Synthesis of (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)olivetolic acid, methyl (1'-/sup 13/C)olivetolate and (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)cannabigerolic acid

Energy Technology Data Exchange (ETDEWEB)

Porwoll, J P; Leete, E [Minnesota Univ., Minneapolis (USA). Dept. of Chemistry

1985-03-01

Potential advanced intermediates in the biosynthesis of delta/sup 9/-tetrahydrocannabinol, the major psychoactive principle of marijuana, have been synthesized labeled with two contiguous /sup 13/C atoms and /sup 14/C. Methyl (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)olivetolate was prepared from lithium (/sup 13/C/sub 2/)acetylide and dimethyl (2-/sup 14/C)malonate. Reaction with geranyl bromide afforded methyl (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)cannabigerolate, and hydrolysis of these methyl esters with lithium propyl mercaptide yielded the corresponding labeled acids. The /sup 13/C-/sup 13/C couplings observable in the /sup 13/C NMR spectra of these /sup 13/C-enriched compounds and their synthetic precursors are recorded. Methyl (1'-/sup 14/C)olivetolate was prepared from /sup 13/CO/sub 2/ to confirm assignments of the /sup 13/C chemical shifts in the pentyl side chain of these compounds.

Synthesis of (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)olivetolic acid, methyl (1'-/sup 13/C)olivetolate and (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)cannabigerolic acid

Energy Technology Data Exchange (ETDEWEB)

Porwoll, J.P.; Leete, E. (Minnesota Univ., Minneapolis (USA). Dept. of Chemistry)

1985-03-01

Potential advanced intermediates in the biosynthesis of delta/sup 9/-tetrahydrocannabinol, the major psychoactive principle of marijuana, have been synthesized labeled with two contiguous /sup 13/C atoms and /sup 14/C. Methyl (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)olivetolate was prepared from lithium (/sup 13/C/sub 2/)acetylide and dimethyl (2-/sup 14/C)malonate. Reaction with geranyl bromide afforded methyl (5,6-/sup 13/C/sub 2/, 1-/sup 14/C)cannabigerolate, and hydrolysis of these methyl esters with lithium propyl mercaptide yielded the corresponding labeled acids. The /sup 13/C-/sup 13/C couplings observable in the /sup 13/C NMR spectra of these /sup 13/C-enriched compounds and their synthetic precursors are recorded. Methyl (1'-/sup 14/C)olivetolate was prepared from /sup 13/CO/sub 2/ to confirm assignments of the /sup 13/C chemical shifts in the pentyl side chain of these compounds.

Site-specific {sup 13}C content by quantitative isotopic {sup 13}C Nuclear Magnetic Resonance spectrometry: A pilot inter-laboratory study

Energy Technology Data Exchange (ETDEWEB)

Chaintreau, Alain; Fieber, Wolfgang; Sommer, Horst [Firmenich SA, Corporate R and D Division, P.O. Box 239, 1211 Geneva 8 (Switzerland); Gilbert, Alexis; Yamada, Keita [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Yoshida, Naohiro [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Earth-Life Science Institute, Tokyo Institute of Technology, Meguro, Tokyo 152-8551 (Japan); Pagelot, Alain [Bruker Biospin SAS, 34 rue de l‘Industrie, 67166 Wissembourg Cedex (France); Moskau, Detlef; Moreno, Aitor [Bruker Biospin AG, Industriestrasse 26, 8117 Fällanden (Switzerland); Schleucher, Jürgen [Department of Medical Biochemistry and Biophysics, Umeå University, S-90187 Umeå (Sweden); Reniero, Fabiano; Holland, Margaret; Guillou, Claude [European Commission, Joint Research Centre – Institute for Health and Consumer Protection, via E. Fermi 2749, I-21027 Ispra (Italy); Silvestre, Virginie; Akoka, Serge [EBSI team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 rue de la Houssinière, BP 92208, F-44322 Nantes cedex 3 (France); Remaud, Gérald S., E-mail: gerald.remaud@univ-nantes.fr [EBSI team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 rue de la Houssinière, BP 92208, F-44322 Nantes cedex 3 (France)

2013-07-25

Graphical abstract: -- Highlights: •First ring test on isotopic {sup 13}C NMR spectrometry. •Evaluation of the intra- and inter-variability of the NMR spectrometers used. •Definition of a protocol for qualification of the performance of the spectrometer. -- Abstract: Isotopic {sup 13}C NMR spectrometry, which is able to measure intra-molecular {sup 13}C composition, is of emerging demand because of the new information provided by the {sup 13}C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic {sup 13}C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular {sup 13}C composition by NMR. The main goals of the ring test were to establish intra- and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic {sup 13}C NMR was then assessed on vanillin from three different origins associated with specific δ{sup 13}C{sub i} profiles. The standard deviation was, on average, between 0.9 and 1.2‰ for intra-variability. The highest standard deviation for inter-variability was 2.1‰. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of δ{sup 13}C{sub i} in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results.

C, Cl and H compound-specific isotope analysis to assess natural versus Fe(0) barrier-induced degradation of chlorinated ethenes at a contaminated site

Energy Technology Data Exchange (ETDEWEB)

Audí-Miró, Carme, E-mail: carmeaudi@ub.edu [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristal.lografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), Martí Franquès s/n, 08028, Barcelona (Spain); Cretnik, Stefan [Institute of Groundwater Ecology, Helmholtz Zentrum München-National Research Center for Environmental Health, Ingolstädter Landstrasse 1, D-85764 Neuherberg (Germany); Torrentó, Clara; Rosell, Mònica [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristal.lografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), Martí Franquès s/n, 08028, Barcelona (Spain); Shouakar-Stash, Orfan [Department of Earth & Environmental Sciences, 200 University Ave. W, N2L 3G1 Waterloo, Ontario (Canada); Otero, Neus [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristal.lografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), Martí Franquès s/n, 08028, Barcelona (Spain); Palau, Jordi [Université de Neuchâtel, CHYN - Centre d' Hydrogéologie, Rue Emile-Argand 11, CH-2000 Neuchâtel (Switzerland); and others

2015-12-15

Highlights: • {sup 13}C to evaluate natural chlorinated ethenes biodegradation. • {sup 13}C to evaluate the efficiency of a zero-valent iron-permeable reactive barrier. • {sup 13}C-{sup 37}Cl to discriminate biotic from abiotic degradation of cis-dichloroethene. • {sup 13}C-{sup 37}Cl-{sup 2}H of cis-DCE and TCE to elucidate different contaminant sources. - Abstract: Compound-specific isotopic analysis of multiple elements (C, Cl, H) was tested to better assess the effect of a zero-valent iron-permeable reactive barrier (ZVI-PRB) installation at a site contaminated with tetrachloroethene (PCE) and trichloroethene (TCE). The focus was on (1) using {sup 13}C to evaluate natural chlorinated ethene biodegradation and the ZVI-PRB efficiency; (2) using dual element {sup 13}C-{sup 37}Cl isotopic analysis to distinguish biotic from abiotic degradation of cis-dichloroethene (cis-DCE); and (3) using {sup 13}C-{sup 37}Cl-{sup 2}H isotopic analysis of cis-DCE and TCE to elucidate different contaminant sources. Both biodegradation and degradation by ZVI-PRB were indicated by the metabolites that were detected and the {sup 13}C data, with a quantitative estimate of the ZVI-PRB efficiency of less than 10% for PCE. Dual element {sup 13}C-{sup 37}Cl isotopic plots confirmed that biodegradation was the main process at the site including the ZVI-PRB area. Based on the carbon isotope data, approximately 45% and 71% of PCE and TCE, respectively, were estimated to be removed by biodegradation. {sup 2}H combined with {sup 13}C and {sup 37}Cl seems to have identified two discrete sources contributing to the contaminant plume, indicating the potential of δ{sup 2}H to discriminate whether a compound is of industrial origin, or whether a compound is formed as a daughter product during degradation.

C, Cl and H compound-specific isotope analysis to assess natural versus Fe(0) barrier-induced degradation of chlorinated ethenes at a contaminated site

International Nuclear Information System (INIS)

Audí-Miró, Carme; Cretnik, Stefan; Torrentó, Clara; Rosell, Mònica; Shouakar-Stash, Orfan; Otero, Neus; Palau, Jordi

2015-01-01

Highlights: • 13 C to evaluate natural chlorinated ethenes biodegradation. • 13 C to evaluate the efficiency of a zero-valent iron-permeable reactive barrier. • 13 C- 37 Cl to discriminate biotic from abiotic degradation of cis-dichloroethene. • 13 C- 37 Cl- 2 H of cis-DCE and TCE to elucidate different contaminant sources. - Abstract: Compound-specific isotopic analysis of multiple elements (C, Cl, H) was tested to better assess the effect of a zero-valent iron-permeable reactive barrier (ZVI-PRB) installation at a site contaminated with tetrachloroethene (PCE) and trichloroethene (TCE). The focus was on (1) using 13 C to evaluate natural chlorinated ethene biodegradation and the ZVI-PRB efficiency; (2) using dual element 13 C- 37 Cl isotopic analysis to distinguish biotic from abiotic degradation of cis-dichloroethene (cis-DCE); and (3) using 13 C- 37 Cl- 2 H isotopic analysis of cis-DCE and TCE to elucidate different contaminant sources. Both biodegradation and degradation by ZVI-PRB were indicated by the metabolites that were detected and the 13 C data, with a quantitative estimate of the ZVI-PRB efficiency of less than 10% for PCE. Dual element 13 C- 37 Cl isotopic plots confirmed that biodegradation was the main process at the site including the ZVI-PRB area. Based on the carbon isotope data, approximately 45% and 71% of PCE and TCE, respectively, were estimated to be removed by biodegradation. 2 H combined with 13 C and 37 Cl seems to have identified two discrete sources contributing to the contaminant plume, indicating the potential of δ 2 H to discriminate whether a compound is of industrial origin, or whether a compound is formed as a daughter product during degradation.

