxy-wide surveys such as HOBYS, EPOS, Hi-GAL, ATLASGAL, GLIMPSE, and MIPSGAL to trace the cloud structure, mass and star formation activities of both the W43 molecular cloud complex and the G035.39-00.33 filament. To explore the detailed formation mechanisms of the molecular cloud in W43 from low-density to very high-density gas, we take advantage of the existing H_I, "1"3CO 1-0 molecular line data from the VGPS and GRS surveys in combination with the new dedicated molecular line surveys with the IRAM 30 m. We characterise the W43 molecular complex as being a massive complex (M(total) ∼ 7.1 *10"6 M. over spatial extent of ∼ 140 pc), which has a high concentration of dense clumps (M(clumps) ∼ 8.4*10"5 M

  1. High-Resolution Liquid Chromatography Tandem Mass Spectrometry Enables Large Scale Molecular Characterization of Dissolved Organic Matter

    Directory of Open Access Journals (Sweden)

    Daniel Petras

    2017-12-01

    Full Text Available Dissolved organic matter (DOM is arguably one of the most complex exometabolomes on earth, and is comprised of thousands of compounds, that together contribute more than 600 × 1015 g carbon. This reservoir is primarily the product of interactions between the upper ocean's microbial food web, yet abiotic processes that occur over millennia have also modified many of its molecules. The compounds within this reservoir play important roles in determining the rate and extent of element exchange between inorganic reservoirs and the marine biosphere, while also mediating microbe-microbe interactions. As such, there has been a widespread effort to characterize DOM using high-resolution analytical methods including nuclear magnetic resonance spectroscopy (NMR and mass spectrometry (MS. To date, molecular information in DOM has been primarily obtained through calculated molecular formulas from exact mass. This approach has the advantage of being non-targeted, accessing the inherent complexity of DOM. Molecular structures are however still elusive and the most commonly used instruments are costly. More recently, tandem mass spectrometry has been employed to more precisely identify DOM components through comparison to library mass spectra. Here we describe a data acquisition and analysis workflow that expands the repertoire of high-resolution analytical approaches available to access the complexity of DOM molecules that are amenable to electrospray ionization (ESI MS. We couple liquid chromatographic separation with tandem MS (LC-MS/MS and a data analysis pipeline, that integrates peak extraction from extracted ion chromatograms (XIC, molecular formula calculation and molecular networking. This provides more precise structural characterization. Although only around 1% of detectable DOM compounds can be annotated through publicly available spectral libraries, community-wide participation in populating and annotating DOM datasets could rapidly increase the

  2. Use of a free-jet expansion, molecular beam mass spectrometer to understand processes involving volatile corrosion products

    International Nuclear Information System (INIS)

    Jacobson, N.S.

    1997-01-01

    Many high-temperature corrosion processes generate volatile products in addition to condensed phase products. Examples of these volatile products are chlorides, oxychlorides, and certain oxides and hydroxyl species. One of the best techniques to identify high temperature vapor molecules is mass spectrometry. Most mass spectrometers operate in high vacuum and are generally used to examine processes ocurring at greatly reduced pressures. However, a free-jet expansion, molecular beam mass spectrometer system allows direct sampling of volatile corrosion products. This instrument is described. Several examples from our studies on chlorination/oxidation of metals and ceramics are discussed. In addition, reactions of Cr 2 O 3 , SiO 2 , and Al 2 O 3 with water vapor, which produce volatile hydroxyl species are discussed. (orig.)

  3. Approaches for the analysis of low molecular weight compounds with laser desorption/ionization techniques and mass spectrometry.

    Science.gov (United States)

    Bergman, Nina; Shevchenko, Denys; Bergquist, Jonas

    2014-01-01

    This review summarizes various approaches for the analysis of low molecular weight (LMW) compounds by different laser desorption/ionization mass spectrometry techniques (LDI-MS). It is common to use an agent to assist the ionization, and small molecules are normally difficult to analyze by, e.g., matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) using the common matrices available today, because the latter are generally small organic compounds themselves. This often results in severe suppression of analyte peaks, or interference of the matrix and analyte signals in the low mass region. However, intrinsic properties of several LDI techniques such as high sensitivity, low sample consumption, high tolerance towards salts and solid particles, and rapid analysis have stimulated scientists to develop methods to circumvent matrix-related issues in the analysis of LMW molecules. Recent developments within this field as well as historical considerations and future prospects are presented in this review.

  4. WISDOM Project - III. Molecular gas measurement of the supermassive black hole mass in the barred lenticular galaxy NGC4429

    Science.gov (United States)

    Davis, Timothy A.; Bureau, Martin; Onishi, Kyoko; van de Voort, Freeke; Cappellari, Michele; Iguchi, Satoru; Liu, Lijie; North, Eve V.; Sarzi, Marc; Smith, Mark D.

    2018-01-01

    As part of the mm-Wave Interferometric Survey of Dark Object Masses project we present an estimate of the mass of the supermassive black hole (SMBH) in the nearby fast-rotating early-type galaxy NGC4429, that is barred and has a boxy/peanut-shaped bulge. This estimate is based on Atacama Large Millimeter/submillimeter Array (ALMA) cycle-2 observations of the 12CO(3-2) emission line with a linear resolution of ≈13 pc (0.18 arcsec × 0.14 arcsec). NGC4429 has a relaxed, flocculent nuclear disc of molecular gas that is truncated at small radii, likely due to the combined effects of gas stability and tidal shear. The warm/dense 12CO(3-2) emitting gas is confined to the inner parts of this disc, likely again because the gas becomes more stable at larger radii, preventing star formation. The gas disc has a low velocity dispersion of 2.2^{+0.68}_{-0.65} km s-1. Despite the inner truncation of the gas disc, we are able to model the kinematics of the gas and estimate a mass of (1.5 ± 0.1^{+0.15}_{-0.35}) × 108 M⊙ for the SMBH in NGC4429 (where the quoted uncertainties reflect the random and systematic uncertainties, respectively), consistent with a previous upper limit set using ionized gas kinematics. We confirm that the V-band mass-to-light ratio changes by ≈30 per cent within the inner 400 pc of NGC4429, as suggested by other authors. This SMBH mass measurement based on molecular gas kinematics, the sixth presented in the literature, once again demonstrates the power of ALMA to constrain SMBH masses.

  5. Detailed Source-Specific Molecular Composition of Ambient Aerosol Organic Matter Using Ultrahigh Resolution Mass Spectrometry and 1H NMR

    Directory of Open Access Journals (Sweden)

    Amanda S. Willoughby

    2016-06-01

    Full Text Available Organic aerosols (OA are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban using ultrahigh resolution mass spectrometry (UHR-MS and proton nuclear magnetic resonance spectroscopy (1H NMR. UHR-MS and 1H NMR show that OA within each source is structurally diverse, and the molecular characteristics are described in detail. Principal component analysis (PCA revealed that (1 aromatic nitrogen species are distinguishing components for these biomass burning aerosols; (2 these urban aerosols are distinguished by having formulas with high O/C ratios and lesser aromatic and condensed aromatic formulas; and (3 these marine aerosols are distinguished by lipid-like compounds of likely marine biological origin. This study provides a unique qualitative approach for enhancing the chemical characterization of OA necessary for molecular source apportionment.

  6. The ATLAS3D project - XX. Mass-size and mass-σ distributions of early-type galaxies: bulge fraction drives kinematics, mass-to-light ratio, molecular gas fraction and stellar initial mass function

    Science.gov (United States)

    Cappellari, Michele; McDermid, Richard M.; Alatalo, Katherine; Blitz, Leo; Bois, Maxime; Bournaud, Frédéric; Bureau, M.; Crocker, Alison F.; Davies, Roger L.; Davis, Timothy A.; de Zeeuw, P. T.; Duc, Pierre-Alain; Emsellem, Eric; Khochfar, Sadegh; Krajnović, Davor; Kuntschner, Harald; Morganti, Raffaella; Naab, Thorsten; Oosterloo, Tom; Sarzi, Marc; Scott, Nicholas; Serra, Paolo; Weijmans, Anne-Marie; Young, Lisa M.

    2013-07-01

    ) and dwarf irregulars (Im), respectively. We use dynamical models to analyse our kinematic maps. We show that σe traces the bulge fraction, which appears to be the main driver for the observed trends in the dynamical (M/L)JAM and in indicators of the (M/L)pop of the stellar population like Hβ and colour, as well as in the molecular gas fraction. A similar variation along contours of σe is also observed for the mass normalization of the stellar initial mass function (IMF), which was recently shown to vary systematically within the ETGs' population. Our preferred relation has the form log _{10} [(M/L)_stars/(M/L)_Salp]=a+b× log _{10}({σ _e}/130 {km s^{-1}}) with a = -0.12 ± 0.01 and b = 0.35 ± 0.06. Unless there are major flaws in all stellar population models, this trend implies a transition of the mean IMF from Kroupa to Salpeter in the interval log _{10}({σ _e}/{km s}^{-1})≈ 1.9-2.5 (or {σ _e}≈ 90-290 km s-1), with a smooth variation in between, consistently with what was shown in Cappellari et al. The observed distribution of galaxy properties on the MP provides a clean and novel view for a number of previously reported trends, which constitute special two-dimensional projections of the more general four-dimensional parameters trends on the MP. We interpret it as due to a combination of two main effects: (i) an increase of the bulge fraction, which increases σe, decreases Re, and greatly enhance the likelihood for a galaxy to have its star formation quenched, and (ii) dry merging, increasing galaxy mass and Re by moving galaxies along lines of roughly constant σe (or steeper), while leaving the population nearly unchanged.

  7. Enhancing Accuracy in Molecular Weight Determination of Highly Heterogeneously Glycosylated Proteins by Native Tandem Mass Spectrometry

    NARCIS (Netherlands)

    Wang, Guanbo; de Jong, Rob N; van den Bremer, Ewald T J; Parren, Paul W H I; Heck, Albert J R

    2017-01-01

    The determination of molecular weights (MWs) of heavily glycosylated proteins is seriously hampered by the physicochemical characteristics and heterogeneity of the attached carbohydrates. Glycosylation impacts protein migration during sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis

  8. Organizing the Cellular and Molecular Heterogeneity in High-Grade Serous Ovarian Cancer by Mass Cytometry

    Science.gov (United States)

    2014-10-01

    Bendall SC, Sung P, Nolan GP, Arvin AM. Single-cell mass cytometry analysis of human tonsil T cell remodeling by varicella zoster virus. Cell Rep...Perspectives on Flow Cytometry 2013, September 20, 2013, Mass Cytometry and Cell Cycle, Mexico City, Mexico (by Web Conference) Nolan: Nuclear

  9. Determination of the Relative Atomic Masses of Metals by Liberation of Molecular Hydrogen

    Science.gov (United States)

    Waghorne, W. Earle; Rous, Andrew J.

    2009-01-01

    Students determine the relative atomic masses of calcium, magnesium, and aluminum by reaction with hydrochloric acid and measurement of the volume of hydrogen gas liberated. The experiment demonstrates stoichiometry and illustrates clearly that mass of the reagent is not the determinant of the amounts in chemical reactions. The experiment is…

  10. Pulsed flow modulation two-dimensional comprehensive gas chromatography-tandem mass spectrometry with supersonic molecular beams.

    Science.gov (United States)

    Poliak, Marina; Fialkov, Alexander B; Amirav, Aviv

    2008-11-07

    Pulsed flow modulation (PFM) two-dimensional comprehensive gas chromatography (GC x GC) was combined with quadrupole-based mass spectrometry (MS) via a supersonic molecular beam (SMB) interface using a triple-quadrupole system as the base platform, which enabled tandem mass spectrometry (MS-MS). PFM is a simple GC x GC modulator that does not consume cryogenic gases while providing tunable second GC x GC column injection time for enabling the use of quadrupole-based mass spectrometry regardless its limited scanning speed. The 20-ml/min second column flow rate involved with PFM is handled, splitless, by the SMB interface without affecting the sensitivity. The combinations of PFM GC x GC-MS with SMB and PFM GC x GC-MS-MS with SMB were explored with the analysis of diazinon and permethrin in coriander. PFM GC x GC-MS with SMB is characterized by enhanced molecular ion and tailing-free fast ion source response time. It enables universal pesticide analysis with full scan and data analysis with reconstructed single ion monitoring on the enhanced molecular ion and another prominent high mass fragment ion. The elimination of the third fragment ion used in standard three ions method results in significantly reduced matrix interference. GC x GC-MS with SMB improves the GC separation, and thereby our ability for sample identification using libraries. GC-MS-MS with SMB provides better reduction (elimination) of matrix interference than GC x GC-MS. However, it is a target method, which is not always applicable. GC x GC-MS-MS does not seem to further reduce matrix interferences over GC-MS-MS and unlike GC x GC-MS, it is incompatible with library identification, but it is beneficial to have both GC x GC and MS-MS capabilities in the same system.

  11. Direct coupling of a dense (supercritical) gas chromatograph to a mass spectrometer using a supersonic molecular beam interface

    International Nuclear Information System (INIS)

    Randall, L.G.; Wahrhaftig, A.L.

    1981-01-01

    A detecting mass spectrometer has been successfully coupled to a dense gas (supercritical fluid) chromatograph to produce an instrument (DGC/MS) that may be an alternative to high performance liquid chromatograph/mass spectrometer instruments (HPLC/MS) and gas chromatograph/mass spectrometer instruments (GC/MS) for analysis of involatile and/or thermally labile compounds. The mobile phase in DGC is a gas held at temperatures above the critical temperature and at pressures sufficient to obtain nearly liquid-like densities. DGC combines advantages of GC and HPLC: rapid separations, moderate operating temperatures, and analysis of involatile compounds. An advantage unique to DGC is the solvent power dependence upon pressure. While several groups have studied DGC, its development has been limited by the lack of a sensitive and selective detector. Hence, work has been directed towards the design and construction of a DGC/MS resulting in a trial instrument capable of chromatographic pressures of at least 300 atm and temperatures from 10 0 to 60 0 C. The DGC/MS coupling has been accomplished by the use of a supersonic molecular beam interface. This application of molecular beam formation appears to be unique in its requirements of a large pressure ratio (approx.10 8 ), low flow rates, and low final pressures. The authors outline characteristics of supersonic jets and molecular beams pertinent to the design of such an instrument. The interface which uses pumping speeds of 2400 and 1200 l/s in the beam forming chambers is described in detail, while the other components: the detecting mass spectrometer, the dense gas supply, and the DGC: are briefly described. Preliminary work with this instrument has established the feasibility of DGC/MS as an analytical technique and further development is recommended

  12. MALDI-TOF mass spectrometry imaging reveals molecular level changes in ultrahigh molecular weight polyethylene joint implants in correlation with lipid adsorption.

    Science.gov (United States)

    Fröhlich, Sophie M; Archodoulaki, Vasiliki-Maria; Allmaier, Günter; Marchetti-Deschmann, Martina

    2014-10-07

    Ultrahigh molecular weight polyethylene (PE-UHMW), a material with high biocompatibility and excellent mechanical properties, is among the most commonly used materials for acetabular cup replacement in artificial joint systems. It is assumed that the interaction with synovial fluid in the biocompartment leads to significant changes relevant to material failure. In addition to hyaluronic acid, lipids are particularly relevant for lubrication in an articulating process. This study investigates synovial lipid adsorption on two different PE-UHMW materials (GUR-1050 and vitamin E-doped) in an in vitro model system by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry imaging (MSI). Lipids were identified by high performance thin layer chromatography (HP-TLC) and tandem mass spectrometry (MS/MS) analysis, with an analytical focus on phospholipids and cholesterol, both being species of high importance for lubrication. Scanning electron microscopy (SEM) analysis was applied in the study to correlate molecular information with PE-UHMW material qualities. It is demonstrated that lipid adsorption preferentially occurs in rough or oxidized polymer regions. Polymer modifications were colocalized with adsorbed lipids and found with high density in regions identified by SEM. Explanted, the in vivo polymer material showed comparable and even more obvious polymer damage and lipid adsorption when compared with the static in vitro model. A three-dimensional reconstruction of MSI data from consecutive PE-UHMW slices reveals detailed information about the diffusion process of lipids in the acetabular cup and provides, for the first time, a promising starting point for future studies correlating molecular information with commonly used techniques for material analysis (e.g., Fourier-transform infrared spectroscopy, nanoindentation).

  13. In situ monitoring of molecular changes during cell differentiation processes in marine macroalgae through mass spectrometric imaging.

    Science.gov (United States)

    Kessler, Ralf W; Crecelius, Anna C; Schubert, Ulrich S; Wichard, Thomas

    2017-08-01

    Matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI) was employed to discriminate between cell differentiation processes in macroalgae. One of the key developmental processes in the algal life cycle is the production of germ cells (gametes and zoids). The gametogenesis of the marine green macroalga Ulva mutabilis (Chlorophyta) was monitored by metabolomic snapshots of the surface, when blade cells differentiate synchronously into gametangia and giving rise to gametes. To establish MSI for macroalgae, dimethylsulfoniopropionate (DMSP), a known algal osmolyte, was determined. MSI of the surface of U. mutabilis followed by chemometric data analysis revealed dynamic metabolomic changes during cell differentiation. DMSP and a total of 55 specific molecular biomarkers, which could be assigned to important stages of the gametogenesis, were detected. Our research contributes to the understanding of molecular mechanisms underlying macroalgal cell differentiation. Graphical abstract Molecular changes during cell differentiation of the marine macroalga Ulva were visualized by matrix assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI).

  14. Media optimization for elevated molecular weight and mass production of pigment-free pullulan.

    Science.gov (United States)

    Yu, Xiaoliu; Wang, Yulei; Wei, Gongyuan; Dong, Yingying

    2012-07-01

    In this study, an Aureobasidium pullulans SZU 1001 mutant, deficient in pigment production, was screened by complex UV and γ-ray mutagenesis. Medium composition optimization for increased pullulan molecular weight and production was conducted using this mutant. Six nutrients: yeast extract, (NH4)2SO4, K2HPO4, NaCl, MgSO4·7H2O and CaCl2 were detected within pullulan production in flasks. It is shown that NaCl and K2HPO4 have significant influences on molecular weight of pullulan, while yeast extract and (NH4)2SO4 significantly affect pullulan yield. To achieve a higher molecular weight and more efficient pullulan production, a response surface methodology approach was introduced to predict an optimal nutrient combination. A molecular weight of 5.74 × 10(6) and pullulan yield on glucose of 51.30% were obtained under batch pullulan fermentation with the optimized media, which increased molecular weight and pullulan production by 97.25% and 11.04%, respectively compared with the control media. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Characterisation of uremic "Middle molecular"fractions by gas chromatography mass spectrometry, isotachophoresis, and liquid chromatography

    NARCIS (Netherlands)

    Schoots, A.C.; Mikkers, F.E.P.; Claessens, H.A.; Smet, de R.; Landschoot, van N.; Ringoir, S.M.G.

    1982-01-01

    Uremic ultrafiltrates (and normal serum, for comparison) were fractionated by means of gel filtration. The collected fractions were further investigated by combined analytical techniques: "high- performance" liquid chromatography, gas chromatography, mass spectrometry, and isotachophoresis.

  16. In-situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zihua; Zhou, Yufan; Yan, Pengfei; Vemuri, Venkata Rama Ses; Xu, Wu; Zhao, Rui; Wang, Xuelin; Thevuthasan, Suntharampillai; Baer, Donald R.; Wang, Chong M.

    2015-08-19

    Dynamic molecular evolution at solid/liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe/observe the solid/liquid interface under reaction conditions, which in essence appears to be similarly true for all the fields involving solid/liquid phases, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization, We use in-situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid electrode/liquid electrolyte interface for a lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to deplete the salt anion and with low concentration of Li+ ions, which essentially leads to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributes to the overpotential of the cell. This unprecedented molecular level dynamic observation at the solid electrode/liquid electrolyte interface provides vital chemical information that is needed for designing of better battery chemistry for enhanced performance, and ultimately opens new avenues for using liquid SIMS to probe molecular evolution at solid/liquid interface in general.

  17. Orientation and properties of the blends on high-molecular mass polyacrylonitrile with trihydroxyethylenedimethacrylate under electron irradiation

    International Nuclear Information System (INIS)

    Lomonosova, N.V.

    1998-01-01

    Molecular orientation of the drawn blends of high- molecular-mass poly(acrylonitrile) containing 5-50 wt % of trihydroxyethylenedimethacrylate and a change in the orientation of the drawn samples upon irradiation with accelerated electrons was studied by methods of birefringence, isometric heating, and IR dichroism. The degree of orientation of the unirradiated blends containing certain amounts of oligomer exceed that of the individual polymer. In the region of large drawing ratios, the differential degree of orientation of the polymer matrix is not affected by the irradiation, while the orientation of the oligomer component increase. High values of the strength (600-730 MPa) and the modulus (18-22 GPa) of the compositions are due to the presence of a crystalline skeleton formed by unfolded chains of the polymer matrix stabilized by the electron irradiation induced cross-linking

  18. Testing a low molecular mass fraction of a mushroom (Lentinus edodes) extract formulated as an oral rinse in a cohort of volunteers

    NARCIS (Netherlands)

    Signoretto, C.; Burlacchini, G.; Marchi, A.; Grillenzoni, M.; Cavalleri, G.; Ciric, L.; Lingström, P.; Pezzati, E.; Daglia, M.; Zaura, E.; Pratten, J.; Spratt, D.A.; Wilson, M.; Canepari, P.

    2011-01-01

    Although foods are considered enhancing factors for dental caries and periodontitis, laboratory researches indicate that several foods and beverages contain components endowed with antimicrobial and antiplaque activities. A low molecular mass (LMM) fraction of an aqueous mushroom extract has been

  19. Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research

    International Nuclear Information System (INIS)

    Horn, R.; Ihmann, K.; Ihmann, J.; Jentoft, F.C.; Geske, M.; Taha, A.; Pelzer, K.; Schloegl, R.

    2006-01-01

    A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000 deg. C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100 μm sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecular beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10 ms. A detection time resolution of up to 20 ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N 2 and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N 2 to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250 deg. C on a Pt catalyst are presented. The detection of CH 3 · radicals is successfully demonstrated

  20. Molecular beam mass spectrometer equipped with a catalytic wall reactor for in situ studies in high temperature catalysis research

    Science.gov (United States)

    Horn, R.; Ihmann, K.; Ihmann, J.; Jentoft, F. C.; Geske, M.; Taha, A.; Pelzer, K.; Schlögl, R.

    2006-05-01

    A newly developed apparatus combining a molecular beam mass spectrometer and a catalytic wall reactor is described. The setup has been developed for in situ studies of high temperature catalytic reactions (>1000°C), which involve besides surface reactions also gas phase reactions in their mechanism. The goal is to identify gas phase radicals by threshold ionization. A tubular reactor, made from the catalytic material, is positioned in a vacuum chamber. Expansion of the gas through a 100μm sampling orifice in the reactor wall into differentially pumped nozzle, skimmer, and collimator chambers leads to the formation of a molecular beam. A quadrupole mass spectrometer with electron impact ion source designed for molecular beam inlet and threshold ionization measurements is used as the analyzer. The sampling time from nozzle to detector is estimated to be less than 10ms. A detection time resolution of up to 20ms can be reached. The temperature of the reactor is measured by pyrometry. Besides a detailed description of the setup components and the physical background of the method, this article presents measurements showing the performance of the apparatus. After deriving the shape and width of the energy spread of the ionizing electrons from measurements on N2 and He we estimated the detection limit in threshold ionization measurements using binary mixtures of CO in N2 to be in the range of several hundreds of ppm. Mass spectra and threshold ionization measurements recorded during catalytic partial oxidation of methane at 1250°C on a Pt catalyst are presented. The detection of CH3• radicals is successfully demonstrated.

  1. Oligo-Alginate with Low Molecular Mass Improves Growth and Physiological Activity of Eucomis autumnalis under Salinity Stress

    Directory of Open Access Journals (Sweden)

    Piotr Salachna

    2018-04-01

    Full Text Available Biopolymers have become increasingly popular as biostimulators of plant growth. One of them, oligo-alginate, is a molecule that regulates plant biological processes and may be used in horticultural practice as a plant growth regulator. Biostimulators are mainly used to improve plant tolerance to abiotic stresses, including salinity. The aim of the study was to assess the effects of salinity and oligo-alginate of various molecular masses on the growth and physiological activity of Eucomis autumnalis. The species is an ornamental and medicinal plant that has been used for a long time in the traditional medicine of South Africa. The bulbs of E. autumnalis were coated using depolymerized sodium alginate of molecular mass 32,000; 42,000, and 64,000 g mol−1. All of these oligo-alginates fractions stimulated plant growth, and the effect was the strongest for the fraction of 32,000 g mol−1. This fraction was then selected for the second stage of the study, when plants were exposed to salt stress evoked by the presence of 100 mM NaCl. We found that the oligo-alginate coating mitigated the negative effects of salinity. Plants treated with the oligomer and watered with NaCl showed smaller reduction in the weight of the above-ground parts and bulbs, pigment content and antioxidant activity as compared with those not treated with the oligo-alginate. The study demonstrated for the first time that low molecular mass oligo-alginate may be used as plant biostimulator that limits negative effects of salinity in E. autumnalis.

  2. Molecular species composition of plant cardiolipin determined by liquid chromatography mass spectrometry

    Science.gov (United States)

    Zhou, Yonghong; Peisker, Helga

    2016-01-01

    Cardiolipin (CL), an anionic phospholipid of the inner mitochondrial membrane, provides essential functions for stabilizing respiratory complexes and is involved in mitochondrial morphogenesis and programmed cell death in animals. The role of CL and its metabolism in plants are less well understood. The measurement of CL in plants, including its molecular species composition, is hampered by the fact that CL is of extremely low abundance, and that plants contain large amounts of interfering compounds including galactolipids, neutral lipids, and pigments. We used solid phase extraction by anion exchange chromatography to purify CL from crude plant lipid extracts. LC/MS was used to determine the content and molecular species composition of CL. Thus, up to 23 different molecular species of CL were detected in different plant species, including Arabidopsis, mung bean, spinach, barley, and tobacco. Similar to animals, plant CL is dominated by highly unsaturated species, mostly containing linoleic and linolenic acid. During phosphate deprivation or exposure to an extended dark period, the amount of CL decreased in Arabidopsis, accompanied with an increased degree in unsaturation. The mechanism of CL remodeling during stress, and the function of highly unsaturated CL molecular species, remains to be defined. PMID:27179363

  3. Feedback from deeply embedded low- and high-mass protostars. Surveying hot molecular gas with Herschel

    NARCIS (Netherlands)

    Karska, Agata

    2014-01-01

    Protostars interact violently with their natal cocoons within dense molecular clouds. Characterizing this feedback is key to understanding the efficiency of the star formation process and the chemical processing of material that will be available for planet formation. In this thesis, the imprints

  4. The molecular mass of dextran used to modify magnetite nanoparticles affects insulin amyloid aggregation

    Czech Academy of Sciences Publication Activity Database

    Sipošová, K.; Pospíšková, K.; Bednáriková, Z.; Šafařík, Ivo; Šafaříková, Miroslava; Kubovčíková, M.; Kopčanský, P.; Gázová, Z.

    2017-01-01

    Roč. 427, April (2017), s. 48-53 ISSN 0304-8853 Institutional support: RVO:60077344 Keywords : amyloid aggregation * nanoparticles * magnetic fluid * dextran * insulin Subject RIV: CE - Biochemistry OBOR OECD: Biochemistry and molecular biology Impact factor: 2.630, year: 2016

  5. Precision spectroscopy of molecular hydrogen ions : Towards frequency metrology of particle masses

    NARCIS (Netherlands)

    Roth, B.; Koelemeij, J.; Schiller, S.; Hilico, L.; Karr, Jean Philippe; Korobov, V.I.; Bakalov, D.

    2008-01-01

    We describe the current status of high-precision ab initio calculations of the spectra of molecular hydrogen ions (H2+ and HD+) and of two experiments for vibrational spectroscopy. The perspectives for a comparison between theory and experiment at a level of 1 part in 109 are considered.

  6. Assessing the regional impact of indonesian biomass burning emissions based on organic molecular tracers and chemical mass balance modeling

    Science.gov (United States)

    Engling, G.; He, J.; Betha, R.; Balasubramanian, R.

    2014-08-01

    Biomass burning activities commonly occur in Southeast Asia (SEA), and are particularly intense in Indonesia during the dry seasons. The effect of biomass smoke emissions on air quality in the city state of Singapore was investigated during a haze episode in October 2006. Substantially increased levels of airborne particulate matter (PM) and associated chemical species were observed during the haze period. Specifically, the enhancement in the concentration of molecular tracers for biomass combustion such as levoglucosan by as much as two orders of magnitude and the diagnostic ratios of individual organic compounds indicated that biomass burning emissions caused a regional smoke haze episode due to their long-range transport by prevailing winds. With the aid of air mass backward trajectories and chemical mass balance modeling, large-scale forest and peat fires in Sumatra and Kalimantan were identified as the sources of the smoke aerosol, exerting a significant impact on air quality in downwind areas, such as Singapore.

  7. The observation of quasi-molecular ions from a tiger snake venom component (Msub(r) 13309) using 252Cf-plasma desorption mass spectrometry

    International Nuclear Information System (INIS)

    Kamensky, I.; Haakansson, P.; Kjellberg, J.; Sundqvist, B.; Fohlman, J.; Peterson, P.A.

    1983-01-01

    A method involving fast heavy-ion bombardment of a solid sample called 252 Cf-plasma desorption mass spectrometry has been used to study a non-enzymatic, non-toxic phospholipase homolog from Australian tiger snake (Notechis scutatus) venom. The protein consists of 119 amino acids in a single polypeptide chain cross-linked by 7 disulfide bridges. The isotopically averaged molecular mass as determined by protein sequence analysis is 13309 atomic mass units (amu). The mass distributions were studied by means of time-of-flight measurements. Quasi-molecular ions associated to the molecule and its dimer were observed. The mass of the quasi-molecular ion corresponding to the molecule was determined to be 13285 +- 25 amu. (Auth.)

  8. Titan's organic aerosols: Molecular composition and structure of laboratory analogues inferred from pyrolysis gas chromatography mass spectrometry analysis

    Science.gov (United States)

    Morisson, Marietta; Szopa, Cyril; Carrasco, Nathalie; Buch, Arnaud; Gautier, Thomas

    2016-10-01

    Analogues of Titan's aerosols are of primary interest in the understanding of Titan's atmospheric chemistry and climate, and in the development of in situ instrumentation for future space missions. Numerous studies have been carried out to characterize laboratory analogues of Titan aerosols (tholins), but their molecular composition and structure are still poorly known. If pyrolysis gas chromatography mass spectrometry (pyr-GCMS) has been used for years to give clues about their chemical composition, highly disparate results were obtained with this technique. They can be attributed to the variety of analytical conditions used for pyr-GCMS analyses, and/or to differences in the nature of the analogues analyzed, that were produced with different laboratory set-ups under various operating conditions. In order to have a better description of Titan's tholin's molecular composition by pyr-GCMS, we carried out a systematic study with two major objectives: (i) exploring the pyr-GCMS analytical parameters to find the optimal ones for the detection of a wide range of chemical products allowing a characterization of the tholins composition as comprehensive as possible, and (ii) highlighting the role of the CH4 ratio in the gaseous reactive medium on the tholin's molecular structure. We used a radio-frequency plasma discharge to synthetize tholins with different concentrations of CH4 diluted in N2. The samples were pyrolyzed at temperatures covering the 200-700°C range. The extracted gases were then analyzed by GCMS for their molecular identification. The optimal pyrolysis temperature for characterizing the molecular composition of our tholins by GCMS analysis is found to be 600°C. This temperature choice results from the best compromise between the number of compounds released, the quality of the signal and the appearance of pyrolysis artifacts. About a hundred molecules are identified as pyrolysates. A common major chromatographic pattern appears clearly for all the

  9. Preparation of the low molecular weight serum proteome for mass spectrometry analysis.

    Science.gov (United States)

    Waybright, Timothy J; Chan, King C; Veenstra, Timothy D; Xiao, Zhen

    2013-01-01

    The discovery of viable biomarkers or indicators of disease states is complicated by the inherent complexity of the chosen biological specimen. Every sample, whether it is serum, plasma, urine, tissue, cells, or a host of others, contains thousands of large and small components, each interacting in multiple ways. The need to concentrate on a group of these components to narrow the focus on a potential biomarker candidate becomes, out of necessity, a priority, especially in the search for immune-related low molecular weight serum biomarkers. One such method in the field of proteomics is to divide the sample proteome into groups based on the size of the protein, analyze each group, and mine the data for statistically significant items. This chapter details a portion of this method, concentrating on a method for fractionating and analyzing the low molecular weight proteome of human serum.

  10. Tracing early evolutionary stages of high-mass star formation with molecular lines

    NARCIS (Netherlands)

    Marseille, M. G.; van der Tak, F. F. S.; Herpin, F.; Jacq, T.

    2010-01-01

    Context. Despite its major role in the evolution of the interstellar medium, the formation of high-mass stars (M >= 10 M(circle dot)) remains poorly understood. Two types of massive star cluster precursors, the so-called massive dense cores (MDCs), have been observed, which differ in terms of their

  11. Alterations in molecular muscle mass regulators after 8 days immobilizing Special Forces mission

    DEFF Research Database (Denmark)

    Jespersen, J. G.; Mikkelsen, Ulla Ramer; Nedergaard, A.

    2015-01-01

    In military operations, declined physical capacity can endanger the life of soldiers. During special support and reconnaissance (SSR) missions, Special Forces soldiers sustain 1-2 weeks full-body horizontal immobilization, which impairs muscle strength and performance. Adequate muscle mass and st...

  12. Mixtures of nonionic and anionic surfactants: interactions with low-molecular-mass homopeptides

    Czech Academy of Sciences Publication Activity Database

    Forgács, E.; Cserháti, T.; Deyl, Zdeněk; Mikšík, Ivan; Eckhardt, Adam

    2001-01-01

    Roč. 917, 1-2 (2001), s. 287-295 ISSN 0021-9673 R&D Projects: GA ČR GV203/96/K128; GA ČR GA203/99/0191; GA ČR GA203/00/D032 Institutional research plan: CEZ:AV0Z5011922 Keywords : molecular interactions * regression analysis * surfactants Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.793, year: 2001

  13. Ultralarge von Willebrand Factor Fibers Mediate Luminal Staphylococcus aureus Adhesion to an Intact Endothelial Cell Layer Under Shear Stress

    NARCIS (Netherlands)

    Pappelbaum, Karin I.; Gorzelanny, Christian; Graessle, Sandra; Suckau, Jan; Laschke, Matthias W.; Bischoff, Markus; Bauer, Corinne; Schorpp-Kistner, Marina; Weidenmaier, Christopher; Schneppenheim, Reinhard; Obser, Tobias; Sinha, Bhanu; Schneider, Stefan W.

    2013-01-01

    Background During pathogenesis of infective endocarditis, Staphylococcus aureus adherence often occurs without identifiable preexisting heart disease. However, molecular mechanisms mediating initial bacterial adhesion to morphologically intact endocardium are largely unknown. Methods and Results

  14. Weathering trend characterization of medium-molecular weight polycyclic aromatic disulfur heterocycles by Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Hegazi, Abdelrahman H; Fathalla, Eiman M; Andersson, Jan T

    2014-09-01

    Different weathering factors act to change petroleum composition once it is spilled into the environment. n-Alkanes, biomarkers, low-molecular weight polyaromatic hydrocarbons and sulfur heterocycles compositional changing in the environment have been extensively studied by different researchers and many parameters have been used for oil source identification and monitoring of weathering and biological degradation processes. In this work, we studied the fate of medium-molecular weight polycyclic aromatic disulfur heterocycles (PAS2Hs), up to ca. 900Da, of artificially weathered Flotta North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. It was found that PAS2Hs in studied crude oil having double bond equivalents (DBE) from 5 to 8 with a mass range from ca 316 to 582Da were less influenced even after six months artificial weathering experiment. However, compounds having DBEs 12, 11 and 10 were depleted after two, four and six months weathering, respectively. In addition, DBE 9 series was more susceptible to weathering than those of DBE 7 and 8. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Chemical modification of DNA: Molecular specificity studied by tandem mass spectrometry and liquid chromatography

    International Nuclear Information System (INIS)

    Chang, Ching-jer; Cooks, R.G.; Chae, Whi-Gun; Wood, J.M.

    1989-01-01

    Chemical modifications of DNA in vitro could be directly studied by C-13 NMR and P-31 NMR, which eliminated all degradation and separation processes. The prospects of utilized the NMR method in the in vitro experiments are limited because of the inherent low sensitivity of NMR and low level of DNA modification. We have developed a reverse-phase ion-paired HPLC method to study DNA modifications by methylating agents. The structural specificity of HPLC is significantly enhanced by conjunction with the specificity of enzymic transformations. The HPLC studies have also revealed the limitation of HPLC method for simultaneous determination of many minor modified nucleosides. This problem has been overcome by tandem mass spectrometry. In conjunction with the resolving power of HPLC in separating isomers, desorption chemical ionization tandem mass spectrometry has been utilized in the determination of the modified nucleosides at the picomole level using stable-isotope labeled compounds as internal references

  16. Mass Spectrometry Imaging of low Molecular Weight Compounds in Garlic (Allium sativum L.) with Gold Nanoparticle Enhanced Target.

    Science.gov (United States)

    Misiorek, Maria; Sekuła, Justyna; Ruman, Tomasz

    2017-11-01

    Garlic (Allium sativum) is the subject of many studies due to its numerous beneficial properties. Although compounds of garlic have been studied by various analytical methods, their tissue distributions are still unclear. Mass spectrometry imaging (MSI) appears to be a very powerful tool for the identification of the localisation of compounds within a garlic clove. Visualisation of the spatial distribution of garlic low-molecular weight compounds with nanoparticle-based MSI. Compounds occurring on the cross-section of sprouted garlic has been transferred to gold-nanoparticle enhanced target (AuNPET) by imprinting. The imprint was then subjected to MSI analysis. The results suggest that low molecular weight compounds, such as amino acids, dipeptides, fatty acids, organosulphur and organoselenium compounds are distributed within the garlic clove in a characteristic manner. It can be connected with their biological functions and metabolic properties in the plant. New methodology for the visualisation of low molecular weight compounds allowed a correlation to be made between their spatial distribution within a sprouted garlic clove and their biological function. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  17. Small renal masses: The molecular markers associated with outcome of patients with kidney tumors 7 cm or less

    Science.gov (United States)

    Spirina, L. V.; Usynin, Y. A.; Kondakova, I. V.; Yurmazov, Z. A.; Slonimskaya, E. M.; Pikalova, L. V.