Identification of animal fats via compound specific δ13C values of individual fatty acids: assessments of results for reference fats and lipid extracts of archaeological pottery vessels

Directory of Open Access Journals (Sweden)

Richard P. Evershed

2002-12-01

Full Text Available The possibility of obtaining molecular information from lipid residues associated with archaeological pottery has dramatically increased the potential for deriving new information on the use of ancient vessels and the commodities processed therein. Motivated by the high proportion of the archaeological potsherds that have been shown to contain animal fats, a new approach invol- ving compound specific stable isotope analysis of remnant fats has been developed to retrieve infor- mation which will allow new insights into animal exploitation, dietary preferences and vessel use amongst prehistoric peoples. The new approach uses the δ13C values of the major saturated fatty acid (C16:0 and C18:0 determined by gas chromatography-combustion-isotope ratio mass spectrometry (GC–C–IRMS to characterise the origins of animal fat recovered from archaeological pottery.

APPLICATION OF A C-13 NMR TOPOLOGICAL MODEL TO THE STRUCTURE ELUCIDATION OF ORGANIC COMPOUNDS

Institute of Scientific and Technical Information of China (English)

袁身刚; 彭琛; 郑崇直

1992-01-01

This paper presents an approach which can elucidate automatically the structures of simple organic compounds from their C-13 NMR spectral data by using a computer. Based on a substructure/C-13 NMR chemical shift topological correlation model, the approach deduces the candidate substructures and the constraints for the substructure assembling from the molecular formula and C-13 NMR spectral data. Then, candidate structures are generated under these constraints by assembling the candidate substructures in a partial superposition manner. Candidate substructures or structures are evaluated once they are generated in order to eliminate those conflicting with the original data as early as possible. The evaluation of a (sub)structure is mainly carried out by simulating its C-13 NMR (sub) spectrum, which is again based on the model, and comparing the simulated spectrum with the original data.

Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

Science.gov (United States)

Julien, Maxime; Nun, Pierrick; Höhener, Patrick; Parinet, Julien; Robins, Richard J; Remaud, Gérald S

2016-01-15

In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. Copyright © 2015 Elsevier B.V. All rights reserved.

Challenges of 13C/12C measurements by CF-IRMS of biochemical samples at sub-nanomolar levels

International Nuclear Information System (INIS)

Whiticar, M.J.; Eek, M.

2001-01-01

Recent refinements to instrumentation and methodology have facilitated measurement of 13 C/ 12 C of individual compounds within complex biogeochemical mixtures by CF-IRMS. Specific challenges such as instrument performance, effective compound partitioning, efficient combustion, effective water removal, and isotope effects during online preparation of gases are discussed and practical improvements are presented. (author)

Synthesis of {sup 13}C- and {sup 14}C-labeled 1192U90, an ortho-amino benzamide with a preclinical atypical antipsychotic profile

Energy Technology Data Exchange (ETDEWEB)

Norman, M.H.; Gabriel, S.D. [Glaxo Wellcome Inc., Research Triangle Park, NC (United States)

1996-03-01

Three isotopic forms of potential antipsychotic agent 1192U90 (2-amino-N-(4-(4-(1,2-benzisthiazol-3-yl)-piperazinyl)butyl)benzam ide) were synthesized: one containing {sup 13}C-isotopes and two containing {sup 14}C-isotopes. The compound in which the ortho-amino benzamide ring is completely {sup 13}C-labeled was prepared in a four-step sequence starting from [{sup 13}C{sub 6}]aniline. The {sup 14}C-labeled compounds were prepared by methods analogous to those previously described for the unlabeled material. The key step involved the condensation of 3-(4-(4aminobutyl)-1-piperazinyl)-1,2-benzisothiazole with isatoic anhydride. The first {sup 14}C-labeled compound (3) was prepared from {sup 14}C-labeled 3-(4-(4-aminobutyl)-1-piperazinyl)-1,2-benzisothiazole, while the second compound (4) derived its isotopic label from [{sup 14}C]isatoic anhydride. Compound 3 had a specific activity of 26.55 mCi/mmol, a radiochemical purity of 99.3%, and a radiochemical yield of 3.4%. Compound 4 had a specific activity of 22.67 mCi/mmol and a radiochemical purity of 99.2%. (author).

Analysis of 13C-mixed triacylglycerol in stool by bulk (EA-IRMS) and compound specific (GC/MS) methods.

Science.gov (United States)

Slater, C; Ling, S C; Preston, T; Weaver, L T

2002-06-01

This paper was presented in poster form at the 17th International Congress of Nutrition, August 27-31, Vienna, Austria (Annals of Nutrition & Metabolism 2001; 45(Suppl.1):349). Some of the data were also presented in poster form at the British Society of Gastroenterology Meeting, March 18-21, Glasgow, UK (Gut 2001; 48(Suppl.1):A91). The 13C-mixed triacylglycerol (MTG) breath test is used to measure intraluminal fat digestion. In normal digestion, 20-40% of the ingested 13C label is recovered in breath CO2. We aimed to identify the proportions of ingested label excreted in stool, as well as breath following ingestion of 13C-MTG by children with impaired exocrine pancreatic function and healthy controls. 13C enrichment of breath samples was measured by continuous flow isotope ratio mass spectrometry (IRMS) and cumulative percent dose recovered (cPDR) in 10 h was calculated. Total 13C of a faecal fat extract from each stool was measured by elemental analyser-IRMS, and 13C enrichment and concentration of the TBDMS derivative of octanoic acid was measured by GC/MS after hydrolysis of the fat extract. Stool 5-day cPDR was calculated. Mean breath cPDR was 35%. Mean cPDR in stool by combustion-IRMS and GC/ MS, respectively, was 0.8% and 1.0%. Therefore, the remaining 64% of the 13C label must remain in the body and variability in breath cPDR is due to postabsorptive rather than predigestive factors.

Transport of C-13-labelled linoleic and C-13-labelled caprylic acid in rat plasma after administration of specific structured triacylglycerols

DEFF Research Database (Denmark)

Vistisen, Bodil; Høy, Carl-Erik

2004-01-01

the transport of dietary C-13-labelled fatty acids in rat plasma to compare the chylomicron fatty acid metabolism after administration of specific structured, long chain and medium chain triacylglycerols. Rats were fed ML*M, M*LM*, L*L*L* or M*M*M* (L=linoleic acid, 18:2n-6, M=caprylic acid, 8:0, * = C-13......-labelled fatty acid) by gavage. A maximum transport of 0.5% of the administered C-13-labelled 18:2n-6 was observed in 1mL rat plasma both after administration of L*L*L* and ML*M, while approximately 0.04% of the administered C-13-labelled 8:0 was detected in 1mL plasma following administration of M......*M*M* or M*LM*. After L*L*L* administration C-13-labelled 20:4n-6 was observed in plasma, probably formed by elongation and desaturation of 18:2n-6 in the enterocyte or liver cells. Furthermore, C-13-labelled 16:0, 48:0, 18: 1n-9 and 20:4n-6 were observed in plasma of rats fed M*M*M* and M*LM* due...

Synthesis of C-13 labeled vitamin E, [4' a-13C]all-rac-α-tocopherol

International Nuclear Information System (INIS)

Urano, Shiro; Muto, Riko; Matsuo, Mitsuyoshi

1985-01-01

Vitamin E with a 13 C-labeled isoprenoid side chain, [4' a- 13 C]-all-rac-α-tocopherol, was synthesized by the coupling reaction of 6-4-methoxymethoxy-2-([methyl- 13 C]5-bromo-4-methyl-pent-1-yl)chroman (8) with 3,7-dimethyl-1-(thiazolin-2-yl)thio-2,6-octadiene. Compound 8 was prepared using 2-(4,4-di-ethoxycarbonylbut-1-yl)-6-methoxymethoxy-2,5,7,8-tetramethyl-chroman as a key intermediate and [ 13 C]methyl iodide as a 13 C source. The total yield of the labeled α-tocopherol based on [ 13 C]methyl iodide was 58.7%. (author)

Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by 13C nuclear magnetic resonance spectrometry

International Nuclear Information System (INIS)

Julien, Maxime; Parinet, Julien; Nun, Pierrick; Bayle, Kevin; Höhener, Patrick; Robins, Richard J.; Remaud, Gérald S.

2015-01-01

Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by 13 C NMR (irm- 13 C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. - Highlights: • Position-Specific Isotope Analysis (PSIA) by 13 C NMR spectrometry. • PSIA on isotope fractionation during several vaporization processes. • PSIA for isotope profiling in environment pollutants. • Intramolecular 13 C reveal normal and inverse effects, bulk values being unchanged. - PSIA in pollutants during evaporation processes shows more detailed information for discerning the nature of the process involved than does bulk isotope measurements

Substitution effect in nuclear magnetic resonance of C-13: α methoxicyclohexanones

International Nuclear Information System (INIS)

Lopez Holland, M.A.G.

1984-01-01

Eletronic and steric interactions between the carbonyl and methoxyl groups in α-methoxicyclohexanones by H-1 and C-13 nuclear magnetic resonance spectroscopy (n.m.r) is studied. Interpretation of H-1 n.m.r measurements based on the carbonyl group anisotropy is made. The asigment of spectral lines to specific nuclear by Lanthanide Shift Reagent Experiments is confirmed. Interpretation of C-13 n.m.r. spectra with respect to molecular effects and emphirical relationships associated with the substituent was analysed. The C-13 chemical shift asignment by comparison with results of partially (SFORD) and fully decompled spectra and also by relating the measured chemical shift with values cited in the literature for similar compounds are made. A qualitative study using I.R. spectroscopy in attempt to evaluate the predominance of one the conformers of the studied compounds in solutions of n-hexan and chloroform is made. (M.J.C.) [pt

NMR study of conjugation effects. 15. /sup 13/C-/sup 13/C spin-spin coupling constants in phenylalkyl ether

Energy Technology Data Exchange (ETDEWEB)

Kalabin, G.A. (Siberian Branch of the Academy of Sciences of the USSR); Krivdin, L.B.; Trofimov, B.A.

1982-07-20

In order to elucidate the /sup 13/C-/sup 13/-C SSCC (spin-spin coupling constants) segment with the electronic excitations induced by the R group, a series of phenyl alkyl ethers, PhOAlk, where Alk = Me(I), Et(II), i-Pr(III), and t-Bu(IV), were studied. This series was chosen because in studying the /sup 13/C CS in monosubstituted benzenes it was observed that the intensity of the ..pi..-electron interaction of the unshared electron pairs of oxygen with the ..pi.. system of the benzene ring was practically the same in some compounds, but increased by 30% in others. This is related to the fact that the latter is characterized by an average noncoplanar conformation, with a dihedral angle between the benzene-ring plane and the C-O-C bond of approx. 45/sup 0/, whereas some compounds have an angle < 20/sup 0/. The reason for the difference is significant steric interaction of the alkyl hydrogens with the o-position of the ring. Thus, consideration of the /sup 13/C-/sup 13/C SSCC of a series of quite similar compounds, especially when compared to the whole set of such SSCC for other monosubstituted benzenes, shows that their relationship to the structure of the substituent R is extremely complex.

Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

Energy Technology Data Exchange (ETDEWEB)

Martinez, Rodolfo A. (Santa Fe, NM), Unkefer; Clifford J. (Los Alamos, NM), Alvarez; Marc, A [Santa Fe, NM

2012-06-12

The present invention is directed to the labeled compounds, ##STR00001## wherein C* is each either .sup.13C and .sup.12C where at least one C* is .sup.13C, each hydrogen of the methylene group is hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is sulfide, sulfinyl, or sulfone, Z is an aryl group such as 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, or a phenyl group ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently either hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group such as NH.sub.2, NHR and NRR' where R and R' are each independently either a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms. The present invention is also directed to the labeled compounds ##STR00003##

Metabolism and transport studies of exogenous compounds thanks to 13C uniform isotopic enrichment

International Nuclear Information System (INIS)

Bravin, F.

2008-12-01

The study of many exogenous compounds does not raise difficulties when they are isolated, purified and in quantities sufficient for the usual detection methods used in biology (Chromatography, NMR, Mass Spectrometry, etc). When they are found in a biological fluid (blood, urines,..), they are often in infinitesimal amount such as the effect of their biological matrices or the background noise that make their detection and their quantification very delicate. The use of internal standards uniformly enriched with carbon 13 and/or nitrogen 15 makes it possible to obtain a signal more easily recognizable and identifiable thanks to the presence of the isotopes (peaks shifted in a mass spectrum for example). This is why, complementary to the analytical and biochemical studies of zearalenone (ZEN) metabolism, we were interested in building mass spectra of molecules enriched (rates between 0 and 1) by various isotopes ( 13 C, 15 N, 18 O and 2 H). In parallel we studied the influence of the 13 C enrichment on the reactivity of a given molecule, from a theoretical and an experimental point of view. (author)

Preparation of 15N-13C-fulminic acid

International Nuclear Information System (INIS)

Wilmes, R.; Winnewisser, M.

1993-01-01

The precursor for the title compound was prepared in a three-step synthesis. The 13 C-label was incorporated in the first step employing 2- 13 C-ethyl acetate and the 15 N-label in the last step, using 15 N-sodium nitrite. Upon pyrolysis the precursor forms three fragments, one of them being the title compound. (Author)

Inferring Phytoplankton, Terrestrial Plant and Bacteria Bulk δ¹³C Values from Compound Specific Analyses of Lipids and Fatty Acids

Science.gov (United States)

Taipale, Sami J.; Peltomaa, Elina; Hiltunen, Minna; Jones, Roger I.; Hahn, Martin W.; Biasi, Christina; Brett, Michael T.

2015-01-01

Stable isotope mixing models in aquatic ecology require δ13C values for food web end members such as phytoplankton and bacteria, however it is rarely possible to measure these directly. Hence there is a critical need for improved methods for estimating the δ13C ratios of phytoplankton, bacteria and terrestrial detritus from within mixed seston. We determined the δ13C values of lipids, phospholipids and biomarker fatty acids and used these to calculate isotopic differences compared to the whole-cell δ13C values for eight phytoplankton classes, five bacterial taxa, and three types of terrestrial organic matter (two trees and one grass). The lipid content was higher amongst the phytoplankton (9.5±4.0%) than bacteria (7.3±0.8%) or terrestrial matter (3.9±1.7%). Our measurements revealed that the δ13C values of lipids followed phylogenetic classification among phytoplankton (78.2% of variance was explained by class), bacteria and terrestrial matter, and there was a strong correlation between the δ13C values of total lipids, phospholipids and individual fatty acids. Amongst the phytoplankton, the isotopic difference between biomarker fatty acids and bulk biomass averaged -10.7±1.1‰ for Chlorophyceae and Cyanophyceae, and -6.1±1.7‰ for Cryptophyceae, Chrysophyceae and Diatomophyceae. For heterotrophic bacteria and for type I and type II methane-oxidizing bacteria our results showed a -1.3±1.3‰, -8.0±4.4‰, and -3.4±1.4‰ δ13C difference, respectively, between biomarker fatty acids and bulk biomass. For terrestrial matter the isotopic difference averaged -6.6±1.2‰. Based on these results, the δ13C values of total lipids and biomarker fatty acids can be used to determine the δ13C values of bulk phytoplankton, bacteria or terrestrial matter with ± 1.4‰ uncertainty (i.e., the pooled SD of the isotopic difference for all samples). We conclude that when compound-specific stable isotope analyses become more widely available, the determination of �

/sup 13/C-/sup 13/C spin-spin coupling constants in structural investigations. II. Conformational structure of vinyl ethers

Energy Technology Data Exchange (ETDEWEB)

Krivdin, L.B.; Shcherbakov, V.V.; Bzhezovskii, V.M.; Kalabin, G.A.

1986-10-10

The /sup 13/C-/sup 13/C spin-spin coupling constants between the carbon nuclei of the vinyl group were measured for a series of vinyl ethers. It was established that the unshared electron pairs of the oxygen atom can make a substantial stereospecific contribution to the direct /sup 13/C-/sup 13/C constants of the adjacent nuclei. The observed effect was used to establish the conformational structure of the compounds.

The /sup 13/C-/sup 13/C spin-spin coupling constants and the conformational equilibrium of alkyl phenyl sulfides

Energy Technology Data Exchange (ETDEWEB)

Krividin, L.B.; Kalabin, G.A.

1985-08-10

The authors measure the direct geminal and vicinal spinspin coupling constants between the C-13 nuclei of the phenyl group in the series of alkyl phenyl sulfides C/sub 6/H/sub 5/SR. It was shown that the variation in most of the discussed constants is determined by the ratio of the planar and orthogonal conformers. Linear relationships were obtained between the C-13-C-13 constants and the fractions of the planar conformer. The C-13-C-13 spin-spin coupling constants in the planar and orthogonal conformers of the compounds were calculated by means of empirical relationships.

Evaluation of [14C] and [13C]Sucrose as Blood-Brain Barrier Permeability Markers.

Science.gov (United States)

Miah, Mohammad K; Chowdhury, Ekram A; Bickel, Ulrich; Mehvar, Reza

2017-06-01

Nonspecific quantitation of [ 14 C]sucrose in blood and brain has been routinely used as a quantitative measure of the in vivo blood-brain barrier (BBB) integrity. However, the reported apparent brain uptake clearance (K in ) of the marker varies widely (∼100-fold). We investigated the accuracy of the use of the marker in comparison with a stable isotope of sucrose ([ 13 C]sucrose) measured by a specific liquid chromatography-tandem mass spectrometry method. Rats received single doses of each marker, and the K in values were determined. Surprisingly, the K in value of [ 13 C]sucrose was 6- to 7-fold lower than that of [ 14 C]sucrose. Chromatographic fractionation after in vivo administration of [ 14 C]sucrose indicated that the majority of the brain content of radioactivity belonged to compounds other than the intact [ 14 C]sucrose. However, mechanistic studies failed to reveal any substantial metabolism of the marker. The octanol:water partition coefficient of [ 14 C]sucrose was >2-fold higher than that of [ 13 C]sucrose, indicating the presence of lipid-soluble impurities in the [ 14 C]sucrose solution. Our data indicate that [ 14 C]sucrose overestimates the true BBB permeability to sucrose. We suggest that specific quantitation of the stable isotope ( 13 C) of sucrose is a more accurate alternative to the current widespread use of the radioactive sucrose as a BBB marker. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Assessing microbial utilization of free versus sorbed Alanine by using position-specific 13C labeling and 13C-PLFA analysis

Science.gov (United States)

Herschbach, Jennifer; Apostel, Carolin; Spielvogel, Sandra; Kuzyakov, Yakov; Dippold, Michaela

2016-04-01

Microbial utilization is a key transformation process of soil organic matter (SOM). Sorption of low molecular weight organic substances (LMWOS) to soil mineral surfaces blocks or delays microbial uptake and therefore mineralization of LMWOS to CO2, as well as all other biochemical transformations. We used position-specific labeling, a tool of isotope applications novel to soil science, combined with 13C-phospholipid fatty acid (PLFA) analysis, to assess microbial utilization of sorbed and non-sorbed Alanine in soil. Alanine has various functional groups enabling different sorption mechanisms via its positive charge (e.g. to clay minerals by cation exchange), as well as via its negative charge (e.g. to iron oxides by ligand exchange). To assess changes in the transformation pathways caused by sorption, we added uniformly and position-specifically 13C and 14C labeled Alanine to the Ap of a loamy Luvisol in a short-term (10 days) incubation experiment. To allow for sorption of the tracer solution to an aliquot of this soil, microbial activity was minimized in this subsample by sterilizing the soil by γ-radiation. After shaking, the remaining solutions were filtered and the non-sorbed Alanine was removed with Millipore water and then added to non-sterilized soil. For the free Alanine treatment, solutions with Alanine of similar amount and isotopic composition were prepared, added to the soil and incubated as well. The respired CO2 was trapped in NaOH and its 14C-activity was determined at increasing times intervals. Microbial utilization of Alanine's individual C positions was evaluated in distinct microbial groups classified by 13C-PLFA analysis. Sorption to soil minerals delayed respiration to CO2 and reduced initial respiration rate by 80%. Irrespective of sorption, the highest amount was respired from the carboxylic position (C-1), whereas the amino-bound (C-2) and the methylic position (C-3) were preferentially incorporated into PLFA of microorganisms due to the

Other compounds isolated from Simira glaziovii and the 1H and 13C NMR chemical shift assignments of new 1-epi-castanopsol

International Nuclear Information System (INIS)

Araujo, Marcelo F. de; Vieira, Ivo J. Curcino; Braz-Filho, Raimundo; Carvalho, Mario G. de

2012-01-01

A new triterpene, 1-epi-castanopsol, besides eleven known compounds: sitosterol, stigmasterol, campesterol, lupeol, lupenone, simirane B, syringaresinol, scopoletin, isofraxidin, 6,7,8-trimethoxycoumarin and harman, were isolated from the wood of Simira glaziovii. The structures of the known compounds were defined by 1D, 2D 1 H, 13 C NMR spectra data analyses and comparison with literature data. The detailed spectral data analyses allowed the definition of the structure of the new 1-epi isomer of castanopsol and performance of 1 H and 13 C NMR chemical shift assignments. (author)

Giant negative thermal expansion in NaZn13-type La(Fe, Si, Co)13 compounds.