    2016-08-01

    The investigation of molecular mechanisms of tumor cell behavior in small renal masses is required to achieve the better cancer survival. The aim of the study is to find molecular markers associated with outcome of patients with kidney tumors 7 cm or less. A homogenous group of 20 patients T1N0M0-1 (mean age 57.6 ± 2.2 years) with kidney cancer was selected for the present analysis. The content of transcription and growth factors was determined by ELISA. The levels of AKT-mTOR signaling pathway components were measured by Western blotting analysis. The molecular markers associated with unfavorable outcome of patients with kidney tumors 7 cm or less were high levels of NF-kB p50, NF-kB p65, HIF-1, HIF-2, VEGF and CAIX. AKT activation with PTEN loss also correlated with the unfavorable outcome of kidney cancer patients with tumor size 7 cm or less. It is observed that the biological features of kidney cancer could predict the outcome of patients.

  18. Organizing the Cellular and Molecular Heterogeneity in High Grade Serous Ovarian Cancer by Mass Cytometry

    Science.gov (United States)

    2015-10-01

    about more informed changes to treatment modalities. To accomplish this vision with HG-SOC, we are using a single cell technology , mass cytometry... extracted from the composite MST. Clusters are represented as bubbles, the size of which corresponds to the number of cells in the cluster. The level of...Fantl WJ, Nolan GP. Transient partial permeabilization with saponin enables cellular barcoding prior to surface marker staining. Cytometry A. 2014 Dec;85

  19. Albumin is synthesized in epididymis and aggregates in a high molecular mass glycoprotein complex involved in sperm-egg fertilization.

    Directory of Open Access Journals (Sweden)

    Kélen Fabíola Arroteia

    Full Text Available The epididymis has an important role in the maturation of sperm for fertilization, but little is known about the epididymal molecules involved in sperm modifications during this process. We have previously described the expression pattern for an antigen in epididymal epithelial cells that reacts with the monoclonal antibody (mAb TRA 54. Immunohistochemical and immunoblotting analyses suggest that the epitope of the epididymal antigen probably involves a sugar moiety that is released into the epididymal lumen in an androgen-dependent manner and subsequently binds to luminal sperm. Using column chromatography, SDS-PAGE with in situ digestion and mass spectrometry, we have identified the protein recognized by mAb TRA 54 in mouse epididymal epithelial cells. The ∼65 kDa protein is part of a high molecular mass complex (∼260 kDa that is also present in the sperm acrosomal vesicle and is completely released after the acrosomal reaction. The amino acid sequence of the protein corresponded to that of albumin. Immunoprecipitates with anti-albumin antibody contained the antigen recognized by mAb TRA 54, indicating that the epididymal molecule recognized by mAb TRA 54 is albumin. RT-PCR detected albumin mRNA in the epididymis and fertilization assays in vitro showed that the glycoprotein complex containing albumin was involved in the ability of sperm to recognize and penetrate the egg zona pellucida. Together, these results indicate that epididymal-derived albumin participates in the formation of a high molecular mass glycoprotein complex that has an important role in egg fertilization.

  20. An evolutionary model for collapsing molecular clouds and their star formation activity. II. Mass dependence of the star formation rate

    Energy Technology Data Exchange (ETDEWEB)

    Zamora-Avilés, Manuel; Vázquez-Semadeni, Enrique [Centro de Radioastronomía y Astrofísica, Universidad Nacional Autónoma de México, Apdo. Postal 3-72, Morelia, Michoacán 58089 (Mexico)

    2014-10-01

    We discuss the evolution and dependence on cloud mass of the star formation rate (SFR) and efficiency (SFE) of star-forming molecular clouds (MCs) within the scenario that clouds are undergoing global collapse and that the SFR is controlled by ionization feedback. We find that low-mass clouds (M {sub max} ≲ 10{sup 4} M {sub ☉}) spend most of their evolution at low SFRs, but end their lives with a mini-burst, reaching a peak SFR ∼10{sup 4} M {sub ☉} Myr{sup –1}, although their time-averaged SFR is only (SFR) ∼ 10{sup 2} M {sub ☉} Myr{sup –1}. The corresponding efficiencies are SFE{sub final} ≲ 60% and (SFE) ≲ 1%. For more massive clouds (M {sub max} ≳ 10{sup 5} M {sub ☉}), the SFR first increases and then reaches a plateau because the clouds are influenced by stellar feedback since earlier in their evolution. As a function of cloud mass, (SFR) and (SFE) are well represented by the fits (SFR) ≈ 100(1 + M {sub max}/1.4 × 10{sup 5} M {sub ☉}){sup 1.68} M {sub ☉} Myr{sup –1} and (SFE) ≈ 0.03(M {sub max}/2.5 × 10{sup 5} M {sub ☉}){sup 0.33}, respectively. Moreover, the SFR of our model clouds follows closely the SFR-dense gas mass relation recently found by Lada et al. during the epoch when their instantaneous SFEs are comparable to those of the clouds considered by those authors. Collectively, a Monte Carlo integration of the model-predicted SFR(M) over a Galactic giant molecular cloud mass spectrum yields values for the total Galactic SFR that are within half an order of magnitude of the relation obtained by Gao and Solomon. Our results support the scenario that star-forming MCs may be in global gravitational collapse and that the low observed values of the SFR and SFE are a result of the interruption of each SF episode, caused primarily by the ionizing feedback from massive stars.

  1. Environmental Forensics: Molecular Insight into Oil Spill Weathering Helps Advance High Magnetic Field FT-ICR Mass Spectrometry

    Science.gov (United States)

    McKenna, Amy

    2013-03-01

    The depletion of terrestrial global oil reserves has shifted oil exploration into offshore and ultra-deep water (> 5000 ft) oil reserves to meet global energy demands. Deep water reservoirs are currently in production in many parts of the world, including the Gulf of Mexico, but production is complicated by the water depth and thick salt caps that challenge reservoir characterization / production. The explosion aboard the Deepwater Horizon in April 2010 resulted in an estimated total release of ~5 million barrels (BP claims that they collected ~1M barrels, for a net release of 4 M) of light, sweet crude oil into the Gulf of Mexico and shifted attention toward the environmental risks associated with offshore oil production. The growing emphasis on deep water and ultra-deep water oil production poses a significant environmental threat, and increased regulations require that oil companies minimize environmental impact to prevent oil spills, and mitigate environmental damage when spills occur. Every oil spill is unique. The molecular transformations that occur to petroleum after contact with seawater depend on the physical and chemical properties of the spilled oil, environmental conditions, and deposition environment. Molecular-level knowledge of the composition, distribution, and total mass of released hydrocarbons is essential to disentangle photo- and bio-degradation, source identification, and long-term environmental impact of hydrocarbons released into the environment. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is unsurpassed in its ability to characterize complex mixtures at the level of elemental composition assignment. Only FT-ICR mass spectrometry can routinely achieve the required minimum resolving power necessary to elucidate molecular-level characterization of crude oil. Conversely, the spectral complexity of petroleum facilitates identification of systematic errors in the accumulation, transfer, excitation, and detection

  2. Mass Spectrometry-Based Proteomics in Molecular Diagnostics: Discovery of Cancer Biomarkers Using Tissue Culture

    Science.gov (United States)

    Paul, Debasish; Kumar, Avinash; Gajbhiye, Akshada; Santra, Manas K.; Srikanth, Rapole

    2013-01-01

    Accurate diagnosis and proper monitoring of cancer patients remain a key obstacle for successful cancer treatment and prevention. Therein comes the need for biomarker discovery, which is crucial to the current oncological and other clinical practices having the potential to impact the diagnosis and prognosis. In fact, most of the biomarkers have been discovered utilizing the proteomics-based approaches. Although high-throughput mass spectrometry-based proteomic approaches like SILAC, 2D-DIGE, and iTRAQ are filling up the pitfalls of the conventional techniques, still serum proteomics importunately poses hurdle in overcoming a wide range of protein concentrations, and also the availability of patient tissue samples is a limitation for the biomarker discovery. Thus, researchers have looked for alternatives, and profiling of candidate biomarkers through tissue culture of tumor cell lines comes up as a promising option. It is a rich source of tumor cell-derived proteins, thereby, representing a wide array of potential biomarkers. Interestingly, most of the clinical biomarkers in use today (CA 125, CA 15.3, CA 19.9, and PSA) were discovered through tissue culture-based system and tissue extracts. This paper tries to emphasize the tissue culture-based discovery of candidate biomarkers through various mass spectrometry-based proteomic approaches. PMID:23586059

  3. observations of hot molecular gas emission from embedded low-mass protostars

    DEFF Research Database (Denmark)

    Visser, R.; Kristensen, L. E.; Bruderer, S.

    2012-01-01

    Aims. Young stars interact vigorously with their surroundings, as evident from the highly rotationally excited CO (up to Eu/k = 4000 K) and H2O emission (up to 600 K) detected by the Herschel Space Observatory in embedded low-mass protostars. Our aim is to construct a model that reproduces...... the observations quantitatively, to investigate the origin of the emission, and to use the lines as probes of the various heating mechanisms. Methods. The model consists of a spherical envelope with a power-law density structure and a bipolar outflow cavity. Three heating mechanisms are considered: passive heating...... such as luminosity and envelope mass. Results. The bulk of the gas in the envelope, heated by the protostellar luminosity, accounts for 3–10% of the CO luminosity summed over all rotational lines up to J = 40–39; it is best probed by low-J CO isotopologue lines such as C18O 2–1 and 3–2. The UV-heated gas and the C...

  4. Mass Spectrometry-Based Proteomics in Molecular Diagnostics: Discovery of Cancer Biomarkers Using Tissue Culture

    Directory of Open Access Journals (Sweden)

    Debasish Paul

    2013-01-01

    Full Text Available Accurate diagnosis and proper monitoring of cancer patients remain a key obstacle for successful cancer treatment and prevention. Therein comes the need for biomarker discovery, which is crucial to the current oncological and other clinical practices having the potential to impact the diagnosis and prognosis. In fact, most of the biomarkers have been discovered utilizing the proteomics-based approaches. Although high-throughput mass spectrometry-based proteomic approaches like SILAC, 2D-DIGE, and iTRAQ are filling up the pitfalls of the conventional techniques, still serum proteomics importunately poses hurdle in overcoming a wide range of protein concentrations, and also the availability of patient tissue samples is a limitation for the biomarker discovery. Thus, researchers have looked for alternatives, and profiling of candidate biomarkers through tissue culture of tumor cell lines comes up as a promising option. It is a rich source of tumor cell-derived proteins, thereby, representing a wide array of potential biomarkers. Interestingly, most of the clinical biomarkers in use today (CA 125, CA 15.3, CA 19.9, and PSA were discovered through tissue culture-based system and tissue extracts. This paper tries to emphasize the tissue culture-based discovery of candidate biomarkers through various mass spectrometry-based proteomic approaches.

  5. Surface properties of heat-induced soluble soy protein aggregates of different molecular masses.

    Science.gov (United States)

    Guo, Fengxian; Xiong, Youling L; Qin, Fang; Jian, Huajun; Huang, Xiaolin; Chen, Jie

    2015-02-01

    Suspensions (2% and 5%, w/v) of soy protein isolate (SPI) were heated at 80, 90, or 100 °C for different time periods to produce soluble aggregates of different molecular sizes to investigate the relationship between particle size and surface properties (emulsions and foams). Soluble aggregates generated in these model systems were characterized by gel permeation chromatography and sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Heat treatment increased surface hydrophobicity, induced SPI aggregation via hydrophobic interaction and disulfide bonds, and formed soluble aggregates of different sizes. Heating of 5% SPI always promoted large-size aggregate (LA; >1000 kDa) formation irrespective of temperature, whereas the aggregate size distribution in 2% SPI was temperature dependent: the LA fraction progressively rose with temperature (80→90→100 °C), corresponding to the attenuation of medium-size aggregates (MA; 670 to 1000 kDa) initially abundant at 80 °C. Heated SPI with abundant LA (>50%) promoted foam stability. LA also exhibited excellent emulsifying activity and stabilized emulsions by promoting the formation of small oil droplets covered with a thick interfacial protein layer. However, despite a similar influence on emulsion stability, MA enhanced foaming capacity but were less capable of stabilizing emulsions than LA. The functionality variation between heated SPI samples is clearly related to the distribution of aggregates that differ in molecular size and surface activity. The findings may encourage further research to develop functional SPI aggregates for various commercial applications. © 2015 Institute of Food Technologists®

  6. Towards Molecular Characterization of Mineral-Organic Matter Interface Using In Situ Liquid Secondary Ion Mass Spectrometry

    Science.gov (United States)

    Zhu, Z.; Yu, X. Y.

    2017-12-01

    Organo-Mineral-Microbe interactions in terrestrial ecosystems are of great interest. Quite a few models have been developed through extensive efforts in this field. However, predictions from current models are far from being accurate, and many debates still exist. One of the major reasons is that most experimental data generated from bulk analysis, and the information of molecular dynamics occurring at mineral-organic matter interface is rare. Such information has been difficult to obtain, due to lack of suitable in situ analysis tools. Recently, we have developed in situ liquid secondary ion mass spectrometry (SIMS) at Pacific Northwest National Laboratory1, and it has shown promise to provide both elemental and molecular information at vacuum-liquid and solid-liquid interfaces.2 In this presentation, we demonstrate that in situ liquid SIMS can provide critical molecular information at solid substrate-live biofilm interface.3 Shewanella oneidensis is used as a model micro-organism and silicon nitride as a model mineral surface. Of particular interest, biologically relevant water clusters have been first observed in the living biofilms. Characteristic fragments of biofilm matrix components such as proteins, polysaccharides, and lipids can be molecularly examined. Furthermore, characteristic fatty acids (e.g., palmitic acid), quinolone signal, and riboflavin fragments were found to respond after the biofilm is treated with Cr(VI), leading to biofilm dispersal. Significant changes in water clusters and quorum sensing signals indicative of intercellular communication in the aqueous environment were observed, suggesting that they might result in fatty acid synthesis and inhibition of riboflavin production. The Cr(VI) reduction seems to follow the Mtr pathway leading to Cr(III) formation. Our approach potentially opens a new avenue for in-situ understanding of mineral-organo or mineral-microbe interfaces using in situ liquid SIMS and super resolution fluorescence

  7. Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography–mass spectrometry

    International Nuclear Information System (INIS)

    Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan; Ho, Hingman; Han, Quanbin; Fan, Xiaohui; Zuo, Zhong

    2015-01-01

    Highlights: • Novel stepwise component detection algorithm (SCDA) for LC–MS datasets. • New isotopic distribution and adduct-ion models for mass spectra. • Automatic component classification based on adduct-ion and isotopic distributions. - Abstract: Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography–mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components’ features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA

  8. Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography–mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan [School of Pharmacy, Faculty of Medicine, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China); Ho, Hingman; Han, Quanbin [School of Chinese Medicine, Hong Kong Baptist University, 7 Baptist University Road, Kowloon Tong, Hong Kong (China); Fan, Xiaohui [College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058 (China); Zuo, Zhong, E-mail: joanzuo@cuhk.edu.hk [School of Pharmacy, Faculty of Medicine, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China)

    2015-01-01

    Highlights: • Novel stepwise component detection algorithm (SCDA) for LC–MS datasets. • New isotopic distribution and adduct-ion models for mass spectra. • Automatic component classification based on adduct-ion and isotopic distributions. - Abstract: Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography–mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components’ features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA.

  9. Intacting Integrity in coping with health issues

    DEFF Research Database (Denmark)

    Jepsen, Stine Leegaard; Bastrup Jørgensen, Lene; Fridlund, Bengt

    2017-01-01

    The aim of this study was to develop a formal substantive theory (FST) on the multidimensional behavioral process of coping with health issues. Intacting integrity while coping with health issues emerged as the core category of this FST. People facing health issues strive to safeguard and keep...

  10. Epispadias in boys with an intact prepuce

    NARCIS (Netherlands)

    Bos, E. M. E.; Kuijper, C. F.; Chrzan, R. J.; Dik, P.; Klijn, A. J.; de Jong, T. P. V. M.

    2014-01-01

    To present an overview of the clinical presentation and pathological anatomy, and the results of surgical correction of 7 cases of epispadias with intact prepuce; a rare condition that has only occasionally been reported in literature. A retrospective search was performed in the surgical and

  11. HYDROCARBON VAPOR DIFFUSION IN INTACT CORE SLEEVES

    Science.gov (United States)

    The diffusion of 2,2,4-trimethylpentane (TMP) and 2,2,5-trimethylhexane (TMH) vapors put of residually contaminated sandy soil from the U.S. Environmental Protection Agency (EPA) field research site at Traverse City, Michigan, was measured and modeled. The headspace of an intact ...

  12. Three-dimensional molecular imaging using mass spectrometry and atomic force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wucher, Andreas [Department of Physics, University of Duisburg-Essen, D-47048 Duisburg (Germany)], E-mail: andreas.wucher@uni-due.de; Cheng Juan; Zheng Leiliang; Willingham, David; Winograd, Nicholas [Department of Chemistry, Pennsylvania State University, University Park, PA 16802 (United States)

    2008-12-15

    We combine imaging ToF-SIMS depth profiling and wide area atomic force microscopy to analyze a test structure consisting of a 300 nm trehalose film deposited on a Si substrate and pre-structured by means of a focused 15-keV Ga{sup +} ion beam. Depth profiling is performed using a 40-keV C{sub 60}{sup +} cluster ion beam for erosion and mass spectral data acquisition. A generic protocol for depth axis calibration is described which takes into account both lateral and in-depth variations of the erosion rate. By extrapolation towards zero analyzed lateral area, an 'intrinsic' depth resolution of about 8 nm is found which appears to be characteristic of the cluster-surface interaction process.

  13. High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2015-03-19

    A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

  14. Surface plasmon resonance sensing: from purified biomolecules to intact cells.

    Science.gov (United States)

    Su, Yu-Wen; Wang, Wei

    2018-04-12

    Surface plasmon resonance (SPR) has become a well-recognized label-free technique for measuring the binding kinetics between biomolecules since the invention of the first SPR-based immunosensor in 1980s. The most popular and traditional format for SPR analysis is to monitor the real-time optical signals when a solution containing ligand molecules is flowing over a sensor substrate functionalized with purified receptor molecules. In recent years, rapid development of several kinds of SPR imaging techniques have allowed for mapping the dynamic distribution of local mass density within single living cells with high spatial and temporal resolutions and reliable sensitivity. Such capability immediately enabled one to investigate the interaction between important biomolecules and intact cells in a label-free, quantitative, and single cell manner, leading to an exciting new trend of cell-based SPR bioanalysis. In this Trend Article, we first describe the principle and technical features of two types of SPR imaging techniques based on prism and objective, respectively. Then we survey the intact cell-based applications in both fundamental cell biology and drug discovery. We conclude the article with comments and perspectives on the future developments. Graphical abstract Recent developments in surface plasmon resonance (SPR) imaging techniques allow for label-free mapping the mass-distribution within single living cells, leading to great expansions in biomolecular interactions studies from homogeneous substrates functionalized with purified biomolecules to heterogeneous substrates containing individual living cells.

  15. Small Particles Intact Capture Experiment (SPICE)

    Science.gov (United States)

    Nishioka, Ken-Ji; Carle, G. C.; Bunch, T. E.; Mendez, David J.; Ryder, J. T.

    1994-01-01

    The Small Particles Intact Capture Experiment (SPICE) will develop technologies and engineering techniques necessary to capture nearly intact, uncontaminated cosmic and interplanetary dust particles (IDP's). Successful capture of such particles will benefit the exobiology and planetary science communities by providing particulate samples that may have survived unaltered since the formation of the solar system. Characterization of these particles may contribute fundamental data to our knowledge of how these particles could have formed into our planet Earth and, perhaps, contributed to the beginnings of life. The term 'uncontaminated' means that captured cosmic and IDP particles are free of organic contamination from the capture process and the term 'nearly intact capture' means that their chemical and elemental components are not materially altered during capture. The key to capturing cosmic and IDP particles that are organic-contamination free and nearly intact is the capture medium. Initial screening of capture media included organic foams, multiple thin foil layers, and aerogel (a silica gel); but, with the exception of aerogel, the requirements of no contamination or nearly intact capture were not met. To ensure no contamination of particles in the capture process, high-purity aerogel was chosen. High-purity aerogel results in high clarity (visual clearness), a useful quality in detection and recovery of embedded captured particles from the aerogel. P. Tsou at the Jet Propulsion Laboratory (JPL) originally described the use of aerogel for this purpose and reported laboratory test results. He has flown aerogel as a 'GAS-can Lid' payload on STS-47 and is evaluating the results. The Timeband Capture Cell Experiment (TICCE), a Eureca 1 experiment, is also flying aerogel and is scheduled for recovery in late April.

  16. Paper Spray Tandem Mass Spectrometry Based on Molecularly Imprinted Polymer Substrate for Cocaine Analysis in Oral Fluid

    Science.gov (United States)

    Tavares, Ludmyla S.; Carvalho, Thays C.; Romão, Wanderson; Vaz, Boniek G.; Chaves, Andréa R.

    2018-03-01

    This study proposes a new direct and fast method of analysis employing paper spray mass spectrometry (PS-MS). The paper used in the proposed method was modified with molecularly imprinted polymers (MIP) to create a specific site for cocaine analysis in oral fluid. MIP membrane was successfully synthetized and employed. The developed method showed to be linear in a concentration range from LOQ to 100 ng mL-1. The experimental value of LOQ obtained was 1 ng mL-1. The inter-day and intra-day precision and accuracy of the PS-MS method presented values lower than 15%. The total recoveries were also evaluated. The PS-MS method for the analysis of cocaine in oral fluid showed to be very promising and the validation parameters showed a good correlation with the literature. [Figure not available: see fulltext.

  17. [Search for potential gastric cancer biomarkers using low molecular weight blood plasma proteome profiling by mass spectrometry].

    Science.gov (United States)

    Shevchenko, V E; Arnotskaia, N E; Ogorodnikova, E V; Davydov, M M; Ibraev, M A; Turkin, I N; Davydov, M I

    2014-01-01

    Gastric cancer, one of the most widespread malignant tumors, still lacks reliable serum/plasma biomarkers of its early detection. In this study we have developed, unified, and tested a new methodology for search of gastric cancer biomarkers based on profiling of low molecular weight proteome (LMWP) (1-17 kDa). This approach included three main components: sample pre-fractionation, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS), data analysis by a bioinformatics software package. Applicability and perspectives of the developed approach for detection of potential gastric cancer markers during LMWP analysis have been demonstrated using 69 plasma samples from patients with gastric cancer (stages I-IV) and 238 control samples. The study revealed peptides/polypeptides, which may be potentially used for detection of this pathology.

  18. Molecular detection of a putatively novel cyprinid herpesvirus in sichel (Pelecus cultratus) during a mass mortality event in Hungary.

    Science.gov (United States)

    Doszpoly, Andor; Papp, Melitta; Deákné, Petra P; Glávits, Róbert; Ursu, Krisztina; Dán, Ádám

    2015-05-01

    In the early summer of 2014, mass mortality of sichel (Pelecus cultratus) was observed in Lake Balaton, Hungary. Histological examination revealed degenerative changes within the tubular epithelium, mainly in the distal tubules and collecting ducts in the kidneys and multifocal vacuolisation in the brain stem and cerebellum. Routine molecular investigations showed the presence of the DNA of an unknown alloherpesvirus in some specimens. Subsequently, three genes of the putative herpesviral genome (DNA polymerase, terminase, and helicase) were amplified and partially sequenced. A phylogenetic tree reconstruction based on the concatenated sequence of these three conserved genes implied that the virus belongs to the genus Cyprinivirus within the family Alloherpesviridae. The sequences of the sichel herpesvirus differ markedly from those of the cypriniviruses CyHV-1, CyHV-2 and CyHV-3, putatively representing a fifth species in the genus.

  19. Molecular regulation of high muscle mass in developing Blonde d'Aquitaine cattle foetuses

    Directory of Open Access Journals (Sweden)

    Isabelle Cassar-Malek

    2017-10-01

    Full Text Available The Blonde d'Aquitaine (BA is a French cattle breed with enhanced muscularity, partly attributable to a MSTN mutation. The BA m. Semitendinosus has a faster muscle fibre isoform phenotype comprising a higher proportion of fast type IIX fibres compared to age-matched Charolais (CH. To better understand the molecular network of modifications in BA compared to CH muscle, we assayed the transcriptomes of the m. Semitendinosus at 110, 180, 210 and 260 days postconception (dpc. We used a combination of differential expression (DE and regulatory impact factors (RIF to compare and contrast muscle gene expression between the breeds. Prominently developmentally regulated genes in both breeds reflected the replacement of embryonic myosin isoforms (MYL4, MYH3 with adult isoforms (MYH1 and the upregulation of mitochondrial metabolism (CKMT2, AGXT2L1 in preparation for birth. However, the transition to a fast, glycolytic muscle phenotype in the MSTN mutant BA is detectable through downregulation of various slow twitch subunits (TNNC1, MYH7, TPM3, CSRP3 beyond 210 dpc, and a small but consistent genome-wide reduction in mRNA encoding the mitoproteome. Across the breeds, NRIP2 is the regulatory gene possessing a network change most similar to that of MSTN.

  20. Capture compound mass spectrometry sheds light on the molecular mechanisms of liver toxicity of two Parkinson drugs.

    Science.gov (United States)

    Fischer, Jenny J; Michaelis, Simon; Schrey, Anna K; Graebner, Olivia Graebner nee; Glinski, Mirko; Dreger, Mathias; Kroll, Friedrich; Koester, Hubert

    2010-01-01

    Capture compound mass spectrometry (CCMS) is a novel technology that helps understand the molecular mechanism of the mode of action of small molecules. The Capture Compounds are trifunctional probes: A selectivity function (the drug) interacts with the proteins in a biological sample, a reactivity function (phenylazide) irreversibly forms a covalent bond, and a sorting function (biotin) allows the captured protein(s) to be isolated for mass spectrometric analysis. Tolcapone and entacapone are potent inhibitors of catechol-O-methyltransferase (COMT) for the treatment of Parkinson's disease. We aimed to understand the molecular basis of the difference of both drugs with respect to side effects. Using Capture Compounds with these drugs as selectivity functions, we were able to unambiguously and reproducibly isolate and identify their known target COMT. Tolcapone Capture Compounds captured five times more proteins than entacapone Capture Compounds. Moreover, tolcapone Capture Compounds isolated mitochondrial and peroxisomal proteins. The major tolcapone-protein interactions occurred with components of the respiratory chain and of the fatty acid beta-oxidation. Previously reported symptoms in tolcapone-treated rats suggested that tolcapone might act as decoupling reagent of the respiratory chain (Haasio et al., 2002b). Our results demonstrate that CCMS is an effective tool for the identification of a drug's potential off targets. It fills a gap in currently used in vitro screens for drug profiling that do not contain all the toxicologically relevant proteins. Thereby, CCMS has the potential to fill a technological need in drug safety assessment and helps reengineer or to reject drugs at an early preclinical stage.

  1. A High Molecular-Mass Anoxybacillus sp. SK3-4 Amylopullulanase: Characterization and Its Relationship in Carbohydrate Utilization

    Directory of Open Access Journals (Sweden)

    Kian Mau Goh

    2013-05-01

    Full Text Available An amylopullulanase of the thermophilic Anoxybacillus sp. SK3-4 (ApuASK was purified to homogeneity and characterized. Though amylopullulanases larger than 200 kDa are rare, the molecular mass of purified ApuASK appears to be approximately 225 kDa, on both SDS-PAGE analyses and native-PAGE analyses. ApuASK was stable between pH 6.0 and pH 8.0 and exhibited optimal activity at pH 7.5. The optimal temperature for ApuASK enzyme activity was 60 °C, and it retained 54% of its total activity for 240 min at 65 °C. ApuASK reacts with pullulan, starch, glycogen, and dextrin, yielding glucose, maltose, and maltotriose. Interestingly, most of the previously described amylopullulanases are unable to produce glucose and maltose from these substrates. Thus, ApuASK is a novel, high molecular-mass amylopullulanase able to produce glucose, maltose, and maltotriose from pullulan and starch. Based on whole genome sequencing data, ApuASK appeared to be the largest protein present in Anoxybacillus sp. SK3-4. The α-amylase catalytic domain present in all of the amylase superfamily members is present in ApuASK, located between the cyclodextrin (CD-pullulan-degrading N-terminus and the α-amylase catalytic C-terminus (amyC domains. In addition, the existence of a S-layer homology (SLH domain indicates that ApuASK might function as a cell-anchoring enzyme and be important for carbohydrate utilization in a streaming hot spring.

  2. TRACING MOLECULAR GAS MASS IN EXTREME EXTRAGALACTIC ENVIRONMENTS: AN OBSERVATIONAL STUDY

    International Nuclear Information System (INIS)

    Zhu Ming; Papadopoulos, Padeli P.; Xilouris, Emmanuel M.; Kuno, Nario; Lisenfeld, Ute

    2009-01-01

    We present a new observational study of the 12 CO(1-0) line emission as an H 2 gas mass tracer under extreme conditions in extragalactic environments. Our approach is to study the full neutral interstellar medium (H 2 , H I, and dust) of two galaxies whose bulk interstellar medium (ISM) resides in environments that mark (and bracket) the excitation extremes of the ISM conditions found in infrared luminous galaxies, the starburst NGC 3310, and the quiescent spiral NGC 157. Our study maintains a robust statistical notion of the so-called X = N(H 2 )/I CO factor (i.e., a large ensemble of clouds is involved) while exploring its dependence on the very different average ISM conditions prevailing within these two systems. These are constrained by fully sampled 12 CO(3-2) and 12 CO(1-0) observations, at a matched beam resolution of half-power beam width ∼15'', obtained with the James Clerk Maxwell Telescope (JCMT) on Mauna Kea (Hawaii) and the 45 m telescope of the Nobeyama Radio Observatory in Japan, combined with sensitive 850 μm and 450 μm dust emission and H I interferometric images which allow a complete view of all the neutral ISM components. Complementary 12 CO(2-1) observations were obtained with the JCMT toward the center of the two galaxies. We found an X factor varying by a factor of 5 within the spiral galaxy NGC 157 and about two times lower than the Galactic value in NGC 3310. In addition, the dust emission spectrum in NGC 3310 shows a pronounced submillimeter 'excess'. We tried to fit this excess by a cold dust component but very low temperatures were required (T C ∼ 5-11 K) with a correspondingly low gas-to-dust mass ratio of ∼5-43. We furthermore show that it is not possible to maintain the large quantities of dust required at these low temperatures in this starburst galaxy. Instead, we conclude that the dust properties need to be different from Galactic dust in order to fit the submillimeter 'excess'. We show that the dust spectral energy

  3. Identification of clinically relevant Corynebacterium strains by Api Coryne, MALDI-TOF-mass spectrometry and molecular approaches.

    Science.gov (United States)

    Alibi, S; Ferjani, A; Gaillot, O; Marzouk, M; Courcol, R; Boukadida, J

    2015-09-01

    We evaluated the Bruker Biotyper matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry (MS) for the identification of 97 Corynebacterium clinical in comparison to identification strains by Api Coryne and MALDI-TOF-MS using 16S rRNA gene and hypervariable region of rpoB genes sequencing as a reference method. C. striatum was the predominant species isolated followed by C. amycolatum. There was an agreement between Api Coryne strips and MALDI-TOF-MS identification in 88.65% of cases. MALDI-TOF-MS was unable to differentiate C. aurimucosum from C. minutissimum and C. minutissimum from C. singulare but reliably identify 92 of 97 (94.84%) strains. Two strains remained incompletely identified to the species level by MALDI-TOF-MS and molecular approaches. They belonged to Cellulomonas and Pseudoclavibacter genus. In conclusion, MALDI-TOF-MS is a rapid and reliable method for the identification of Corynebacterium species. However, some limits have been noted and have to be resolved by the application of molecular methods. Copyright © 2015. Published by Elsevier SAS.

  4. Use of Accelerator Mass Spectrometry in Human Health and Molecular Toxicology.

    Science.gov (United States)

    Enright, Heather A; Malfatti, Michael A; Zimmermann, Maike; Ognibene, Ted; Henderson, Paul; Turteltaub, Kenneth W

    2016-12-19

    Accelerator mass spectrometry (AMS) has been adopted as a powerful bioanalytical method for human studies in the areas of pharmacology and toxicology. The exquisite sensitivity (10 -18 mol) of AMS has facilitated studies of toxins and drugs at environmentally and physiologically relevant concentrations in humans. Such studies include risk assessment of environmental toxicants, drug candidate selection, absolute bioavailability determination, and more recently, assessment of drug-target binding as a biomarker of response to chemotherapy. Combining AMS with complementary capabilities such as high performance liquid chromatography (HPLC) can maximize data within a single experiment and provide additional insight when assessing drugs and toxins, such as metabolic profiling. Recent advances in the AMS technology at Lawrence Livermore National Laboratory have allowed for direct coupling of AMS with complementary capabilities such as HPLC via a liquid sample moving wire interface, offering greater sensitivity compared to that of graphite-based analysis, therefore enabling the use of lower 14 C and chemical doses, which are imperative for clinical testing. The aim of this review is to highlight the recent efforts in human studies using AMS, including technological advancements and discussion of the continued promise of AMS for innovative clinical based research.

  5. Molecularly imprinted polymer (MIP) membrane assisted direct spray ionization mass spectrometry for agrochemicals screening in foodstuffs.

    Science.gov (United States)

    Pereira, Igor; Rodrigues, Marcella Ferreira; Chaves, Andréa Rodrigues; Vaz, Boniek Gontijo

    2018-02-01

    Paper spray ionization (PSI) has some limitations such as low sensitivity and ionization suppression when complex samples are analyzed. The use of sample preparation devices directly coupled to MS can avoid these restrictions. Molecularly imprinted polymers (MIPs) are materials widely used as adsorbent in sample preparation methods such as solid-phase extraction and solid-phase microextraction, and they can provide specifics cavities with affinity to a target molecule. Here, we introduce a new MIP membrane spray ionization method combining MIP and PSI. MIP was synthesized directly on a cellulose membrane. Monuron and 2,4,5-T (2,4,5-trichlorophenoxyacetic acid) were used as template molecules in MIP synthesis for diuron and 2,4-D (2,4-dichlorophenoxyacetic acid) analyte sequesters, respectively. Apple, banana and grape methanolic extracts were used as matrices. The MIP membrane spray showed signal intensities of diuron and 2,4-D that were much higher compared to those obtained by non-imprinted polymers(NIP). Calibration curves exhibited R 2 > 0.99 for diuron and 2,4-D in all fruit extracts analyzed. LODs were found less than 0.60µgL -1 and LLOQs were found less than 2.00µgL -1 . The coefficients of variation and relative errors were less than 15% for almost all analyses. The apparent recovery test results ranged between 92,5% and 116.9%. Finally, the MIP membrane spray method was employed for the quantification of diuron and 2,4-D in real samples. Diuron contents were only found in three bananas (4.0, 6.5, and 9.9µgL -1 ). The proposed MIP membrane spray ionization method was straightforward, fast to carry out and provided satisfactory results for analyses of diuron and 2,4-D in apple, banana and grape samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Mass spectrometry for the elucidation of the subtle molecular structure of biodegradable polymers and their degradation products.

    Science.gov (United States)

    Kowalczuk, Marek; Adamus, Grażyna

    2016-01-01

    Contemporary reports by Polish authors on the application of mass spectrometric methods for the elucidation of the subtle molecular structure of biodegradable polymers and their degradation products will be presented. Special emphasis will be given to natural aliphatic (co)polyesters (PHA) and their synthetic analogues, formed through anionic ring-opening polymerization (ROP) of β-substituted β-lactones. Moreover, the application of MS techniques for the evaluation of the structure of biodegradable polymers obtained in ionic and coordination polymerization of cyclic ethers and esters as well as products of step-growth polymerization, in which bifunctional or multifunctional monomers react to form oligomers and eventually long chain polymers, will be discussed. Furthermore, the application of modern MS techniques for the assessment of polymer degradation products, frequently bearing characteristic end groups that can be revealed and differentiated by MS, will be discussed within the context of specific degradation pathways. Finally, recent Polish accomplishments in the area of mass spectrometry will be outlined. © 2015 Wiley Periodicals, Inc.

  7. High field FT-ICR mass spectrometry for molecular characterization of snow board from Moscow regions.

    Science.gov (United States)

    Mazur, Dmitry M; Harir, Mourad; Schmitt-Kopplin, Philippe; Polyakova, Olga V; Lebedev, Albert T

    2016-07-01

    High field Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry analysis of eight snow samples from Moscow city allowed us to identify more than 2000 various elemental compositions corresponding to regional air pollutants. The hierarchical cluster analysis (HCA) of the data showed good concordance of three main groups of samples with the main wind directions. The North-West group (A1) is represented by several homologous CHOS series of aliphatic organic aerosols. They may form as a result of enhanced photochemical reactions including oxidation of hydrocarbons with sulfonations due to higher amount of SO2 emissions in the atmosphere in this region. Group A2, corresponding to the South-East part of Moscow, contains large amount of oxidized hydrocarbons of different sources that may form during oxidation in atmosphere. These hydrocarbons appear correlated to emissions from traffic, neighboring oil refinery, and power plants. Another family of compounds specific for this region involves CHNO substances formed during oxidation processes including NOx and NO3 radical since emissions of NOx are higher in this part of the city. Group A3 is rich in CHO type of compounds with high H/C and low O/C ratios, which is characteristic of oxidized hydrocarbon-like organic aerosol. CHNO types of compounds in A3 group are probably nitro derivatives of condensed hydrocarbons such as PAH. This non-targeted profiling revealed site specific distribution of pollutants and gives a chance to develop new strategies in air quality control and further studies of Moscow environment. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Evaluation of PCR electrospray-ionization mass spectrometry for rapid molecular diagnosis of bovine mastitis.

    Science.gov (United States)

    Perreten, Vincent; Endimiani, Andrea; Thomann, Andreas; Wipf, Juliette R K; Rossano, Alexandra; Bodmer, Michèle; Raemy, Andreas; Sannes-Lowery, Kristin A; Ecker, David J; Sampath, Rangarajan; Bonomo, Robert A; Washington, Cicely

    2013-06-01

    Bovine mastitis, an inflammatory disease of the mammary gland, is one of the most costly diseases affecting the dairy industry. The treatment and prevention of this disease is linked heavily to the use of antibiotics in agriculture and early detection of the primary pathogen is essential to control the disease. Milk samples (n=67) from cows suffering from mastitis were analyzed for the presence of pathogens using PCR electrospray-ionization mass spectrometry (PCR/ESI-MS) and were compared with standard culture diagnostic methods. Concurrent identification of the primary mastitis pathogens was obtained for 64% of the tested milk samples, whereas divergent results were obtained for 27% of the samples. The PCR/ESI-MS failed to identify some of the primary pathogens in 18% of the samples, but identified other pathogens as well as microorganisms in samples that were negative by culture. The PCR/ESI-MS identified bacteria to the species level as well as yeasts and molds in samples that contained a mixed bacterial culture (9%). The sensitivity of the PCR/ESI-MS for the most common pathogens ranged from 57.1 to 100% and the specificity ranged from 69.8 to 100% using culture as gold standard. The PCR/ESI-MS also revealed the presence of the methicillin-resistant gene mecA in 16.2% of the milk samples, which correlated with the simultaneous detection of staphylococci including Staphylococcus aureus. We demonstrated that PCR/ESI-MS, a more rapid diagnostic platform compared with bacterial culture, has the significant potential to serve as an important screening method in the diagnosis of bovine clinical mastitis and has the capacity to be used in infection control programs for both subclinical and clinical disease. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  9. Localization by whole-body autoradiography of intact and fragmented radiolabeled antibodies in a metastatic human colonic cancer model

    International Nuclear Information System (INIS)

    Fand, Irwin; Sharkey, R.M.; Grundy, J.P.; Goldenberg, D.M.

    1992-01-01

    In this report, we have employed macroautoradiography to compare the tumor targeting of 125 I-labeled anti-carcinoembryonic antigen (CEA) MAb (NP-4) to 125 I-labeled anti-colon-specific antigen-p (CSAp) MAb (Mu-9) and their labeled F(ab') 2 and Fab' fragments, in nude mice each bearing large dorsal human colonic tumor xenografts, and small nodular tumors in the liver and lungs. Using intact MAbs (NP-4 and Mu-9), clearance of background radioactivity was delayed to 3-7 days post-treatment. Treatment with F(ab') 2 and Fab' fragments of both NP-4 and Mu-9 MAbs, however, promoted clearance of background 125 I-radioactivity which was well advanced by 6-24 h and complete by 24-48 h after injection. Localization of 125 I-radioactivity in large and micrometastatic tumor perimeters was the most characteristic uptake pattern observed for both intact and fragmented MAbs. Qualitative analysis of macroautoradiographic images and quantitative densitometry indicated that the higher tumor-to-blood ratios achieved with labeled F(ab') 2 and Fab' fragments at early time points, compared to labeled whole immunoglobulin, appeared to be more a function of rapid plasma clearance, tumor mass, location of xenografts and specific tumor growth patterns than increased tumor penetrance by lower molecular weight univalent and bivalent immune fragments. (Author)

  10. KINEMATIC STRUCTURE OF MOLECULAR GAS AROUND HIGH-MASS YSO, PAPILLON NEBULA, IN N159 EAST IN THE LARGE MAGELLANIC CLOUD: A NEW PERSPECTIVE WITH ALMA

    Energy Technology Data Exchange (ETDEWEB)

    Saigo, Kazuya; Harada, Ryohei; Kawamura, Akiko [Chile Observatory, National Astronomical Observatory of Japan, National Institutes of Natural Science, 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Onishi, Toshikazu; Tokuda, Kazuki; Morioka, Yuuki [Department of Physical Science, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Nayak, Omnarayani; Meixner, Margaret [The Johns Hopkins University, Department of Physics and Astronomy, 366 Bloomberg Center, 3400 N. Charles Street, Baltimore, MD 21218 (United States); Sewiło, Marta [NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Indebetouw, Remy [Department of Astronomy, University of Virginia, P.O. Box 400325, Charlottesville, VA 22904 (United States); Torii, Kazufumi; Ohama, Akio; Hattori, Yusuke; Yamamoto, Hiroaki; Tachihara, Kengo [Department of Physics, Nagoya University, Chikusa-ku, Nagoya 464-8602 (Japan); Minamidani, Tetsuhiro [Nobeyama Radio Observatory, 462-2 Nobeyama Minamimaki-mura, Minamisaku-gun, Nagano 384-1305 (Japan); Inoue, Tsuyoshi [Division of Theoretical Astronomy, National Astronomical Observatory (Japan); Madden, Suzanne; Lebouteiller, Vianney [Laboratoire AIM, CEA, Universite Paris VII, IRFU/Service d’Astrophysique, Bat. 709, F-91191 Gif-sur-Yvette (France); Galametz, Maud [Institute of Astronomy, University of Cambridge, Madingley Road, Cambridge CB3 0HA (United Kingdom); and others

    2017-01-20

    We present the ALMA Band 3 and Band 6 results of {sup 12}CO(2-1), {sup 13}CO(2-1), H30 α recombination line, free–free emission around 98 GHz, and the dust thermal emission around 230 GHz toward the N159 East Giant Molecular Cloud (N159E) in the Large Magellanic Cloud (LMC). LMC is the nearest active high-mass star-forming face-on galaxy at a distance of 50 kpc and is the best target for studing high-mass star formation. ALMA observations show that N159E is the complex of filamentary clouds with the width and length of ∼1 pc and several parsecs. The total molecular mass is 0.92 × 10{sup 5} M {sub ⊙} from the {sup 13}CO(2-1) intensity. N159E harbors the well-known Papillon Nebula, a compact high-excitation H ii region. We found that a YSO associated with the Papillon Nebula has the mass of 35 M {sub ⊙} and is located at the intersection of three filamentary clouds. It indicates that the formation of the high-mass YSO was induced by the collision of filamentary clouds. Fukui et al. reported a similar kinematic structure toward two YSOs in the N159 West region, which are the other YSOs that have the mass of ≳35 M {sub ⊙}. This suggests that the collision of filamentary clouds is a primary mechanism of high-mass star formation. We found a small molecular hole around the YSO in Papillon Nebula with a sub-parsec scale. It is filled by free–free and H30 α emission. The temperature of the molecular gas around the hole reaches ∼80 K. It indicates that this YSO has just started the distruction of parental molecular cloud.

  11. KINEMATIC STRUCTURE OF MOLECULAR GAS AROUND HIGH-MASS YSO, PAPILLON NEBULA, IN N159 EAST IN THE LARGE MAGELLANIC CLOUD: A NEW PERSPECTIVE WITH ALMA

    International Nuclear Information System (INIS)

    Saigo, Kazuya; Harada, Ryohei; Kawamura, Akiko; Onishi, Toshikazu; Tokuda, Kazuki; Morioka, Yuuki; Nayak, Omnarayani; Meixner, Margaret; Sewiło, Marta; Indebetouw, Remy; Torii, Kazufumi; Ohama, Akio; Hattori, Yusuke; Yamamoto, Hiroaki; Tachihara, Kengo; Minamidani, Tetsuhiro; Inoue, Tsuyoshi; Madden, Suzanne; Lebouteiller, Vianney; Galametz, Maud

    2017-01-01

    We present the ALMA Band 3 and Band 6 results of 12 CO(2-1), 13 CO(2-1), H30 α recombination line, free–free emission around 98 GHz, and the dust thermal emission around 230 GHz toward the N159 East Giant Molecular Cloud (N159E) in the Large Magellanic Cloud (LMC). LMC is the nearest active high-mass star-forming face-on galaxy at a distance of 50 kpc and is the best target for studing high-mass star formation. ALMA observations show that N159E is the complex of filamentary clouds with the width and length of ∼1 pc and several parsecs. The total molecular mass is 0.92 × 10 5 M ⊙ from the 13 CO(2-1) intensity. N159E harbors the well-known Papillon Nebula, a compact high-excitation H ii region. We found that a YSO associated with the Papillon Nebula has the mass of 35 M ⊙ and is located at the intersection of three filamentary clouds. It indicates that the formation of the high-mass YSO was induced by the collision of filamentary clouds. Fukui et al. reported a similar kinematic structure toward two YSOs in the N159 West region, which are the other YSOs that have the mass of ≳35 M ⊙ . This suggests that the collision of filamentary clouds is a primary mechanism of high-mass star formation. We found a small molecular hole around the YSO in Papillon Nebula with a sub-parsec scale. It is filled by free–free and H30 α emission. The temperature of the molecular gas around the hole reaches ∼80 K. It indicates that this YSO has just started the distruction of parental molecular cloud.

  12. Measurement of diffusive properties of intact rock

    Energy Technology Data Exchange (ETDEWEB)

    Harvey, K B

    1996-12-01

    In the Postclosure Assessment of a Reference System for the Disposal of Canada`s Nuclear Fuel Waste (Goodwin et al. 1994) the disposal vault is assumed to be surrounded by a zone of intact rock, referred to as the `exclusion zone.` A sensitivity analysis of the relative effectiveness of the several engineered and natural barriers that contribute to the safety of the reference disposal system has shown that this zone of intact rock is the most effective of these barriers to the movement of radionuclides through the reference system. Peer review of the geosphere model used in the case study for the EIS (Environmental Impact Statement) of the Canadian Nuclear Fuel Waste Management Program has identified the need to quantify the properties of the intact rock surrounding the disposal vault that would control the transport of radionuclides by diffusion. The Postclosure Assessment also identified the need for appropriate values of the free water diffusion coefficient (D{sub o}) for {sup 129}1 and {sup 14}C. The measurement of rock resistivity allows the calculation of the Formation Factor for a rock This review describes the Formation Factor, diffusivity, permeability, and porosity, and how these properties might be measured or inferred for insitu rock under the conditions that apply to the intact rock surrounding a potential disposal vault. The importance of measuring the intrinsic diffusion coefficient (D{sup i}) of diffusing species under solution salinities simulating those of groundwaters is emphasised, and a method of measurement is described that is independent of the diffusing medium, and which would be appropriate for measurements made in chemically complex media such as groundwaters. (author). 95 refs., 4 tabs., 39 figs.

  13. Measurement of diffusive properties of intact rock

    International Nuclear Information System (INIS)

    Harvey, K.B.

    1996-12-01

    In the Postclosure Assessment of a Reference System for the Disposal of Canada's Nuclear Fuel Waste (Goodwin et al. 1994) the disposal vault is assumed to be surrounded by a zone of intact rock, referred to as the 'exclusion zone.' A sensitivity analysis of the relative effectiveness of the several engineered and natural barriers that contribute to the safety of the reference disposal system has shown that this zone of intact rock is the most effective of these barriers to the movement of radionuclides through the reference system. Peer review of the geosphere model used in the case study for the EIS (Environmental Impact Statement) of the Canadian Nuclear Fuel Waste Management Program has identified the need to quantify the properties of the intact rock surrounding the disposal vault that would control the transport of radionuclides by diffusion. The Postclosure Assessment also identified the need for appropriate values of the free water diffusion coefficient (D o ) for 129 1 and 14 C. The measurement of rock resistivity allows the calculation of the Formation Factor for a rock This review describes the Formation Factor, diffusivity, permeability, and porosity, and how these properties might be measured or inferred for insitu rock under the conditions that apply to the intact rock surrounding a potential disposal vault. The importance of measuring the intrinsic diffusion coefficient (D i ) of diffusing species under solution salinities simulating those of groundwaters is emphasised, and a method of measurement is described that is independent of the diffusing medium, and which would be appropriate for measurements made in chemically complex media such as groundwaters. (author). 95 refs., 4 tabs., 39 figs

  14. The ATLAS(3D) project - XX. Mass-size and mass-Sigma distributions of early-type galaxies : bulge fraction drives kinematics, mass-to-light ratio, molecular gas fraction and stellar initial mass function

    NARCIS (Netherlands)

    Cappellari, Michele; McDermid, Richard M.; Alatalo, Katherine; Blitz, Leo; Bois, Maxime; Bournaud, Frederic; Bureau, M.; Crocker, Alison F.; Davies, Roger L.; Davis, Timothy A.; de Zeeuw, P. T.; Duc, Pierre-Alain; Emsellem, Eric; Khochfar, Sadegh; Krajnovic, Davor; Kuntschner, Harald; Morganti, Raffaella; Naab, Thorsten; Oosterloo, Tom; Sarzi, Marc; Scott, Nicholas; Serra, Paolo; Weijmans, Anne-Marie; Young, Lisa M.

    2013-01-01

    In the companion Paper XV of this series, we derive accurate total mass-to-light ratios (M/L)(JAM) approximate to (M/L)(r = R-e) within a sphere of radius r = R-e centred on the galaxy, as well as stellar (M/L)(stars) (with the dark matter removed) for the volume-limited and nearly mass-selected

  15. Autism Spectrum Disorder and intact executive functioning.

    Science.gov (United States)

    Ferrara, R; Ansermet, F; Massoni, F; Petrone, L; Onofri, E; Ricci, P; Archer, T; Ricci, S

    2016-01-01

    Earliest notions concerning autism (Autism Spectrum Disorders, ASD) describe the disturbance in executive functioning. Despite altered definition, executive functioning, expressed as higher cognitive skills required complex behaviors linked to the prefrontal cortex, are defective in autism. Specific difficulties in children presenting autism or verbal disabilities at executive functioning levels have been identified. Nevertheless, the developmental deficit of executive functioning in autism is highly diversified with huge individual variation and may even be absent. The aim of the present study to examine the current standing of intact executive functioning intact in ASD. Analysis of ASD populations, whether high-functioning, Asperger's or autism Broad Phenotype, studied over a range of executive functions including response inhibition, planning, cognitive flexibility, cognitive inhibition, and alerting networks indicates an absence of damage/impairment compared to the typically-developed normal control subjects. These findings of intact executive functioning in ASD subjects provide a strong foundation on which to construct applications for growth environments and the rehabilitation of autistic subjects.

  16. Feasible pickup from intact ossicular chain with floating piezoelectric microphone.

    Science.gov (United States)

    Kang, Hou-Yong; Na, Gao; Chi, Fang-Lu; Jin, Kai; Pan, Tie-Zheng; Gao, Zhen

    2012-02-22

    Many microphones have been developed to meet with the implantable requirement of totally implantable cochlear implant (TICI). However, a biocompatible one without destroying the intactness of the ossicular chain still remains under investigation. Such an implantable floating piezoelectric microphone (FPM) has been manufactured and shows an efficient electroacoustic performance in vitro test at our lab. We examined whether it pick up sensitively from the intact ossicular chain and postulated whether it be an optimal implantable one. Animal controlled experiment: five adult cats (eight ears) were sacrificed as the model to test the electroacoustic performance of the FPM. Three groups were studied: (1) the experiment group (on malleus): the FPM glued onto the handle of the malleus of the intact ossicular chains; (2) negative control group (in vivo): the FPM only hung into the tympanic cavity; (3) positive control group (Hy-M30): a HiFi commercial microphone placed close to the site of the experiment ear. The testing speaker played pure tones orderly ranged from 0.25 to 8.0 kHz. The FPM inside the ear and the HiFi microphone simultaneously picked up acoustic vibration which recorded as .wav files to analyze. The FPM transformed acoustic vibration sensitively and flatly as did the in vitro test across the frequencies above 2.0 kHz, whereas inefficiently below 1.0 kHz for its overloading mass. Although the HiFi microphone presented more efficiently than the FPM did, there was no significant difference at 3.0 kHz and 8.0 kHz. It is feasible to develop such an implantable FPM for future TICIs and TIHAs system on condition that the improvement of Micro Electromechanical System and piezoelectric ceramic material technology would be applied to reduce its weight and minimize its size.

  17. Feasible pickup from intact ossicular chain with floating piezoelectric microphone

    Directory of Open Access Journals (Sweden)

    Kang Hou-Yong

    2012-02-01

    Full Text Available Abstract Objectives Many microphones have been developed to meet with the implantable requirement of totally implantable cochlear implant (TICI. However, a biocompatible one without destroying the intactness of the ossicular chain still remains under investigation. Such an implantable floating piezoelectric microphone (FPM has been manufactured and shows an efficient electroacoustic performance in vitro test at our lab. We examined whether it pick up sensitively from the intact ossicular chain and postulated whether it be an optimal implantable one. Methods Animal controlled experiment: five adult cats (eight ears were sacrificed as the model to test the electroacoustic performance of the FPM. Three groups were studied: (1 the experiment group (on malleus: the FPM glued onto the handle of the malleus of the intact ossicular chains; (2 negative control group (in vivo: the FPM only hung into the tympanic cavity; (3 positive control group (Hy-M30: a HiFi commercial microphone placed close to the site of the experiment ear. The testing speaker played pure tones orderly ranged from 0.25 to 8.0 kHz. The FPM inside the ear and the HiFi microphone simultaneously picked up acoustic vibration which recorded as .wav files to analyze. Results The FPM transformed acoustic vibration sensitively and flatly as did the in vitro test across the frequencies above 2.0 kHz, whereas inefficiently below 1.0 kHz for its overloading mass. Although the HiFi microphone presented more efficiently than the FPM did, there was no significant difference at 3.0 kHz and 8.0 kHz. Conclusions It is feasible to develop such an implantable FPM for future TICIs and TIHAs system on condition that the improvement of Micro Electromechanical System and piezoelectric ceramic material technology would be applied to reduce its weight and minimize its size.

  18. Molecular characterization of primary humic-like substances in fine smoke particles by thermochemolysis-gas chromatography-mass spectrometry

    Science.gov (United States)

    Fan, Xingjun; Wei, Siye; Zhu, Mengbo; Song, Jianzhong; Peng, Ping'an

    2018-05-01

    In this study, the molecular structures of primary humic-like substances (HULIS) in fine smoke particles emitted from the combustion of biomass materials (including rice straw, corn straw, and pine branches) and coal, and atmospheric HULIS were determined by off-line tetramethylammonium hydroxide thermochemolysis coupled with gas chromatography and mass spectrometry (TMAH-GC/MS). A total of 89 pyrolysates were identified by the thermochemolysis of primary and atmospheric HULIS. The main groups were polysaccharide derivatives, N-containing compounds, lignin derivatives, aromatic acid methyl ester, aliphatic acid methyl ester, and diterpenoid derivatives. Both the type and distribution of pyrolysates among primary HULIS were comparable to those in atmospheric HULIS. This indicates that primary HULIS from combustion processes are important contributors to atmospheric HULIS. Some distinct differences were also observed. The aromatic compounds, including lignin derivatives and aromatic acid methyl ester, were the major pyrolysates (53.0%-84.9%) in all HULIS fractions, suggesting that primary HULIS significantly contributed aromatic structures to atmospheric HULIS. In addition, primary HULIS from biomass burning (BB) contained a relatively high abundance of lignin and polysaccharide derivatives, which is consistent with the large amounts of lignin and cellulose structures contained in biomass materials. Aliphatic acid methyl ester and benzyl methyl ether were prominent pyrolysates in atmospheric HULIS. Moreover, some molecular markers of specific sources were obtained from the thermochemolysis of primary and atmospheric HULIS. For example, polysaccharide derivatives, pyridine and pyrrole derivatives, and lignin derivatives can be used as tracers of fresh HULIS emitted from BB. Diterpenoid derivatives are important markers of HULIS from pine wood combustion sources. Finally, the differences in pyrolysate types and the distributions between primary and atmospheric HULIS

  19. MHOs toward HMOs: A Search for Molecular Hydrogen Emission-Line Objects toward High-mass Outflows

    Energy Technology Data Exchange (ETDEWEB)

    Wolf-Chase, Grace [Astronomy Department Adler Planetarium 1300 S. Lake Shore Drive Chicago, IL 60605 (United States); Arvidsson, Kim [Trull School of Sciences and Mathematics Schreiner University 2100 Memorial Blvd. Kerrville, TX 78028 (United States); Smutko, Michael, E-mail: gwolfchase@adlerplanetarium.org [Center for Interdisciplinary Exploration and Research in Astrophysics (CIERA), and Dept. of Physics and Astronomy, Northwestern University, 2131 Tech Drive, Evanston, IL 60208 (United States)

    2017-07-20

    We present the results of a narrow-band near-infrared imaging survey for Molecular Hydrogen emission-line Objects (MHOs) toward 26 regions containing high-mass protostellar candidates and massive molecular outflows. We have detected a total of 236 MHOs, 156 of which are new detections, in 22 out of the 26 regions. We use H{sub 2} 2.12 μ m/H{sub 2} 2.25 μ m flux ratios, together with morphology, to separate the signatures of fluorescence associated with photo-dissociation regions (PDRs) from shocks associated with outflows in order to identify the MHOs. PDRs have typical low flux ratios of ∼1.5–3, while the vast majority of MHOs display flux ratios typical of C-type shocks (∼6–20). A few MHOs exhibit flux ratios consistent with expected values for J-type shocks (∼3–4), but these are located in regions that may be contaminated with fluorescent emission. Some previously reported MHOs have low flux ratios, and are likely parts of PDRs rather than shocks indicative of outflows. We identify a total of 36 outflows across the 22 target regions where MHOs were detected. In over half these regions, MHO arrangements and fluorescent structures trace features present in CO outflow maps, suggesting that the CO emission traces a combination of dynamical effects, which may include gas entrained in expanding PDRs as well as bipolar outflows. Where possible, we link MHO complexes to distinct outflows and identify candidate driving sources.

  20. Molecular imaging of myocardial infarction with Gadofluorine P – A combined magnetic resonance and mass spectrometry imaging approach

    Directory of Open Access Journals (Sweden)

    Fabian Lohöfer

    2018-04-01

    Full Text Available Background: Molecular MRI is becoming increasingly important for preclinical research. Validation of targeted gadolinium probes in tissue however has been cumbersome up to now. Novel methodology to assess gadolinium distribution in tissue after in vivo application is therefore needed. Purpose: To establish combined Magnetic Resonance Imaging (MRI and Mass Spectrometry Imaging (MSI for improved detection and quantification of Gadofluorine P deposition in scar formation and myocardial remodeling. Materials and methods: Animal studies were performed according to institutionally approved protocols. Myocardial infarction was induced by permanent ligation of the left ascending artery (LAD in C57BL/6J mice. MRI was performed at 7T at 1 week and 6 weeks after myocardial infarction. Gadofluorine P was used for dynamic T1 mapping of extracellular matrix synthesis during myocardial healing and compared to Gd-DTPA. After in vivo imaging contrast agent concentration as well as distribution in tissue were validated and quantified by spatially resolved Matrix-Assisted Laser Desorption Ionization (MALDI MSI and Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry (LA-ICP-MS imaging. Results: Both Gadofluorine P enhancement as well as local tissue content in the myocardial scar were highest at 15 minutes post injection. R1 values increased from 1 to 6 weeks after MI (1.62 s−1 vs 2.68 s−1, p = 0.059 paralleled by an increase in Gadofluorine P concentration in the infarct from 0.019 mM at 1 week to 0.028 mM at 6 weeks (p = 0.048, whereas Gd-DTPA enhancement showed no differences (3.95 s−1 vs 3.47 s−1, p = 0.701. MALDI-MSI results were corroborated by elemental LA-ICP-MS of Gadolinium in healthy and infarcted myocardium. Histology confirmed increased extracellular matrix synthesis at 6 weeks compared to 1 week. Conclusion: Adding quantitative MSI to MR imaging enables a quantitative validation of Gadofluorine P distribution in the heart

  1. Fragment profiling of low molecular weight heparins using reversed phase ion pair liquid chromatography-electrospray mass spectrometry.

    Science.gov (United States)

    Xu, Xiaohui; Li, Daoyuan; Chi, Lequan; Du, Xuzhao; Bai, Xue; Chi, Lianli

    2015-04-30

    Low molecular weight heparins (LMWHs) are linear and highly charged carbohydrate polymers prepared by chemical or enzymatic depolymerization of heparin. Compared to unfractionated heparin (UFH), LMWHs are prevalently used as clinical anticoagulant drugs due to their lower side effects and better bioavailability. The work presented herein provides a rapid and powerful fragment mapping method for structural characterization of LMWHs. The chain fragments of two types of LMWHs, enoxaparin and nadroparin, were generated by controlled enzymatic digestion with each of heparinase I (Hep I, Enzyme Commission (EC) # 4.2.2.7), heparinase II (Hep II, no EC # assigned) and heparinase III (Hep III, EC # 4.2.2.8). Reversed phase ion pair high performance liquid chromatography (RPIP-HPLC) coupled with electrospray ion trap time-of-flight mass spectrometry (ESI-IT-TOF-MS) was used to profile the oligosaccharide chains ranging from disaccharides to decasaccharides. A database containing all theoretical structural compositions was established to assist the mass spectra interpretation. The six digests derived by three enzymes from two types of LMWHs exhibited distinguishable fingerprinting patterns. And a total of 94 enoxaparin fragments and 109 nadroparin fragments were detected and identified. Besides the common LMWH oligosaccharides, many components containing characteristic LMWH structures such as saturated L-idopyranosuronic acid, 2,5-anhydro-D-mannitol, 1,6-anhydro-D-aminopyranose, as well as odd number oligosaccharides were also revealed. Quantitative comparison of major components derived from innovator and generic nadroparin products was presented. This approach to profile LMWHs' fragments offers a highly reproducible, high resolution and information-rich tool for evaluating the quality of this category of anticoagulant drugs or comparing structural similarities among samples from various sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Extremely stable soluble high molecular mass multi-protein complex with DNase activity in human placental tissue.

    Directory of Open Access Journals (Sweden)

    Evgeniya E Burkova

    Full Text Available Human placenta is an organ which protects, feeds, and regulates the grooving of the embryo. Therefore, identification and characterization of placental components including proteins and their multi-protein complexes is an important step to understanding the placenta function. We have obtained and analyzed for the first time an extremely stable multi-protein complex (SPC, ∼ 1000 kDa from the soluble fraction of three human placentas. By gel filtration on Sepharose-4B, the SPC was well separated from other proteins of the placenta extract. Light scattering measurements and gel filtration showed that the SPC is stable in the presence of NaCl, MgCl2, acetonitrile, guanidinium chloride, and Triton in high concentrations, but dissociates efficiently in the presence of 8 M urea, 50 mM EDTA, and 0.5 M NaCl. Such a stable complex is unlikely to be a casual associate of different proteins. According to SDS-PAGE and MALDI mass spectrometry data, this complex contains many major glycosylated proteins with low and moderate molecular masses (MMs 4-14 kDa and several moderately abundant (79.3, 68.5, 52.8, and 27.2 kDa as well as minor proteins with higher MMs. The SPC treatment with dithiothreitol led to a disappearance of some protein bands and revealed proteins with lower MMs. The SPCs from three placentas efficiently hydrolyzed plasmid supercoiled DNA with comparable rates and possess at least two DNA-binding sites with different affinities for a 12-mer oligonucleotide. Progress in study of placental protein complexes can promote understanding of their biological functions.

  3. Automated setup for characterization of intact histone tails in Suz12-/- stem cells

    DEFF Research Database (Denmark)

    Sidoli, Simone; Schwämmle, Veit; Hansen, Thomas Aarup

    Epigenetics is defined as the study of heritable changes that occur without modifying the DNA sequence. Histone proteins are crucial components of epigenetic mechanisms and regulation, since they are fundamental for chromatin structure. Mass spectrometry-based proteomics is already an integrated...... developed a high-resolving and automated LC-MS/MS setup to characterize intact histone tails (middle-down strategy)...

  4. Comparative evaluation of low-molecular-mass proteins from Mycobacterium tuberculosis identifies members of the ESAT-6 family as immunodominant T-cell antigens

    DEFF Research Database (Denmark)

    Skjøt, Rikke L. V.; Oettinger, Thomas; Rosenkrands, Ida

    2000-01-01

    . The molecules were characterized, mapped in a two-dimensional electrophoresis reference map of short-term culture filtrate, and compared with another recently identified low-mass protein, CFP10 (F. X. Berthet, P, B. Rasmussen, I. Rosenkrands, P. Andersen, and B. Gicquel. Microbiology 144:3195-3203, 1998......), and the well-described ESAT-6 antigen. Genetic analyses demonstrated that TB10.4 as well as CFP10 belongs to the ESAT-6 family of low-mass proteins, whereas TB7.3 is a low-molecular-mass protein outside this family. The proteins were expressed in Escherichia coli, and their immunogenicity was tested...

  5. Molecular analysis of sulphur-rich brown coals by flash pyrolysis-gas chromatography-mass spectrometry: The type III-S kerogen

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Las Heras, F.X.C. de; Leeuw, J.W. de

    1992-01-01

    The molecular composition of five brown coals from three different basins (Maestrazgo, Mequinenza and Rubielos) in Spain was investigated by flash pyrolysis-gas chromatography and flash pyrolysis-gas chromatography-mass spectrometry. In these techniques, the macromolecular material is thermally

  6. Effects of fruit and vegetable low molecular mass fractions on gene expression in gingival cells challenged with Prevotella intermedia and Actinomyces naeslundii

    NARCIS (Netherlands)

    Canesi, L.; Borghi, C.; Stauder, M.; Lingström, P.; Papetti, A.; Pratten, J.; Signoretto, C.; Spratt, D.A.; Wilson, M.; Zaura, E.; Pruzzo, C.

    2011-01-01

    Low molecular mass (LMM) fractions obtained from extracts of raspberry, red chicory, and Shiitake mushrooms have been shown to be an useful source of specific antibacterial, antiadhesion/coaggregation, and antibiofilm agent(s) that might be used for protection towards caries and gingivitis. In this

  7. Glass transition and the rigid amorphous phase in semicrystalline blends of bacterial polyhydroxybutyrate PHB with low molecular mass atactic R,S-PHB-diol

    NARCIS (Netherlands)

    Hoehne, G.W.H.

    2004-01-01

    The glass transition and the crystallinity of blends of isotactic bacterial PHB and low molecular mass atactic R, S-PHB-diols was investigated by means of differential scanning calorimetry (DSC), temperature-modulated DSC and dielectric spectroscopy. It was found that (i) Tg of crystallized blends

  8. Fructans and water suppression on intact and fragmented rhizophores of Vernonia herbacea

    Directory of Open Access Journals (Sweden)

    Gláucia M. Dias-Tagliacozzo

    2004-07-01

    Full Text Available In order to evaluate the involvement of fructans in drought tolerance, experiments were conducted using intact plants and excised rhizophores of Vernonia herbacea. The water content in rhizophores of intact plants was maintained for 30 days when plants were watered every 7 and 15 days, whereas plants remained alive up to 60 days without water. Total fructan, oligo- to polysaccharides ratio and mean molecular mass of polysaccharides increased in these plants indicating depolymerization of median size molecules. In apical fragments of rhizophores kept dry the oligosaccharides increased in relation to polysaccharides one day after excision in treated tissues. This was reflected in the HPLC profile of the oligosaccharides in which the proportion of free fructose and fructans with DP 4-10 increased markedly. Results indicate that fructan metabolism is involved in drought tolerance of V. herbacea.A vegetação herbácea do cerrado brasileiro apresenta sistemas subterrâneos ricos em frutanos e estacionalmente expostos à restrição hídrica. A fim de avaliar o envolvimento dos frutanos na tolerância à dessecação foram conduzidos experimentos utilizando plantas intactas e fragmentos de rizóforos de Vernonia herbacea. O conteúdo de água nos rizóforos de plantas intactas foi mantido por 30 dias, quando as plantas foram molhadas a cada 7 ou 15 dias, sendo que as plantas permaneceram vivas até 60 dias sem água. O conteúdo total de frutanos, a razão oligo/polissacarídeos e a massa molecular média dos polissacarídeos nessas plantas aumentaram, indicando haver ocorrido despolimerização de moléculas com tamanho intermediário das cadeias. Nos fragmentos apicais de rizóforos submetidos à dessecação, os oligossacarídeos aumentaram em relação aos polissacarídeos, um dia após a excisão dos tecidos tratados. Essas alterações foram facilmente detectadas através dos perfis de oligossacarídeos analisados por HPLC, nos quais a propor

  9. Surfactant sodium lauryl sulfate enhances skin vaccination: molecular characterization via a novel technique using ultrafiltration capillaries and mass spectrometric proteomics.

    Science.gov (United States)

    Huang, Chun-Ming; Wang, Chao-Cheng; Kawai, Mikako; Barnes, Stephen; Elmets, Craig A

    2006-03-01

    The skin is a highly accessible organ and thus provides an attractive immune environment for cost-effective, simple, and needle-free delivery of vaccines and immunomodulators. In this study, we pretreated mouse skin with an anionic surfactant, sodium lauryl sulfate (SLS), for a short period of time (10 min) followed by epicutaneous vaccination with hen egg lysozyme antigen. We demonstrated for the first time that pretreatment of skin with surfactant SLS significantly enhances the production of antibody to hen egg lysozyme. Short term pretreatment with SLS disorganized the stratum corneum, extracted partial lamellar lipids, induced the maturation of Langerhans cells, and did not result in epidermis thickening. To reveal the mechanism underlying these changes, particularly at the molecular level, we used a novel proteomic technique using ultrafiltration capillaries and mass spectrometry to identify in vivo proteins/peptides secreted in the SLS-pretreated skin. Two secretory proteins, named as calcium-binding protein S100A9 and thymosin beta4, were identified by this novel technique. These two proteins thus may provide new insight into the enhancing effect of surfactants on skin vaccination.

  10. Molecular-level evidence provided by ultrahigh resolution mass spectrometry for oil-derived doc in groundwater at Bemidji, Minnesota

    Science.gov (United States)

    Islam, Ananna; Ahmed, Arif; Hur, Manhoi; Thorn, Kevin A.; Kim, Sunghwan

    2016-01-01

    Dissolved organic matter samples extracted from ground water at the USGS Bemidji oil spill site in Minnesota were investigated by ultrahigh resolution mass spectrometry. Principle component analysis (PCA) of the elemental composition assignments of the samples showed that the score plots for the contaminated sites were well separated from those for the uncontaminated sites. Additionally, spectra obtained from the same sampling site 7 and 19 years after the spill were grouped together in the score plot, strongly suggesting a steady state of contamination within the 12 year interval. The double bond equivalence (DBE) of Ox class compounds was broader for the samples from the contaminated sites, because of the complex nature of oil and the consequent formation of compounds with saturated and/or aromatic structures from the oxygenated products of oil. In addition, Ox class compounds with a relatively smaller number of x (x < 8; x = number of oxygen) and OxS1 class compounds were more abundant in the samples from the contaminated sites, because of the lower oxygen and higher sulfur contents of the oil compared to humic substances. The molecular-level signatures presented here can be a fundamental basis for in-depth analysis of oil contamination.

  11. A Novel High-Molecular-Mass Bacteriocin Produced by Enterococcus faecium: Biochemical Features and Mode of Action.

    Science.gov (United States)

    Vasilchenko, A S; Vasilchenko, A V; Valyshev, A V; Rogozhin, E A

    2018-02-08

    Discovery of a novel bacteriocin is always an event in sciences, since cultivation of most bacterial species is a general problem in microbiology. This statement is reflected by the fact that number of bacteriocins is smaller for tenfold comparing to known antimicrobial peptides. We cultivated Enterococcus faecium on simplified medium to reduce amount of purification steps. This approach allows to purify the novel heavy weight bacteriocin produced by E. faecium ICIS 7. The novelty of this bacteriocin, named enterocin-7, was confirmed by N-terminal sequencing and by comparing the structural-functional properties with available data. Purified enterocin-7 is characterized by a sequence of amino acid residues having no homology in UniProt/SwissProt/TrEMBL databases: NH2 - Asp - Ala - His - Leu - Ser - Glu - Val - Ala - Glu - Arg - Phe - Glu - Asp - Leu - Gly. Isolated thermostable protein has a molecular mass of 65 kDa, which allows it to be classified into class III in bacteriocin classification schemes. Enterocin-7 displayed a broad spectrum of activity against some Gram-positive and Gram-negative microorganisms. Fluorescent microscopy and spectroscopy showed the permeabilizing mechanism of the action of enterocin-7, which is realized within a few minutes.

  12. Molecular-level evidence provided by ultrahigh resolution mass spectrometry for oil-derived doc in groundwater at Bemidji, Minnesota

    Science.gov (United States)

    Islam, Ananna; Ahmed, Arif; Hur, Manhoi; Thorn, Kevin A.; Kim, Sunghwan

    2016-01-01

    Dissolved organic matter samples extracted from ground water at the USGS Bemidji oil spill site in Minnesota were investigated by ultrahigh resolution mass spectrometry. Principle component analysis (PCA) of the elemental composition assignments of the samples showed that the score plots for the contaminated sites were well separated from those for the uncontaminated sites. Additionally, spectra obtained from the same sampling site 7 and 19 years after the spill were grouped together in the score plot, strongly suggesting a steady state of contamination within the 12 year interval. The double bond equivalence (DBE) of Ox class compounds was broader for the samples from the contaminated sites, because of the complex nature of oil and the consequent formation of compounds with saturated and/or aromatic structures from the oxygenated products of oil. In addition, Ox class compounds with a relatively smaller number of x (x molecular-level signatures presented here can be a fundamental basis for in-depth analysis of oil contamination.

  13. How can we conserve intact tropical peatlands?

    Science.gov (United States)

    Lawson, Ian; Roucoux, Katherine

    2017-04-01

    The scientific community has, for more than three decades, been expressing increasing alarm about the fate of peatlands in parts of Indonesia and Malaysia, where extensive land-use conversion and drainage for rice and oil palm have greatly compromised peatland hydrology, ecology, biological richness, and carbon storage. The discourse in the literature on these peatlands is now moving on from attempts to preserve the last remaining fragments of peat-swamp forest, towards discussion of how best to restore damaged ecosystems, and whether it is possible to manage plantations more 'sustainably'. It is becoming increasingly clear, however, that peatlands occur quite widely in other parts of the lowland tropics, including parts of Amazonia and the Congo Basin, and many of these peatlands can reasonably be described as 'intact': although few if any parts of the tropics are totally unaffected by human actions, the hydrology and functional ecology of these systems appear to be close to a 'natural' state. The question then arises as to what should be done with the knowledge of their existence. Here we analyse the arguments in favour of protecting intact peatlands, and the potential conflicts with other priorities such as economic development and social justice. We evaluate alternative mechanisms for protecting intact peatlands, focusing on the particular issues raised by peatlands as opposed to other kinds of tropical ecosystem. We identify ways in which natural science agendas can help to inform these arguments, using our own contributions in palaeoecology and carbon mapping as examples. Finally, we argue for a radical reconsideration of research agendas in tropical peatlands, highlighting the potential contribution of methodologies borrowed from the social sciences and humanities.