Science.gov (United States)

Huang, Rongjin; Liu, Yanying; Fan, Wei; Tan, Jie; Xiao, Furen; Qian, Lihe; Li, Laifeng

2013-08-07

La(Fe, Si)13-based compounds are well-known magnetocaloric materials, which show a pronounced negative thermal expansion (NTE) around the Curie temperature but have not been considered as NTE materials for industrial applications. The NaZn13-type LaFe13-xSix and LaFe11.5-xCoxSi1.5 compounds were synthesized, and their linear NTE properties were investigated. By optimizing the chemical composition, the sharp volume change in La(Fe, Si)13-based compounds was successfully modified into continuous expansion. By increasing the amount of Co dopant in LaFe11.5-xCoxSi1.5, the NTE shifts toward a higher temperature region, and also the NTE operation-temperature window becomes broader. Typically, the linear NTE coefficient identified in the LaFe10.5Co1.0Si1.5 compound reaches as much as -26.1 × 10(-6) K(-1), with an operation-temperature window of 110 K from 240 to 350 K, which includes room temperature. Such control of the specific composition and the NTE properties of La(Fe, Si)13-based compounds suggests their potential application as NTE materials.

Reconstructing past climate using a multi-specific 13C-approach

Science.gov (United States)

Ferrio, Juan Pedro; Aguilera, Mónica; Voltas, Jordi

2010-05-01

Carbon isotope composition (δ13C) in tree-rings has become routinely used in palaeoclimatic research for the assessment of changes in water availability in seasonally dry climates. Long tree-ring chronologies, however, are relatively scarce, whereas the original climate signal of wood δ13C is usually well preserved in fossil charcoal [1, 4] Accordingly, charcoal δ13C records are an alternative to classic dendroclimatology to characterize past changes in water availability (e.g. precipitation). In this work, we explore the potential for palaeoenvironmental research of two co-occuring Mediterranean species with contrasting strategies to cope with drought [2]: Aleppo pine (Pinus halepensis Mill.) and holm oak (Quercus ilex L.). We hypothesize that the differential sensitivity of pine and oak to climate variables can be exploited to refine palaeoclimate reconstructions based on δ13C in wood or charcoal. For this purpose, we put together published tree-core-δ13C data from 40 sites across Spain [2, 3] and new δ13C data from 15 sites where both species co-existed in mixed stands. The sites were selected to represent the range of variation in thermal and precipitation regimes for these species, while avoiding any correlation between precipitation and temperature across sites. Five dominant or codominant trees were selected per site, and microcores including the most recently formed tree rings were obtained with a Trephor tool [5]. Fragments were oven-dried at 60 ° C for 48 h and milled separately to a fine powder using a ball mill (Retsch MM301, Haan, Germany) for δ13C analysis. Current meteorological data (monthly estimates of air mean temperature (minimum, mean and maximum), precipitation and solar radiation) was obtained from the Digital Climatic Atlas of the Iberian Peninsula (http://opengis.uab.es/wms/iberia/index.htm) (spatial resolution of 200 m). A family of models (either linear or exponential) best predicting monthly and annual precipitation from δ13C

Gas chromatographic isolation technique for compound-specific radiocarbon analysis

International Nuclear Information System (INIS)

Uchida, M.; Kumamoto, Y.; Shibata, Y.; Yoneda, M.; Morita, M.; Kawamura, K.

2002-01-01

Full text: We present here a gas chromatographic isolation technique for the compound-specific radiocarbon analysis of biomarkers from the marine sediments. The biomarkers of fatty acids, hydrocarbon and sterols were isolated with enough amount for radiocarbon analysis using a preparative capillary gas chromatograph (PCGC) system. The PCGC systems used here is composed of an HP 6890 GC with FID, a cooled injection system (CIS, Gerstel, Germany), a zero-dead-volume effluent splitter, and a cryogenic preparative collection device (PFC, Gerstel). For AMS analysis, we need to separate and recover sufficient quantity of target individual compounds (>50 μgC). Yields of target compounds from C 14 n-alkanes to C 40 to C 30 n-alkanes and approximately that of 80% for higher molecular weights compounds more than C 30 n-alkanes. Compound specific radiocarbon analysis of organic compounds, as well as compound-specific stable isotope analysis, provide valuable information on the origins and carbon cycling in marine system. Above PCGC conditions, we applied compound-specific radiocarbon analysis to the marine sediments from western north Pacific, which showed the possibility of a useful chronology tool for estimating the age of sediment using organic matter in paleoceanographic study, in the area where enough amounts of planktonic foraminifera for radiocarbon analysis by accelerator mass spectrometry (AMS) are difficult to obtain due to dissolution of calcium carbonate. (author)

Preparation of 2H- and 13C-labelled precursors of 2-hydroxy-1, 3-butadiene

International Nuclear Information System (INIS)

Turecek, F.

1987-01-01

2-exo-Vinylbicyclo[2.2.1]hept-5-en-2-ols, specifically labelled with 2 H at C-3 and in the vinyl group were prepared from bicyclo[2.2.1]hept-5-en-2-one in several steps. [4- 13 C]oct-1-en-3-one was prepared in five steps from 13 CO 2 . These compounds serve as precursors for the preparation of specifically labelled neutral and ionized 2-hydroxy-1, 3-butadienes. (author)

Stable carbon isotope analysis (δ13C values) of polybrominated diphenyl ethers and their UV-transformation products

International Nuclear Information System (INIS)

Rosenfelder, Natalie; Bendig, Paul; Vetter, Walter

2011-01-01

Polybrominated diphenyl ethers (PBDEs) are frequently detected in food and environmental samples. We used compound specific isotope analysis to determine the δ 13 C values of individual PBDEs in two technical mixtures. Within the same technical product (DE-71 or DE-79), BDE congeners were the more depleted in 13 C the higher brominated they were. In contrast, the products of light-induced hydrodebromination of BDE 47 and technical DE-79 were more enriched in 13 C because of more stable bonds between 13 C and bromine. As a result, the δ 13 C values of the irradiated solution progressed diametrically compared to those of the technical synthesis. The ratio of the δ 13 C values of BDE 47 to BDE 99 and of BDE 99 to BDE 153 are thus suggested as indicators to distinguish native technical products from transformation products. Ratios 1) is typical of transformation products. - Highlights: → δ 13 C values of PBDEs were determined by means of compound specific isotope analysis. → PBDEs in technical mixtures were the more depleted in 13 C the higher they were brominated. → Solutions of individual PBDEs and technical PBDE mixtures were irradiated by UV light. → δ 13 C values of irradiated PBDEs and technical PBDEs progressed diametrically. → Ratios of the δ 13 C values were used to distinguish native from transformed PBDEs. - Diametrically progressing δ 13 C values in technical mixtures and UV-transformation products of DE-79 may be useful for source appointment of PBDEs in environmental samples

Dissipation kinetics of asparagine in soil measured by compound-specific analysis with metabolite tracking

DEFF Research Database (Denmark)

Czaban, Weronika; Rasmussen, Jim; Nicolaisen, Mogens

2016-01-01

labeled glutamic acid were detected in soil. This highlights the fast turnover of amino acid in soil and that the estimation of concentration of the formed compounds is important when evaluating plant available organic N. Efficiency of the compound-specific analysis showed to be a powerful technique......Estimating the potential for direct plant acquisition of organic N, in particular amino acids, requires assessment of their turnover times in soil. It is well known from 14C studies that mineralization of amino acids occurs within hours, but mineralization to 14CO2 does not indicate the rate...... of disappearance of the intact amino acid or the possible formation of metabolites during amino acid dissipation. We here used compound-specific isotope analysis with metabolite tracking to investigate the dissipation rate of universally labeled intact 13C15N-asparagine at two concentrations and the subsequent...

Synthesis and purification of 13C labelled xanthine derivatives

International Nuclear Information System (INIS)

Boukraa, M.S.; Deruaz, D.; Bannier, A.; Desage, M.; Brazier, J.L.

1995-01-01

3-[Methyl- 13 )C]xanthine, 7-[Methyl- 13 )C]xanthine, 1,3-[Dimethyl- 13 )C 2 ]xanthine (theophylline-1,3-[ 13 )CH 3 ] 2 ), 1,7-[Dimethyl- 13 )C 2 ]xanthine (paraxanthine-1,7[ 13 )CH 3 ] 2 ), and 3,7-[Dimethyl- 13 )C 2 ]xanthine (theobromine-3,7-[ 13 )CH 3 ] 2 were synthesized by nucleophilic substitution reaction(SN 2 ) from xanthine (X) and iodomethane-[ 13 C]. The 3-isobutylparaxanthine-7-[ 13 CH 3 ] was prepared from 3-isobutyl-1-methylxanthine (IBMX). The compounds were purified by reverse phase semipreparative liquid chromatography and their chemical structure and purity verified by GC-MS. (Author)

Biogenic volatile organic compound and respiratory CO2 emissions after 13C-labeling: online tracing of C translocation dynamics in poplar plants.