  14. Peptidylation for the determination of low-molecular-weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Tang, Feng; Cen, Si-Ying; He, Huan; Liu, Yi; Yuan, Bi-Feng; Feng, Yu-Qi

    2016-05-23

    Determination of low-molecular-weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) has been a great challenge in the analytical research field. Here we developed a universal peptide-based derivatization (peptidylation) strategy for the sensitive analysis of low-molecular-weight compounds by MALDI-TOF-MS. Upon peptidylation, the molecular weights of target analytes increase, thus avoiding serious matrix ion interference in the low-molecular-weight region in MALDI-TOF-MS. Since peptides typically exhibit good signal response during MALDI-TOF-MS analysis, peptidylation endows high detection sensitivities of low-molecular-weight analytes. As a proof-of-concept, we analyzed low-molecular-weight compounds of aldehydes and thiols by the developed peptidylation strategy. Our results showed that aldehydes and thiols can be readily determined upon peptidylation, thus realizing the sensitive and efficient determination of low-molecular-weight compounds by MALDI-TOF-MS. Moreover, target analytes also can be unambiguously detected in biological samples using the peptidylation strategy. The established peptidylation strategy is a universal strategy and can be extended to the sensitive analysis of various low-molecular-weight compounds by MALDI-TOF-MS, which may be potentially used in areas such as metabolomics.

  15. Quantitative proteomic analysis of intact plastids.

    Science.gov (United States)

    Shiraya, Takeshi; Kaneko, Kentaro; Mitsui, Toshiaki

    2014-01-01

    Plastids are specialized cell organelles in plant cells that are differentiated into various forms including chloroplasts, chromoplasts, and amyloplasts, and fulfill important functions in maintaining the overall cell metabolism and sensing environmental factors such as sunlight. It is therefore important to grasp the mechanisms of differentiation and functional changes of plastids in order to enhance the understanding of vegetality. In this chapter, details of a method for the extraction of intact plastids that makes analysis possible while maintaining the plastid functions are provided; in addition, a quantitative shotgun method for analyzing the composition and changes in the content of proteins in plastids as a result of environmental impacts is described.

  16. Effects of hydrolysed casein, intact casein and intact whey protein on energy expenditure and appetite regulation

    DEFF Research Database (Denmark)

    Bendtsen, Line Quist; Lorenzen, Janne Kunchel; Gomes, Sisse

    2014-01-01

    Casein and whey differ in amino acid composition and in the rate of absorption; however, the absorption rate of casein can be increased to mimic that of whey by exogenous hydrolysis. The objective of the present study was to compare the effects of hydrolysed casein (HC), intact casein (IC......) and intact whey (IW) on energy expenditure (EE) and appetite regulation, and thereby to investigate the influence of amino acid composition and the rate of absorption. In the present randomised cross-over study, twenty-four overweight and moderately obese young men and women consumed three isoenergetic...

  17. Xenopus egg cytoplasm with intact actin.

    Science.gov (United States)

    Field, Christine M; Nguyen, Phuong A; Ishihara, Keisuke; Groen, Aaron C; Mitchison, Timothy J

    2014-01-01

    We report optimized methods for preparing Xenopus egg extracts without cytochalasin D, that we term "actin-intact egg extract." These are undiluted egg cytoplasm that contains abundant organelles, and glycogen which supplies energy, and represents the least perturbed cell-free cytoplasm preparation we know of. We used this system to probe cell cycle regulation of actin and myosin-II dynamics (Field et al., 2011), and to reconstitute the large, interphase asters that organize early Xenopus embryos (Mitchison et al., 2012; Wühr, Tan, Parker, Detrich, & Mitchison, 2010). Actin-intact Xenopus egg extracts are useful for analysis of actin dynamics, and interaction of actin with other cytoplasmic systems, in a cell-free system that closely mimics egg physiology, and more generally for probing the biochemistry and biophysics of the egg, zygote, and early embryo. Detailed protocols are provided along with assays used to check cell cycle state and tips for handling and storing undiluted egg extracts. © 2014 Elsevier Inc. All rights reserved.

  18. SIFamide peptides in clawed lobsters and freshwater crayfish (Crustacea, Decapoda, Astacidea): a combined molecular, mass spectrometric and electrophysiological investigation.

    Science.gov (United States)

    Dickinson, Patsy S; Stemmler, Elizabeth A; Cashman, Christopher R; Brennan, Henry R; Dennison, Bobbi; Huber, Kristen E; Peguero, Braulio; Rabacal, Whitney; Goiney, Christopher C; Smith, Christine M; Towle, David W; Christie, Andrew E

    2008-04-01

    Recently, we identified the peptide VYRKPPFNGSIFamide (Val(1)-SIFamide) in the stomatogastric nervous system (STNS) of the American lobster Homarus americanus using matrix-assisted laser desorption/ionization-Fourier transform mass spectrometry (MALDI-FTMS). Given that H. americanus is the only species thus far shown to possess this peptide, and that a second SIFamide isoform, Gly(1)-SIFamide, is broadly conserved in other decapods, including another astacidean, the crayfish Procambarus clarkii, we became interested both in confirming our identification of Val(1)-SIFamide via molecular methods and in determining the extent to which this isoform is conserved within other members of the infraorder Astacidea. Here, we present the identification and characterization of an H. americanus prepro-SIFamide cDNA that encodes the Val(1) isoform. Moreover, we demonstrate via MALDI-FTMS the presence of Val(1)-SIFamide in a second Homarus species, Homarus gammarus. In contrast, only the Gly(1) isoform was detected in the other astacideans investigated, including the lobster Nephrops norvegicus, a member of the same family as Homarus, and the crayfish Cherax quadricarinatus, P. clarkii and Pacifastacus leniusculus, which represent members of each of the extant families of freshwater astacideans. These results suggest that Val(1)-SIFamide may be a genus (Homarus)-specific isoform. Interestingly, both Val(1)- and Gly(1)-SIFamide possess an internal dibasic site, Arg(3)-Lys(4), raising the possibility of the ubiquitously conserved isoform PPFNGSIFamide. However, this octapeptide was not detected via MALDI-FTMS in any of the investigated species, and when applied to the isolated STNS of H. americanus possessed little bioactivity relative to the full-length Val(1) isoform. Thus, it appears that the dodeca-variants Val(1)- and Gly(1)-SIFamide are the sole bioactive isoforms of this peptide family in clawed lobsters and freshwater crayfish.

  19. Different low-molecular-mass organic acids specifically control leaching of arsenic and lead from contaminated soil.

    Science.gov (United States)

    Ash, Christopher; Tejnecký, Václav; Borůvka, Luboš; Drábek, Ondřej

    2016-04-01

    Low-molecular-mass organic acids (LMMOA) are of key importance for mobilisation and fate of metals in soil, by functioning as ligands that increase the amount of dissolved metal in solution or by dissociation of metal binding minerals. Column leaching experiments were performed on soil polluted with As and Pb, in order to determine the specificity of LMMOA related release for individual elements, at varying organic acid concentrations. Acetic, citric and oxalic acids were applied in 12h leaching experiments over a concentration range (0.5-25 mM) to soil samples that represent organic and mineral horizons. The leaching of As followed the order: oxalic>citric>acetic acid in both soils. Arsenic leaching was attributed primarily to ligand-enhanced dissolution of mineral oxides followed by As released into solution, as shown by significant correlation between oxalic and citric acids and content of Al and Fe in leaching solutions. Results suggest that subsurface mineral soil layers are more vulnerable to As toxicity. Leaching of Pb from both soils followed the order: citric>oxalic>acetic acid. Mineral soil samples were shown to be more susceptible to leaching of Pb than samples characterised by a high content of organic matter. The leaching efficiency of citric acid was attributed to formation of stable complexes with Pb ions, which other acids are not capable of. Results obtained in the study are evidence that the extent of As and Pb leaching in contaminated surface and subsurface soil depends significantly on the types of carboxylic acid involved. The implications of the type of acid and the specific element that can be mobilised become increasingly significant where LMMOA concentrations are highest, such as in rhizosphere soil. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. CO{sub 2} capture using fly ash-derived activated carbons impregnated with low molecular mass amines

    Energy Technology Data Exchange (ETDEWEB)

    Smith, K.M.; Arenillas, A.; Drage, T.C.; Snape, C.E. [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre

    2005-07-01

    Two different approaches to develop high capacity CO{sub 2} sorbents are presented. Firstly, the modification of the surface chemistry of low cost carbons by impregnation with a basic nitrogen-containing polymer (i.e.polyethylenimine) is described. Relatively low molecular mass (MM) amines, namely diethanolamine (DEA, MM 105) and tetraethylenepentaamineacrylonitrile (TEPAN, MM 311) are used to produce high capacity CO{sub 2} sorbents from activated carbons derived from unburned carbon in fly ash, which have low mesoporosities. The CO{sub 2} adsorption capacity and thermal stability of the prepared sorbents was measured as a function of temperature in a thermogravimetric analyser. The results indicate that TEPAN is more effective than DEA; at a temperature of 75{sup o}C, fly ash-derived activated carbons loaded with TEPAN achieved CO{sub 2} adsorption capacities in excess of 5 wt%, which compares fabvourably with the CO{sub 2} absorption capacity of 6.5 wt% achieved with a mesoporous silica loaded with TEPAN, and outperforms fly ash-derived activated carbons loaded with PEI. TEPAN has also been shown to have a higher thermal stability than DEA. The second approach involves the development of high nitrogen content carbon matrix adsorbents by carbonisation and subsequent thermal or chemical activation of a range of materials (polyacrylonitrile, glucose-amine mixtures, melamine and urea/melamine-formaldehyde resins). The results show that although the amount of nitrogen incorporated to the final adsorbent is important, the N-functionality seems to be more relevant for increasing CO{sub 2} uptake. However, the adsorbent obtained from carbazole-sugar co-pyrolysis, despite the lower amount of N incorporated, shows high CO{sub 2} uptake, up to 9 wt%, probably because the presence of more basic functionalities as determined by XPS analysis. 9 refs., 2 figs.

  1. Stable quasi-solid-state dye-sensitized solar cell using ionic gel electrolyte with low molecular mass organogelator

    International Nuclear Information System (INIS)

    Tao, Li; Huo, Zhipeng; Dai, Songyuan; Zhu, Jun; Zhang, Changneng; Pan, Xu; Huang, Yang; Yang, Shangfeng; Zhang, Bing; Yao, Jianxi

    2015-01-01

    Long-term stability is essential for the application and commercialization of dye-sensitized solar cells (DSCs). A quasi-solid-state DSC (QS-DSC) with excellent long-term stability is fabricated using ionic gel electrolyte (IGE) with N,N′-methylenebisdodecanamide as low molecular mass organogelator (LMOG). The gel to solution transition temperature (T gel ) of this IGE is 127 °C, well above the working temperature of the device, which contributes to the thermal properties of the IGE and the device. The electrochemical properties of the IGE and the kinetic processes of electron transport and recombination of the QS-DSC are investigated by means of electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). Due to the obstructed diffusion of redox species caused by the network of IGE, the electron recombination at the TiO 2 photoelectrode/electrolyte interface in the QS-DSC is accelerated. More importantly, compared with the ionic liquid electrolyte (ILE) based DSC, the QS-DSC based on the IGE exhibits excellent thermal and light-soaking stabilities during the accelerated aging tests for 1000 h. Especially, there is almost no degradation in the short-circuit current density (J sc ) in the IGE based QS-DSC, while the J sc of the ILE based DSC decreased to 85–94% of their initial values. - Highlights: • A novel IGE with high T gel is obtained by using a diamide derivative as LMOG. • The IGE based QS-DSC is very stable during the accelerated aging tests. • The influences of gelation on the electron kinetic processes are investigated

  2. Stable quasi-solid-state dye-sensitized solar cell using ionic gel electrolyte with low molecular mass organogelator

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Li [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Huo, Zhipeng, E-mail: zhipenghuo@163.com [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Dai, Songyuan, E-mail: sydai@ncepu.edu.cn [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Beijing Key Lab of Novel Thin Film Solar Cells, North China Electric Power University, Beijing 102206 (China); Zhu, Jun; Zhang, Changneng; Pan, Xu; Huang, Yang [Key Laboratory of Novel Thin Film Solar Cells, Division of Solar Energy Materials and Engineering, Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Yang, Shangfeng [Hefei National Laboratory for Physical Sciences at Microscale, Department of Materials Science and Engineering, University of Science and Technology of China (USTC), Hefei 230026 (China); Zhang, Bing; Yao, Jianxi [Beijing Key Lab of Novel Thin Film Solar Cells, North China Electric Power University, Beijing 102206 (China)

    2015-02-15

    Long-term stability is essential for the application and commercialization of dye-sensitized solar cells (DSCs). A quasi-solid-state DSC (QS-DSC) with excellent long-term stability is fabricated using ionic gel electrolyte (IGE) with N,N′-methylenebisdodecanamide as low molecular mass organogelator (LMOG). The gel to solution transition temperature (T{sub gel}) of this IGE is 127 °C, well above the working temperature of the device, which contributes to the thermal properties of the IGE and the device. The electrochemical properties of the IGE and the kinetic processes of electron transport and recombination of the QS-DSC are investigated by means of electrochemical impedance spectroscopy (EIS) and controlled intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). Due to the obstructed diffusion of redox species caused by the network of IGE, the electron recombination at the TiO{sub 2} photoelectrode/electrolyte interface in the QS-DSC is accelerated. More importantly, compared with the ionic liquid electrolyte (ILE) based DSC, the QS-DSC based on the IGE exhibits excellent thermal and light-soaking stabilities during the accelerated aging tests for 1000 h. Especially, there is almost no degradation in the short-circuit current density (J{sub sc}) in the IGE based QS-DSC, while the J{sub sc} of the ILE based DSC decreased to 85–94% of their initial values. - Highlights: • A novel IGE with high T{sub gel} is obtained by using a diamide derivative as LMOG. • The IGE based QS-DSC is very stable during the accelerated aging tests. • The influences of gelation on the electron kinetic processes are investigated.

  3. Chemometric Analysis of High Molecular Mass Glutenin Subunits and Image Data of Bread Crumb Structure from Croatian Wheat Cultivars

    Directory of Open Access Journals (Sweden)

    Zorica Jurković

    2002-01-01

    Full Text Available The aim of this work is to investigate functional relationships among wheat properties, high molecular mass (weight (HMW glutenin subunits and bread quality produced from eleven Croatian wheat cultivars by chemometric analysis. HMW glutenin subunits were fractionated by sodium dodecylsulfate polyacrylamid gel electrophoresis (SDS-PAGE and subsequently analysed by scanning densitometry in order to quantify HMW glutenin fractions. Wheat properties are characterised by four variables: protein content, sedimentation value, wet gluten and gluten index. Bread quality is assessed by the standard measurement of loaf volume, and visual quality of bread slice is quantified by 8 parameters by the use of computer image analysis. The data matrix with 21 columns (measured variables and 11 rows (cultivars is analysed for determination of number of latent variables. It was found that the first two latent variables account for 92, 85 and 87 % of variance of wheat quality properties, HMW glutenin fractions, and the bread quality parameters, respectively. Classification and functional relationships are discussed from the case data (cultivars and variable projections to the planes of the first two latent variables. Between Glu-D1y proportion and the bread quality parameters (standard parameter loaf volume and bread crumb cell area fraction determined by image analysis the strongest positive correlations are found r = 0.651 and r = 0.885, respectively. Between Glu-B1x proportion and the bread quality parameters the strongest negative correlations are found r =-0.535 and r = –0.841, respectively. The results are discussed in view of possible development of new and improvement of existing wheat cultivars and optimisation of bread production.

  4. Simultaneous determination of albumin and low-molecular-mass thiols in plasma by HPLC with UV detection.

    Science.gov (United States)

    Borowczyk, Kamila; Wyszczelska-Rokiel, Monika; Kubalczyk, Paweł; Głowacki, Rafał

    2015-02-15

    In this paper, we describe a simple and robust HPLC based method for determination of total low- and high-molecular-mass thiols, protein S-linked thiols and reduced albumin in plasma. The method is based on derivatization of analytes with 2-chloro-1-methylquinolinium tetrafluoroborate, separation and quantification by reversed-phase liquid chromatography followed by UV detection. Disulfides were converted to their thiol counterparts by reductive cleavage with tris(2-carboxyethyl)phosphine. Linearity in detector response for total thiols was observed over the range of 1-40 μmol L(-1) for Hcy and glutathione (GSH), 5-100 μmol L(-1) for Cys-Gly, 20-300 μmol L(-1) for Cys and 3.1-37.5 μmol L(-1) (0.2-2.4gL(-1)) for human serum albumin (HSA). For the protein S-bound forms these values were as follows: 0.5-30 μmol L(-1) for Hcy and GSH, 2.5-60 μmol L(-1) for Cys-Gly and 5-200 μmol L(-1) for Cys. The LOQs for total HSA, Cys, Hcy, Cys-Gly and GSH were 0.5, 0.2, 0.4, 0.3 and 0.4 μmol L(-1), respectively. The estimated validation parameters for all analytes are more than sufficient to allow the analytical method to be used for monitoring of the total and protein bound thiols as well as redox status of HSA in plasma. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Genetic disruptions of Drosophila Pavlovian learning leave extinction learning intact.

    Science.gov (United States)

    Qin, H; Dubnau, J

    2010-03-01

    Individuals who experience traumatic events may develop persistent posttraumatic stress disorder. Patients with this disorder are commonly treated with exposure therapy, which has had limited long-term success. In experimental neurobiology, fear extinction is a model for exposure therapy. In this behavioral paradigm, animals are repeatedly exposed in a safe environment to the fearful stimulus, which leads to greatly reduced fear. Studying animal models of extinction already has lead to better therapeutic strategies and development of new candidate drugs. Lack of a powerful genetic model of extinction, however, has limited progress in identifying underlying molecular and genetic factors. In this study, we established a robust behavioral paradigm to study the short-term effect (acquisition) of extinction in Drosophila melanogaster. We focused on the extinction of olfactory aversive 1-day memory with a task that has been the main workhorse for genetics of memory in flies. Using this paradigm, we show that extinction can inhibit each of two genetically distinct forms of consolidated memory. We then used a series of single-gene mutants with known impact on associative learning to examine the effects on extinction. We find that extinction is intact in each of these mutants, suggesting that extinction learning relies on different molecular mechanisms than does Pavlovian learning.

  6. Comparative evaluation of low-molecular-mass proteins from Mycobacterium tuberculosis identifies members of the ESAT-6 family as immunodominant T-cell antigens

    DEFF Research Database (Denmark)

    Skjøt, R L; Oettinger, T; Rosenkrands, I

    2000-01-01

    Culture filtrate from Mycobacterium tuberculosis contains protective antigens of relevance for the generation of a new antituberculosis vaccine. We have identified two previously uncharacterized M. tuberculosis proteins (TB7.3 and TB10.4) from the highly active low-mass fraction of culture filtrate....... The molecules were characterized, mapped in a two-dimensional electrophoresis reference map of short-term culture filtrate, and compared with another recently identified low-mass protein, CFP10 (F. X. Berthet, P. B. Rasmussen, I. Rosenkrands, P. Andersen, and B. Gicquel. Microbiology 144:3195-3203, 1998......), and the well-described ESAT-6 antigen. Genetic analyses demonstrated that TB10.4 as well as CFP10 belongs to the ESAT-6 family of low-mass proteins, whereas TB7.3 is a low-molecular-mass protein outside this family. The proteins were expressed in Escherichia coli, and their immunogenicity was tested...

  7. Isolation of intact sub-dermal secretory cavities from Eucalyptus

    Directory of Open Access Journals (Sweden)

    Goodger Jason QD

    2010-09-01

    Full Text Available Abstract Background The biosynthesis of plant natural products in sub-dermal secretory cavities is poorly understood at the molecular level, largely due to the difficulty of physically isolating these structures for study. Our aim was to develop a protocol for isolating live and intact sub-dermal secretory cavities, and to do this, we used leaves from three species of Eucalyptus with cavities that are relatively large and rich in essential oils. Results Leaves were digested using a variety of commercially available enzymes. A pectinase from Aspergillus niger was found to allow isolation of intact cavities after a relatively short incubation (12 h, with no visible artifacts from digestion and no loss of cellular integrity or cavity contents. Several measurements indicated the potential of the isolated cavities for further functional studies. First, the cavities were found to consume oxygen at a rate that is comparable to that estimated from leaf respiratory rates. Second, mRNA was extracted from cavities, and it was used to amplify a cDNA fragment with high similarity to that of a monoterpene synthase. Third, the contents of the cavity lumen were extracted, showing an unexpectedly low abundance of volatile essential oils and a sizeable amount of non-volatile material, which is contrary to the widely accepted role of secretory cavities as predominantly essential oil repositories. Conclusions The protocol described herein is likely to be adaptable to a range of Eucalyptus species with sub-dermal secretory cavities, and should find wide application in studies of the developmental and functional biology of these structures, and the biosynthesis of the plant natural products they contain.

  8. A new infusion pathway intactness monitoring system.

    Science.gov (United States)

    Ogawa, Hidekuni; Yonezawa, Yoshiharu; Maki, Hiromichi; Ninomiya, Ishio; Sata, Koji; Hamada, Shingo; Caldwell, W Morton

    2006-01-01

    A new infusion pathway monitoring system has been developed for hospital and home use. The system consists of linear integrated circuits and a low-power 8-bit single chip microcomputer which constantly monitors the infusion pathway intactness. An AC (alternating current) voltage is induced on the patient's body by electrostatic coupling from the normal 100 volt, 60 Hz AC power line wiring field in the patient's room. The induced AC voltage can be recorded by a main electrode wrapped around the infusion polyvinyl chloride tube. A reference electrode is wrapped on the electrode to monitor the AC voltage around the main electrode. If the injection needle or infusion tube becomes detached, then the system detects changes in the induced AC voltages and alerts the nursing station, via the nurse call system or PHS (personal handy phone system).

  9. Reconciling certification and intact forest landscape conservation.

    Science.gov (United States)

    Kleinschroth, Fritz; Garcia, Claude; Ghazoul, Jaboury

    2018-05-29

    In 2014, the Forest Stewardship Council (FSC) added a new criterion to its principles that requires protection of intact forest landscapes (IFLs). An IFL is an extensive area of forest that lacks roads and other signs of human activity as detected through remote sensing. In the Congo basin, our analysis of road networks in formally approved concessionary logging areas revealed greater loss of IFL in certified than in noncertified concessions. In areas of informal (i.e., nonregulated) extraction, road networks are known to be less detectable by remote sensing. Under the current definition of IFL, companies certified under FSC standards are likely to be penalized relative to the noncertified as well as the informal logging sector on account of their planned road networks, despite an otherwise better standard of forest management. This could ultimately undermine certification and its wider adoption, with implications for the future of sustainable forest management.

  10. An energy-filtering device coupled to a quadrupole mass spectrometer for soft-landing molecular ions on surfaces with controlled energy

    Energy Technology Data Exchange (ETDEWEB)

    Bodin, A.; Laloo, R.; Abeilhou, P.; Guiraud, L.; Gauthier, S.; Martrou, D. [Nanosciences Group, CEMES, CNRS UPR 8011 and University Toulouse III - Paul Sabatier, 29 rue Jeanne Marvig, BP94347, F-31055 Toulouse Cedex 4 (France)

    2013-09-15

    We have developed an energy-filtering device coupled to a quadrupole mass spectrometer to deposit ionized molecules on surfaces with controlled energy in ultra high vacuum environment. Extensive numerical simulations as well as direct measurements show that the ion beam flying out of a quadrupole exhibits a high-energy tail decreasing slowly up to several hundred eV. This energy distribution renders impossible any direct soft-landing deposition of molecular ions. To remove this high-energy tail by energy filtering, a 127° electrostatic sector and a specific triplet lenses were designed and added after the last quadrupole of a triple quadrupole mass spectrometer. The results obtained with this energy-filtering device show clearly the elimination of the high-energy tail. The ion beam that impinges on the sample surface satisfies now the soft-landing criterion for molecular ions, opening new research opportunities in the numerous scientific domains involving charges adsorbed on insulating surfaces.

  11. Inkjet-printed gold nanoparticle surfaces for the detection of low molecular weight biomolecules by laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Marsico, Alyssa L M; Creran, Brian; Duncan, Bradley; Elci, S Gokhan; Jiang, Ying; Onasch, Timothy B; Wormhoudt, Joda; Rotello, Vincent M; Vachet, Richard W

    2015-11-01

    Effective detection of low molecular weight compounds in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is often hindered by matrix interferences in the low m/z region of the mass spectrum. Here, we show that monolayer-protected gold nanoparticles (AuNPs) can serve as alternate matrices for the very sensitive detection of low molecular weight compounds such as amino acids. Amino acids can be detected at low fmol levels with minimal interferences by properly choosing the AuNP deposition method, density, size, and monolayer surface chemistry. By inkjet-printing AuNPs at various densities, we find that AuNP clusters are essential for obtaining the greatest sensitivity. Graphical Abstract ᅟ.

  12. Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

    Directory of Open Access Journals (Sweden)

    R. M. Dickhut

    2008-09-01

    Full Text Available Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223 component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia and 78% (New York of these peaks were assigned molecular formulas using only carbon (C, hydrogen (H, oxygen (O, nitrogen (N, and sulfur (S as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.

  13. [Determination of the distribution of relative molecular mass of organic matter by high pressure size exclusion chromatography with UV and TOC detectors].

    Science.gov (United States)

    Zhang, Han; Dong, Bing-Zhi

    2012-09-01

    An on-line high pressure size exclusion chromatography (HPSEC) with UV and TOC detectors was adapted to examine the distribution of relative molecular mass of natural organic matter (NOM). Through synchronous determination of UV254 and TOC responses in a wide range of relative molecular mass, it was possible to accurately characterize the structure of NOM, especially for some non-aromatic and non-conjugated double bond organics which have low response to UV. It was found that, TOC detector was capable of detecting all kinds of organic matters, including sucrose, sodium alginate and other hydrophilic organic compounds. The sample volume had a positively linear correlation with the TOC response, indicating that the larger volume would produce stronger responses. The effect of ion strength was relatively low, shown by the small decrease of peak area (1.2% ) from none to 0.2 mol x L(-1) NaCl. The pH value of tested samples should be adjusted to neutral or acidic because when the samples were alkaline, the results might be inaccurate. Compared to the sample solvents adopted as ultrapure water, the samples prepared by mobile phase solvents had less interference to salt boundary peak. The on-line HPSEC-UV-TOC can be used accurately to characterize the distribution of relative molecular mass and its four fractions in River Xiang.

  14. Comparison of Intact PTH and Bio-Intact PTH Assays Among Non-Dialysis Dependent Chronic Kidney Disease Patients.

    Science.gov (United States)

    Einbinder, Yael; Benchetrit, Sydney; Golan, Eliezer; Zitman-Gal, Tali

    2017-09-01

    The third-generation bio-intact parathyroid hormone (PTH) (1-84) assay was designed to overcome problems associated with the detection of C-terminal fragments by the second-generation intact PTH assay. The two assays have been compared primarily among dialysis populations. The present study evaluated the correlations and differences between these two PTH assays among patients with chronic kidney disease (CKD) stages 3 to 5 not yet on dialysis. Blood samples were collected from 98 patients with CKD stages 3 to 5. PTH concentrations were measured simultaneously by using the second-generation - PTH intact-STAT and third-generation bio-intact 1-84 PTH assays. Other serum biomarkers of bone mineral disorders were also assessed. CKD stage was calculated by using the CKD-Epidemiology Collaboration (EPI) formula. Serum bio-intact PTH concentrations were strongly correlated but significantly lower than the intact PTH concentrations (r=0.963, Pbio-intact PTH) positively correlated with urea (r=0.523, r=0.504; P=0.002, respectively), phosphorus (r=0.532, r=0.521; Pbio-intact PTH assay detected significantly lower PTH concentrations compared with intact PTH assay. Additional studies that correlate the diagnosis and management of CKD mineral and bone disorders with bone histomorphometric findings are needed to determine whether bio-intact PTH assay results are better surrogate markers in these early stages of CKD. © The Korean Society for Laboratory Medicine

  15. Analysis of quinocide in unprocessed primaquine diphosphate and primaquine diphosphate tablets using gas chromatography-mass spectrometry with supersonic molecular beams.

    Science.gov (United States)

    Brondz, Ilia; Fialkov, Alexander B; Amirav, Aviv

    2009-01-30

    Malaria is one of the most widespread and deadly diseases on the planet. Every year, about 500 million new cases are diagnosed, and the annual death toll is about 3 million. Primaquine has strong antiparasitic effects against gametocytes and can therefore prevent the spread of the parasite from treated patients to mosquitoes. It is also used in radical cures and prevents relapse. Consequently, primaquine is an often-used drug. In this study the separation of unprocessed primaquine from the contaminant quinocide based on gas chromatography-mass spectrometry with supersonic molecular beam (SMB) is presented and 7.5 mg primaquine diphosphate tablets were analyzed. We present a novel method for fast determination of quinocide which is an isomer of primaquine as the main contaminant in unprocessed primaquine and in its medical form as tablets by gas chromatography-mass spectrometry with SMB (also named supersonic GC-MS). Supersonic GC-MS provides enhanced molecular ion without any ion source related peak tailing plus extended range of compounds amenable for GC-MS analysis. In addition, major isomer mass spectral effects were revealed in the mass spectra of primaquine and quinocide which facilitated the unambiguous identification of quinocide in primaquine tablets. Fast GC-MS analysis is demonstrated with less then 2 min elution time of the drug and its main contaminants.

  16. Identification of the chemical constituents of Chinese medicine Yi-Xin-Shu capsule by molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation.

    Science.gov (United States)

    Wang, Hong-ping; Chen, Chang; Liu, Yan; Yang, Hong-Jun; Wu, Hong-Wei; Xiao, Hong-Bin

    2015-11-01

    The incomplete identification of the chemical components of traditional Chinese medicinal formula has been one of the bottlenecks in the modernization of traditional Chinese medicine. Tandem mass spectrometry has been widely used for the identification of chemical substances. Current automatic tandem mass spectrometry acquisition, where precursor ions were selected according to their signal intensity, encounters a drawback in chemical substances identification when samples contain many overlapping signals. Compounds in minor or trace amounts could not be identified because most tandem mass spectrometry information was lost. Herein, a molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation method for complex Chinese medicine chemical constituent analysis was developed. The precursor ions were selected according to their two-dimensional characteristics of retention times and mass-to-charge ratio ranges from herbal compounds, so that all precursor ions from herbal compounds were included and more minor chemical constituents in Chinese medicine were identified. Compared to the conventional automatic tandem mass spectrometry setups, the approach is novel and can overcome the drawback for chemical substances identification. As an example, 276 compounds from the Chinese Medicine of Yi-Xin-Shu capsule were identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pathophysiology of preterm labor with intact membranes.

    Science.gov (United States)

    Talati, Asha N; Hackney, David N; Mesiano, Sam

    2017-11-01

    Preterm labor with intact membranes is a major cause of spontaneous preterm birth (sPTB). To prevent sPTB a clear understanding is needed of the hormonal interactions that initiate labor. The steroid hormone progesterone acting via its nuclear progesterone receptors (PRs) in uterine cells is essential for the establishment and maintenance of pregnancy and disruption of PR signaling (i.e., functional progesterone/PR withdrawal) is key trigger for labor. The process of parturition is also associated with inflammation within the uterine tissues and it is now generally accepted that inflammatory stimuli from multiple extrinsic and intrinsic sources induce labor. Recent studies suggest inflammatory stimuli induce labor by affecting PR transcriptional activity in uterine cells to cause functional progesterone/PR withdrawal. Advances in understanding the functional interaction of inflammatory load on the pregnancy uterus and progesterone/PR signaling is opening novel areas of research and may lead to rational therapeutic strategies to effectively prevent sPTB. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Excitons in intact cells of photosynthetic bacteria.

    Science.gov (United States)

    Freiberg, Arvi; Pajusalu, Mihkel; Rätsep, Margus

    2013-09-26

    Live cells and regular crystals seem fundamentally incompatible. Still, effects characteristic to ideal crystals, such as coherent sharing of excitation, have been recently used in many studies to explain the behavior of several photosynthetic complexes, especially the inner workings of the light-harvesting apparatus of the oldest known photosynthetic organisms, the purple bacteria. To this date, there has been no concrete evidence that the same effects are instrumental in real living cells, leaving a possibility that this is an artifact of unnatural study conditions, not a real effect relevant to the biological operation of bacteria. Hereby, we demonstrate survival of collective coherent excitations (excitons) in intact cells of photosynthetic purple bacteria. This is done by using excitation anisotropy spectroscopy for tracking the temperature-dependent evolution of exciton bands in light-harvesting systems of increasing structural complexity. The temperature was gradually raised from 4.5 K to ambient temperature, and the complexity of the systems ranged from detergent-isolated complexes to complete bacterial cells. The results provide conclusive evidence that excitons are indeed one of the key elements contributing to the energetic and dynamic properties of photosynthetic organisms.

  19. Positive Youth Development, Life Satisfaction and Problem Behaviors of Adolescents in Intact and Non-Intact Families in Hong Kong

    Directory of Open Access Journals (Sweden)

    Daniel Tan Lei Shek

    2013-08-01

    Full Text Available This study investigated whether Chinese adolescents living in intact and non-intact families differed in their positive development, life satisfaction, and risk behavior. A total of 3,328 Secondary 1 students responded to measures of positive youth development (such as resilience and psychosocial competencies, life satisfaction, and risk behavior (substance abuse, delinquency, Internet addiction, consumption of pornographic materials, self-harm, and behavioral intention to engage in problem behavior. Findings revealed that adolescents growing up in intact families reported higher levels of positive developmental outcomes and life satisfaction as compared with adolescents from non-intact families. Adolescents in non-intact families also reported higher levels of risk behaviors than those growing up in intact families.

  20. Solvent Composition-Dependent Signal-Reduction of Molecular Ions Generated from Aromatic Compounds in (+) Atmospheric Pressure Photo Ionization Mass Spectrometry.

    Science.gov (United States)

    Lee, Seulgidaun; Ahmed, Arif; Kim, Sunghwan

    2018-03-30

    The ionization process is essential for successful mass spectrometry (MS) analysis because of its influence on selectivity and sensitivity. In particular, certain solvents reduce the ionization of the analyte, thereby reducing the overall sensitivity in APPI. Since the sensitivity varies greatly depending on the solvents, a fundamental understanding of the mechanism is required. Standard solutions were analyzed by (+) Atmospheric pressure photo ionization (APPI) QExactive ion trap mass spectrometer (Thermo Scientific). Each solution was infused directly to the APPI source at a flow rate 100 μl/min and the APPI source temperature was 300 °C. Other operating mass spectrometric parameters were maintained under the same conditions. Quantum mechanical calculations were carried out using the Gaussian 09 suite program. Density functional theory was used to calculate the reaction enthalpies (∆H) of reaction between toluene and other solvents. The experimental and theoretical results showed good agreement. The abundances of analyte ions were well correlated with the calculated ∆H values. Therefore, the results strongly support the suggested signal reduction mechanism. In addition, linear correlations between the abundance of toluene and analyte molecular ions were observed, which also supports the suggested mechanism. A solvent composition-dependent signal reduction mechanism was suggested and evaluated for the (+) atmospheric pressure photo ionization (APPI) mass spectrometry analysis of poly-aromatic hydrocarbons (PAHs) generating mainly molecular ions. Overall, the evidence provided in this work suggests that reactions between solvent cluster(s) and toluene molecular ions are responsible for the observed signal reductions. This article is protected by copyright. All rights reserved.

  1. MALDI-TOF mass spectrometry analysis of small molecular weight compounds (under 10 KDa) as biomarkers of rat hearts undergoing arecoline challenge.

    Science.gov (United States)

    Chen, Tung-Sheng; Chang, Mu-Hsin; Kuo, Wei-Wen; Lin, Yueh-Min; Yeh, Yu-Lan; Day, Cecilia Hsuan; Lin, Chien-Chung; Tsai, Fuu-Jen; Tsai, Chang-Hai; Huang, Chih-Yang

    2013-04-01

    Statistical and clinical reports indicate that betel nut chewing is strongly associated with progression of oral cancer because some ingredients in betel nuts are potential cancer promoters, especially arecoline. Early diagnosis for cancer biomarkers is the best strategy for prevention of cancer progression. Several methods are suggested for investigating cancer biomarkers. Among these methods, gel-based proteomics approach is the most powerful and recommended tool for investigating biomarkers due to its high-throughput. However, this proteomics approach is not suitable for screening biomarkers with molecular weight under 10 KDa because of the characteristics of gel electrophoresis. This study investigated biomarkers with molecular weight under 10 KDa in rats with arecoline challenge. The centrifuging vials with membrane (10 KDa molecular weight cut-off) played a crucial role in this study. After centrifuging, the filtrate (containing compounds with molecular weight under 10 KDa) was collected and spotted on a sample plate for MALDI-TOF mass spectrometry analysis. Compared to control, three extra peaks (m/z values were 1553.1611, 1668.2097 and 1740.1832, respectively) were found in sera and two extra peaks were found in heart tissue samples (408.9719 and 524.9961, respectively). These small compounds should play important roles and may be potential biomarker candidates in rats with arecoline. This study successfully reports a mass-based method for investigating biomarker candidates with small molecular weight in different types of sample (including serum and tissue). In addition, this reported method is more time-efficient (1 working day) than gel-based proteomics approach (5~7 working days).

  2. 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.

  3. Molecular Form Differences Between Prostate-Specific Antigen (PSA) Standards Create Quantitative Discordances in PSA ELISA Measurements

    Science.gov (United States)

    McJimpsey, Erica L.