Science.gov (United States)

Ghirardo, Andrea; Gutknecht, Jessica; Zimmer, Ina; Brüggemann, Nicolas; Schnitzler, Jörg-Peter

2011-02-28

Globally plants are the primary sink of atmospheric CO(2), but are also the major contributor of a large spectrum of atmospheric reactive hydrocarbons such as terpenes (e.g. isoprene) and other biogenic volatile organic compounds (BVOC). The prediction of plant carbon (C) uptake and atmospheric oxidation capacity are crucial to define the trajectory and consequences of global environmental changes. To achieve this, the biosynthesis of BVOC and the dynamics of C allocation and translocation in both plants and ecosystems are important. We combined tunable diode laser absorption spectrometry (TDLAS) and proton transfer reaction mass spectrometry (PTR-MS) for studying isoprene biosynthesis and following C fluxes within grey poplar (Populus x canescens) saplings. This was achieved by feeding either (13)CO(2) to leaves or (13)C-glucose to shoots via xylem uptake. The translocation of (13)CO(2) from the source to other plant parts could be traced by (13)C-labeled isoprene and respiratory (13)CO(2) emission. In intact plants, assimilated (13)CO(2) was rapidly translocated via the phloem to the roots within 1 hour, with an average phloem transport velocity of 20.3±2.5 cm h(-1). (13)C label was stored in the roots and partially reallocated to the plants' apical part one day after labeling, particularly in the absence of photosynthesis. The daily C loss as BVOC ranged between 1.6% in mature leaves and 7.0% in young leaves. Non-isoprene BVOC accounted under light conditions for half of the BVOC C loss in young leaves and one-third in mature leaves. The C loss as isoprene originated mainly (76-78%) from recently fixed CO(2), to a minor extent from xylem-transported sugars (7-11%) and from photosynthetic intermediates with slower turnover rates (8-11%). We quantified the plants' C loss as respiratory CO(2) and BVOC emissions, allowing in tandem with metabolic analysis to deepen our understanding of ecosystem C flux.

Synthesis of [2-13C, 2-14C] 2-aminoethanol, [1-13C, 1-14C] 2-chloroethylamine, N,N'-bis([1-13C, 1-14C] 2-chloroethyl)-N-nitrosourea(BCNU) and N-([1-13C, 1-14C] 2-chloroethyl)-N-nitrosourea(CNU)

International Nuclear Information System (INIS)

Narayan, R.; Chang, C-j.

1982-01-01

[2- 13 C, 2- 14 C]2-Aminoethanol hydrochloride was prepared in good yield from Na*CN in a two step sequence by first converting the Na*CN to OHCH 2 *CN and then reducing the nitrile directly with a solution of borane-tetrahydrofuran complex. The reaction procedure was simple and the pure product could be obtained readily. Using this specifically labelled precursor, the synthesis of [1- 13 C, 1- 14 C]2-chloroethylamine hydrochloride, N-([1- 13 C, 1- 14 C]2-chloroethyl)-N-nitrosourea(CNU) and N,N'-bis([1- 13 C, 1- 14 C]2-chloroethyl)-N-nitrosourea(BCNU) in good yield without isotope scrambling was also reported. (author)

Quantitative analysis of deuterium using the isotopic effect on quaternary {sup 13}C NMR chemical shifts

Energy Technology Data Exchange (ETDEWEB)

Darwish, Tamim A., E-mail: tamim.darwish@ansto.gov.au [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); Yepuri, Nageshwar Rao; Holden, Peter J. [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); James, Michael [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

2016-07-13

Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual {sup 1}H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D{sub 2}O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary {sup 13}C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing {sup 13}C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve {sup 13}C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ({sup 1}H, {sup 2}H) resolves closely separated quaternary {sup 13}C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up. - Graphical abstract: The relative intensities of quaternary {sup 13}C {"1H,"2H} resonances are equal despite the different relaxation delays, allowing the relative abundance of the different deuterated isotopologues to be calculated using NMR fast

Other compounds isolated from Simira glaziovii and the {sup 1}H and {sup 13}C NMR chemical shift assignments of new 1-epi-castanopsol

Energy Technology Data Exchange (ETDEWEB)

Araujo, Marcelo F. de; Vieira, Ivo J. Curcino [Universidade Federal Rural do Rio de Janeiro, Seropedica, RJ (Brazil). Dept. de Quimica; Braz-Filho, Raimundo [Universidade Estadual do Norte Fluminense (UENF), Campos dos Goytacases, RJ (Brazil). Centro de Ciencias Tecnologicas. Lab. de Ciencias Quimicas; Carvalho, Mario G. de, E-mail: mgeraldo@ufrrj.br [Universidade Federal do Rio de Janeiro (NPPN/UFRJ), RJ (Brazil). Centro de Ciencias da Saude. Nucleo de Pesquisa em Produtos Naturais

2012-07-01

A new triterpene, 1-epi-castanopsol, besides eleven known compounds: sitosterol, stigmasterol, campesterol, lupeol, lupenone, simirane B, syringaresinol, scopoletin, isofraxidin, 6,7,8-trimethoxycoumarin and harman, were isolated from the wood of Simira glaziovii. The structures of the known compounds were defined by 1D, 2D {sup 1}H, {sup 13}C NMR spectra data analyses and comparison with literature data. The detailed spectral data analyses allowed the definition of the structure of the new 1-epi isomer of castanopsol and performance of {sup 1}H and {sup 13}C NMR chemical shift assignments. (author)

A new method to reconstruct fish diet and movement patterns from δ 13 C values in otolith amino acids

KAUST Repository

McMahon, Kelton W.; Fogel, Marilyn L.; Johnson, Beverly J.; Houghton, Leah A.; Thorrold, Simon R.; Gillanders, Bronwyn

2011-01-01

Fish ecologists have used geochemical values in otoliths to examine habitat use, migration, and population connectivity for decades. However, it remains difficult to determine an unambiguous dietary δ 13C signature from bulk analysis of otolith. Studies to date have focused on the aragonite component of otoliths with less attention paid to the organic fraction. We describe the application of compound-specific stable isotope analysis (SIA) to analyze amino acid (AA) δ 13C values from small amounts (<1 mg) of otolith powder. We examined δ 13C values of otolith and muscle AAs from a reef-associated snapper (Lutjanus ehrenbergii (Peters, 1869)) collected along a carbon isotope gradient (isoscape) from seagrass beds to coral reefs. Carbon isotope values in otolith and muscle samples were highly correlated within and among coastal habitats. Moreover, δ 13C values of otolith AAs provided a purely dietary record that avoided dilution from dissolved inorganic carbon. Otolith AAs served as a robust tracer of δ 13C values at the base of the food web, making compound-specific SIA a powerful tool for dietary reconstructions and tracking the movement of fishes across isoscapes.

A new method to reconstruct fish diet and movement patterns from δ 13 C values in otolith amino acids

KAUST Repository

McMahon, Kelton W.

2011-08-01

Fish ecologists have used geochemical values in otoliths to examine habitat use, migration, and population connectivity for decades. However, it remains difficult to determine an unambiguous dietary δ 13C signature from bulk analysis of otolith. Studies to date have focused on the aragonite component of otoliths with less attention paid to the organic fraction. We describe the application of compound-specific stable isotope analysis (SIA) to analyze amino acid (AA) δ 13C values from small amounts (<1 mg) of otolith powder. We examined δ 13C values of otolith and muscle AAs from a reef-associated snapper (Lutjanus ehrenbergii (Peters, 1869)) collected along a carbon isotope gradient (isoscape) from seagrass beds to coral reefs. Carbon isotope values in otolith and muscle samples were highly correlated within and among coastal habitats. Moreover, δ 13C values of otolith AAs provided a purely dietary record that avoided dilution from dissolved inorganic carbon. Otolith AAs served as a robust tracer of δ 13C values at the base of the food web, making compound-specific SIA a powerful tool for dietary reconstructions and tracking the movement of fishes across isoscapes.

Conditions to obtain precise and true measurements of the intramolecular {sup 13}C distribution in organic molecules by isotopic {sup 13}C nuclear magnetic resonance spectrometry

Energy Technology Data Exchange (ETDEWEB)

Bayle, Kevin [EBSI Team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 Rue de la Houssinière, BP 92208, F-44322, Nantes Cedex 3 (France); Gilbert, Alexis [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Earth–Life Science Institute, Tokyo Institute of Technology, Meguro, Tokyo 152-8551 (Japan); Julien, Maxime [EBSI Team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 Rue de la Houssinière, BP 92208, F-44322, Nantes Cedex 3 (France); Yamada, Keita [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Silvestre, Virginie; Robins, Richard J.; Akoka, Serge [EBSI Team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 Rue de la Houssinière, BP 92208, F-44322, Nantes Cedex 3 (France); Yoshida, Naohiro [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Earth–Life Science Institute, Tokyo Institute of Technology, Meguro, Tokyo 152-8551 (Japan); Remaud, Gérald S., E-mail: gerald.remaud@univ-nantes.fr [EBSI Team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 Rue de la Houssinière, BP 92208, F-44322, Nantes Cedex 3 (France)

2014-10-10

Highlights: • Evaluation of the trueness and precision criteria of isotopic {sup 13}C NMR spectrometry. • Use of bi-labelled [1,2-{sup 13}C{sub 2}]acetic acid to determine the performance of the instrumental response. • Inter-calibration of the {sup 13}C intramolecular composition of acetic acid using the technique GC-Py–irm-MS. - Abstract: Intramolecular {sup 13}C composition gives access to new information on the (bio) synthetic history of a given molecule. Isotopic {sup 13}C NMR spectrometry provides a general tool for measuring the position-specific {sup 13}C content. As an emerging technique, some aspects of its performance are not yet fully delineated. This paper reports on (i) the conditions required to obtain satisfactory trueness and precision for the determination of the internal {sup 13}C distribution, and (ii) an approach to determining the “absolute” position-specific {sup 13}C content. In relation to (i), a precision of <1% can be obtained whatever the molecule on any spectrometer, once quantitative conditions are met, in particular appropriate proton decoupling efficiency. This performance is a prerequisite to the measurement of isotope fractionation either on the transformed or residual compound when a chemical reaction or process is being studied. The study of the trueness has revealed that the response of the spectrometer depends on the {sup 13}C frequency range of the studied molecule, i.e. the chemical shift range. The “absolute value” and, therefore, the trueness of the {sup 13}C NMR measurements has been assessed on acetic acid and by comparison to the results obtained on the fragments from COOH and CH{sub 3} by isotopic mass spectrometry coupled to a pyrolysis device (GC-Py–irm-MS), this technique being the reference method for acetic acid. Of the two NMR spectrometers used in this work, one gave values that corresponded to those obtained by GC-Py–irm-MS (thus, the “true” value) while the other showed a bias, which was

Inter-laboratory comparison of elemental analysis and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS). Part I: delta13C measurements of selected compounds for the development of an isotopic Grob-test.