    2016-01-01

    The prostate-specific antigen (PSA) assays currently employed for the detection of prostate cancer (PCa) lack the specificity needed to differentiate PCa from benign prostatic hyperplasia and have high false positive rates. The PSA calibrants used to create calibration curves in these assays are typically purified from seminal plasma and contain many molecular forms (intact PSA and cleaved subforms). The purpose of this study was to determine if the composition of the PSA molecular forms found in these PSA standards contribute to the lack of PSA test reliability. To this end, seminal plasma purified PSA standards from different commercial sources were investigated by western blot (WB) and in multiple research grade PSA ELISAs. The WB results revealed that all of the PSA standards contained different mass concentrations of intact and cleaved molecular forms. Increased mass concentrations of intact PSA yielded higher immunoassay absorbance values, even between lots from the same manufacturer. Standardization of seminal plasma derived PSA calibrant molecular form mass concentrations and purification methods will assist in closing the gaps in PCa testing measurements that require the use of PSA values, such as the % free PSA and Prostate Health Index by increasing the accuracy of the calibration curves. PMID:26911983

  4. Molecular Form Differences Between Prostate-Specific Antigen (PSA) Standards Create Quantitative Discordances in PSA ELISA Measurements

    Science.gov (United States)

    McJimpsey, Erica L.

    2016-02-01

    The prostate-specific antigen (PSA) assays currently employed for the detection of prostate cancer (PCa) lack the specificity needed to differentiate PCa from benign prostatic hyperplasia and have high false positive rates. The PSA calibrants used to create calibration curves in these assays are typically purified from seminal plasma and contain many molecular forms (intact PSA and cleaved subforms). The purpose of this study was to determine if the composition of the PSA molecular forms found in these PSA standards contribute to the lack of PSA test reliability. To this end, seminal plasma purified PSA standards from different commercial sources were investigated by western blot (WB) and in multiple research grade PSA ELISAs. The WB results revealed that all of the PSA standards contained different mass concentrations of intact and cleaved molecular forms. Increased mass concentrations of intact PSA yielded higher immunoassay absorbance values, even between lots from the same manufacturer. Standardization of seminal plasma derived PSA calibrant molecular form mass concentrations and purification methods will assist in closing the gaps in PCa testing measurements that require the use of PSA values, such as the % free PSA and Prostate Health Index by increasing the accuracy of the calibration curves.

  5. Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry

    Science.gov (United States)

    Souda, Puneet; Ryan, Christopher M.; Cramer, William A.; Whitelegge, Julian

    2011-01-01

    Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein’s native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electroncapture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. PMID:21982782

  6. In vitro and in vivo gene delivery using chitosan/hyaluronic acid nanoparticles: Influences of molecular mass of hyaluronic acid and lyophilization on transfection efficiency.

    Science.gov (United States)

    Sato, Toshinori; Nakata, Mitsuhiro; Yang, Zhihong; Torizuka, Yu; Kishimoto, Satoko; Ishihara, Masayuki

    2017-08-01

    Lyophilization is an effective method for preserving nonviral gene vectors. To improve the stability and transgene expression of lyophilized plasmid DNA (pDNA) complexes, we coated the surfaces of pDNA/chitosan complexes with hyaluronic acid (HA) of varying molecular masses. The transgene expression of pDNA/chitosan/HA ternary complexes was characterized in vitro and in vivo. pDNA complexes were lyophilized overnight and the resultant products with spongy, porous consistencies were stored at -30, 4 or 25°C for 2 weeks. Rehydrated complexes were characterized using gel retardation assays, aiming to confirm complex formation, measure particle size and evaluate zeta potential, as well as conduct luciferase gene reporter assays. The anti-tumor effects of pDNA ternary complexes were evaluated using suicide gene (pTK) coding thymidine kinase in Huh7-implanted mice. Transfection efficiencies of pDNA/chitosan/HA ternary complexes were dependent on the average molecular masses of HA. The coating of pDNA/chitosan complexes with HA maintained the cellular transfection efficiencies of lyophilized pDNA ternary complexes. Furthermore, intratumoral injection of lyophilized, rehydrated pDNA ternary complexes into tumor-bearing mice showed a significant suppression of tumor growth. The coating of pDNA/chitosan complexes with high-molecular-weight HA augmented the stability and cellular transfection ability of the complexes after lyophilization-rehydration. Copyright © 2017 John Wiley & Sons, Ltd.

  7. Intact interval timing in circadian CLOCK mutants.

    Science.gov (United States)

    Cordes, Sara; Gallistel, C R

    2008-08-28

    While progress has been made in determining the molecular basis for the circadian clock, the mechanism by which mammalian brains time intervals measured in seconds to minutes remains a mystery. An obvious question is whether the interval-timing mechanism shares molecular machinery with the circadian timing mechanism. In the current study, we trained circadian CLOCK +/- and -/- mutant male mice in a peak-interval procedure with 10 and 20-s criteria. The mutant mice were more active than their wild-type littermates, but there were no reliable deficits in the accuracy or precision of their timing as compared with wild-type littermates. This suggests that expression of the CLOCK protein is not necessary for normal interval timing.

  8. Isolation of intact elastin fibers devoid of microfibrils.

    NARCIS (Netherlands)

    Daamen, W.F.; Hafmans, T.G.M.; Veerkamp, J.H.; Kuppevelt, A.H.M.S.M. van

    2005-01-01

    Purification protocols for elastin generally result in greatly damaged elastin fibers and this likely influences the biological response. We here describe a novel protocol for the isolation of elastin whereby the fibers stay intact, and introduce the term "elastin fiber" for intact elastic fibers

  9. 50 CFR 622.38 - Landing fish intact.

    Science.gov (United States)

    2010-10-01

    ... that is operating under the respective trip limits. Such cut-off fish also may be sold. A maximum of... 50 Wildlife and Fisheries 8 2010-10-01 2010-10-01 false Landing fish intact. 622.38 Section 622.38... Landing fish intact. The operator of a vessel that fishes in the EEZ is responsible for ensuring that fish...

  10. Determination of high molecular mass compounds from Amazonian plant's leaves; Determinacao de compostos de massa molecular alta em folhas de plantas da Amazonia

    Energy Technology Data Exchange (ETDEWEB)

    Siqueira, Denilson Soares de; Pereira, Alberto dos Santos; Aquino Neto, Francisco Radler de [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica]. E-mail: ladetec@iq.gov.br; Cabral, Jose Augusto; Ferreira, Carlos Alberto Cid [Instituto Nacional de Pesquisas da Amazonia (INPA), Manaus, AM (Brazil); Simoneit, Bernd R.T. [Oregon State Univ., Corvallis, OR (United States). College of Oceanic and Atmospheric Sciences. Petroleum and Environmental Geochemistry Group; Elias, Vladimir O. [Analytical Solution, Rio de Janeiro, RJ (Brazil)

    2003-10-01

    The fractions of dichloromethane extracts of leaves from andiroba (Carapa guianensis - Meliaceae), caapi (Banisteriopsis caapi - Malpighiaceae), cocoa (Theobroma cacao - Sterculiaceae), Brazil nut (Bertholletia excelsa - Lecytidaceae), cupuacu (Theobroma grandiflorum - Sterculiaceae), marupa (Simaruba amara - Simaroubaceae) and rubber tree (Hevea brasiliensis - Euphorbiaceae), were analyzed by HT-HRGC and HT-HRGC-MS. Esters of homologous series of fatty acids and long chain alcohols, phytol, amyrines and tocopherols were characterized. The characterization of the compounds was based mainly in mass spectra data and in addition by usual spectrometric data ({sup 1}H and {sup 13}C NMR, IR). (author)

  11. Serum steroid levels in intact and endocrine ablated BALB/c nude mice and their intact littermates

    DEFF Research Database (Denmark)

    Brünner, N; Svenstrup, B; Spang-Thomsen, M

    1986-01-01

    An investigation was made of the serum steroid levels found in intact and endocrine ablated nude mice of both sexes and in their intact homozygous littermates. The results showed that nude mice have a normal steroidogenesis, but with decreased levels of circulating steroids compared to those...

  12. Mass Transport Properties of LiD-U Mixtures from Orbital FreeMolecular Dynamics Simulations and a Pressure-Matching Mixing Rule

    International Nuclear Information System (INIS)

    Burakovsky, Leonid; Kress, Joel D.; Collins, Lee A.

    2012-01-01

    Mass transport properties for LiD-U mixtures were calculated using a pressure matching mixture rule for the mixing of LiD and of U properties simulated with Orbital Free Molecular Dynamics (OFMD). The mixing rule was checked against benchmark OFMD simulations for the fully interacting three-component (Li, D, U) system. To obtain transport coefficients for LiD-U mixtures of different (LiD) x U (1-x) compositions as functions of temperature and mixture density is a tedious task. Quantum molecular dynamics (MD) simulations can be employed, as in the case LiD or U. However, due to the presence of the heavy constituent U, such simulations proceed so slowly that only a limited number of numerical data points in the (x, ρ, T) phase space can be obtained. To finesse this difficulty, transport coefficients for a mixture can be obtained using a pressure-matching mixing rule discussed. For both LiD and U, the corresponding transport coefficients were obtained earlier from quantum molecular dynamics simulations. In these simulations, the quantum behavior of the electrons was represented using an orbital free (OF) version of density functional theory, and ions were advanced in time using classical molecular dynamics. The total pressure of the system, P = nk B T/V + P e , is the sum of the ideal gas pressure of the ions plus the electron pressure. The mass self-diffusion coefficient for species α, D α , the mutual diffusion coefficient for species α and β, Dαβ, and the shear viscosity, η, are computed from the appropriate autocorrelation function. The details of similar QMD calculations on LiH are described in Ref. [1] for 0.5 eV < T < 3 eV, and in Ref. [2] for 2 eV < T < 6 eV.

  13. Evidence for radical anion formation during liquid secondary ion mass spectrometry analysis of oligonucleotides and synthetic oligomeric analogues: a deconvolution algorithm for molecular ion region clusters.

    Science.gov (United States)

    Laramée, J A; Arbogast, B; Deinzer, M L

    1989-10-01

    It is shown that one-electron reduction is a common process that occurs in negative ion liquid secondary ion mass spectrometry (LSIMS) of oligonucleotides and synthetic oligonucleosides and that this process is in competition with proton loss. Deconvolution of the molecular anion cluster reveals contributions from (M-2H).-, (M-H)-, M.-, and (M + H)-. A model based on these ionic species gives excellent agreement with the experimental data. A correlation between the concentration of species arising via one-electron reduction [M.- and (M + H)-] and the electron affinity of the matrix has been demonstrated. The relative intensity of M.- is mass-dependent; this is rationalized on the basis of base-stacking. Base sequence ion formation is theorized to arise from M.- radical anion among other possible pathways.

  14. Electrospray ionization mass spectrometry: a technique to access the information beyond the molecular weight of the analyte.

    Science.gov (United States)

    Banerjee, Shibdas; Mazumdar, Shyamalava

    2012-01-01

    The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research.

  15. Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte

    Science.gov (United States)

    Banerjee, Shibdas; Mazumdar, Shyamalava

    2012-01-01

    The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research. PMID:22611397

  16. Intact Four-atom Organic Tetracation Stabilized by Charge Localization in the Gas Phase.

    Science.gov (United States)

    Yatsuhashi, Tomoyuki; Toyota, Kazuo; Mitsubayashi, Naoya; Kozaki, Masatoshi; Okada, Keiji; Nakashima, Nobuaki

    2016-10-05

    Several features distinguish intact multiply charged molecular cations (MMCs) from other species such as monocations and polycations: high potential energy, high electron affinity, a high density of electronic states with various spin multiplicities, and charge-dependent reactions. However, repulsive Coulombic interactions make MMCs quite unstable, and hence small organic MMCs are currently not readily available. Herein, we report that the isolated four-atom molecule diiodoacetylene survives after the removal of four electrons via tunneling. We show that the tetracation remains metastable towards dissociation because of the localization (91-95 %) of the positive charges on the terminal iodine atoms, ensuring minimum Coulomb repulsion between adjacent atoms as well as maximum charge-induced attractive dipole interactions between iodine and carbon. Our approach making use of iodines as the positively charged sites enables small organic MMCs to remain intact. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Theory of infrared microspectroscopy for intact fibers.

    Science.gov (United States)

    Davis, Brynmor J; Carney, P Scott; Bhargava, Rohit

    2011-01-15

    Infrared microspectroscopy is widely used for the chemical analysis of small samples. In particular, spectral properties of small cylindrical samples are important in forensic analysis, understanding relationships between microstructure and mechanical properties in fibers or fiber composites, and development of cosmetics and drugs for hair. The diameters of the constituent cylinders are typically of the order of the central wavelength of light used to probe the sample. Hence, structure and material spectral response are coupled and recorded spectra are usually distorted to the extent of becoming useless for molecular identification. In this paper, we apply rigorous optical theory to predict the spectral distortions observed in IR microspectroscopic data of fibers. The theory is used, first, to compute the changes that are observed for cylinders of various dimensions under different instrument configurations when compared to the bulk spectrum from the same material. We provide a method to recover intrinsic material spectral response from fibers by correcting for distortion introduced by the cylindrical structure. The theory reported here should enable the routine use of IR microspectroscopy and imaging for the molecular analysis of cylindrical domains in complex materials.

  18. Molecular dynamic simulations of the sputtering of multilayer organic systems

    CERN Document Server

    Postawa, Z; Piaskowy, J; Krantzman, K; Winograd, N; Garrison, B J

    2003-01-01

    Sputtering of organic overlayers has been modeled using molecular dynamics computer simulations. The investigated systems are composed of benzene molecules condensed into one, two and three layers on an Ag left brace 1 1 1 right brace surface. The formed organic overlayers were bombarded with 4 keV Ar projectiles at normal incidence. The development of the collision cascade in the organic overlayer was investigated. The sputtering yield, mass, internal and kinetic energy distributions of ejected particles have been analyzed as a function of the thickness of the organic layer. The results show that all emission characteristics are sensitive to the variation of layer thickness. Although most of the ejected intact benzene molecules originate from the topmost layer, the emission of particles located initially in second and third layers is significant. The analysis indicates that the metallic substrate plays a dominant role in the ejection of intact organic molecules.

  19. Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography-mass spectrometry for trace analysis of bisphenol A in water sample

    International Nuclear Information System (INIS)

    Kawaguchi, Migaku; Hayatsu, Yoshio; Nakata, Hisao; Ishii, Yumiko; Ito, Rie; Saito, Koichi; Nakazawa, Hiroyuki

    2005-01-01

    We have developed a molecularly imprinted polymer (MIP) using a stable isotope labeled compound as the template molecule and called it the ''isotope molecularly imprinted polymer'' (IMIP). In this study, bisphenol A (BPA) was used as the model compound. None imprinted polymer (NIP), MIP, dummy molecularly imprinted polymer (DMIP) and IMIP were prepared by the suspension polymerization method using without template, BPA, 4-tert-butylphenol (BP) and bisphenol A-d 16 (BPA-d 16 ), respectively. The polymers were subjected to molecularly imprinted solid phase extraction (MI-SPE), and the extracted samples were subjected to liquid chromatography-mass spectrometry (LC-MS). Although the leakage of BPA-d 16 from the IMIP was observed and that of BPA was not observed. The selectivity factors of MIP and IMIP for BPA were 4.45 and 4.43, respectively. Therefore, IMIP had the same molecular recognition ability as MIP. When MI-SPE with IMIP was used and followed by LC-MS in the analysis of river water sample, the detection limit of BPA was 1 ppt with high sensitivity. Moreover, the average recovery was higher than 99.8% (R.S.D.: 3.7%) by using bisphenol A- 13 C 12 (BPA- 13 C 12 ) as the surrogate standard. In addition, the IMIP were employed in MI-SPE of BPA in river water sample by LC-MS. The concentration of BPA in the river water sample was determined to be 32 pg ml -1 . We confirmed that it was possible to measure trace amounts of a target analyte by MI-SPE using IMIP

  20. Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi; Talarico, Giovanni

    2015-01-01

    A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

  1. Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

    KAUST Repository

    Falivene, Laura

    2015-10-02

    A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

  2. Subtle differences in molecular recognition between modified glycopeptide antibiotics and bacterial receptor peptides identified by electrospray ionization mass spectrometry

    DEFF Research Database (Denmark)

    Jørgensen, Thomas J. D.; Staroske, T; Roepstorff, P

    1999-01-01

    showing that electrospray ionization mass spectrometry (ESI-MS) can be used in the rapid quantitative analysis of mixtures of vancomycin-group antibiotics and their bacterial cell-wall receptors allowing the identification of even subtle differences in binding constants. Differences in affinities...

  3. Analysis of wax ester molecular species by high performance liquid chromatography/atmospheric pressure chemical ionisation mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Vrkoslav, Vladimír; Urbanová, Klára; Cvačka, Josef

    2010-01-01

    Roč. 1217, č. 25 (2010), s. 4184-4194 ISSN 0021-9673 R&D Projects: GA ČR GA203/09/0139 Institutional research plan: CEZ:AV0Z40550506 Keywords : Beeswax * Branched esters * Human hair * Jojoba * Mass spectrometry Subject RIV: CC - Organic Chemistry Impact factor: 4.194, year: 2010

  4. Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

    Science.gov (United States)

    Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

    2012-03-01

    A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

  5. Molecular mass spectrometry in metallodrug development: A case of mapping transferrin-mediated transformations for a ruthenium(III) anticancer drug

    Energy Technology Data Exchange (ETDEWEB)

    Jarosz, Maciej [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Matczuk, Magdalena, E-mail: mmatczuk@ch.pw.edu.pl [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Pawlak, Katarzyna [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Timerbaev, Andrei R. [Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygin St. 19, 119991 Moscow (Russian Federation)

    2014-12-03

    Highlights: • Extra- and intra-cellular interactions of Ru(III) anticancer drug candidate. • ESI-TOF-MS mapping of the ruthenium species bound to transferring. • ESI-QqQ-MS identification of released Ru species under cytosol simulated conditions. - Abstract: Electrospray ionization mass spectrometry (ESI-MS) techniques have been used to characterize the speciation of a Ru(III) anticancer drug, indazolium trans-[tetrachloridobis(1H-indazole) ruthenate(III)], upon its binding to transferrin and the impact of cellular reducing components on drug–transferrin adducts. Using time-of-flight ESI-MS, the polymorphism of apo- (iron-free) and holo-form (iron-saturated) of the protein was confirmed. While the ruthenium moieties bound to each of five isoforms under simulated extracellular conditions are essentially identical in numbers for apo- and holo-transferrin, distinct differences were found in the composition of Ru(III) species attached to either of the protein forms, which are dominated by differently coordinated aquated complexes. On the other hand, at least one of the Ru-N bonds in metal-organic framework remains intact even after prolonged interaction with the protein. Triple quadrupole tandem ESI-MS measurements demonstrated that the ruthenium species released from drug adducts with holo-transferrin in simulated cancer cytosol are underwent strong ligand exchange (as compared to the protein-bound forms) but most strikingly, they contain the metal center in the reduced Ru(II) state. In vitro probing the extra- and intracellular interactions of promising Ru(III) drug candidate performed by ESI-MS is thought to shed light on the transportation to tumor cells by transferrin and on the activation to more reactive species by the reducing environment of solid tumors.

  6. Analysis of iminosugars and other low molecular weight carbohydrates in Aglaonema sp. extracts by hydrophilic interaction liquid chromatography coupled to mass spectrometry.

    Science.gov (United States)

    Rodríguez-Sánchez, S; García-Sarrió, M J; Quintanilla-López, J E; Soria, A C; Sanz, M L

    2015-12-04

    A method by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry (HILIC-MS(2)) has been successfully developed for the simultaneous analysis of bioactive iminosugars and other low molecular weight carbohydrates in Aglaonema leaf extracts. Among other experimental chromatographic conditions, mobile phase eluents, additives and column temperature were evaluated in terms of retention time, resolution, peak width and symmetry provided for target carbohydrates. In general, narrow peaks (wh: 0.2-0.6min) with good symmetry (As: 0.9-1.3) and excellent resolution (Rs>1.8) were obtained for iminosugars using an acetonitrile:water gradient with 5mM ammonium acetate in both eluents at 55°C. Tandem mass spectra were used to confirm the presence of previously detected iminosugars in Aglaonema extracts and to tentatively identify for the first time others such as miglitol isomer, glycosyl-miglitol isomers and glycosyl-DMDP isomers. Concentration of total iminosugars varied from 1.35 to 2.84mgg(-1) in the extracts of the different Aglaonema samples analyzed. To the best of our knowledge, this is the first time that a HILIC-MS(2) method has been proposed for the simultaneous analysis of iminosugars and other low molecular weight carbohydrates of Aglaonema sp. extracts. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Characterization of methane oxidation in a simulated landfill cover system by comparing molecular and stable isotope mass balances.

    Science.gov (United States)

    Schulte, Marcel; Jochmann, Maik A; Gehrke, Tobias; Thom, Andrea; Ricken, Tim; Denecke, Martin; Schmidt, Torsten C

    2017-11-01

    Biological methane oxidation may be regarded as a method of aftercare treatment for landfills to reduce climate relevant methane emissions. It is of social and economic interest to estimate the behavior of bacterial methane oxidation in aged landfill covers due to an adequate long-term treatment of the gas emissions. Different approaches assessing methane oxidation in laboratory column studies have been investigated by other authors recently. However, this work represents the first study in which three independent approaches, ((i) mass balance, (ii) stable isotope analysis, and (iii) stoichiometric balance of product (CO 2 ) and reactant (CH 4 ) by CO 2 /CH 4 -ratio) have been compared for the estimation of the biodegradation by a robust statistical validation on a rectangular, wide soil column. Additionally, an evaluation by thermal imaging as a potential technique for the localization of the active zone of bacterial methane oxidation has been addressed in connection with stable isotope analysis and CO 2 /CH 4 -ratios. Although landfills can be considered as open systems the results for stable isotope analysis based on a closed system correlated better with the mass balance than calculations based on an open system. CO 2 /CH 4 -ratios were also in good agreement with mass balance. In general, highest values for biodegradation were determined from mass balance, followed by CO 2 /CH 4 -ratio, and stable isotope analysis. The investigated topsoil proved to be very suitable as a potential cover layer by removing up to 99% of methane for CH 4 loads of 35-65gm -2 d -1 that are typical in the aftercare phase of landfills. Finally, data from stable isotope analysis and the CO 2 /CH 4 -ratios were used to trace microbial activity within the reactor system. It was shown that methane consumption and temperature increase, as a cause of high microbial activity, correlated very well. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2012-04-01

    Full Text Available Atmospheric water soluble organic nitrogen (WSON is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W, which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2281 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+, CHON compounds that contained sulfur (CHONS+, CHON compounds that contained phosphorus (CHONP+, CHON compounds that contained both sulfur and phosphorus (CHONSP+, and compounds that contained only carbon, hydrogen, and nitrogen (CHN+. Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Despite their prevalence in continental rainwater, no organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March which have anthropogenic air mass origins and samples collected during the warm season (April to September with remote

  9. Simultaneous detection of low and high molecular weight carbonylated compounds derived from lipid peroxidation by electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Milic, Ivana; Hoffmann, Ralf; Fedorova, Maria

    2013-01-02

    Reactive oxygen species (ROS) and other oxidative agents such as free radicals can oxidize polyunsaturated fatty acids (PUFA) as well as PUFA in lipids. The oxidation products can undergo consecutive reactions including oxidative cleavages to yield a chemically diverse group of products, such as lipid peroxidation products (LPP). Among them are aldehydes and ketones ("reactive carbonyls") that are strong electrophiles and thus can readily react with nucleophilic side chains of proteins, which can alter the protein structure, function, cellular distribution, and antigenicity. Here, we report a novel technique to specifically derivatize both low molecular and high molecular weight carbonylated LPP with 7-(diethylamino)coumarin-3-carbohydrazide (CHH) and analyze all compounds by electrospray ionization-mass spectrometry (ESI-MS) in positive ion mode. CHH-derivatized compounds were identified by specific neutral losses or fragment ions. The fragment ion spectra displayed additional signals that allowed unambiguous identification of the lipid, fatty acids, cleavage sites, and oxidative modifications. Oxidation of docosahexaenoic (DHA, 22:6), arachidonic (AA, 20:4), linoleic (LA, 18:2), and oleic acids (OA, 18:1) yielded 69 aliphatic carbonyls, whose structures were all deduced from the tandem mass spectra. When four phosphatidylcholine (PC) vesicles containing the aforementioned unsaturated fatty acids were oxidized, we were able to deduce the structures of 122 carbonylated compounds from the tandem mass spectra of a single shotgun analysis acquired within 15 min. The high sensitivity (LOD ∼ 1 nmol/L for 4-hydroxy-2-nonenal, HNE) and a linear range of more than 3 orders of magnitude (10 nmol/L to 10 μmol/L for HNE) will allow further studies on complex biological samples including plasma.

  10. Investigation of the spectroscopy and relaxation dynamics of benzaldehyde using molecular orbital calculations and laser ionization time-of-flight mass spectroscopy

    Science.gov (United States)

    da Silva, Maria Cristina Rodrigues

    1998-11-01

    Molecular orbital methods and laser ionization mass spectrometry measurements are used to investigate the spectroscopy and relaxation dynamics of benzaldehyde following excitation to its S2(/pi/pi/sp/*) state. Energies, equilibrium geometries and vibrational frequencies of ground and low-lying excited states of benzaldehyde neutral and cation determined by ab initio calculations provide a theoretical description of the electronic spectroscopy of benzaldehyde and of the changes occurring on excitation and ionization. The S2(/pi/pi/sp/*)[/gets]S0 excitation spectrum of jet-cooled benzaldehyde acquired using two-color laser ionization mass spectrometry techniques is interpreted with the aid of these calculations. The spectrum is dominated by the origin band and by transitions involving some of the ring modes consistent with the results of the molecular orbital calculations that indicate that the major geometric changes on excitation to S2 are located in the aromatic ring. Ten fundamental vibrations of the S2(/pi/pi/sp/*) state are assigned. The dissociation dynamics of benzaldehyde into benzene and carbon monoxide following excitation to its S2(/pi/pi/sp/*) state are investigated under jet- cooled conditions by two-color laser ionization mass spectrometry using a pump-probe technique. This experimental arrangement allows monitoring the benzaldehyde reactant and the benzene product ion signals as a function of the time delay between the excitation and ionization steps. A kinetic model is proposed to explain the observed biexponential decay of the benzaldehyde signal and the single exponential growth of the benzene product signal in terms of a sequential decay of two excited states of benzaldehyde, one of which leads to formation of benzene molecules in its lowest triplet state. Reactant disappearance and product appearance rates are determined for a number of vibronic transitions of the S2 state. They are found to increase with excitation energy without any indication

  11. Insight into the Supramolecular Architecture of Intact Diatom Biosilica from DNP-Supported Solid-State NMR Spectroscopy.

    Science.gov (United States)

    Jantschke, Anne; Koers, Eline; Mance, Deni; Weingarth, Markus; Brunner, Eike; Baldus, Marc

    2015-12-07

    Diatom biosilica is an inorganic/organic hybrid with interesting properties. The molecular architecture of the organic material at the atomic and nanometer scale has so far remained unknown, in particular for intact biosilica. A DNP-supported ssNMR approach assisted by microscopy, MS, and MD simulations was applied to study the structural organization of intact biosilica. For the first time, the secondary structure elements of tightly biosilica-associated native proteins in diatom biosilica were characterized in situ. Our data suggest that these proteins are rich in a limited set of amino acids and adopt a mixture of random-coil and β-strand conformations. Furthermore, biosilica-associated long-chain polyamines and carbohydrates were characterized, thereby leading to a model for the supramolecular organization of intact biosilica. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Hydrophilic interaction chromatography coupled matrix assisted laser desorption/ionization mass spectrometry for molecular analysis of organic compounds in medicines, tea, and coffee.

    Science.gov (United States)

    Wang, Ren-Qi; Bao, Kai; Croué, Jean-Philippe; Ng, Siu Choon

    2013-11-21

    Natural occurring organic compounds from food, natural organic matter, as well as metabolic products have received intense attention in current chemical and biological studies. Examination of unknown compounds in complex sample matrices is hampered by the limited choices for data readout and molecular elucidation. Herein, we report a generic method of hydrophilic interaction chromatography (HILIC) coupled with matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the rapid characterization of ingredients in pharmaceutical compounds, tea, and coffee. The analytes were first fractionated using a cationic HILIC column prior to MALDI-MS analyses. It was found that the retention times of a compound arising from different samples were consistent under the same conditions. Accordingly, molecules can be readily characterized by both the mass and chromatographic retention time. The retention behaviors of acidic and basic compounds on the cationic HILIC column were found to be significantly influenced by the pH of mobile phases, whereas neutral compounds depicted a constant retention time at different pH. The general HILIC-MALDI-MS method is feasible for fast screening of naturally occurring organic compounds. A series of homologs can be determined if they have the same retention behavior. Their structural features can be elucidated by considering their mass differences and hydrophilic properties as determined by HILIC chromatogram.

  13. Hydrophilic interaction chromatography coupled matrix assisted laser desorption/ionization mass spectrometry for molecular analysis of organic compounds in medicines, tea, and coffee

    KAUST Repository

    Wang, Renqi

    2013-01-01

    Natural occurring organic compounds from food, natural organic matter, as well as metabolic products have received intense attention in current chemical and biological studies. Examination of unknown compounds in complex sample matrices is hampered by the limited choices for data readout and molecular elucidation. Herein, we report a generic method of hydrophilic interaction chromatography (HILIC) coupled with matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the rapid characterization of ingredients in pharmaceutical compounds, tea, and coffee. The analytes were first fractionated using a cationic HILIC column prior to MALDI-MS analyses. It was found that the retention times of a compound arising from different samples were consistent under the same conditions. Accordingly, molecules can be readily characterized by both the mass and chromatographic retention time. The retention behaviors of acidic and basic compounds on the cationic HILIC column were found to be significantly influenced by the pH of mobile phases, whereas neutral compounds depicted a constant retention time at different pH. The general HILIC-MALDI-MS method is feasible for fast screening of naturally occurring organic compounds. A series of homologs can be determined if they have the same retention behavior. Their structural features can be elucidated by considering their mass differences and hydrophilic properties as determined by HILIC chromatogram. © 2013 The Royal Society of Chemistry.

  14. Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Ren, Shuoyi; Yu, Jianwei; Ji, Feng; Luo, Wenbin; Yang, Min

    2012-10-15

    Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH(4) against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. High field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter from the South Atlantic Ocean

    Science.gov (United States)

    Hertkorn, N.; Harir, M.; Koch, B. P.; Michalke, B.; Grill, P.; Schmitt-Kopplin, P.

    2012-01-01

    resonance envelopes typical of an intricate mixture of natural organic matter with noticeable peaks of anomerics and C-aromatics carbon whereas oxygenated aromatics and ketones were of too low abundance to result in noticeable humps at the S/N ratio provided. Integration according to major substructure regimes revealed continual increase of carboxylic acids and ketones from surface to deep marine DOM, reflecting a progressive oxygenation of marine DOM, with concomitant decline of carbohydrate-related substructures. Isolation of marine DOM by means of SPE likely discriminated against carbohydrates but produced materials with beneficial NMR relaxation properties: a substantial fraction of dissolved organic molecules present allowed the acquisition of two-dimensional NMR spectra with exceptional resolution. JRES, COSY and HMBC NMR spectra were capable to depict resolved molecular signatures of compounds exceeding a certain minimum abundance. Here, JRES spectra suffered from limited resolution whereas HMBC spectra were constrained because of limited S/N ratio. Hence, COSY NMR spectra appeared best suited to depict organic complexity in marine DOM. The intensity and number of COSY cross peaks was found maximal for sample FMAX and conformed to about 1500 molecules recognizable in variable abundance. Surface DOM (FISH) produced a slightly (~25%) lesser number of cross peaks with remarkable positional accordance to FMAX (~80% conforming COSY cross peaks were found in FISH and FMAX). With increasing water depth, progressive attenuation of COSY cross peaks was caused by fast transverse NMR relaxation of yet unknown origin. However, most of the faint COSY cross peak positions of deep water DOM conformed to those observed in the surface DOM, suggesting the presence of a numerous set of identical molecules throughout the entire ocean column even if the investigated water masses belonged to different oceanic regimes and currents. Aliphatic chemical environments of methylene (CH2) and

  16. Electro-spray ionization - mass spectrometry (ESI/MS) and molecular modelling, two complementary approaches. Application to calixarenes

    International Nuclear Information System (INIS)

    Allain, F.; Virelizier, H.; Moulin, Ch.; Lamare, V.; Dozol, J.F.

    2001-01-01

    The molecular dynamics simulation and the experimental results obtained by the ESI/MS technique have shown that the stability of the calixarene - alkaline cation complexes is dependent of the medium. Indeed, in solution, the calixarene presents a strong affinity for cesium whereas in gaseous phase, the strong affinity is for sodium. The stability of the [calixarene+Na] + complexes depends of the nature of the medium too; these two techniques having shown that the presence of a small quantity of water in the dilution solvent stabilizes the complex. At last, calixarenes with benzo groups on their crown have an affinity for sodium which is weak in solution but strong in gaseous phase. These different results show the excellent complementarity between the two techniques. (O.M.)

  17. Differential transcriptional profiling of damaged and intact adjacent dorsal root ganglia neurons in neuropathic pain.

    Directory of Open Access Journals (Sweden)

    A K Reinhold

    Full Text Available Neuropathic pain, caused by a lesion in the somatosensory system, is a severely impairing mostly chronic disease. While its underlying molecular mechanisms are not thoroughly understood, neuroimmune interactions as well as changes in the pain pathway such as sensitization of nociceptors have been implicated. It has been shown that not only are different cell types involved in generation and maintenance of neuropathic pain, like neurons, immune and glial cells, but, also, intact adjacent neurons are relevant to the process. Here, we describe an experimental approach to discriminate damaged from intact adjacent neurons in the same dorsal root ganglion (DRG using differential fluorescent neuronal labelling and fluorescence-activated cell sorting (FACS. Two fluorescent tracers, Fluoroemerald (FE and 1-dioctadecyl-3,3,3,3-tetramethylindocarbocyanine perchlorate (DiI, were used, whose properties allow us to distinguish between damaged and intact neurons. Subsequent sorting permitted transcriptional analysis of both groups. Results and qPCR validation show a strong regulation in damaged neurons versus contralateral controls as well as a moderate regulation in adjacent neurons. Data for damaged neurons reveal an mRNA expression pattern consistent with established upregulated genes like galanin, which supports our approach. Moreover, novel genes were found strongly regulated such as corticotropin-releasing hormone (CRH, providing novel targets for further research. Differential fluorescent neuronal labelling and sorting allows for a clear distinction between primarily damaged neuropathic neurons and "bystanders," thereby facilitating a more detailed understanding of their respective roles in neuropathic processes in the DRG.

  18. Hemolymph Melanization in the Silkmoth Bombyx mori Involves Formation of a High Molecular Mass Complex That Metabolizes Tyrosine*

    Science.gov (United States)

    Clark, Kevin D.; Strand, Michael R.

    2013-01-01

    The phenoloxidase (PO) cascade regulates the melanization of blood (hemolymph) in insects and other arthropods. Most studies indicate that microbial elicitors activate the PO cascade, which results in processing of the zymogen PPO to PO. PO is then thought to oxidize tyrosine and o-diphenols to quinones, which leads to melanin. However, different lines of investigation raise questions as to whether these views are fully correct. Here we report that hemolymph from the silkmoth, Bombyx mori, rapidly melanizes after collection from a wound site. Prior studies indicated that in vitro activated PPO hydroxylates Tyr inefficiently. Measurement of in vivo substrate titers, however, suggested that Tyr was the only PO substrate initially present in B. mori plasma and that it is rapidly metabolized by PO. Fractionation of plasma by gel filtration chromatography followed by bioassays indicated that melanization activity was primarily associated with a high mass complex (∼670 kDa) that contained PO. The prophenoloxidase-activating protease inhibitor Egf1.0 blocked formation of this complex and Tyr metabolism, but the addition of phenylthiourea to plasma before fractionation enhanced complex formation and Tyr metabolism. Mass spectrometry analysis indicated that the complex contained PO plus other proteins. Taken together, our results indicate that wounding alone activates the PO cascade in B. mori. They also suggest that complex formation is required for efficient use of Tyr as a substrate. PMID:23553628

  19. Molecular characterization of phytoplankton dissolved organic matter (DOM) and sulfur components using high resolution Orbitrap mass spectrometry.

    Science.gov (United States)

    Mangal, Vaughn; Stock, Naomi L; Guéguen, Celine

    2016-03-01

    Orbitrap high resolution mass spectrometry (HRMS) with electrospray ionization in both positive and negative polarity was conducted on Suwannee River fulvic acid (SRFA), Pony Lake fulvic acid (PLFA) standards, and dissolved organic matter (DOM) released by freshwater phytoplankton (Scenedesmus obliquus, Euglena mutabilis, and Euglena gracilis). Three-dimensional van Krevelen diagrams expressing various oxygenation states of sulfur molecules and abundance plots of sulfur-containing species were constructed. Orbitrap HRMS analysis of SRFA found a high density of peaks in the lignin region (77 %) and low density of protein material (6.53 %), whereas for PLFA, 25 % of the total peaks were lignin related compared to 56 % of peaks in protein regions, comparable with other HRMS studies. Phytoplankton-derived DOM of S. obliquus, E. mutabilis, and E. gracilis was dominated by protein molecules at respective percentages of 36, 46, and 49 %, and is consistent with previous experiments examining phytoplankton-derived DOM composition. The normalized percentage of SO-containing compounds was determined among the three phytoplankton to be 56 % for Scenedesmus, 54 % for E. mutabilis, and 47 % for E. gracilis, suggesting variation between sulfur content in phytoplankton-derived DOM and differences in metal binding capacities. These results suggest the level of resolution by Orbitrap mass spectrometry is sufficient for preliminary characterization of phytoplankton DOM at an affordable cost relative to other HRMS techniques.

  20. Alternative CHCA-based matrices for the analysis of low molecular weight compounds by UV-MALDI-tandem mass spectrometry.