Science.gov (United States)

Serra, F; Janeiro, A; Calderone, G; Rojas, J M Moreno; Rhodes, C; Gonthier, L A; Martin, F; Lees, M; Mosandl, A; Sewenig, S; Hener, U; Henriques, B; Ramalho, L; Reniero, F; Teixeira, A J; Guillou, C

2007-03-01

This study was directed towards investigating suitable compounds to be used as stable isotope reference materials for gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) calibration. Several compounds were selected from those used in the 'Grob-test' mixture. Oxygen- and nitrogen-containing substances were added to these compounds to allow the mixture to be used as a possible multi-isotopic calibration tool for 2H/1H, 13C/12C, 15N/14N and 18O/16O ratio determinations. In this paper we present the results of delta13C measurements performed by the consortium of the five laboratories taking part in this inter-calibration exercise. All the compounds were individually assessed for homogeneity, short-term stability and long-term stability by means of EA-IRMS, as required by the bureau communitaire de reference (BCR) Guide for Production of Certified Reference Materials. The results were compared then with the GC-C-IRMS measurements using both polar and non-polar columns, and the final mixture of selected compounds underwent a further certification exercise assessing limits of accuracy and reproducibility under specified GC-C-IRMS conditions. Copyright 2007 John Wiley & Sons, Ltd.

Compound specific radiocarbon content of lignin oxidation products from the Altamaha river and Coastal Georgia

Energy Technology Data Exchange (ETDEWEB)

Culp, Randy, E-mail: rculp@uga.edu [Center for Applied Isotope Studies, University of Georgia, Athens, Georgia (United States)

2013-01-15

Compound-specific isotope analysis (CSIA) is a powerful tool in organic geochemistry by providing detailed information about an individual organic compound's history with regard to its source and process of formation. Most CSIA involves measurement of the stable isotope ratio of carbon ({sup 13}C/{sup 12}C) and hydrogen (D/H) following separation by gas or liquid chromatography. New applications are being developed using compound-specific radiocarbon ({sup 14}C) content for delineating age of materials, rates of decomposition and residence time in various environments. This paper details the isotopic work on specific lignin monomers derived from terrestrial plants transported and deposited within the Altamaha River, estuary and off-shore Georgia in the Atlantic Ocean. By using gas chromatographic separation and identification of selected lignin oxidation products (LOP), the harvesting of these compounds using preparative fraction collection, and measurement of their {sup 14}C content using accelerator mass spectrometry, details of the age and presence of specific biomarkers unique to a given terrestrial source are revealed. Radiocarbon ages determined from water-column particulate organic carbon and sediment LOPs indicate a range of ages from modern to well over 5,000 years for the former and latter respectively. Transport mechanisms and particle size associations on mineral grains may play a significant role in {sup 14}C distribution in estuary and near-shore coastal environments. This data indicates higher than modern {sup 14}C activities in large particle-size sediment fractions in contrast to older LOP {sup 14}C ages found associated with the same coarse grain sediments. Individual LOP ages substantiate older terrestrial materials persist in the off-shore environment even though in the presence of modern marine {sup 14}C sources.

Bis(1,3-dithiole) Compounds

DEFF Research Database (Denmark)

Andersen, Jan Rud; Engler, E. M.; Green, D. C.

1977-01-01

There is described the preparation of bis-1,3-dithiole compounds (I) which are key synthetic precursors for the preparation of new polymeric metal bis(dithiolene) (i.e., II) and tetrathiafulvalene compounds (i.e., III): (Image Omitted)...

Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

Science.gov (United States)

Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

2018-06-29

The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NMR structure analysis of uniformly 13C-labeled carbohydrates.

Science.gov (United States)

Fontana, Carolina; Kovacs, Helena; Widmalm, Göran

2014-06-01

In this study, a set of nuclear magnetic resonance experiments, some of them commonly used in the study of (13)C-labeled proteins and/or nucleic acids, is applied for the structure determination of uniformly (13)C-enriched carbohydrates. Two model substances were employed: one compound of low molecular weight [(UL-(13)C)-sucrose, 342 Da] and one compound of medium molecular weight ((13)C-enriched O-antigenic polysaccharide isolated from Escherichia coli O142, ~10 kDa). The first step in this approach involves the assignment of the carbon resonances in each monosaccharide spin system using the anomeric carbon signal as the starting point. The (13)C resonances are traced using (13)C-(13)C correlations from homonuclear experiments, such as (H)CC-CT-COSY, (H)CC-NOESY, CC-CT-TOCSY and/or virtually decoupled (H)CC-TOCSY. Based on the assignment of the (13)C resonances, the (1)H chemical shifts are derived in a straightforward manner using one-bond (1)H-(13)C correlations from heteronuclear experiments (HC-CT-HSQC). In order to avoid the (1) J CC splitting of the (13)C resonances and to improve the resolution, either constant-time (CT) in the indirect dimension or virtual decoupling in the direct dimension were used. The monosaccharide sequence and linkage positions in oligosaccharides were determined using either (13)C or (1)H detected experiments, namely CC-CT-COSY, band-selective (H)CC-TOCSY, HC-CT-HSQC-NOESY or long-range HC-CT-HSQC. However, due to the short T2 relaxation time associated with larger polysaccharides, the sequential information in the O-antigen polysaccharide from E. coli O142 could only be elucidated using the (1)H-detected experiments. Exchanging protons of hydroxyl groups and N-acetyl amides in the (13)C-enriched polysaccharide were assigned by using HC-H2BC spectra. The assignment of the N-acetyl groups with (15)N at natural abundance was completed by using HN-SOFAST-HMQC, HNCA, HNCO and (13)C-detected (H)CACO spectra.

Compound- and position-specific carbon isotopic signatures of abiogenic hydrocarbons from on-land serpentinite-hosted Hakuba Happo hot spring in Japan

Science.gov (United States)

Suda, Konomi; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Ueno, Yuichiro

2017-06-01

It has been proposed that serpentinite-hosted hydrothermal/hot spring systems played a significant role in the origin and early evolution of life on early Earth because abiogenic synthesis of organic compounds may accompany serpentinization. However, production mechanisms for apparently abiogenic hydrocarbons that have been observed in the ongoing serpentinizing systems are still poorly constrained. We report a new geochemical study of hydrocarbons in an on-land serpentinite-hosted hot spring in Hakuba Happo, Japan. We have conducted both compound-specific and position-specific carbon isotopic analyses of the observed C1 to C5 hydrocarbons. A positive linear relationship between the δ13C values and the inverse carbon number is found in C1 to C5 straight-chain alkanes in the Happo sample. This isotopic trend is consistent with a simple polymerization model developed in this study. Our model assumes that, for any particular alkane, all of the subsequently added carbons have the same isotopic composition, and those are depleted in 13C with respect to the first carbon in the growing carbon chain. The fit of this model suggests that Happo alkanes can be produced via polymerization from methane with a constant kinetic isotopic fractionation of -8.9 ± 1.0‰. A similar carbon isotopic relationship among alkanes has been observed in some serpentinite-hosted seafloor hydrothermal systems, indicating that the same process is responsible for the abiological hydrocarbon in general serpentinization fields, not only in the Hakuba Happo hot spring. Moreover, our model is also applicable to other potentially abiogenic natural gases and experimentally synthesized hydrocarbon products. For the first time, the intramolecular 13C composition of propane from a natural sample derived from a serpentinite-hosted system was determined. The intramolecular 13C distribution in propane shows the important potential to identify different polymerization mechanisms that cannot be discriminated

Metabolic Response of Soil Microorganisms to Frost: A New Perspective from Position-specific 13C Labeling

Science.gov (United States)

Bore, E. K.; Apostel, C.; Halicki, S.; Dippold, M. A.; Kuzyakov, Y.