    Science.gov (United States)

    Porta, Tiffany; Grivet, Chantal; Knochenmuss, Richard; Varesio, Emmanuel; Hopfgartner, Gérard

    2011-02-01

    Analysis of low molecular weight compounds (LMWC) in complex matrices by vacuum matrix-assisted laser desorption/ionization (MALDI) often suffers from matrix interferences, which can severely degrade limits of quantitation. It is, therefore, useful to have available a range of suitable matrices, which exhibit complementary regions of interference. Two newly synthesized α-cyanocinnamic acid derivatives are reported here; (E)-2-cyano-3-(naphthalen-2-yl)acrylic acid (NpCCA) and (2E)-3-(anthracen-9-yl)-2-cyanoprop-2enoic acid (AnCCA). Along with the commonly used α-cyano-4-hydroxycinnamic acid (CHCA), and the recently developed 4-chloro-α-cyanocinnamic acid (Cl-CCA) matrices, these constitute a chemically similar series of matrices covering a range of molecular weights, and with correspondingly differing ranges of spectral interference. Their performance was compared by measuring the signal-to-noise ratios (S/N) of 47 analytes, mostly pharmaceuticals, with the different matrices using the selected reaction monitoring (SRM) mode on a triple quadrupole instrument equipped with a vacuum MALDI source. AnCCA, NpCCA and Cl-CCA were found to offer better signal-to-noise ratios in SRM mode than CHCA, but Cl-CCA yielded the best results for 60% of the compounds tested. To better understand the relative performance of this matrix series, the proton affinities (PAs) were measured using the kinetic method. Their relative values were: AnCCA > CHCA > NpCCA > Cl-CCA. This ordering is consistent with the performance data. The synthesis of the new matrices is straightforward and they provide (1) tunability of matrix background interfering ions and (2) enhanced analyte response for certain classes of compounds. Copyright © 2011 John Wiley & Sons, Ltd.

  1. RCW 36 in the Vela Molecular Ridge: Evidence for high-mass star-cluster formation triggered by cloud-cloud collision

    Science.gov (United States)

    Sano, Hidetoshi; Enokiya, Rei; Hayashi, Katsuhiro; Yamagishi, Mitsuyoshi; Saeki, Shun; Okawa, Kazuki; Tsuge, Kisetsu; Tsutsumi, Daichi; Kohno, Mikito; Hattori, Yusuke; Yoshiike, Satoshi; Fujita, Shinji; Nishimura, Atsushi; Ohama, Akio; Tachihara, Kengo; Torii, Kazufumi; Hasegawa, Yutaka; Kimura, Kimihiro; Ogawa, Hideo; Wong, Graeme F.; Braiding, Catherine; Rowell, Gavin; Burton, Michael G.; Fukui, Yasuo

    2018-05-01

    A collision between two molecular clouds is one possible candidate for high-mass star formation. The H II region RCW 36, located in the Vela molecular ridge, contains a young star cluster (˜ 1 Myr old) and two O-type stars. We present new CO observations of RCW 36 made with NANTEN2, Mopra, and ASTE using 12CO(J = 1-0, 2-1, 3-2) and 13CO(J = 2-1) emission lines. We have discovered two molecular clouds lying at the velocities VLSR ˜ 5.5 and 9 km s-1. Both clouds are likely to be physically associated with the star cluster, as verified by the good spatial correspondence among the two clouds, infrared filaments, and the star cluster. We also found a high intensity ratio of ˜ 0.6-1.2 for CO J = 3-2/1-0 toward both clouds, indicating that the gas temperature has been increased due to heating by the O-type stars. We propose that the O-type stars in RCW 36 were formed by a collision between the two clouds, with a relative velocity separation of 5 km s-1. The complementary spatial distributions and the velocity separation of the two clouds are in good agreement with observational signatures expected for O-type star formation triggered by a cloud-cloud collision. We also found a displacement between the complementary spatial distributions of the two clouds, which we estimate to be 0.3 pc assuming the collision angle to be 45° relative to the line-of-sight. We estimate the collision timescale to be ˜ 105 yr. It is probable that the cluster age found by Ellerbroek et al. (2013b, A&A, 558, A102) is dominated by the low-mass members which were not formed under the triggering by cloud-cloud collision, and that the O-type stars in the center of the cluster are explained by the collisional triggering independently from the low-mass star formation.

  2. High-field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter

    Directory of Open Access Journals (Sweden)

    N. Hertkorn

    2013-03-01

    exceptional resolution and depicted resolved molecular signatures in excess of a certain minimum abundance. Classical methyl groups terminating aliphatic chains represented ~15% of total methyl in all samples investigated. A noticeable fraction of methyl (~2% was bound to olefinic carbon. Methyl ethers were abundant in surface marine SPE-DOM, and the chemical diversity of carbohydrates was larger than that of freshwater and soil DOM. In all samples, we identified sp2-hybridized carbon chemical environments with discrimination of isolated and conjugated olefins and α,β-unsaturated double bonds. Olefinic proton and carbon atoms were more abundant than aromatic ones; olefinic unsaturation in marine SPE-DOM will be more directly traceable to ultimate biogenic precursors than aromatic unsaturation. The abundance of furan, pyrrol and thiophene derivatives was marginal, whereas benzene derivatives, phenols and six-membered nitrogen heterocycles were prominent; a yet unassigned set of six-membered N-heterocycles with likely more than one single nitrogen occurred in all samples. Various key polycyclic aromatic hydrocarbon substructures suggested the presence of thermogenic organic matter at all water depths. Progressive NMR cross-peak attenuation from surface to deep marine SPE-DOM was particularly strong in COSY NMR spectra and indicated a continual disappearance of biosignatures as well as entropy gain from an ever increased molecular diversity. Nevertheless, a specific near-seafloor SPE-DOM signature of unsaturated molecules recognized in both NMR and Fourier transform ion cyclotron mass spectrometry (FTICR/MS possibly originated from sediment leaching. The conformity of key NMR and FTICR/MS signatures suggested the presence of a large set of identical molecules throughout the entire ocean column even though the investigated water masses belonged to different oceanic regimes and currents. FTICR/MS showed abundant CHO, CHNO, CHOS and CHNOS molecular series with slightly increasing

  3. Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

    Science.gov (United States)

    Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

    2014-08-05

    The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

  4. Molecular Characterization of Organosulfates in Urban Aerosols during the Spring Festival by FT-ICR Mass Spectrometry

    Science.gov (United States)

    Xie, Q.; Fu, P.

    2017-12-01

    Aerosol particles collected at daytime and nighttime in Beijing during the spring festival, including the episodes of various gradient level pollution and short-term pollution raised by fireworks, were analyzed using 15T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS). Organosulfates (OSs), tracers for secondary organic aerosol formation, were identified through accurate mass measurements. Both the total number and the arbitrary abundance of OSs were consistent with the total OC concentrations of the aerosol samples. Nitrooxy-organosulfates were more abundant in the nighttime than those in the daytime due to high NOX concentrations at night. Although all subgroups OSs increased with the deterioration of air quality, especially for the relative abundance of aromatic OSs with high double bond equivalents, the percentage contributions of aliphatic OSs with low degree of unsaturation decreased. It was worth to note that aliphatic OSs with a wide range in carbon-chain length of C6-40 were identified in this study. The candidates for their potential precursors were alkanes and fatty acids. Moreover, a large number of aromatic OSs, about two thirds of OSs, were detected. The rapid formation of these compounds in New Year's Eve with plentiful aromatics from firework burning suggests that they may be derived from PAHs. The high carbon and oxygen contents of OSs may indicate the presence of dimmers, even polymers. Our results support the important contribution of anthropogenic precursors to OSs in ambient aerosols on the basis of aromatic and aliphatic OSs, which may have a significant impact on the hygroscopic properties of ambient aerosol particles.

  5. Revisiting shape selectivity in liquid chromatography for polycyclic aromatic hydrocarbons (PAHs) - six-ring and seven-ring Cata-condensed PAH isomers of molecular mass 328 Da and 378 Da.

    Science.gov (United States)

    Oña-Ruales, Jorge O; Sander, Lane C; Wilson, Walter B; Wise, Stephen A

    2018-01-01

    The relationship of reversed-phase liquid chromatography (RPLC) retention on a polymeric C 18 stationary phase and the shape of polycyclic aromatic hydrocarbons (PAHs) was investigated for three-ring to seven-ring cata-condensed isomers. We report the first RPLC separation for six-ring and seven-ring cata-condensed PAH isomers. Correlations of LC retention and shape parameters (length-to-breath ratio, L/B and thickness, T) were investigated for 2 three-ring isomers (molecular mass 178 Da), 5 four-ring isomers (molecular mass 228 Da), 11 five-ring isomers (molecular mass 278 Da), 17 six-ring isomers (molecular mass 328 Da), and 20 seven-ring isomers (molecular mass 378 Da). Significant linear correlations were found for all isomer groups (r = 0.71 to 0.94). Nonplanarity of the PAH isomers was found to influence retention (i.e., nonplanar isomers eluting earlier than expected based on L/B) and linear correlations of retention vs. T for isomer groups containing nonplanar isomers were significant (r = 0.71 to 0.86). Graphical abstract.

  6. The intact capture of hypervelocity dust particles using underdense foams

    Science.gov (United States)

    Maag, Carl R.; Borg, J.; Tanner, William G.; Stevenson, T. J.; Bibring, J.-P.

    1994-01-01

    The impact of a hypervelocity projectile (greater than 3 km/s) is a process that subjects both the impactor and the impacted material to a large transient pressure distribution. The resultant stresses cause a large degree of fragmentation, melting, vaporization, and ionization (for normal densities). The pressure regime magnitude, however, is directly related to the density relationship between the projectile and target materials. As a consequence, a high-density impactor on a low-density target will experience the lowest level of damage. Historically, there have been three different approaches toward achieving the lowest possible target density. The first employs a projectile impinging on a foil or film of moderate density, but whose thickness is much less than the particle diameter. This results in the particle experiencing a pressure transient with both a short duration and a greatly reduced destructive effect. A succession of these films, spaced to allow nondestructive energy dissipation between impacts, will reduce the impactor's kinetic energy without allowing its internal energy to rise to the point where destruction of the projectile mass will occur. An added advantage to this method is that it yields the possibility of regions within the captured particle where a minimum of thermal modification has taken place. Polymer foams have been employed as the primary method of capturing particles with minimum degradation. The manufacture of extremely low bulk density materials is usually achieved by the introduction of voids into the material base. It must be noted, however, that a foam structure only has a true bulk density of the mixture at sizes much larger than the cell size, since for impact processes this is of paramount importance. The scale at which the bulk density must still be close to that of the mixture is approximately equal to the impactor. When this density criterion is met, shock pressures during impact are minimized, which in turn maximizes the

  7. Glycation and glycoxidation of low-density lipoproteins by glucose and low-molecular mass aldehydes. Formation of modified and oxidized particles

    DEFF Research Database (Denmark)

    Knott, Heather M; Brown, Bronwyn E; Davies, Michael Jonathan

    2003-01-01

    by the adduction of glucose or species derived from glucose, such as low-molecular mass aldehydes, to proteins. These reactions can be nonoxidative (glycation) or oxidative (glycoxidation) and result in the conversion of low-density lipoproteins (LDL) to a form that is recognized by the scavenger receptors...... with glucose. These processes are rapid and unaffected by low concentrations of copper ions. In contrast, lipid and protein oxidation are slow processes and occur to a limited extent in the absence of added copper ions. No evidence was obtained for the stimulation of lipid or protein oxidation by glucose...... or methylglyoxal in the presence of copper ions, whereas glycolaldehyde stimulated such reactions to a modest extent. These results suggest that the earliest significant events in this system are metal ion-independent glycation (modification) of the protein component of LDL, whilst oxidative events (glycoxidation...

  8. First detection of koi herpesvirus from koi, Cyprinus carpio L. experiencing mass mortalities in Iran: clinical, histopathological and molecular study.

    Science.gov (United States)

    Rahmati-Holasoo, H; Zargar, A; Ahmadivand, S; Shokrpoor, S; Ezhari, S; Ebrahimzadeh Mousavi, H A

    2016-10-01

    Koi herpesvirus (KHV) is the aetiological agent of an emerging disease (KHVD) associated with mass mortalities in koi and common carp and reported from at least 30 countries. We report the first detection of KHV from koi in Iran using clinical, histopathological and molecular studies. KHV-infected fish showed reduced swimming activity, sunken eyes and increased mucus production on skin and fins. On post-mortem examination, gill necrosis was observed in the majority of fish. Histopathologically, the gill showed diffuse necrosis of the branchial epithelial cells. Margination of chromatin was detected in gills, kidney, heart, spleen, intestine and brain. In addition, sequence analyses of the TK gene, ORF 136 and marker I and II, demonstrates that Iranian KHV isolates were identical and classified as variant A1 of TUSMT1 (J strain) and displayed the I(++) II(+) allele of this Asian genotype. © 2016 John Wiley & Sons Ltd.

  9. Effect of repeat unit structure and molecular mass of lactic acid bacteria hetero-exopolysaccharides on binding to milk proteins

    DEFF Research Database (Denmark)

    Birch, Johnny; HarÐarson, HörÐur Kári; Khan, Sanaullah

    2017-01-01

    -exopolysaccharides (HePSs) of 0.14–4.9 MDa from lactic acid bacteria to different milk proteins (β-casein, κ-casein, native and heat-treated β-lactoglobulin) at pH 4.0–5.0. Maximum binding capacity (RUmax) and apparent affinity (KA,app) were HePS- and protein-dependent and varied for example 10- and 600-fold......, respectively, in the complexation with native β-lactoglobulin at pH 4.0. Highest RUmax and KA,app were obtained with heat-treated β-lactoglobulin and β-casein, respectively. Overall, RUmax and KA,app decreased 6- and 20-fold, respectively, with increasing pH from 4.0 to 5.0. KA,app was influenced by ionic......Interactions of exopolysaccharides and proteins are of great importance in food science, but complicated to analyze and quantify at the molecular level. A surface plasmon resonance procedure was established to characterize binding of seven structure-determined, branched hetero...

  10. Determination of low-molecular-weight dicarboxylic acids in atmospheric aerosols by injection-port derivatization and gas chromatography-mass spectrometry

    Science.gov (United States)

    Ding, W.; Hsu, C.

    2008-12-01

    Currently, the investigations on aerosol water-soluble organic compounds (WSOCs) formed by burning biomass have become increasingly concerned with the role of these compounds in atmospheric chemistry and their effect on climate, because they have great potential to influence cloud formation, precipitation, and climate on both global and regional scales. Of these compounds, low-molecular weight (LMW) dicarboxylic acids (from C2 to C10) have attracted the most interest because of their properties as specific tracers for the burning of biomass. In this study, a modified injection-port derivatization and gas chromatography - mass spectrometry method was developed and evaluated for rapid determination of LMW dicarboxylic acids in atmospheric aerosol samples. The parameters related to the derivatization process (i.e., type of ion-pair reagent, injection-port temperature and concentration of ion-pair reagent) were optimized. Tetrabutylammonium hydroxide (TBA-OH) dissolved in methanol used as the ion-pair solution gave excellent yield for di-butyl ester low-molecular weight derivatives. Solid-phase extraction method instead of rotary evaporation was used to concentrate analytes from filter extracts. The recovery from filter extracts ranged from 67 to 86% with relative standard deviation (RSD) less than 13%. The concentrations of dicarboxylated C2, C3, C4, C5 and C6-C10 in atmospheric aerosols ranged from 91-240 ng/m3, 11-56 ng/m3, 12-49 ng/m3, 8-35 ng/m3 and n.d. to 17 ng/m3, respectively. Oxalic (C2) acid was the dominant dicarboxylic acids detected in aerosol samples. The total concentrations of the LMW dicarboxylic acids (from C2 to C10) correspond to 2.2 to 2.6% of the total aerosol mass.

  11. Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

    Energy Technology Data Exchange (ETDEWEB)

    Borretzen, Peer [Department of Plant and Environmental Sciences, P.O. Box 50003, Norwegian University of Life Sciences, N-1432 As (Norway)], E-mail: peer.borretzen@gmail.com; Salbu, Brit [Department of Plant and Environmental Sciences, P.O. Box 50003, Norwegian University of Life Sciences, N-1432 As (Norway)

    2009-04-15

    Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order {sup 109}Cd {approx_equal} {sup 65}Zn < {sup 134}Cs < {sup 60}Co. The significance increases with higher suspended sediment load and with higher K{sub d}. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.

  12. Mass yield distributions for the reactions Ca+Ca, Nb+Nb and Ca+Ca at E/A=800 MeV in the molecular-dynamical model

    International Nuclear Information System (INIS)

    Kiselev, S.M.

    1987-01-01

    Mass yield distributions obtained on the basis of the molecular-dynamical model are presented for the Ca+Ca, Nb+Nb reactions at E/A=400 MeV and Ca+Ca reaction at E/A=800 MeV. For the fragments with masses upto quarter of the mass of initial nucleus the model predicts a power law for mass spectra with almost the same value of the exponent. Such the behaviour is roughly a result of the superposition of the fireball breakup and the disintegration of spectator regions rather than the evidence of a liquid-gas-like phase transition in hot nuclear matter

  13. Molecular composition of rainwater and aerosol during rain events in León, Spain, using high resolution mass spectrometry.

    Science.gov (United States)

    Fee, Anna

    2017-04-01

    Anna Fee (1), Markus Kalberer (1), Roberto Fraile (2), Amaya Castro (2), Ana. I. Calvo (2), Carlos Blanco-Alegre (2), Fernanda Oduber (2) and Mário Cerqueira (3). 1 Department of Chemistry, University of Cambridge, UK. 2 Department of Applied Chemistry and Physics, IMARENAB, University of León, Spain. 3 Department of Environmental Planning, University of Aveiro, Portugal. A wide range of atmospheric compounds which are present in rainwater are often also present in aerosol. They can be taken up during cloud droplet formation (in-cloud scavenging) or washed out during precipitation (below-cloud scavenging). Such compounds including aromatic hydrocarbons and organic nitrogen containing compounds are hazardous to health. In this study, the organic chemical composition of rainwater and aerosol from rain events in León, Spain, is being analysed using high resolution mass spectrometry. Collected rainwater along with high volume and low volume filters from rain events which occurred during spring, summer and winter of 2016 have been selected for analysis. Rainwater samples were prepared using Polymeric Reversed Phase Solid Phase Extraction (SPE) and filters have been extracted in water with and without SPE. Three different SPE polymer based sorbents were tested; one for extracting neutral compounds and two which are more suitable for extracting organic compounds containing sulphate and other polar functional groups. The sorbent for extracting neutral compounds was found to yield a higher number of compounds from the sample extraction than the other two varieties. Kendrick masses, Van Krevelen plots and carbon oxidation states have been investigated to identify compounds and patterns. Preliminary results show a predominance in peaks with O/C ratios between 0.2 and 0.7 and H/C ratios between 1 and 2 in both rain and aerosol samples which indicates substituted aromatic compounds. Cellulose material and fatty acids may also be present. The rain samples also have a

  14. Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

    Science.gov (United States)

    Cho, Yunjo; Jin, Jang Mi; Witt, Matthias; Birdwell, Justin E.; Na, Jeong-Geol; Roh, Nam-Sun; Kim, Sunghwan

    2013-01-01

    Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

  15. The fate of injectant coal in blast furnaces: The origin of extractable materials of high molecular mass in blast furnace carryover dusts

    Energy Technology Data Exchange (ETDEWEB)

    Dong, S.N.; Wu, L.; Paterson, N.; Herod, A.A.; Dugwell, D.R.; Kandiyoti, R. [University of London Imperial College of Science & Technology, London (United Kingdom). Dept. of Chemical Engineering

    2005-07-01

    The aim of the work was to investigate the fate of injectant coal in blast furnaces and the origin of extractable materials in blast furnace carryover dusts. Two sets of samples including injectant coal and the corresponding carryover dusts from a full sized blast furnace and a pilot scale rig have been examined. The samples were extracted using 1-methyl-2-pyrrolidinone (NMP) solvent and the extracts studied by size exclusion chromatography (SEC). The blast furnace carryover dust extracts contained high molecular weight carbonaceous material, of apparent mass corresponding to 10{sup 7}-10{sup 8} u, by polystyrene calibration. In contrast, the feed coke and char prepared in a wire mesh reactor under high temperature conditions did not give any extractable material. Meanwhile, controlled combustion experiments in a high-pressure wire mesh reactor suggest that the extent of combustion of injectant coal in the blast furnace tuyeres and raceways is limited by time of exposure and very low oxygen concentration. It is thus likely that the extractable, soot-like material in the blast furnace dust originated in tars is released by the injectant coal. Our results suggest that the unburned tars were thermally altered during the upward path within the furnace, giving rise to the formation of heavy molecular weight (soot-like) materials.

  16. Determination of Tributyltin in Seafood Based on Magnetic Molecularly Imprinted Polymers Coupled with High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Hua Yang

    2017-01-01

    Full Text Available In this study, Fe3O4 was adopted as a carrier for surface molecular imprinting with two-stage polymerization. First, the functional monomer (methacrylic acid, MAA was modified on the surface of Fe3O4, which was then polymerized with the template molecule (tributyltin, TBT, cross linking agent (ethylene glycol dimethacrylate, EGDMA, and porogen (acetonitrile, hereby successfully preparing Fe3O4@MIPs prone to specifically identify TBT. The physical properties of Fe3O4@MIPs were then characterized, and adsorption and selection capacities were also assessed. Compared with conventional imprinting polymers, this magnetic molecular imprinting polymer (MIP displayed significantly increased and more specific adsorption. Meanwhile, its pretreatment was simpler and faster due to magnetic separation characteristics. Using magnetic MIPs as adsorbents for enrichment and separation, detection limit, recovery rate, and linear range were 1.0 ng g−1, 79.74–95.72%, and 5 ng g−1~1000 ng g−1, respectively, for a number of seafood samples. High-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS was used to analyze Tegillarca granosa, mussels, large yellow croaker, and other specimens, with recovery rates of 79.74–95.72% and RSD of 1.3%–4.7%. Overall, this method has a shorter total analysis time, lower detection limit, and wider linear range and can be more effectively applied to determine MAA in seawater and seafood.

  17. Molecular imaging of banknote and questioned document using solvent-free gold nanoparticle-assisted laser desorption/ionization imaging mass spectrometry.

    Science.gov (United States)

    Tang, Ho-Wai; Wong, Melody Yee-Man; Chan, Sharon Lai-Fung; Che, Chi-Ming; Ng, Kwan-Ming

    2011-01-01

    Direct chemical analysis and molecular imaging of questioned documents in a non/minimal-destructive manner is important in forensic science. Here, we demonstrate that solvent-free gold-nanoparticle-assisted laser desorption/ionization mass spectrometry is a sensitive and minimal destructive method for direct detection and imaging of ink and visible and/or fluorescent dyes printed on banknotes or written on questioned documents. Argon ion sputtering of a gold foil allows homogeneous coating of a thin layer of gold nanoparticles on banknotes and checks in a dry state without delocalizing spatial distributions of the analytes. Upon N(2) laser irradiation of the gold nanoparticle-coated banknotes or checks, abundant ions are desorbed and detected. Recording the spatial distributions of the ions can reveal the molecular images of visible and fluorescent ink printed on banknotes and determine the printing order of different ink which may be useful in differentiating real banknotes from fakes. The method can also be applied to identify forged parts in questioned documents, such as number/writing alteration on a check, by tracing different writing patterns that come from different pens.

  18. 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).

  19. Association of clearance of middle- and large-molecular-weight substance with arterial stiffness and left ventricular mass in children receiving renal replacement therapy.

    Science.gov (United States)

    Özdemir, Kadriye; Yilmaz, Ebru; Dincel, Nida; Bozabali, Sibel; Apaydin, Sukriye; Gun, Zubeyr H; Sozeri, Betul; Mir, Sevgi

    2017-12-01

    The prominent cause of mortality in children receiving dialysis treatment is cardiovascular diseases. Risk factors related to chronic renal disease, are effective in the development of cardiovascular diseases. The aim of study was to investigate cardiovascular system (CVS) involvement for functional and structural alterations in children receiving dialysis, and display any association between cardiovascular morbidity and uremic toxins. 20 dialysis patients and 20 healthy controls were included to the study. Clearance of small, middle and large molecular-weight uremic toxins was evaluated in blood samples collected 30 minutes before (D0) and 2 hour after dialysis (D2), and change value was calculated as D0-D2/D0. Cardiovascular involvement was determined by comparing arterial stiffness, carotid intima-media thickness (CIMT) and Left Ventricular Mass Index (LVMI) with the control group. Four patients receiving hemodialysis and two patients in continuous ambulatory peritoneal dialysis (CAPD) group who have significant differences in all functional and structural parameters were detected. Four dialysis patients with detected cardiovascular disease have distinctively lower beta-2 microglobulin and homocysteine clearances compared to the patients with no CVS involvement. The clearance of middle and large molecular-weight substances should be closely monitored in children receiving dialysis.

  20. Environmentally Friendly Procedure Based on Supercritical Fluid Chromatography and Tandem Mass Spectrometry Molecular Networking for the Discovery of Potent Antiviral Compounds from Euphorbia semiperfoliata.

    Science.gov (United States)

    Nothias, Louis-Félix; Boutet-Mercey, Stéphanie; Cachet, Xavier; De La Torre, Erick; Laboureur, Laurent; Gallard, Jean-François; Retailleau, Pascal; Brunelle, Alain; Dorrestein, Pieter C; Costa, Jean; Bedoya, Luis M; Roussi, Fanny; Leyssen, Pieter; Alcami, José; Paolini, Julien; Litaudon, Marc; Touboul, David

    2017-10-27

    A supercritical fluid chromatography-based targeted purification procedure using tandem mass spectrometry and molecular networking was developed to analyze, annotate, and isolate secondary metabolites from complex plant extract mixture. This approach was applied for the targeted isolation of new antiviral diterpene esters from Euphorbia semiperfoliata whole plant extract. The analysis of bioactive fractions revealed that unknown diterpene esters, including jatrophane esters and phorbol esters, were present in the samples. The purification procedure using semipreparative supercritical fluid chromatography led to the isolation and identification of two new jatrophane esters (13 and 14) and one known (15) and three new 4-deoxyphorbol esters (16-18). The structure and absolute configuration of compound 16 were confirmed by X-ray crystallography. This compound was found to display antiviral activity against Chikungunya virus (EC 50 = 0.45 μM), while compound 15 proved to be a potent and selective inhibitor of HIV-1 replication in a recombinant virus assay (EC 50 = 13 nM). This study showed that a supercritical fluid chromatography-based protocol and molecular networking can facilitate and accelerate the discovery of bioactive small molecules by targeting molecules of interest, while minimizing the use of toxic solvents.

  1. Sequencing Larger Intact Proteins (30-70 kDa) with Activated Ion Electron Transfer Dissociation

    Science.gov (United States)

    Riley, Nicholas M.; Westphall, Michael S.; Coon, Joshua J.

    2018-01-01

    The analysis of intact proteins via mass spectrometry can offer several benefits to proteome characterization, although the majority of top-down experiments focus on proteoforms in a relatively low mass range (AI-ETD) to proteins in the 30-70 kDa range. AI-ETD leverages infrared photo-activation concurrent to ETD reactions to improve sequence-informative product ion generation. This method generates more product ions and greater sequence coverage than conventional ETD, higher-energy collisional dissociation (HCD), and ETD combined with supplemental HCD activation (EThcD). Importantly, AI-ETD provides the most thorough protein characterization for every precursor ion charge state investigated in this study, making it suitable as a universal fragmentation method in top-down experiments. Additionally, we highlight several acquisition strategies that can benefit characterization of larger proteins with AI-ETD, including combination of spectra from multiple ETD reaction times for a given precursor ion, multiple spectral acquisitions of the same precursor ion, and combination of spectra from two different dissociation methods (e.g., AI-ETD and HCD). In all, AI-ETD shows great promise as a method for dissociating larger intact protein ions as top-down proteomics continues to advance into larger mass ranges. [Figure not available: see fulltext.

  2. Thermal deposition of intact tetrairon(III) single-molecule magnets in high-vacuum conditions.

    Science.gov (United States)

    Margheriti, Ludovica; Mannini, Matteo; Sorace, Lorenzo; Gorini, Lapo; Gatteschi, Dante; Caneschi, Andrea; Chiappe, Daniele; Moroni, Riccardo; de Mongeot, Francesco Buatier; Cornia, Andrea; Piras, Federica M; Magnani, Agnese; Sessoli, Roberta

    2009-06-01

    A tetrairon(III) single-molecule magnet is deposited using a thermal evaporation technique in high vacuum. The chemical integrity is demonstrated by time-of-flight secondary ion mass spectrometry on a film deposited on Al foil, while superconducting quantum interference device magnetometry and alternating current susceptometry of a film deposited on a kapton substrate show magnetic properties identical to the pristine powder. High-frequency electron paramagnetic resonance spectra confirm the characteristic behavior for a system with S = 5 and a large Ising-type magnetic anisotropy. All these results indicate that the molecules are not damaged during the deposition procedure keeping intact the single-molecule magnet behavior.

  3. Identification and molecular characterization of 48 kDa calcium binding protein as calreticulin from finger millet (Eleusine coracana) using peptide mass fingerprinting and transcript profiling.

    Science.gov (United States)

    Singh, Manoj; Metwal, Mamta; Kumar, Vandana A; Kumar, Anil

    2016-01-30

    Attempts were made to identify and characterize the calcium binding proteins (CaBPs) in grain filling stages of finger millet using proteomics, bioinformatics and molecular approaches. A distinctly observed blue color band of 48 kDa stained by Stains-all was eluted and analyzed as calreticulin (CRT) using nano liquid chromatography-tandem mass spectrometry (nano LC-MS). Based on the top hits of peptide mass fingerprinting results, conserved primers were designed for isolation of the CRT gene from finger millet using calreticulin sequences of different cereals. The deduced nucleotide sequence analysis of 600 bp amplicon showed up to 91% similarity with CRT gene(s) of rice and other plant species and designated as EcCRT1. Transcript profiling of EcCRT1 showed different levels of relative expression at different stages of developing spikes. The higher expression of EcCRT1 transcripts and protein were observed in later stages of developing spikes which might be due to greater translational synthesis of EcCRT1 protein during seed maturation in finger millet. Preferentially higher synthesis of this CaBP during later stages of grain filling may be responsible for the sequestration of calcium in endoplasmic reticulum of finger millet grains. © 2015 Society of Chemical Industry.

  4. Evaluation of different hydrophilic stationary phases for the simultaneous determination of iminosugars and other low molecular weight carbohydrates in vegetable extracts by liquid chromatography tandem mass spectrometry.

    Science.gov (United States)

    Rodríguez-Sánchez, S; Quintanilla-López, J E; Soria, A C; Sanz, M L

    2014-11-01

    Iminosugars are considered potential drug candidates for the treatment of several diseases, mainly as a result of their α-glycosidase inhibition properties. A method by hydrophilic interaction liquid chromatography tandem mass spectrometry has been optimized for the first time for the simultaneous determination of complex mixtures of bioactive iminosugars and other low molecular weight carbohydrates (LMWC) in vegetable extracts. Three hydrophilic stationary phases (sulfoalkylbetaine zwitterionic, polyhydroxyethyl aspartamide and ethylene bridge hybrid (BEH) with trifunctionally bonded amide) were compared under both basic and acidic conditions. The best sensitivity (limits of detection between 0.025 and 0.28ngmL -1 ) and overall chromatographic performance in terms of resolution, peak width and analysis time were obtained with the BEH amide column using 0.1% ammonium hydroxide as a mobile phase additive. The optimized method was applied to the analysis of extracts of hyacinth bulbs, buckwheat seeds and mulberry leaves. Iminosugar and other LMWC structures were tentatively assigned by their high resolution daughter ions mass spectra. Several iminosugars such as glycosyl-fagomine in mulberry extract were also described for the first time. Among the extracts analysed, mulberry showed the widest diversity of iminosugars, whereas the highest content of them was found in hyacinth bulb (2.5mgg -1 ) followed by mulberry (1.95 mgg -1 ). Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Low-molecular weight protein profiling of genetically modified maize using fast liquid chromatography electrospray ionization and time-of-flight mass spectrometry.

    Science.gov (United States)

    Koc, Anna; Cañuelo, Ana; Garcia-Reyes, Juan F; Molina-Diaz, Antonio; Trojanowicz, Marek

    2012-06-01

    In this work, the use of liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC-TOFMS) has been evaluated for the profiling of relatively low-molecular weight protein species in both genetically modified (GM) and non-GM maize. The proposed approach consisted of a straightforward sample fractionation with different water and ethanol-based buffer solutions followed by separation and detection of the protein species using liquid chromatography with a small particle size (1.8 μm) C(18) column and electrospray-time-of-flight mass spectrometry detection in the positive ionization mode. The fractionation of maize reference material containing different content of transgenic material (from 0 to 5% GM) led to five different fractions (albumins, globulins, zeins, zein-like glutelins, and glutelins), all of them containing different protein species (from 2 to 52 different species in each fraction). Some relevant differences in the quantity and types of protein species were observed in the different fractions of the reference material (with different GM contents) tested, thus revealing the potential use of the proposed approach for fast protein profiling and to detect tentative GMO markers in maize. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Profiling analysis of low molecular weight heparins by multiple heart-cutting two dimensional chromatography with quadruple time-of-flight mass spectrometry.

    Science.gov (United States)

    Ouyang, Yilan; Zeng, Yangyang; Rong, Yinxiu; Song, Yue; Shi, Lv; Chen, Bo; Yang, Xinlei; Xu, Naiyu; Linhardt, Robert J; Zhang, Zhenqing

    2015-09-01

    Low molecular weight heparins (LMWHs) are polydisperse and microheterogenous mixtures of polysaccharides used as anticoagulant drugs. Profiling analysis is important for obtaining deeper insights into the structure of LMWHs. Previous oligosaccharide mapping methods are relatively low resolution and are unable to show an entire picture of the structural complexity of LMWHs. In the current study a profiling method was developed relying on multiple heart-cutting, two-dimensional, ultrahigh performance liquid chromatography with quadruple time-of-flight mass spectrometry. This represents an efficient, automated, and robust approach for profiling LMWHs. Using size-exclusion chromatography and ion-pairing reversed-phase chromatography in a two-dimensional separation, LMW components of different sizes and LMW components of the same size but with different charges and polarities can be resolved, providing a more complete picture of a LMWH. Structural information on each component was then obtained with quadrupole time-of-flight mass spectrometry. More than 80 and 120 oligosaccharides were observed and unambiguously assigned from the LMWHs, nadroparin and enoxaparin, respectively. This method might be useful for quality control of LMWHs and as a powerful tool for heparin-related glycomics.

  7. Assessment of geomechanical properties of intact Opalinus Clay - Expert report

    International Nuclear Information System (INIS)

    Amann, F.; Vogelhuber, M.

    2015-11-01

    This comprehensive report published by the Swiss Federal Nuclear Safety Inspectorate ENSI presents an expert report published on the assessment of the geomechanical properties of intact Opalinus Clay. This review report addresses the conceptual constitutive framework for repositories in Opalinus Clay. The author addresses the geomechanical fundamentals that are necessary in order to adequately judge experiments on intact Opalinus Clay and the interpretation of the results. The report assesses in detail the various test series on intact Opalinus Clay carried out along with the interpretations made by experts and NAGRA. Further assessments are quoted including those on sample geometries tested, effective strength properties, undrained shear strength properties and elastic properties. The results of work done by other experts are also presented and discussed. The report is completed with a list of relevant literature

  8. Assessment of geomechanical properties of intact Opalinus Clay - Expert report

    Energy Technology Data Exchange (ETDEWEB)

    Amann, F. [Eidgenössische Technische Hochschule ETHZ, Zürich (Switzerland); Vogelhuber, M. [Dr. von Moos AG, Geotechnisches Büro, Zürich (Switzerland)

    2015-11-15

    This comprehensive report published by the Swiss Federal Nuclear Safety Inspectorate ENSI presents an expert report published on the assessment of the geomechanical properties of intact Opalinus Clay. This review report addresses the conceptual constitutive framework for repositories in Opalinus Clay. The author addresses the geomechanical fundamentals that are necessary in order to adequately judge experiments on intact Opalinus Clay and the interpretation of the results. The report assesses in detail the various test series on intact Opalinus Clay carried out along with the interpretations made by experts and NAGRA. Further assessments are quoted including those on sample geometries tested, effective strength properties, undrained shear strength properties and elastic properties. The results of work done by other experts are also presented and discussed. The report is completed with a list of relevant literature.

  9. Prototypic and Arkypallidal Neurons in the Dopamine-Intact External Globus Pallidus

    Science.gov (United States)

    Abdi, Azzedine; Mallet, Nicolas; Mohamed, Foad Y.; Sharott, Andrew; Dodson, Paul D.; Nakamura, Kouichi C.; Suri, Sana; Avery, Sophie V.; Larvin, Joseph T.; Garas, Farid N.; Garas, Shady N.; Vinciati, Federica; Morin, Stéphanie; Bezard, Erwan

    2015-01-01

    Studies in dopamine-depleted rats indicate that the external globus pallidus (GPe) contains two main types of GABAergic projection cell; so-called “prototypic” and “arkypallidal” neurons. Here, we used correlative anatomical and electrophysiological approaches in rats to determine whether and how this dichotomous organization applies to the dopamine-intact GPe. Prototypic neurons coexpressed the transcription factors Nkx2-1 and Lhx6, comprised approximately two-thirds of all GPe neurons, and were the major GPe cell type innervating the subthalamic nucleus (STN). In contrast, arkypallidal neurons expressed the transcription factor FoxP2, constituted just over one-fourth of GPe neurons, and innervated the striatum but not STN. In anesthetized dopamine-intact rats, molecularly identified prototypic neurons fired at relatively high rates and with high regularity, regardless of brain state (slow-wave activity or spontaneous activation). On average, arkypallidal neurons fired at lower rates and regularities than prototypic neurons, and the two cell types could be further distinguished by the temporal coupling of their firing to ongoing cortical oscillations. Complementing the activity differences observed in vivo, the autonomous firing of identified arkypallidal neurons in vitro was slower and more variable than that of prototypic neurons, which tallied with arkypallidal neurons displaying lower amplitudes of a “persistent” sodium current important for such pacemaking. Arkypallidal neurons also exhibited weaker driven and rebound firing compared with prototypic neurons. In conclusion, our data support the concept that a dichotomous functional organization, as actioned by arkypallidal and prototypic neurons with specialized molecular, structural, and physiological properties, is fundamental to the operations of the dopamine-intact GPe. PMID:25926446

  10. Novel molecular-level evidence of iodine binding to natural organic matter from Fourier transform ion cyclotron resonance mass spectrometry

    International Nuclear Information System (INIS)

    Xu, Chen; Chen, Hongmei; Sugiyama, Yuko; Zhang, Saijin; Li, Hsiu-Ping; Ho, Yi-Fang; Chuang, Chia-ying; Schwehr, Kathleen A.; Kaplan, Daniel I.; Yeager, Chris; Roberts, Kimberly A.; Hatcher, Patrick G.; Santschi, Peter H.

    2013-01-01

    Major fractions of radioiodine ( 129 I) are associated with natural organic matter (NOM) in the groundwater and surface soils of the Savannah River Site (SRS). Electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was applied to elucidate the interactions between inorganic iodine species (iodide and iodate) and a fulvic acid (FA) extracted from a SRS surface soil. Iodate is likely reduced to reactive iodine species by the lignin- and tannin-like compounds or the carboxylic-rich alicyclic molecules (CRAM), during which condensed aromatics and lignin-like compounds were generated. Iodide is catalytically oxidized into reactive iodine species by peroxides, while FA is oxidized by peroxides into more aliphatic and less aromatic compounds. Only 9% of the total identified organo-iodine compounds derived from molecules originally present in the FA, whereas most were iodine binding to newly-produced compounds. The resulting iodinated molecules were distributed in three regions in the van Krevelen diagrams, denoting unsaturated hydrocarbons, lignin and protein. Moreover, characteristics of these organo-iodine compounds, such as their relatively low O/C ratios ( 2 or -HNCOR groups and a ring-activating functionality to favor the electrophilic substitution. The ESI-FTICR-MS technique provides novel evidence to better understand the reactivity and scavenging properties of NOM towards radioiodine and possible influence of NOM on 129 I migration. Highlights: ► IO 3 − reduced by lignin-, tannin-like compounds/carboxylic-rich alicyclic molecules ► Condensed aromatic and lignin-like compounds generated after iodate-iodination ► Aliphatic and less aromatic compounds formed after iodide-iodination ► Organo-iodine identified as unsaturated hydrocarbons, lignin and protein ► Organo-iodine with low O/C ratios imply less environmental mobility

  11. Comprehensive speciation of low-molecular weight selenium metabolites in mustard seeds using HPLC-electrospray linear trap/Orbitrap tandem mass spectrometry.

    Science.gov (United States)

    Ouerdane, Laurent; Aureli, Federica; Flis, Paulina; Bierla, Katarzyna; Preud'homme, Hugues; Cubadda, Francesco; Szpunar, Joanna

    2013-09-01

    An analytical methodology based on high-resolution high mass accuracy electrospray ionization (ESI) tandem MS assisted by Se-specific detection using inductively coupled plasma mass spectrometry (ICP MS) was developed for speciation of selenium (Se) in seeds of black mustard (Brassica nigra) grown on Se-rich soil. Size-exclusion LC-ICP MS allowed the determination of the Se distribution according to the molecular mass and the control of the species stability during extraction. The optimization of hydrophilic interaction of LC and cation-exchange HPLC resulted in analytical conditions making it possible to detect and characterize over 30 Se species using ESI MS, including a number of minor (<0.5%) metabolites. Selenoglucosinolates were found to be the most important class of species accounting for at least 15% of the total Se present and over 50% of all the metabolites. They were found particularly unstable during aqueous extraction leading to the loss of Se by volatilization as methylselenonitriles and methylselenoisothiocyanates identified using gas chromatography (GC) with the parallel ICP MS and atmospheric pressure chemical ionization (APCI) MS/MS detection. However, selenoglucosinolates could be efficiently recovered by extraction with 70% methanol. Other classes of identified species included selenoamino acids, selenosugars, selenosinapine and selenourea derivatives. The three types of reactions leading to the formation of selenometabolites were: the Se-S substitution in the metabolic pathway, oxidative reactions of -SeH groups with endogenous biomolecules, and chemical reactions, e.g., esterification, of Se-containing molecules and other biomolecules through functional groups not involving Se.

  12. Molecular Characterization and Reactivity of Dissolved Organic Matter by High Resolution Nanospray Ionization Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS)

    Science.gov (United States)

    Sleighter, R. L.; Hatcher, S. A.; Hatcher, P. G.

    2006-12-01

    The ultrahigh resolving power of FTICR-MS allows for the intense characterization of dissolved organic matter (DOM). DOM is the largest reactive component of the global carbon cycle, and an improved understanding of its composition is necessary to determine the transport and eventual fate of pollutants. The seasonal and spatial variations in DOM composition are investigated by taking surface water samples from five different sampling sites, four times a year. Water sampling begins at the Dismal Swamp in North Carolina, continues north up the Elizabeth River to the Chesapeake Bay, and concludes approximately ten miles off the coast in the Atlantic Ocean. DOM was extracted from the water samples using C18 extraction disks and were prepared in 50:50 methanol:water. Ammonium hydroxide was added prior to nanospray in order to solubilize the DOM as well as to increase the ionization efficiency. The samples were continuously infused into the Apollo II ion source with an Advion TriVersa NanoMate system of a Bruker 12 Tesla Apex QE FTICR-MS with resolving powers exceeding 400,000. All samples were analyzed in negative ion mode and were externally and internally calibrated prior to data analysis. Our DOM mass spectra consist of a multitude of peaks spanning the range of 200-850 m/z. Complexity is apparent from the detection of up to 20 peaks per nominal mass at nearly every mass throughout that range. A molecular formula calculator generated molecular formula matches from which van Krevelen plots were constructed for characterization purposes. A wide range of molecules were observed each containing oxygen, sulfur and nitrogen functional groups. We utilize the van Krevelen diagram to assist in clustering the molecules according to their functional group compositions. To test the hypothesis that formation of adducts to DOM serve to protect peptides from bacterial degradation, microcosm experiments were performed with a small isotopically enriched peptide, GGGR. This peptide

  13. Automated Online Solid-Phase Derivatization for Sensitive Quantification of Endogenous S-Nitrosoglutathione and Rapid Capture of Other Low-Molecular-Mass S-Nitrosothiols.

    Science.gov (United States)

    Wang, Xin; Garcia, Carlos T; Gong, Guanyu; Wishnok, John S; Tannenbaum, Steven R

    2018-02-06

    S-Nitrosothiols (RSNOs) constitute a circulating endogenous reservoir of nitric oxide and have important biological activities. In this study, an online coupling of solid-phase derivatization (SPD) with liquid chromatography-mass spectrometry (LC-MS) was developed and applied in the analysis of low-molecular-mass RSNOs. A derivatizing-reagent-modified polymer monolithic column was prepared and adapted for online SPD-LC-MS. Analytes from the LC autosampler flowed through the monolithic column for derivatization and then directly into the LC-MS for analysis. This integration of the online derivatization, LC separation, and MS detection facilitated system automation, allowing rapid, laborsaving, and sensitive detection of RSNOs. S-Nitrosoglutathione (GSNO) was quantified using this automated online method with good linearity (R 2 = 0.9994); the limit of detection was 0.015 nM. The online SPD-LC-MS method has been used to determine GSNO levels in mouse samples, 138 ± 13.2 nM of endogenous GSNO was detected in mouse plasma. Besides, the GSNO concentrations in liver (64.8 ± 11.3 pmol/mg protein), kidney (47.2 ± 6.1 pmol/mg protein), heart (8.9 ± 1.8 pmol/mg protein), muscle (1.9 ± 0.3 pmol/mg protein), hippocampus (5.3 ± 0.9 pmol/mg protein), striatum (6.7 ± 0.6 pmol/mg protein), cerebellum (31.4 ± 6.5 pmol/mg protein), and cortex (47.9 ± 4.6 pmol/mg protein) were also successfully quantified. When the derivatization was performed within 8 min, followed by LC-MS detection, samples could be rapidly analyzed compared with the offline manual method. Other low-molecular-mass RSNOs, such as S-nitrosocysteine and S-nitrosocysteinylglycine, were captured by rapid precursor-ion scanning, showing that the proposed method is a potentially powerful tool for capture, identification, and quantification of RSNOs in biological samples.

  14. Novel molecular-level evidence of iodine binding to natural organic matter from Fourier transform ion cyclotron resonance mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Chen, E-mail: xuchen66@tamu.edu [Laboratory for Environmental and Oceanographic Research, Department of Marine Sciences, Texas A and M University, Building 3029, Galveston, TX 77551 (United States); Chen, Hongmei [Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States); Sugiyama, Yuko [Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States); University of Hyogo, 1-1-12, Shinzaike-honcho, Himeji, Hyogo 670-0092 (Japan); Zhang, Saijin; Li, Hsiu-Ping; Ho, Yi-Fang; Chuang, Chia-ying; Schwehr, Kathleen A. [Laboratory for Environmental and Oceanographic Research, Department of Marine Sciences, Texas A and M University, Building 3029, Galveston, TX 77551 (United States); Kaplan, Daniel I. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Yeager, Chris [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Roberts, Kimberly A. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Hatcher, Patrick G. [Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA 23529 (United States); Santschi, Peter H. [Laboratory for Environmental and Oceanographic Research, Department of Marine Sciences, Texas A and M University, Building 3029, Galveston, TX 77551 (United States)

    2013-04-01

    Major fractions of radioiodine ({sup 129}I) are associated with natural organic matter (NOM) in the groundwater and surface soils of the Savannah River Site (SRS). Electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was applied to elucidate the interactions between inorganic iodine species (iodide and iodate) and a fulvic acid (FA) extracted from a SRS surface soil. Iodate is likely reduced to reactive iodine species by the lignin- and tannin-like compounds or the carboxylic-rich alicyclic molecules (CRAM), during which condensed aromatics and lignin-like compounds were generated. Iodide is catalytically oxidized into reactive iodine species by peroxides, while FA is oxidized by peroxides into more aliphatic and less aromatic compounds. Only 9% of the total identified organo-iodine compounds derived from molecules originally present in the FA, whereas most were iodine binding to newly-produced compounds. The resulting iodinated molecules were distributed in three regions in the van Krevelen diagrams, denoting unsaturated hydrocarbons, lignin and protein. Moreover, characteristics of these organo-iodine compounds, such as their relatively low O/C ratios (< 0.2 or < 0.4) and yet some degree of un-saturation close to that of lignin, have multiple important environmental implications concerning possibly less sterically-hindered aromatic ring system for iodine to get access to and a lower hydrophilicity of the molecules thus to retard their migration in the natural aquatic systems. Lastly, ∼ 69% of the identified organo-iodine species contains nitrogen, which is presumably present as -NH{sub 2} or -HNCOR groups and a ring-activating functionality to favor the electrophilic substitution. The ESI-FTICR-MS technique provides novel evidence to better understand the reactivity and scavenging properties of NOM towards radioiodine and possible influence of NOM on {sup 129}I migration. Highlights: ► IO{sub 3}{sup

  15. Bioavailability and in vivo metabolism of intact glucosinolates

    DEFF Research Database (Denmark)

    Sørensen, Jens Christian; Frandsen, Heidi Blok; Jensen, Søren Krogh

    2016-01-01

    Health benefits associated with consumption of cruciferous vegetables have received considerable attention with a hitherto focus on the role and bioactivity of glucosinolate degradation products. We investigated the in vivo metabolism of intact glucosinolates by following their fate in digesta an...

  16. Intact collagen and atelocollagen sponges: Characterization and ESEM observation

    International Nuclear Information System (INIS)

    Ruozi, Barbara; Tosi, Giovanni; Leo, Eliana; Parma, Bruna; Vismara, Susanna; Forni, Flavio; Vandelli, Maria Angela

    2007-01-01

    In this study we have investigated the chemical-physical and morphological properties of intact and atelocollagen sponges used for tissue engineering. The porous sponges were prepared by lyophilization and their physico-chemical characteristics (water binding capacity, denaturing temperature, amino group content) were investigated. Considering the importance of the 'in vivo' interactions between these sponges and the tissue, our attention was addressed (a) to clarify the relationships between the morphology and the amount of water absorbed and (b) to evaluate the influence of pepsin-alkaline treatment on the reorganization of the atelocollagen fibres. Conventional scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM) were employed to study the morphology and wetting behaviour of the intact and atelocollagen sponges. The observations by SEM indicated remarkable differences both in the structure and dimension of the pores between intact and atelocollagen sponges. At the data are related to a different water binding capacity. However, the ESEM observations, achieved by changing the relative humidity in the operative chamber, demonstrated that the water adsorbed can be removed with major difficulty from atelocollagen sponges than from intact ones

  17. Phosphorylation of intact erythrocytes in human muscular dystrophy

    International Nuclear Information System (INIS)

    Johnson, R.M.; Nigro, M.

    1986-01-01

    The uptake of exogenous 32 Pi into the membrane proteins of intact erythrocytes was measured in 8 patients with Duchenne muscular dystrophy. No abnormalities were noted after autoradiographic analysis. This contrasts with earlier results obtained when isolated membranes were phosphorylated with gamma-[ 32 P]ATP, and suggests a possible reinterpretation of those experiments

  18. Behavior Management Style of Single Parents and Intact Families.

    Science.gov (United States)

    Smith, Douglas K.; And Others

    Studies examining the behavior management styles of parents as a function of family intactness and parent employment status are lacking. To assess parental style of behavior management, the Parental Management Questionnaire (PMQ) was completed by 1,957 parents of elementary school children (50% response rate). The PMQ is based on Aronfreed's…

  19. Non-intact zona improves development of murine preimplantation ...

    African Journals Online (AJOL)

    ajl5

    2012-09-25

    Sep 25, 2012 ... 2College of Animal Science and Technology, Northwest A & F University, Yangling, ... Key words: Mouse, non-intact zona embryos, adenovirus vector with green fluorescent protein (pAd-GFP), .... Based on microscopic examination, the ZP of some ..... permeable structure of ZP that allowed penetration of.

  20. Pharmacokinetics of erythropoietin in intact and anephric dogs

    International Nuclear Information System (INIS)

    Fu, J.S.; Lertora, J.J.; Brookins, J.; Rice, J.C.; Fisher, J.W.

    1988-01-01

    The present studies were performed to determine the pharmacokinetic parameters of erythropoietin in intact and anephric dogs by use of unlabeled crude native erythropoietin (nEp) and iodine 125-labeled purified recombinant erythropoietin (rEp) given by intravenous infusion for 15 minutes. Sephadex G-75 gel filtration was used to confirm that the 125I-rEp molecule remained iodinated in dog plasma during the 24-hour period of these studies. The plasma disappearance of erythropoietin conformed to a biexponential equation for both nEp and 125I-rEp, with the central compartment being larger than the peripheral compartment. The mean distribution half-life of 75.3 +/- 21.2 minutes for nEp was significantly (p less than 0.05) longer than that of 125I-rEp (23.7 +/- 5.0 minutes) in intact dogs. The intercompartmental clearance (CIic) for nEp (0.018 +/- 0.006 L/kg/hr) was significantly smaller than that of 125I-rEp (0.068 +/- 0.018 L/kg/hr) in intact dogs (p less than 0.05). There were no significant differences in apparent volume of distribution, elimination half-life, and elimination clearance (CIe) for nEp and rEp in intact dogs. The mean elimination half-life for 125I-rEp in intact dogs (9.0 +/- 0.6 hours) and anephric dogs (13.8 +/- 1.4 hours) was significantly different (p less than 0.05). The CIe for 125I-rEp in anephric dogs (0.008 +/- 0.001 L/kg/hr) was significantly (p less than 0.05) smaller than that of 125I-rEp in intact dogs (0.011 +/- 0.001 L/kg/hr). There were no significant differences in apparent volume of distribution, distribution half-life, and CIic for 125I-rEp in intact and anephric dogs

  1. Adnexal mass in tubal pregnancy

    International Nuclear Information System (INIS)

    Lee, Hee Jung; Kim, Jung Sik; Chu, Yang Ku

    1993-01-01

    Off the evaluation of clinical significance and pathologic correlation of echogenic adnexal mass in tubal pregnancy, which is separated from ipsilateral ovary, we performed a retrospective analysis of 15 proved tubal pregnancies. All showed hematosalpinx containing blood coagulum and chorionic villi with intact fallopian tube.The echogenicity of the adnexal mass was considered to represent the nonclotted or clotted blood within the fallopian tube. We conclude that the discrete, echogenic adnexal mass is the suggestive finding of unrupturedtubal pregnancy

  2. Threats to intact tropical peatlands and opportunities for their conservation.

    Science.gov (United States)

    Roucoux, K H; Lawson, I T; Baker, T R; Del Castillo Torres, D; Draper, F C; Lähteenoja, O; Gilmore, M P; Honorio Coronado, E N; Kelly, T J; Mitchard, E T A; Vriesendorp, C F

    2017-12-01

    Large, intact areas of tropical peatland are highly threatened at a global scale by the expansion of commercial agriculture and other forms of economic development. Conserving peatlands on a landscape scale, with their hydrology intact, is of international conservation importance to preserve their distinctive biodiversity and ecosystem services and maintain their resilience to future environmental change. We explored threats to and opportunities for conserving remaining intact tropical peatlands; thus, we excluded peatlands of Indonesia and Malaysia, where extensive deforestation, drainage, and conversion to plantations means conservation in this region can protect only small fragments of the original ecosystem. We focused on a case study, the Pastaza-Marañón Foreland Basin (PMFB) in Peru, which is among the largest known intact tropical peatland landscapes in the world and is representative of peatland vulnerability. Maintenance of the hydrological conditions critical for carbon storage and ecosystem function of peatlands is, in the PMFB, primarily threatened by expansion of commercial agriculture linked to new transport infrastructure that is facilitating access to remote areas. There remain opportunities in the PMFB and elsewhere to develop alternative, more sustainable land-use practices. Although some of the peatlands in the PMFB fall within existing legally protected areas, this protection does not include the most carbon-dense (domed pole forest) areas. New carbon-based conservation instruments (e.g., REDD+, Green Climate Fund), developing markets for sustainable peatland products, transferring land title to local communities, and expanding protected areas offer pathways to increased protection for intact tropical peatlands in Amazonia and elsewhere, such as those in New Guinea and Central Africa which remain, for the moment, broadly beyond the frontier of commercial development. © 2017 The Authors. Conservation Biology published by Wiley Periodicals, Inc

  3. Conformational sensitivity of conjugated poly(ethylene oxide)-poly(amidoamine) molecules to cations adducted upon electrospray ionization – A mass spectrometry, ion mobility and molecular modeling study

    Energy Technology Data Exchange (ETDEWEB)

    Tintaru, Aura [Aix-Marseille Université – CNRS, UMR 7273, Institut de Chimie Radicalaire, Marseille (France); Chendo, Christophe [Aix-Marseille Université – CNRS, FR 1739, Fédération des Sciences Chimiques de Marseille, Spectropole, Marseille (France); Wang, Qi [Aix-Marseille Université – CNRS, UMR 6114, Centre Interdisciplinaire de Nanosciences de Marseille, Marseille (France); Viel, Stéphane [Aix-Marseille Université – CNRS, UMR 7273, Institut de Chimie Radicalaire, Marseille (France); Quéléver, Gilles; Peng, Ling [Aix-Marseille Université – CNRS, UMR 6114, Centre Interdisciplinaire de Nanosciences de Marseille, Marseille (France); Posocco, Paola [University of Trieste, Molecular Simulation Engineering (MOSE) Laboratory, Department of Engineering and Architecture (DEA), Trieste (Italy); National Interuniversity Consortium for Material Science and Technology (INSTM), Research Unit MOSE-DEA, University of Trieste, Trieste (Italy); Pricl, Sabrina, E-mail: sabrina.pricl@di3.units.it [University of Trieste, Molecular Simulation Engineering (MOSE) Laboratory, Department of Engineering and Architecture (DEA), Trieste (Italy); National Interuniversity Consortium for Material Science and Technology (INSTM), Research Unit MOSE-DEA, University of Trieste, Trieste (Italy); Charles, Laurence, E-mail: laurence.charles@univ-amu.fr [Aix-Marseille Université – CNRS, UMR 7273, Institut de Chimie Radicalaire, Marseille (France)

    2014-01-15

    Graphical abstract: -- Highlights: •ESI-MS/MS, IMS and molecular modeling were combined to study PEO-PAMAM conformation. •Protonated and lithiated molecules were studied, with charge states from 2 to 4. •Protonation mostly occurred on PAMAM, with PEO units enclosing the protonated group. •Lithium adduction on PEO units lead to more expanded conformations. •Charge location strongly influenced PEO-PAMAM dissociation behavior. -- Abstract: Tandem mass spectrometry and ion mobility spectrometry experiments were performed on multiply charged molecules formed upon conjugation of a poly(amidoamine) (PAMAM) dendrimer with a poly(ethylene oxide) (PEO) linear polymer to evidence any conformational modification as a function of their charge state (2+ to 4+) and of the adducted cation (H{sup +}vs Li{sup +}). Experimental findings were rationalized by molecular dynamics simulations. The G0 PAMAM head-group could accommodate up to three protons, with protonated terminal amine group enclosed in a pseudo 18-crown-6 ring formed by the PEO segment. This particular conformation enabled a hydrogen bond network which allowed long-range proton transfer to occur during collisionally activated dissociation. In contrast, lithium adduction was found to mainly occur onto oxygen atoms of the polyether, each Li{sup +} cation being coordinated by a 12-crown-4 pseudo structure. As a result, for the studied polymeric segment (M{sub n} = 1500 g mol{sup −1}), PEO-PAMAM hybrid molecules exhibited a more expanded shape when adducted to lithium as compared to proton.

  4. Highly sensitive determination of polycyclic aromatic hydrocarbons in ambient air dust by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction

    Energy Technology Data Exchange (ETDEWEB)

    Krupadam, Reddithota J.; Bhagat, Bhagyashree; Khan, Muntazir S. [National Environmental Engineering Research Institute, Nagpur (India)

    2010-08-15

    A method based on solid-phase extraction with a molecularly imprinted polymer (MIP) has been developed to determine five probable human carcinogenic polycyclic aromatic hydrocarbons (PAHs) in ambient air dust by gas chromatography-mass spectrometry (GC-MS). Molecularly imprinted poly(vinylpyridine-co-ethylene glycol dimethacrylate) was chosen as solid-phase extraction (SPE) material for PAHs. The conditions affecting extraction efficiency, for example surface properties, concentration of PAHs, and equilibration times were evaluated and optimized. Under optimum conditions, pre-concentration factors for MIP-SPE ranged between 80 and 93 for 10 mL ambient air dust leachate. PAHs recoveries from MIP-SPE after extraction from air dust were between 85% and 97% and calibration graphs of the PAHs showed a good linearity between 10 and 1000 ng L{sup -1} (r=0.99). The extraction efficiency of MIP for PAHs was compared with that of commercially available SPE materials - powdered activated carbon (PAC) and polystyrene-divinylbenzene resin (XAD) - and it was shown that the extraction capacity of the MIP was better than that of the other two SPE materials. Organic matter in air dust had no effect on MIP extraction, which produced a clean extract for GC-MS analysis. The detection limit of the method proposed in this article is 0.15 ng L{sup -1} for benzo[a]pyrene, which is a marker molecule of air pollution. The method has been applied to the determination of probable carcinogenic PAHs in air dust of industrial zones and satisfactory results were obtained. (orig.)

  5. Highly sensitive determination of polycyclic aromatic hydrocarbons in ambient air dust by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction.

    Science.gov (United States)

    Krupadam, Reddithota J; Bhagat, Bhagyashree; Khan, Muntazir S

    2010-08-01

    A method based on solid--phase extraction with a molecularly imprinted polymer (MIP) has been developed to determine five probable human carcinogenic polycyclic aromatic hydrocarbons (PAHs) in ambient air dust by gas chromatography-mass spectrometry (GC-MS). Molecularly imprinted poly(vinylpyridine-co-ethylene glycol dimethacrylate) was chosen as solid-phase extraction (SPE) material for PAHs. The conditions affecting extraction efficiency, for example surface properties, concentration of PAHs, and equilibration times were evaluated and optimized. Under optimum conditions, pre-concentration factors for MIP-SPE ranged between 80 and 93 for 10 mL ambient air dust leachate. PAHs recoveries from MIP-SPE after extraction from air dust were between 85% and 97% and calibration graphs of the PAHs showed a good linearity between 10 and 1000 ng L(-1) (r = 0.99). The extraction efficiency of MIP for PAHs was compared with that of commercially available SPE materials--powdered activated carbon (PAC) and polystyrene-divinylbenzene resin (XAD)--and it was shown that the extraction capacity of the MIP was better than that of the other two SPE materials. Organic matter in air dust had no effect on MIP extraction, which produced a clean extract for GC-MS analysis. The detection limit of the method proposed in this article is 0.15 ng L(-1) for benzo[a]pyrene, which is a marker molecule of air pollution. The method has been applied to the determination of probable carcinogenic PAHs in air dust of industrial zones and satisfactory results were obtained.

  6. Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level.

    Science.gov (United States)

    Grabowsky, Jana; Streibel, Thorsten; Sklorz, Martin; Chow, Judith C; Watson, John G; Mamakos, Athanasios; Zimmermann, Ralf

    2011-12-01

    The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong

  7. Electrophoretic extraction of low molecular weight cationic analytes from sodium dodecyl sulfate containing sample matrices for their direct electrospray ionization mass spectrometry.

    Science.gov (United States)

    Kinde, Tristan F; Lopez, Thomas D; Dutta, Debashis

    2015-03-03

    While the use of sodium dodecyl sulfate (SDS) in separation buffers allows efficient analysis of complex mixtures, its presence in the sample matrix is known to severely interfere with the mass-spectrometric characterization of analyte molecules. In this article, we report a microfluidic device that addresses this analytical challenge by enabling inline electrospray ionization mass spectrometry (ESI-MS) of low molecular weight cationic samples prepared in SDS containing matrices. The functionality of this device relies on the continuous extraction of analyte molecules into an SDS-free solvent stream based on the free-flow zone electrophoresis (FFZE) technique prior to their ESI-MS analysis. The reported extraction was accomplished in our current work in a glass channel with microelectrodes fabricated along its sidewalls to realize the desired electric field. Our experiments show that a key challenge to successfully operating such a device is to suppress the electroosmotically driven fluid circulations generated in its extraction channel that otherwise tend to vigorously mix the liquid streams flowing through this duct. A new coating medium, N-(2-triethoxysilylpropyl) formamide, recently demonstrated by our laboratory to nearly eliminate electroosmotic flow in glass microchannels was employed to address this issue. Applying this surface modifier, we were able to efficiently extract two different peptides, human angiotensin I and MRFA, individually from an SDS containing matrix using the FFZE method and detect them at concentrations down to 3.7 and 6.3 μg/mL, respectively, in samples containing as much as 10 mM SDS. Notice that in addition to greatly reducing the amount of SDS entering the MS instrument, the reported approach allows rapid solvent exchange for facilitating efficient analyte ionization desired in ESI-MS analysis.

  8. [Chromatographic mass spectrometric determination of low-molecular-weight aromatic compounds of microbial origin in the serum from patients with sepsis].

    Science.gov (United States)

    Beloborodova, N V; Arkhipova, A S; Beloborodov, D M; Boĭko, N B; Mel'ko, A I; Olenin, A Iu

    2006-02-01

    The investigation quantitatively determined the content of low-molecular-weight aromatic compounds of microbial origin in the sera of 34 individuals by chromatographic mass spectrometry. An "Agilent Technogies 6890N" gas chromatograph with a 5973 mass selective detector was applied; chromatographic separation of components was effected on an Hp-5MS quartz capillary column. Aromatic small molecules originating from microbes (SMOM) were determined in the sera of 7 patients with sepsis. The diagnosis of sepsis was documented by the presence of the systemic inflammation syndrome and by that of bacteriemia and/or artificial ventilation-associated pneumonia along with the level of procalcitonin of higher than 10 ng/ml. The levels of aromatic SMOM were compared in 10 healthy donors, 8 preoperative cardiosurgical patients, and 9 patients with different abnormalities without sepsis treated in an intensive care unit (ICU). Serum phenylacetic and 3-phenylpropionic acids were found to be prevalent in the healthy donors and postoperative cardiosurgical patients. In ICU patients with different complications without sepsis, more than half the compounds under study were undetectable, the others were found in very low concentrations, which may be accounted for by antibiotic therapy. At the same time, almost the whole spectrum of the test compounds (other than 3-phenylpropionic acid) with the highest concentrations of 3-phenyllactic, p-hydroxyphenylacetic, 3-(p-hydroxyphenyl)lactic and 2-hydroxybutanic acids, was detectable in septic patients receiving a more intensive therapy. The differences were statistically significant (by the Mann-Whitney U-test; p < 0.05). By taking into account the potentially high biological activity of the test compounds, studies are to be continued in this area.

  9. The Multilevel Mixed Intact Group Analysis: A Mixed Method to Seek, Detect, Describe, and Explain Differences Among Intact Groups

    Science.gov (United States)

    Schoonenboom, Judith

    2016-01-01

    Educational innovations often involve intact subgroups, such as school classes or university departments. In small-scale educational evaluation research, typically involving 1 to 20 subgroups, differences among these subgroups are often neglected. This article presents a mixed method from a qualitative perspective, in which differences among…

  10. The Multilevel Mixed Intact Group Analysis: A Mixed Method to Seek, Detect, Describe and Explain Differences Between Intact Groups

    NARCIS (Netherlands)

    Schoonenboom, J.I.

    2014-01-01

    Educational innovations often involve intact subgroups, such as school classes or university departments. In small-scale educational evaluation research, typically involving 1 to 20 subgroups, differences among these subgroups are often neglected. This article presents a mixed method from a

  11. Determination of low-molecular-weight dicarboxylic acids in atmospheric aerosols by injection-port derivatization and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Hsu, Ching-Lin; Ding, Wang-Hsien

    2009-12-15

    A rapid and environmental-friendly injection-port derivatization with gas chromatography-mass spectrometry (GC-MS) method was developed to determine selected low-molecular weight (LMW) dicarboxylic acids (from C2 to C10) in atmospheric aerosol samples. The parameters related to the derivatization process (i.e., type of ion-pair reagent, injection-port temperature and concentration of ion-pair reagent) were optimized. Tetrabutylammonium hydroxide (TBA-OH) 20 mM in methanol gave excellent yield for di-butyl ester dicarboxylate derivatives at injection-port temperature at 300 degrees C. Solid-phase extraction (SPE) method instead of rotary evaporation was used to concentrate analytes from filter extracts. The recovery from filter extracts ranged from 78 to 95% with relative standard deviation (RSD) less than 12%. Limits of quantitation (LOQs) ranged from 25 to 250 pg/m(3). The concentrations of di-carboxylated C2-C5 and total C6-C10 in particles of atmospheric aerosols ranged from 91.9 to 240, 11.3 to 56.7, 9.2 to 49.2, 8.7 to 35.3 and n.d. to 37.8 ng/m(3), respectively. Oxalic acid (C2) was the dominant LMW-dicarboxylic acids detected in aerosol samples. The quantitative results were comparable to the results obtained by the off-line derivatization.

  12. Molecular Characterization of Thiols in Fossil Fuels by Michael Addition Reaction Derivatization and Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

    Science.gov (United States)

    Wang, Meng; Zhao, Suoqi; Liu, Xuxia; Shi, Quan

    2016-10-04

    Thiols widely occur in sediments and fossil fuels. However, the molecular composition of these compounds is unclear due to the lack of appropriate analytical methods. In this work, a characterization method for thiols in fossil fuels was developed on the basis of Michael addition reaction derivatization followed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Model thiol compound studies showed that thiols were selectively reacted with phenylvinylsulfone and transformed to sulfones with greater than 98% conversions. This method was applied to a coker naphtha, light and heavy gas oils, and crude oils from various geological sources. The results showed that long alkyl chain thiols are readily present in petroleum, which have up to 30 carbon atoms. Large DBE dispersity of thiols indicates that naphthenic and aromatic thiols are also present in the petroleum. This method is capable of detecting thiol compounds in the part per million range by weight. This method allows characterization of thiols in a complex hydrocarbon matrix, which is complementary to the comprehensive analysis of sulfur compounds in fossil fuels.

  13. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part III: 2,5-Dimethylfuran.

    Science.gov (United States)

    Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2014-03-01

    This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model.

  14. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part II: 2-Methylfuran

    Science.gov (United States)

    Tran, Luc-Sy; Togbé, Casimir; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2013-01-01

    This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed. PMID:24518895

  15. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part II: 2-Methylfuran.

    Science.gov (United States)

    Tran, Luc-Sy; Togbé, Casimir; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2014-03-01

    This is Part II of a series of three papers which jointly address the combustion chemistry of furan and its alkylated derivatives 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) under premixed low-pressure flame conditions. Some of them are considered to be promising biofuels. With furan as a common basis studied in Part I of this series, the present paper addresses two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of MF which were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) for equivalence ratios φ=1.0 and 1.7, identical conditions to those for the previously reported furan flames. Mole fractions of reactants, products as well as stable and reactive intermediates were measured as a function of the distance above the burner. Kinetic modeling was performed using a comprehensive reaction mechanism for all three fuels given in Part I and described in the three parts of this series. A comparison of the experimental results and the simulation shows reasonable agreement, as also seen for the furan flames in Part I before. This set of experiments is thus considered to be a valuable additional basis for the validation of the model. The main reaction pathways of MF consumption have been derived from reaction flow analyses, and differences to furan combustion chemistry under the same conditions are discussed.

  16. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part III: 2,5-Dimethylfuran

    Science.gov (United States)

    Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2013-01-01

    This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model. PMID:24518851

  17. Insulin-like growth factor II (IGF II) in human brain: regional distribution of IGF II and of higher molecular mass forms

    International Nuclear Information System (INIS)

    Haselbacher, G.K.; Schwab, M.E.; Pasi, A.; Humbel, R.E.

    1985-01-01

    Twenty-four distinct areas of human brain were analyzed for the presence of insulin-like growth factor (IGF). As reported for cerebrospinal fluid, only IGF II-like immunoreactivity, but no significant amounts of IGF I-like immunoreactivity, could be found. Upon gel permeation chromatography, two to five distinct size classes were separated on the basis of their immunoreactivity. Radioimmunoassays and a bioassay also gave results indistinguishable from those of serum IGF II. The highest amounts of IGF II-like immunoreactivity occur in the anterior pituitary. This is up to 100 times more than in most other brain regions analyzed. The higher molecular mass immunoreactive species were partially characterized. After immunoaffinity purification, the 38- and 26-kDa species are active in a bioassay. Specific IGF-binding protein activity could be shown after purification of the 38- and 26-kDa species on an IGF-affinity column. The 13-kDa species released significant amounts of 7.5-kDa material. The results are interpreted as evidence for the presence of IGF II synthesized locally in human brain

  18. An investigation of electronic states of some molecules and molecular cations using mass analyzed threshold ionization and photoinduced Rydberg ionization spectroscopy

    Science.gov (United States)

    Hofstein, Jason David

    1999-11-01

    Mass analyzed threshold ionization (MATI) experiments have enabled mapping of the n-dependent Rydberg state survival probability for a series of molecules. Utilizing vacuum and extreme ultraviolet (VUV/XUV) photons, one photon Rydberg manifold spectra of argon, hydrogen chloride, nitrogen, benzene, and oxygen were produced, and the prospects of photoinduced Rydberg ionization (PIRI) experiments examined. It was found that the widths of Rydberg manifolds for the molecules studied are quite different. Hydrogen chloride and nitrogen have the narrowest manifold width, followed by benzene, and then oxygen. These varying widths are most strongly correlated with the angular momentum (i.e., quantum defect) of the initially prepared Rydberg orbital. PIRI experiments required the use of a static cell, rather than a molecular jet assembly, for the more efficient production of higher amounts of VUV/XUV radiation, and hence more Rydberg signal needed to observe PIRI. Armed with the ability to produce tunable VUV/XUV radiation, and to determine the feasibility of a PIRI experiment, the MATI and fragment PIRI spectra of trans-1,3-butadiene (BD) were recorded. The MATI spectrum is vibrationally resolved and was analyzed with the help of ab initio calculations and other published results. The fragment PIRI spectrum of the Aproduction of C3H3+ dominates, but at higher photon energies, C2H4 + is also produced. The production of each fragment showed a definite PIRI wavelength dependence.

  19. Molecular-level characterization of crude oil compounds combining reversed-phase high-performance liquid chromatography with off-line high-resolution mass spectrometry

    Science.gov (United States)

    Sim, Arum; Cho, Yunju; Kim, Daae; Witt, Matthias; Birdwell, Justin E.; Kim, Byung Ju; Kim, Sunghwan

    2014-01-01

    A reversed-phase separation technique was developed in a previous study (Loegel et al., 2012) and successfully applied to the de-asphalted fraction of crude oil. However, to the best of our knowledge, the molecular-level characterization of oil fractions obtained by reversed-phase high-performance liquid chromatography (HPLC) coupled with high-resolution mass spectrometry (MS) has not yet been reported. A detailed characterization of the oil fractions prepared by reversed-phase HPLC was performed in this study. HPLC fractionation was carried out on conventional crude oil and an oil shale pyrolysate. The analyses of the fractions showed that the carbon number of alkyl chains and the double bond equivalent (DBE) value were the major factors determining elution order. The compounds with larger DBE (presumably more condensed aromatic structures) and smaller carbon number (presumably compounds with short side chains) were eluted earlier but those compounds with lower DBE values (presumably less aromatic structures) and higher carbon number (presumably compounds with longer alkyl chains) eluted later in the chromatograms. This separation behavior is in good agreement with that expected from the principles of reversed-phase separation. The data presented in this study show that reversed-phase chromatography is effective in separating crude oil compounds and can be combined with ultrahigh-resolution MS data to better understand natural oils and oil shale pyrolysates.