2016-12-01

Cold adapted organisms and their biomolecules have received considerable attention in the last few decades, particularly in light of the perceived biotechnological potential. Mostly, these studies are based on pure isolated cultures from permafrost or permafrost samples with inherently adapted microbes. However, microbial activities in agricultural soils that are predominantly exposed to freeze conditions during winter in temperate ecosystems remain unclear. To analyze microbial metabolism at low soil temperatures, isotopomeres of position-specifically 13C labeled glucose were incubated at three temperature; 5 (control), -5 -20 oC. Soils were sampled after 1, 3 and 10 days (and after 30 days for samples at -20 °C). 13C was quantifed in CO2, bulk soil, microbial biomass and dissolved organic carbon (DOC). Highest 13C recovery in CO2 was obtained from C-1 position in control soil. Consequently, metabolic activity was dominated by pentose phosphate pathway at 5 °C. In contrast, metabolic behaviors switched towards a preferential respiration of the glucose C-4 position at -5 and -20 °C. High 13C recovery from C-4 position confirms previous studies suggesting that fermentation increases at subzero temperature. A 3-fold higher 13C recovery in microbial biomass at -5 °C than under control conditions points towards synthesis of intracellular antifreeze metabolites such as glycerol and ethanol and it is consistent with fermentative metabolism. A 5-fold higher 13C in bulk soil than microbial biomass at -20 °C does not reflect non-metabolized glucose because 13C recovery in DOC was less than 0.4% at day 1. Therefore, high 13C recovery in bulk soil at -20 °C was attributed to extracellular metabolites secreted to overcome frost. The shift in antifreeze mechanisms with temperature was brought about by shift in microbial community structure as indicated by incorporation into 13C into PLFA which was 2-fold higher in gram negative bacteria under control than frozen

Activating AMP-activated protein kinase by an α1 selective activator compound 13 attenuates dexamethasone-induced osteoblast cell death

International Nuclear Information System (INIS)

Guo, Shiguang; Mao, Li; Ji, Feng; Wang, Shouguo; Xie, Yue; Fei, Haodong; Wang, Xiao-dong

2016-01-01

Excessive glucocorticoid (GC) usage may lead to non-traumatic femoral head osteonecrosis. Dexamethasone (Dex) exerts cytotoxic effect to cultured osteoblasts. Here, we investigated the potential activity of Compound 13 (C13), a novel α1 selective AMP-activated protein kinase (AMPK) activator, against the process. Our data revealed that C13 pretreatment significantly attenuated Dex-induced apoptosis and necrosis in both osteoblastic-like MC3T3-E1 cells and primary murine osteoblasts. AMPK activation mediated C13′ cytoprotective effect in osteoblasts. The AMPK inhibitor Compound C, shRNA-mediated knockdown of AMPKα1, or dominant negative mutation of AMPKα1 (T172A) almost abolished C13-induced AMPK activation and its pro-survival effect in osteoblasts. On the other hand, forced AMPK activation by adding AMPK activator A-769662 or exogenous expression a constitutively-active (ca) AMPKα1 (T172D) mimicked C13's actions and inhibited Dex-induced osteoblast cell death. Meanwhile, A-769662 or ca-AMPKα1 almost nullified C13's activity in osteoblast. Further studies showed that C13 activated AMPK-dependent nicotinamide adenine dinucleotide phosphate (NADPH) pathway to inhibit Dex-induced reactive oxygen species (ROS) production in MC3T3-E1 cells and primary murine osteoblasts. Such effects by C13 were almost reversed by Compound C or AMPKα1 depletion/mutation. Together, these results suggest that C13 alleviates Dex-induced osteoblast cell death via activating AMPK signaling pathway. - Highlights: • Compound 13 (C13) attenuates dexamethasone (Dex)-induced osteoblast cell death. • C13-induced cytoprotective effect against Dex in osteoblasts requires AMPK activation. • Forced AMPK activation protects osteoblasts from Dex, nullifying C13's activities. • C13 increases NADPH activity and inhibits Dex-induced oxidative stress in osteoblasts.

Activating AMP-activated protein kinase by an α1 selective activator compound 13 attenuates dexamethasone-induced osteoblast cell death

Energy Technology Data Exchange (ETDEWEB)

Guo, Shiguang [Department of Intensive Care Unit, Huai' an First People' s Hospital, Nanjing Medical University, Huai' an (China); Mao, Li [Department of Endocrinology, Huai' an First People' s Hospital, Nanjing Medical University, Huai' an (China); Ji, Feng, E-mail: huaiaifengjidr@163.com [Department of Orthopedics, Huai' an First People' s Hospital, Nanjing Medical University, Huai' an (China); Wang, Shouguo; Xie, Yue; Fei, Haodong [Department of Orthopedics, Huai' an First People' s Hospital, Nanjing Medical University, Huai' an (China); Wang, Xiao-dong, E-mail: xiaodongwangsz@163.com [The Center of Diagnosis and Treatment for Children' s Bone Diseases, The Children' s Hospital Affiliated to Soochow University, Suzhou (China)

2016-03-18

Excessive glucocorticoid (GC) usage may lead to non-traumatic femoral head osteonecrosis. Dexamethasone (Dex) exerts cytotoxic effect to cultured osteoblasts. Here, we investigated the potential activity of Compound 13 (C13), a novel α1 selective AMP-activated protein kinase (AMPK) activator, against the process. Our data revealed that C13 pretreatment significantly attenuated Dex-induced apoptosis and necrosis in both osteoblastic-like MC3T3-E1 cells and primary murine osteoblasts. AMPK activation mediated C13′ cytoprotective effect in osteoblasts. The AMPK inhibitor Compound C, shRNA-mediated knockdown of AMPKα1, or dominant negative mutation of AMPKα1 (T172A) almost abolished C13-induced AMPK activation and its pro-survival effect in osteoblasts. On the other hand, forced AMPK activation by adding AMPK activator A-769662 or exogenous expression a constitutively-active (ca) AMPKα1 (T172D) mimicked C13's actions and inhibited Dex-induced osteoblast cell death. Meanwhile, A-769662 or ca-AMPKα1 almost nullified C13's activity in osteoblast. Further studies showed that C13 activated AMPK-dependent nicotinamide adenine dinucleotide phosphate (NADPH) pathway to inhibit Dex-induced reactive oxygen species (ROS) production in MC3T3-E1 cells and primary murine osteoblasts. Such effects by C13 were almost reversed by Compound C or AMPKα1 depletion/mutation. Together, these results suggest that C13 alleviates Dex-induced osteoblast cell death via activating AMPK signaling pathway. - Highlights: • Compound 13 (C13) attenuates dexamethasone (Dex)-induced osteoblast cell death. • C13-induced cytoprotective effect against Dex in osteoblasts requires AMPK activation. • Forced AMPK activation protects osteoblasts from Dex, nullifying C13's activities. • C13 increases NADPH activity and inhibits Dex-induced oxidative stress in osteoblasts.

Measurement of δ13C values of soil amino acids by GC-C-IRMS using trimethylsilylation: a critical assessment.

Science.gov (United States)

Rubino, Mauro; Milin, Sylvie; D'Onofrio, Antonio; Signoret, Patrick; Hatté, Christine; Balesdent, Jérôme

2014-01-01

In this study, we evaluated trimethylsilyl (TMS) derivatives as derivatization reagents for the compound-specific stable carbon isotope analysis of soil amino acids by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). We used non-proteinogenic amino acids to show that the extraction-derivatization-analysis procedure provides a reliable method to measure δ(13)C values of amino acids extracted from soil. However, we found a number of drawbacks that significantly increase the final total uncertainty. These include the following: production of multiple peaks for each amino acid, identified as di-, tri- and tetra-TMS derivatives; a number of TMS-carbon (TMS-C) atoms added lower than the stoichiometric one, possibly due to incomplete combustion; different TMS-C δ(13)C for di-, tri- and tetra-TMS derivatives. For soil samples, only four amino acids (leucine, valine, threonine and serine) provide reliable δ(13)C values with a total average uncertainty of 1.3 ‰. We conclude that trimethylsilyl derivatives are only suitable for determining the (13)C incorporation in amino acids within experiments using (13)C-labelled tracers but cannot be applied for amino acids with natural carbon isotope abundance until the drawbacks described here are overcome and the measured total uncertainty significantly decreased.

Compound specific radiocarbon content of lignin oxidation products from the Altamaha river and Coastal Georgia

International Nuclear Information System (INIS)

Culp, Randy

2013-01-01

Compound-specific isotope analysis (CSIA) is a powerful tool in organic geochemistry by providing detailed information about an individual organic compound’s history with regard to its source and process of formation. Most CSIA involves measurement of the stable isotope ratio of carbon ( 13 C/ 12 C) and hydrogen (D/H) following separation by gas or liquid chromatography. New applications are being developed using compound-specific radiocarbon ( 14 C) content for delineating age of materials, rates of decomposition and residence time in various environments. This paper details the isotopic work on specific lignin monomers derived from terrestrial plants transported and deposited within the Altamaha River, estuary and off-shore Georgia in the Atlantic Ocean. By using gas chromatographic separation and identification of selected lignin oxidation products (LOP), the harvesting of these compounds using preparative fraction collection, and measurement of their 14 C content using accelerator mass spectrometry, details of the age and presence of specific biomarkers unique to a given terrestrial source are revealed. Radiocarbon ages determined from water-column particulate organic carbon and sediment LOPs indicate a range of ages from modern to well over 5,000 years for the former and latter respectively. Transport mechanisms and particle size associations on mineral grains may play a significant role in 14 C distribution in estuary and near-shore coastal environments. This data indicates higher than modern 14 C activities in large particle-size sediment fractions in contrast to older LOP 14 C ages found associated with the same coarse grain sediments. Individual LOP ages substantiate older terrestrial materials persist in the off-shore environment even though in the presence of modern marine 14 C sources.

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

Science.gov (United States)

Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Structure–kinetic relationship study of CDK8/CycC specific compounds

Science.gov (United States)

Schneider, Elisabeth V.; Böttcher, Jark; Huber, Robert; Maskos, Klaus; Neumann, Lars

2013-01-01

In contrast with the very well explored concept of structure–activity relationship, similar studies are missing for the dependency between binding kinetics and compound structure of a protein ligand complex, the structure–kinetic relationship. Here, we present a structure–kinetic relationship study of the cyclin-dependent kinase 8 (CDK8)/cyclin C (CycC) complex. The scaffold moiety of the compounds is anchored in the kinase deep pocket and extended with diverse functional groups toward the hinge region and the front pocket. These variations can cause the compounds to change from fast to slow binding kinetics, resulting in an improved residence time. The flip of the DFG motif (“DMG” in CDK8) to the inactive DFG-out conformation appears to have relatively little influence on the velocity of binding. Hydrogen bonding with the kinase hinge region contributes to the residence time but has less impact than hydrophobic complementarities within the kinase front pocket. PMID:23630251

The synthesis of Org 3770 labelled with 3H, 13C and 14C

International Nuclear Information System (INIS)

Kaspersen, F.M.; Rooij, F.A.M. van; Sperling, E.G.M.; Wieringa, J.H.