  20. Testing a Low Molecular Mass Fraction of a Mushroom (Lentinus edodes Extract Formulated as an Oral Rinse in a Cohort of Volunteers

    Directory of Open Access Journals (Sweden)

    Caterina Signoretto

    2011-01-01

    Full Text Available Although foods are considered enhancing factors for dental caries and periodontitis, laboratory researches indicate that several foods and beverages contain components endowed with antimicrobial and antiplaque activities. A low molecular mass (LMM fraction of an aqueous mushroom extract has been found to exert these activities in in vitro experiments against potential oral pathogens. We therefore conducted a clinical trial in which we tested an LMM fraction of shiitake mushroom extract formulated in a mouthrinse in 30 young volunteers, comparing the results with those obtained in two identical cohorts, one of which received water (placebo and the other Listerine. Plaque index, gingival index and bacterial counts in plaque samples were determined in all volunteers over the 11 days of the clinical trial. Statistically significant differences (P<0.05 were obtained for the plaque index on day 12 in subjects treated with mushroom versus placebo, while for the gingival index significant differences were found for both mushroom versus placebo and mushroom versus Listerine. Decreases in total bacterial counts and in counts of specific oral pathogens were observed for both mushroom extract and Listerine in comparison with placebo. The data suggest that a mushroom extract may prove beneficial in controlling dental caries and/or gingivitis/periodontitis.

  1. Organic secondary ion mass spectrometry: sensitivity enhancement by gold deposition.

    Science.gov (United States)

    Delcorte, A; Médard, N; Bertrand, P

    2002-10-01

    Hydrocarbon oligomers, high-molecular-weight polymers, and polymer additives have been covered with 2-60 nmol of gold/cm2 in order to enhance the ionization efficiency for static secondary ion mass spectrometry (s-SIMS) measurements. Au-cationized molecules (up to -3,000 Da) and fragments (up to the trimer) are observed in the positive mass spectra of metallized polystyrene (PS) oligomer films. Beyond 3,000 Da, the entanglement of polymer chains prevents the ejection of intact molecules from a "thick" organic film. This mass limit can be overcome by embedding the polymer chains in a low-molecular-weight matix. The diffusion of organic molecules over the metal surfaces is also demonstrated for short PS oligomers. In the case of high-molecular-weight polymers (polyethylene, polypropylene, PS) and polymer additives (Irganox 1010, Irgafos 168), the metallization procedure induces a dramatic increase of the fingerprint fragment ion yields as well as the formation of new Aucationized species that can be used for chemical diagnostics. In comparison with the deposition of submonolayers of organic molecules on metallic surfaces, metal evaporation onto organic samples provides a comparable sensitivity enhancement. The distinct advantage of the metal evaporation procedure is that it can be used for any kind of organic sample, irrespective of thickness, opening new perspectives for "real world" sample analysis and chemical imaging by s-SIMS.

  2. Does human leukocyte elastase degrade intact skin elastin?

    DEFF Research Database (Denmark)

    Schmelzer, Christian E H; Jung, Michael C; Wohlrab, Johannes

    2012-01-01

    This study aimed to investigate the susceptibility of intact fibrillar human elastin to human leukocyte elastase and cathepsin G. Elastin is a vital protein of the extracellular matrix of vertebrates, and provides exceptional properties including elasticity and tensile strength to many tissues...... and organs, including the aorta, lung, cartilage, elastic ligaments and skin, and is thus critical for their long-term function. Mature elastin is an insoluble and extremely durable protein that undergoes very little turnover, but sustained exposure to proteases may lead to irreversible and severe damage......, and thus to functional loss of the elastic fiber network. Hence, it is a key issue to understand which enzymes actually initiate elastolysis under certain pathological conditions or during intrinsic aging. In this paper, we provide a complete workflow for isolation of pure and intact elastin from very...

  3. SOLITARY CHEMORECEPTOR CELL SURVIVAL IS INDEPENDENT OF INTACT TRIGEMINAL INNERVATION

    Science.gov (United States)

    Gulbransen, Brian; Silver, Wayne; Finger, Tom

    2008-01-01

    Nasal solitary chemoreceptor cells (SCCs) are a population of specialized chemosensory epithelial cells presumed to broaden trigeminal chemoreceptivity in mammals (Finger et al., 2003). SCCs are innervated by peptidergic trigeminal nerve fibers (Finger et al., 2003) but it is currently unknown if intact innervation is necessary for SCC development or survival. We tested the dependence of SCCs on innervation by eliminating trigeminal nerve fibers during development with neurogenin-1 knockout mice, during early postnatal development with capsaicin desensitization, and during adulthood with trigeminal lesioning. Our results demonstrate that elimination of innervation at any of these times does not result in decreased SCC numbers. In conclusion, neither SCC development nor mature cell maintenance is dependent on intact trigeminal innervation. PMID:18300260

  4. Direct detection of radicals in intact soybean nodules

    DEFF Research Database (Denmark)

    Mathieu, C; Moreau, S; Frendo, P

    1998-01-01

    Electron paramagnetic resonance spectroscopy has been employed to examine the nature of the metal ions and radicals present in intact root nodules of soybean plants grown in the absence of nitrate. The spectra obtained from nodules of different ages using this non-invasive technique show dramatic...... differences, suggesting that there are both qualitative and quantitative changes in the metal ion and radical species present. A major component of the spectra obtained from young nodules is assigned to a complex (Lb-NO) of nitric oxide (NO.) with the heme protein leghemoglobin (Lb). This Lb-NO species, which...... has not been previously detected in intact root nodules of plants grown in the absence of nitrate, is thought to be formed by reaction of nitric oxide with iron(II) leghemoglobin. The nitric oxide may be generated from arginine via a nitric oxide synthase-like activity present in the nodules...

  5. Isolation and Properties of Intact Chromoplasts from Tomato Fruits

    OpenAIRE

    Norio, Iwatsuki; Ryuichi, Moriyama; Tadashi, Asahi; Laboratory of Biochemistry, Faculty of Agriculture, Nagoya University; Laboratory of Biochemistry, Faculty of Agriculture, Nagoya University; Laboratory of Biochemistry, Faculty of Agriculture, Nagoya University

    1984-01-01

    Intact chromoplasts were isolated from tomato fruits at different ripening stages by Percoll density gradient centrifugation. The isolated chromoplast fractions were contaminated very little by other organelles, although the fraction from fully ripened fruits contained some mitochondria and microbodies. As the transformation of chloroplasts to chromoplasts proceeded, the density of the plastids decreased from 1.096 to 1.075g・cm^ and the decrease was related to a decrease in chlorophyll and an...

  6. Protein Analysis by Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Cindic, M.

    2008-04-01

    Full Text Available Soft ionization techniques, electrospray (ESI and matrix-assisted laser desorption/ionization (MALDI make the analysis of biomolecules by mass spectrometry (MS possible. MS is used for determination of the molecular weight of peptides and protein, sequence analysis, characterization of protein-ligand interactions etc. The detection limit, resolution and mass accuracy depend on instrument used (Table 1. Impurities (buffers, salts, detergents can reduce the ion intensities or even totally suppress them, so a separation method (chromatography, 2D-gel electrophoresis must be used for purification of the sample.Molecular mass of intact protein can be determined by ESI or MALDI MS. Multiply charged ions are produced by ESI MS, while singly charged ions are predominant in MALDI spectra (Fig. 2.Sequence analysis of proteins by MS can be performed using peptide mass fingerprint. In this method, proteins are separated by 2-D gel electrophoresis and digested with specific protease (Table 2 or digested and then separated by two-dimensional chromatography (Fig. 1. The obtained peptide mixtures are analyzed by MS or MALDI-TOF technique. The masses determined by MS are compared with calculated masses from database entries. Different algorithms have been developed for protein identification. Example of posttranslational modifications (N- and O-glycosylation and protein sequence complex analysis after dual digestion (endoproteinase digestion followed by endoglycosidase digestion is shown in Fig. 3.It is known that detection of peptides by MS is influenced by intrinsic properties like amino acid composition, the basicity of the C-terminal amino acid, hydrophobicity, etc. Arginine-containing peptides dominate in MS spectra of tryptic digest, so the chemical derivatization of lysine terminal residue by O-methilisourea or 2-methoxy-4,5-1H-imidazole was suggested (Fig. 4.The peptide mass fingerprint method can be improved further by peptide fragmentation using tandem

  7. Global forest loss disproportionately erodes biodiversity in intact landscapes.

    Science.gov (United States)

    Betts, Matthew G; Wolf, Christopher; Ripple, William J; Phalan, Ben; Millers, Kimberley A; Duarte, Adam; Butchart, Stuart H M; Levi, Taal

    2017-07-27

    Global biodiversity loss is a critical environmental crisis, yet the lack of spatial data on biodiversity threats has hindered conservation strategies. Theory predicts that abrupt biodiversity declines are most likely to occur when habitat availability is reduced to very low levels in the landscape (10-30%). Alternatively, recent evidence indicates that biodiversity is best conserved by minimizing human intrusion into intact and relatively unfragmented landscapes. Here we use recently available forest loss data to test deforestation effects on International Union for Conservation of Nature Red List categories of extinction risk for 19,432 vertebrate species worldwide. As expected, deforestation substantially increased the odds of a species being listed as threatened, undergoing recent upgrading to a higher threat category and exhibiting declining populations. More importantly, we show that these risks were disproportionately high in relatively intact landscapes; even minimal deforestation has had severe consequences for vertebrate biodiversity. We found little support for the alternative hypothesis that forest loss is most detrimental in already fragmented landscapes. Spatial analysis revealed high-risk hot spots in Borneo, the central Amazon and the Congo Basin. In these regions, our model predicts that 121-219 species will become threatened under current rates of forest loss over the next 30 years. Given that only 17.9% of these high-risk areas are formally protected and only 8.9% have strict protection, new large-scale conservation efforts to protect intact forests are necessary to slow deforestation rates and to avert a new wave of global extinctions.

  8. Antimicrobial activity of a new intact skin antisepsis formulation.

    Science.gov (United States)

    Russo, Antonello; Viotti, Pier Luigi; Vitali, Matteo; Clementi, Massimo

    2003-04-01

    Different antiseptic formulations have shown limitations when applied to disinfecting intact skin, notably short-term tolerability and/or efficacy. The purpose of this study was optimizing a new antiseptic formulation specifically targeted at intact skin disinfection and evaluating its in vitro microbicidal activity and in vivo efficacy. The biocidal properties of the antiseptic solution containing 0.5% chloramine-T diluted in 50% isopropyl alcohol (Cloral; Eurospital SpA Trieste, Italy) were measured in vitro versus gram-positive-, gram-negative-, and acid-alcohol-resistant germs and fungi with standard suspension tests in the presence of fetal bovine serum. Virus-inhibiting activity was evaluated in vitro against human cytomegalovirus, herpes simplex virus, poliovirus, hepatitis B virus, and hepatitis C virus. Tests used different methods for the different biologic and in vitro replication capacity of these human viruses. Lastly, Cloral tolerability and skin colonization retardation efficacy after disinfection were studied in vivo. The antiseptic under review showed fast and sustained antimicrobial activity. The efficacy of Cloral against clinically important bacterial and viral pathogens and fungi was highlighted under the experimental conditions described in this article. Finally, microbial regrowth lag and no side effects were documented in vivo after disinfection of 11 volunteers. A stable chloramine-T solution in isopropyl alcohol may be suggested for intact skin antisepsis.

  9. Investigations on the role of hemoglobin in sulfide metabolism by intact human red blood cells.

    Science.gov (United States)

    Bianco, Christopher L; Savitsky, Anton; Feelisch, Martin; Cortese-Krott, Miriam M

    2018-03-01

    In addition to their role as oxygen transporters, red blood cells (RBCs) contribute to cardiovascular homeostasis by regulating nitric oxide (NO) metabolism via interaction of hemoglobin (Hb) with nitrite and NO itself. RBCs were proposed to also participate in sulfide metabolism. Although Hb is known to react with sulfide, sulfide metabolism by intact RBCs has not been characterized so far. Therefore we explored the role of Hb in sulfide metabolism in intact human RBCs. We find that upon exposure of washed RBCs to sulfide, no changes in oxy/deoxyhemoglobin (oxy/deoxyHb) are observed by UV-vis and EPR spectroscopy. However, sulfide reacts with methemoglobin (metHb), forming a methemoglobin-sulfide (metHb-SH) complex. Moreover, while metHb-SH is stable in cell-free systems even in the presence of biologically relevant thiols, it gradually decomposes to produce oxyHb, inorganic polysulfides and thiosulfate in intact cells, as detected by EPR and mass spectrometry. Taken together, our results demonstrate that under physiological conditions RBCs are able to metabolize sulfide via intermediate formation of a metHb-SH complex, which subsequently decomposes to oxyHb. We speculate that decomposition of metHb-SH is preceded by an inner-sphere electron transfer, forming reduced Hb (which binds oxygen to form oxyHb) and thiyl radical (a process we here define as "reductive sulfhydration"), which upon release, gives rise to the oxidized products, thiosulfate and polysulfides. Thus, not only is metHb an efficient scavenger and regulator of sulfide in blood, intracellular sulfide itself may play a role in keeping Hb in the reduced oxygen-binding form and, therefore, be involved in RBC physiology and function. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

  10. Boundaries of mass resolution in native mass spectrometry

    NARCIS (Netherlands)

    Lössl, Philip|info:eu-repo/dai/nl/371559693; Snijder, Joost|info:eu-repo/dai/nl/338018328; Heck, Albert J R|info:eu-repo/dai/nl/105189332

    Over the last two decades, native mass spectrometry (MS) has emerged as a valuable tool to study intact proteins and noncovalent protein complexes. Studied experimental systems range from small-molecule (drug)-protein interactions, to nanomachineries such as the proteasome and ribosome, to even

  11. Molecular spectroscopy

    International Nuclear Information System (INIS)

    Kokh, Eh.; Zonntag, B.

    1981-01-01

    The latest investigation results on molecular spectroscopy with application of synchrotron radiation in the region of vacuum ultraviolet are generalized. Some results on investigation of excited, superexcited and ionized molecule states with the use of adsorption spectroscopy, photoelectron spectroscopy, by fluorescent and mass-spectrometric methods are considered [ru

  12. Mass spectrometry imaging enriches biomarker discovery approaches with candidate mapping.

    Science.gov (United States)

    Scott, Alison J; Jones, Jace W; Orschell, Christie M; MacVittie, Thomas J; Kane, Maureen A; Ernst, Robert K

    2014-01-01

    Integral to the characterization of radiation-induced tissue damage is the identification of unique biomarkers. Biomarker discovery is a challenging and complex endeavor requiring both sophisticated experimental design and accessible technology. The resources within the National Institute of Allergy and Infectious Diseases (NIAID)-sponsored Consortium, Medical Countermeasures Against Radiological Threats (MCART), allow for leveraging robust animal models with novel molecular imaging techniques. One such imaging technique, MALDI (matrix-assisted laser desorption ionization) mass spectrometry imaging (MSI), allows for the direct spatial visualization of lipids, proteins, small molecules, and drugs/drug metabolites-or biomarkers-in an unbiased manner. MALDI-MSI acquires mass spectra directly from an intact tissue slice in discrete locations across an x, y grid that are then rendered into a spatial distribution map composed of ion mass and intensity. The unique mass signals can be plotted to generate a spatial map of biomarkers that reflects pathology and molecular events. The crucial unanswered questions that can be addressed with MALDI-MSI include identification of biomarkers for radiation damage that reflect the response to radiation dose over time and the efficacy of therapeutic interventions. Techniques in MALDI-MSI also enable integration of biomarker identification among diverse animal models. Analysis of early, sublethally irradiated tissue injury samples from diverse mouse tissues (lung and ileum) shows membrane phospholipid signatures correlated with histological features of these unique tissues. This paper will discuss the application of MALDI-MSI for use in a larger biomarker discovery pipeline.

  13. Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

    Science.gov (United States)

    Pedesseau, Laurent; Jouanna, Paul

    2004-12-01

    The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation Ck⇔μk between the concentrations Ck and the chemical potentials μk of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation Ck⇔μk implies in fact two problems: a direct problem Ck⇒μk and an inverse problem μk⇒Ck. Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 Å thick gypsum interface. The major unexpected observation is the repulsion of SO42- ions towards the reference solution and the attraction of Ca2+ ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime

  14. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part I: Furan.

    Science.gov (United States)

    Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2014-03-01

    Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has - to the best of our knowledge - not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

  15. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part I: Furan

    Science.gov (United States)

    Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2013-01-01

    Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has – to the best of our knowledge – not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

  16. Release of low molecular weight silicones and platinum from silicone breast implants.

    Science.gov (United States)

    Lykissa, E D; Kala, S V; Hurley, J B; Lebovitz, R M

    1997-12-01

    We have conducted a series of studies addressing the chemical composition of silicone gels from breast implants as well as the diffusion of low molecular weight silicones (LM-silicones) and heavy metals from intact implants into various surrounding media, namely, lipid-rich medium (soy oil), aqueous tissue culture medium (modified Dulbecco's medium, DMEM), or an emulsion consisting of DMEM plus 10% soy oil. LM-silicones in both implants and surrounding media were detected and quantitated using gas chromatography (GC) coupled with atomic emission (GC-AED) as well as mass spectrometric (GC/MS) detectors, which can detect silicones in the nanogram range. Platinum, a catalyst used in the preparation of silicone gels, was detected and quantitated using inductive argon-coupled plasma/mass spectrometry (ICP-MS), which can detect platinum in the parts per trillion range. Our results indicate that GC-detectable low molecular weight silicones contribute approximately 1-2% to the total gel mass and consist predominantly of cyclic and linear poly-(dimethylsiloxanes) ranging from 3 to 20 siloxane [(CH3)2-Si-O] units (molecular weight 200-1500). Platinum can be detected in implant gels at levels of approximately 700 micrograms/kg by ICP-MS. The major component of implant gels appears to be high molecular weight silicone polymers (HM-silicones) too large to be detected by GC. However, these HM-silicones can be converted almost quantitatively (80% by mass) to LM-silicones by heating implant gels at 150-180 degrees C for several hours. We also studied the rates at which LM-silicones and platinum leak through the intact implant outer shell into the surrounding media under a variety of conditions. Leakage of silicones was greatest when the surrounding medium was lipid-rich, and up to 10 mg/day LM-silicones was observed to diffuse into a lipid-rich medium per 250 g of implant at 37 degrees C. This rate of leakage was maintained over a 7-day experimental period. Similarly, platinum was

  17. High-molecular-weight adiponectin is selectively reduced in women with polycystic ovary syndrome independent of body mass index and severity of insulin resistance.

    LENUS (Irish Health Repository)

    O'Connor, A

    2010-03-01

    Context: High-molecular-weight (HMW) adiponectin contributes to insulin resistance (IR), which is closely associated with the pathophysiology of polycystic ovary syndrome (PCOS). Abnormalities in adipocyte function have been identified in PCOS and potentially contribute to lower adiponectin concentrations. Objective: Our objective was to determine which variables in plasma and adipose tissue influence HMW adiponectin in a well characterized cohort of women with PCOS. Design: This was a cross-sectional study. Settings and Participants: A teaching hospital. Women with PCOS (n = 98) and body mass index (BMI)-matched controls (n = 103) (including 68 age-, BMI-, and IR-matched pairs). Interventions: A standard 75-g oral glucose tolerance test was performed for each participant. Subcutaneous adipose tissue samples were taken by needle biopsy for a subset of PCOS women (n = 9) and controls (n = 8). Main Outcome Measures: Serum levels of HMW adiponectin and their relation to indices of insulin sensitivity, body composition, and circulating androgens as well as adipose tissue expression levels of ADIPOQ, TNFalpha, PPARgamma, and AR were assessed. Results: HMW adiponectin was significantly lower in women with PCOS compared with both BMI- and BMI- and IR-matched controls (P = 0.009 and P = 0.027, respectively). Although BMI and IR were the main predictors of HMW adiponectin, an interaction between waist to hip ratio and plasma testosterone contributed to its variance (P = 0.026). Adipose tissue gene expression analysis demonstrated that AR and TNFalpha (P = 0.008 and P = 0.035, respectively) but not ADIPOQ mRNA levels were increased in PCOS compared with controls. Conclusions: HMW adiponectin is selectively reduced in women with PCOS, independent of BMI and IR. Gene expression analysis suggests that posttranscriptional\\/translational modification contributes to reduced HMW adiponectin in PCOS.

  18. Microwave synthesis of gibberellin acid 3 magnetic molecularly imprinted polymer beads for the trace analysis of gibberellin acids in plant samples by liquid chromatography-mass spectrometry detection.

    Science.gov (United States)

    Zhang, Zhuomin; Tan, Wei; Hu, Yuling; Li, Gongke; Zan, Song

    2012-02-21

    In this study, novel GA3 magnetic molecularly imprinted polymer (mag-MIP) beads were synthesized by a microwave irradiation method, and the beads were applied for the trace analysis of gibberellin acids (GAs) in plant samples including rice and cucumber coupled with high performance liquid chromatography-mass spectrometry (HPLC-MS). The microwave synthetic procedure was optimized in detail. In particular, the interaction between GA3 and functional monomers was further studied for the selection of the optimal functional monomers during synthesis. It can be seen that the interaction between GA3 and acrylamide (AM) finally selected was stronger than that between GA3 and other functional monomers. GA3 mag-MIP beads were characterized by a series of physical tests. GA3 mag-MIP beads had a porous and homogeneous surface morphology with stable chemical, thermal and magnetic properties. Moreover, GA3 mag-MIP beads demonstrated selective and specific absorption behavior for the target compounds during unsaturated extraction, which resulted in a higher extraction capacity (∼708.4 pmol for GA3) and selectivity than GA3 mag-non-imprinted polymer beads. Finally, an analytical method of GA3 mag-AM-MIP bead extraction coupled with HPLC-MS detection was established and applied for the determination of trace GA1, GA3, GA4 and GA7 in rice and cucumber samples. It was satisfactory that GA4 could be actually found to be 121.5 ± 1.4 μg kg(-1) in real rice samples by this novel analytical method. The recoveries of spiked rice and cucumber samples were found to be 76.0-109.1% and 79.9-93.6% with RSDs of 2.8-8.8% and 3.1-7.7% (n = 3), respectively. The proposed method is efficient and applicable for the trace analysis of GAs in complicated plant samples.

  19. Determination of fluoroquinolone antibiotics in environmental water samples based on magnetic molecularly imprinted polymer extraction followed by liquid chromatography-tandem mass spectrometry

    International Nuclear Information System (INIS)

    Chen Ligang; Zhang Xiaopan; Xu Yang; Du Xiaobo; Sun Xin; Sun Lei; Wang Hui; Zhao Qi; Yu Aimin; Zhang Hanqi; Ding Lan

    2010-01-01

    A simple method based on magnetic separation for selective extraction of fluoroquinolones (FQs) from environmental water samples has been developed using magnetic molecularly imprinted polymer (MMIP) as sorbent. The MMIP has been prepared using ciprofloxacin as template molecule, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linking agent and Fe 3 O 4 magnetite as magnetic component. The polymer has been characterized by scanning electron microscopy, Fourier-transform infrared spectrometry and vibrating sample magnetometry. Various parameters affecting the extraction efficiency were evaluated in order to achieve optimal concentration and reduce non-specific interactions. The analytes desorbed from the polymers were determined by liquid chromatography-tandem mass spectrometry. The matrix effect was evaluated by using different washing solvents for removing interfering compounds from the MMIPs after sample loading. Under the optimal conditions, the linearity of the method obtained is in the range of 20-2000 ng L -1 . The detection limits of FQs are in the range of 3.2-6.2 ng L -1 . The relative standard deviations of intra- and inter-day tests ranging from 2.5 to 7.2% and from 3.6 to 9.1% are obtained. In all three spiked levels (20, 100 and 200 ng L -1 ), the recoveries of FQs are in the range of 76.3-94.2%. The proposed method was successfully applied to determine FQs including ciprofloxacin, enrofloxacin, lomefloxacin, levofloxacin, fleroxacin and sparfloxacin in different water samples, such as lake water, river water, primary and final sewage effluent. Ciprofloxacin and fleroxacin were found in primary and final sewage effluent samples with the contents in the range of 26-87 ng L -1 .

  20. Determination of fluoroquinolone antibiotics in environmental water samples based on magnetic molecularly imprinted polymer extraction followed by liquid chromatography-tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Chen Ligang; Zhang Xiaopan; Xu Yang [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, Jilin (China); Du Xiaobo; Sun Xin [College of Physics, Jilin University, 2699 Qianjin Street, Changchun 130012 (China); Sun Lei; Wang Hui; Zhao Qi; Yu Aimin; Zhang Hanqi [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, Jilin (China); Ding Lan, E-mail: dinglan@jlu.edu.cn [College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, Jilin (China)

    2010-03-03

    A simple method based on magnetic separation for selective extraction of fluoroquinolones (FQs) from environmental water samples has been developed using magnetic molecularly imprinted polymer (MMIP) as sorbent. The MMIP has been prepared using ciprofloxacin as template molecule, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linking agent and Fe{sub 3}O{sub 4} magnetite as magnetic component. The polymer has been characterized by scanning electron microscopy, Fourier-transform infrared spectrometry and vibrating sample magnetometry. Various parameters affecting the extraction efficiency were evaluated in order to achieve optimal concentration and reduce non-specific interactions. The analytes desorbed from the polymers were determined by liquid chromatography-tandem mass spectrometry. The matrix effect was evaluated by using different washing solvents for removing interfering compounds from the MMIPs after sample loading. Under the optimal conditions, the linearity of the method obtained is in the range of 20-2000 ng L{sup -1}. The detection limits of FQs are in the range of 3.2-6.2 ng L{sup -1}. The relative standard deviations of intra- and inter-day tests ranging from 2.5 to 7.2% and from 3.6 to 9.1% are obtained. In all three spiked levels (20, 100 and 200 ng L{sup -1}), the recoveries of FQs are in the range of 76.3-94.2%. The proposed method was successfully applied to determine FQs including ciprofloxacin, enrofloxacin, lomefloxacin, levofloxacin, fleroxacin and sparfloxacin in different water samples, such as lake water, river water, primary and final sewage effluent. Ciprofloxacin and fleroxacin were found in primary and final sewage effluent samples with the contents in the range of 26-87 ng L{sup -1}.

  1. Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions

    International Nuclear Information System (INIS)

    Gilchrist, Elizabeth S.; Nesterenko, Pavel N.; Smith, Norman W.; Barron, Leon P.

    2015-01-01

    Highlights: • IC selectivity at high contents of organic solvent in eluent and elevated temperature is studied. • Solvent-enhanced IC coupled to high resolution MS is beneficial for sensitive detection of ions. • The first application of IC-HRMS to the detection of low explosives in fingermarks is shown. - Abstract: There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5–50 mM hydroxide with 0–80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20–45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30–40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks

  2. Electrochemical Determination of Low Molecular Mass Thiols Content in Potatoes (Solanum tuberosum Cultivated in the Presence of Various Sulphur Forms and Infected by Late Blight (Phytophora infestans

    Directory of Open Access Journals (Sweden)

    Rene Kizek

    2008-05-01

    Full Text Available In the present paper potato plants were cultivated in the presence of ammonium sulphate or elemental sulphur supplementation into the soil to reveal the effects of different sulphur forms on content of nitrogen, phosphorus, potassium, calcium, magnesium and sulphur, and yield of tubers. During the investigation of the influence of different sulphur forms on yield of potato tubers we did not observe significant changes. Average weight of tubers of control plants per one experimental pot was 355 g. Application of sulphur in both forms resulted in moderate potato tubers weight reduction per one experimental pot compared to control group; average value ranged from 320 to 350 g per one experimental pot. Further we treated the plants with two different supplementation of sulphur with cadmium(II ions (4 mg of cadmium(II acetate per kilogram of the soil. The significantly lowest cadmium content (p < 0.05 was determined in tissues of plants treated with the highest dosage of elemental sulphur (0.64 mg Cd/kg compared to control plants (0.82 mg Cd/kg. We also aimed our attention on the cadmium content in proteins, lipids or soluble carbohydrates and ash. Application of sulphate as well as elemental sulphur resulted in significant cadmium content reduction in lipid fraction compared to control plants. In addition to this we quantified content of low molecular mass thiols in potatoes tissues. To determine the thiols content we employed differential pulse voltammetry Brdicka reaction. After twelve days of the treatment enhancing of thiols level was observed in all experimental groups regardless to applied sulphur form and its concentration. Finally we evaluated the effect of sulphur supplementation on Phytophora infestans infection of potato plants.

  3. Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions

    Energy Technology Data Exchange (ETDEWEB)

    Gilchrist, Elizabeth S. [Analytical & Environmental Science Division, Department of Forensic & Analytical Science, King’s College London, 150 Stamford Street, London, SE1 9NH (United Kingdom); Nesterenko, Pavel N. [Australian Centre for Research on Separation Science, School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart 7001 (Australia); Smith, Norman W. [Analytical & Environmental Science Division, Department of Forensic & Analytical Science, King’s College London, 150 Stamford Street, London, SE1 9NH (United Kingdom); Barron, Leon P., E-mail: leon.barron@kcl.ac.uk [Analytical & Environmental Science Division, Department of Forensic & Analytical Science, King’s College London, 150 Stamford Street, London, SE1 9NH (United Kingdom)

    2015-03-20

    Highlights: • IC selectivity at high contents of organic solvent in eluent and elevated temperature is studied. • Solvent-enhanced IC coupled to high resolution MS is beneficial for sensitive detection of ions. • The first application of IC-HRMS to the detection of low explosives in fingermarks is shown. - Abstract: There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5–50 mM hydroxide with 0–80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20–45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30–40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks.

  4. A putative low-molecular-mass penicillin-binding protein (PBP) of Mycobacterium smegmatis exhibits prominent physiological characteristics of DD-carboxypeptidase and beta-lactamase.

    Science.gov (United States)

    Bansal, Ankita; Kar, Debasish; Murugan, Rajagopal A; Mallick, Sathi; Dutta, Mouparna; Pandey, Satya Deo; Chowdhury, Chiranjit; Ghosh, Anindya S

    2015-05-01

    DD-carboxypeptidases (DD-CPases) are low-molecular-mass (LMM) penicillin-binding proteins (PBPs) that are mainly involved in peptidoglycan remodelling, but little is known about the dd-CPases of mycobacteria. In this study, a putative DD-CPase of Mycobacterium smegmatis, MSMEG_2433 is characterized. The gene for the membrane-bound form of MSMEG_2433 was cloned and expressed in Escherichia coli in its active form, as revealed by its ability to bind to the Bocillin-FL (fluorescent penicillin). Interestingly, in vivo expression of MSMEG_2433 could restore the cell shape oddities of the septuple PBP mutant of E. coli, which was a prominent physiological characteristic of DD-CPases. Moreover, expression of MSMEG_2433 in trans elevated beta-lactam resistance in PBP deletion mutants (ΔdacAdacC) of E. coli, strengthening its physiology as a dd-CPase. To confirm the biochemical reason behind such physiological behaviours, a soluble form of MSMEG_2433 (sMSMEG_2433) was created, expressed and purified. In agreement with the observed physiological phenomena, sMSMEG_2433 exhibited DD-CPase activity against artificial and peptidoglycan-mimetic DD-CPase substrates. To our surprise, enzymic analyses of MSMEG_2433 revealed efficient deacylation for beta-lactam substrates at physiological pH, which is a unique characteristic of beta-lactamases. In addition to the MSMEG_2433 active site that favours dd-CPase activity, in silico analyses also predicted the presence of an omega-loop-like region in MSMEG_2433, which is an important determinant of its beta-lactamase activity. Based on the in vitro, in vivo and in silico studies, we conclude that MSMEG_2433 is a dual enzyme, possessing both DD-CPase and beta-lactamase activities. © 2015 The Authors.

  5. Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer.

    Science.gov (United States)

    Köhler, Markus; Oßwald, Patrick; Krueger, Dominik; Whitside, Ryan

    2018-02-19

    This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This flexible tool offers a detailed observation of chemical gas-phase kinetics in reacting flows under well-controlled conditions. The vast range of operating conditions available in a laminar flow reactor enables access to extraordinary combustion applications that are typically not achievable by flame experiments. These include rich conditions at high temperatures relevant for gasification processes, the peroxy chemistry governing the low temperature oxidation regime or investigations of complex technical fuels. The presented setup allows measurements of quantitative speciation data for reaction model validation of combustion, gasification and pyrolysis processes, while enabling a systematic general understanding of the reaction chemistry. Validation of kinetic reaction models is generally performed by investigating combustion processes of pure compounds. The flow reactor has been enhanced to be suitable for technical fuels (e.g. multi-component mixtures like Jet A-1) to allow for phenomenological analysis of occurring combustion intermediates like soot precursors or pollutants. The controlled and comparable boundary conditions provided by the experimental design allow for predictions of pollutant formation tendencies. Cold reactants are fed premixed into the reactor that are highly diluted (in around 99 vol% in Ar) in order to suppress self-sustaining combustion reactions. The laminar flowing reactant mixture passes through a known temperature field, while the gas composition is determined at the reactors exhaust as a function of the oven temperature. The flow reactor is operated at atmospheric pressures with temperatures up to 1,800 K. The measurements themselves are performed by decreasing the temperature monotonically at a rate of -200 K/h. With the sensitive MBMS technique, detailed speciation data is acquired and

  6. Left ventricular mechanical adaptation to chronic aortic regurgitation in intact dogs

    International Nuclear Information System (INIS)

    Florenzano, F.; Glantz, S.A.

    1987-01-01

    Increased and end-diastolic wall stress has been hypothesized to stimulate left ventricular (LV) hypertrophy following volume overload. The authors instrumented intact-chest dogs with radiopaque markers in both ventricles and created volume overload by puncturing one aortic valve cusp. An x-ray system with biplane fluoroscopic and cineradiographic capabilities was used. End-diastolic stress increased immediately, then fell over 3 mo as the heart hypertrophied. End-systolic stress did not change significantly. Chamber contractility, quantified as E/sub max/, the end-systolic pressure-volume line slope, increased. E/sub max/ normalized by multiplying by LV mass increased following the lesion before but not after β-blockade with propranolol and did not change significantly over time, suggesting that chamber contractility changed because of increased mass and sympathetic tone rather than changed intrinsic muscle function. LV mass did not initially correlate with lesion size, but steady-state mass did. Over the range of lesions the authors produced, increased end-diastolic wall stress appears to stimulate hypertrophy at a fixed rate, which stops when end-diastolic wall stress has been reduced to an acceptable level

  7. Determination of the carbon isotopic composition of whole/intact biological specimens using at-line direct thermal desorption to effect thermally assisted hydrolysis/methylation

    NARCIS (Netherlands)

    Akoto, L.; Vreuls, R.J.J.; Irth, H.; Floris, V.; Hoogveld, H.L.; Pel, R.

    2008-01-01

    In this paper, we discuss the use of a direct thermal desorption (DTD) interface as an alternative to Curie-point flash pyrolysis system as an inlet technique in gas chromatography–combustion isotope-ratio mass spectrometry (GC/C-IRMS) analysis of whole/intact phytoplankton and zooplankton

  8. Determination of Oxidized Phosphatidylcholines by Hydrophilic Interaction Liquid Chromatography Coupled to Fourier Transform Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Pia Sala

    2015-04-01

    Full Text Available A novel liquid chromatography-mass spectrometry (LC-MS approach for analysis of oxidized phosphatidylcholines by an Orbitrap Fourier Transform mass spectrometer in positive electrospray ionization (ESI coupled to hydrophilic interaction liquid chromatography (HILIC was developed. This method depends on three selectivity criteria for separation and identification: retention time, exact mass at a resolution of 100,000 and collision induced dissociation (CID fragment spectra in a linear ion trap. The process of chromatography development showed the best separation properties with a silica-based Kinetex column. This type of chromatography was able to separate all major lipid classes expected in mammalian samples, yielding increased sensitivity of oxidized phosphatidylcholines over reversed phase chromatography. Identification of molecular species was achieved by exact mass on intact molecular ions and CID tandem mass spectra containing characteristic fragments. Due to a lack of commercially available standards, method development was performed with copper induced oxidation products of palmitoyl-arachidonoyl-phosphatidylcholine, which resulted in a plethora of lipid species oxidized at the arachidonoyl moiety. Validation of the method was done with copper oxidized human low-density lipoprotein (LDL prepared by ultracentrifugation. In these LDL samples we could identify 46 oxidized molecular phosphatidylcholine species out of 99 possible candidates.

  9. 21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Greatly Expands Mass Spectrometry Toolbox

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, Jared B.; Lin, Tzu-Yung; Leach, Franklin E.; Tolmachev, Aleksey V.; Tolić, Nikola; Robinson, Errol W.; Koppenaal, David W.; Paša-Tolić, Ljiljana

    2016-10-12

    We provide the initial performance evaluation of a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer operating at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory. The spectrometer constructed for the 21T system employs a commercial dual linear ion trap mass spectrometer coupled to a FTICR spectrometer designed and built in-house. Performance gains from moving to higher magnetic field strength are exemplified by the measurement of peptide isotopic fine structure, complex natural organic matter mixtures, and large proteins. Accurate determination of isotopic fine structure was demonstrated for doubly charged substance P with minimal spectral averaging, and 8,158 molecular formulas assigned to Suwannee River Fulvic Acid standard with RMS error of 10 ppb. We also demonstrated superior performance for intact proteins; namely, broadband isotopic resolution of the entire charge state distribution of apotransferrin (78 kDa) and facile isotopic resolution of monoclonal antibody under a variety of acquisition parameters (e.g. 6 s time-domains with absorption mode processing yielded resolution of approximately 1M at m/z =2,700).

  10. The uptake of radioactive iodine in rat intact Graafian follicles

    International Nuclear Information System (INIS)

    Lieberman, L.M.; Lieberman, G.L.; Lieberman, M.E.

    1984-01-01

    The concentration of iodine-131 in the ovaries of mammals has important implications in the use of I-131 for the diagnosis and treatment of thyroid disease in women. The authors studied the I-131 uptake in whole ovaries and in isolated Graafian follicles of sexually mature rats. Adult female Sprague-Dawley rats, in groups of 5-6 animals, were injected IP with 10-50 μCi of I-131, at 3, 12, and 24 hrs prior to the day of proestrus and killed on the day of proestrus. The thyroid gland and ovaries were removed intact and these organs, as well as eight other tissue specimens, were weighed. The large preovulatory follicles (6-9/ovary) were then isolated under a dissecting microscope and the remaining ovary weighed. All samples were counted in a gamma well counter and the % dose/g estimated. The thyroid gland showed 23.7% dose/org