1989-01-01

The syntheses of 1,2,3,4,10,14b-hexahydro-2-methylpyrazino[2,1-a]pyrido[2,3-c][2]benazepine (Org 3770) labelled with 3 H (and 2 H), 13 C and 14 C are described. Tritiated Org 3770 was prepared either by exchange under alkaline conditions with tritiated water or catalytic reductive dehalogenation of a chloro analogue with 3 H 2 . 13 C-labelled material was obtained in a seven-step synthesis starting from 13 C-labelled benzene whereas 14 C-Org 3770 was prepared in a three-step synthesis starting with 14 CO 2 . All labelled compounds were analyzed by TLC, HPLC, MS and NMR. (author)

40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this section...

Phase equilibria, phases and compounds in the Ti-C system

International Nuclear Information System (INIS)

Gusev, Aleksandr I

2002-01-01

The results of experimental and theoretical investigations of the phase equilibria in the titanium-carbon system are generalised. The generalised thermodynamic characteristics of disordered titanium carbide TiC y , are reported. Peculiarities of the crystal structures of all the known and hypothetical compounds of titanium with carbon are considered in detail. The X-ray diffraction patterns which allow identification of all these compounds are presented. The phase diagrams of the Ti-C system constructed with allowance for atomic ordering of non-stoichio metric carbide, TiC y , and for the existence of the molecular cluster-like compounds Ti 8 C 12 and Ti 13 C 22 (TiC 2 ) are discussed. The bibliography includes 142 references.

Phase equilibria, phases and compounds in the Ti-C system

International Nuclear Information System (INIS)

Gusev, A.I.

2002-01-01

The results of experimental and theoretical investigations related to the phase equilibria in the titanium-carbon system are generalized. The generalized thermodynamic characteristics of the disordered titanium carbide TiC y are given. The crystal structure of all the discovered and hypothetical compounds of titanium with carbon are considered in detail. The x-ray diffraction patterns which allow one to identify all these compounds are given. The phase diagrams of the Ti-C system constructed with allowance for atomic ordering of non-stoichiometric TiC y carbide and for the existence of the compounds Ti 8 C 12 and Ti 13 C 22 (TiC 2 ) of the molecule cluster type are discussed [ru

C-13 NMR spectra of all-trans-N-retinylidene-n-butylamine as an analogue of the Schiff base linkage compound in visual pigment

Energy Technology Data Exchange (ETDEWEB)

Tokito, Y; Inoue, Y; Chujo, R [Tokyo Inst. of Tech. (Japan). Faculty of Science; Miyoshi, Y

1975-01-01

In the process of visual excitation, a visual pigment, rhodopsin, plays a role of a photoreceptor, and it has been known that the first step in the process is the photoisomerization of the rhodopsin visual chromophore. The bathochromic shift has been regarded as the result of the formation of Schiff base linkage of retinal with opsin. In this study, C-13 NMR spectra were obtained for the analogue of the compound with Schiff base linkage in the visual pigment, and the chemical shift change for going from all trans-retinal to all trans-N-retinylidene-n-butylamine (NRB) was discussed. Further, the effect of N protonation in NRB was examined as the reflection of the function of visual pigment. The compound with Schiff base linkage of all trans-retinal with n-butylamine, namely NRB, was used. The nuclear magnetic resonance (NMR) spectra of carbon-13 Fourier transformation were obtained for this sample at natural abundance with a JNM PS-100 spectrometer. In the C-13 FT NMR spectrum of NRB, besides eight peaks in the C-13 NMR of all trans-retinal, four peaks were observed in higher field region. They originated from the portion of n-butylamine in the compound with Schiff base linkage. The peaks in lower field region were assigned to eleven conjugated polyene carbons by the measurement of spin-lattice relaxation time and shift. The chemical shift change for going from retinal to NRB is shown. It is concluded that the ..pi..-electrons in polyene chains are considerably delocalized by the collapse of bond alteration in the retinal forming Schiff base linkage.

The metabolism of [3-(13)C]lactate in the rat brain is specific of a pyruvate carboxylase-deprived compartment.

Science.gov (United States)

Bouzier, A K; Thiaudiere, E; Biran, M; Rouland, R; Canioni, P; Merle, M

2000-08-01

Lactate metabolism in the adult rat brain was investigated in relation with the concept of lactate trafficking between astrocytes and neurons. Wistar rats were infused intravenously with a solution containing either [3-(13)C]lactate (534 mM) or both glucose (750 mM) and [3-(13)C]lactate (534 mM). The time courses of both the concentration and (13)C enrichment of blood glucose and lactate were determined. The data indicated the occurrence of [3-(13)C]lactate recycling through liver gluconeogenesis. The yield of glucose labeling was, however, reduced when using the glucose-containing infusate. After a 20-min or 1-h infusion, perchloric acid extracts of the brain tissue were prepared and subsequently analyzed by (13)C- and (1)H-observed/(13)C-edited NMR spectroscopy. The (13)C labeling of amino acids indicated that [3-(13)C]lactate was metabolized in the brain. Based on the alanine C3 enrichment, lactate contribution to brain metabolism amounted to 35% under the most favorable conditions used. By contrast with what happens with [1-(13)C]glucose metabolism, no difference in glutamine C2 and C3 labeling was evidenced, indicating that lactate was metabolized in a compartment deprived of pyruvate carboxylase activity. This result confirms, for the first time from an in vivo study, that lactate is more specifically a neuronal substrate.

One-azabicyclic compounds. 22. Stereochemistry and /sup 13/C NMR spectra of salts of pyrrolizidine and its homologs with protonic acids

Energy Technology Data Exchange (ETDEWEB)

Subbotin, O.A.; Skvortsov, I.M.

1986-06-01

/sup 13/C NMR spectra were obtained for pyrrolizidinium salts and their homologs and their signals were assigned. With the exception of highly strained cis-3,8-H-cis-5,8-H-3,5-dimethylpyrrolizidine (VI), all the bases studied upon their direct mixing with CF/sub 3/CO/sub 2/H form salts only with cis-fused rings in the cation. Mixtures of salts with cis- and trans-fused pyrrolizidinium fragments are formed upon the reaction of cis-3,8-H-methyl- (III) and cis-3,8-H-cis-5,8-H-3,5-dimethylpyrrolizidine (VI) under conditions close to those for kinetically-controlled amine protonation. The /sup 13/C NMR spectra of the isomeric pyrrolizidinium salts obtained as a result of the absorption of base VI by sulfuric acid were used to evaluate the conformational equilibrium in the starting compound VI. The /sup 13/C NMR chemical shifts of unsubstituted trans-fused pyrrolizidinium salts were predicted.

Investigations on the isoprenoid biosynthesis in the green alga Scenedesmus obliquus by using the 13C-labelling technique

International Nuclear Information System (INIS)

Schwender, J.

1995-01-01

The biosynthesis of several prenyllipids (isoprenoid lipids) of the green alga Scendesmus obliquus was investigated. The aim was to verify, whether the biosynthesis of isopentenyl diphosphate (IPP) in Scenedesmus proceeds according to the classical acetate mevalonate pathway or to an alternative pathway. An alternative pathway for IPP formation has recently been detected in some eubacteria by the group of Prof. M. Rohmer. Some inhibition tests were performed with mevinolin, a specific inhibitor of HMG-CoA reductase which yields mevalonic acid. Mevinolin should block the biosynthesis of such isoprenoids which are formed via the acetate mevalonate pathway. Scenedesmus was grown heterotrophically on 13 C-labelled glucose or acetate. After isolation and purification of 13 C-labelled phytol (side chains of chlorophylls), β-carotene, lutein, plastoquinone-9 and three sterol compounds, the enrichment of 13 C at different carbon-positions of the labelled compounds was determined. This was achieved by the 13 C-NMR technique in cooperation with Miriam Seemann of the group of Prof. M. Rohmer in Mullhouse/France. (orig.) [de

Syntheses of DL-[2-13C]leucine and its use in the preparation of [3-DL-[2-13C]leucine]oxytocin and [8-DL-[2-13C]leucine]oxytocin

International Nuclear Information System (INIS)

Viswanatha, V.; Larsen, B.; Hruby, V.J.

1979-01-01

DL-[2- 13 C]Leucine was prepared by condensing the sodium salt of ethyl acetamido-[2- 13 C]cyanoacetate with isobutylbromide in hexamethylphosphoroustriamide followed by acid hydrolysis. N-BOC-DL-[2- 13 C]Leucine was prepared and incorporated into [8-DL-[2- 13 C]leucine]oxytocin by total synthesis. The 13 C-labeled hormone derivative [8-[2- 13 C]leucine]oxytocin was separated from its 8-position diastereoisomer by partition chromatography. The specifically 13 C-labeled peptide hormone diastereoisomeric analog [3-DL-[2- 13 C]leucine]oxytocin also was prepared by solid phase peptide synthesis. No suitable solvent system for partition chromatography separation of the latter diastereoisomeric peptide mixture could be found. However an excellent preparative separation of the diastereoisomers could be obtained by reverse phase high pressure liquid chromatography on a partisil 10 M9 ODS column using the solvent system 0.05 M ammonium acetate (pH 4.0), acetonitrile (81:19, v/v) to give pure [3-[2- 13 C]leucine]oxytocin and [3-D-[2- 13 C]leucine]oxytocin. An excellent separation of [8-[2- 13 C]leucine]oxytocin and the corresponding delata-D-leucine diastereoisomer derivative could also be accomplished by high pressure liquid chromatography. (author)

Direct monitoring by carbon-13 nuclear magnetic resonance spectroscopy of the metabolism and metabolic rate of 13C-labeled compounds in vivo.

Science.gov (United States)

Iida, K; Hidoh, O; Fukami, J; Kajiwara, M

1991-01-01

Carbon-13 nuclear magnetic resonance spectroscopy has been used to observe the transformations of [1-13C]-D-glucose to [1,1'-13C2]-D-trehalose, and [3-13C]-L-alanine to [2-13C]-L-glutamic acid in the living body of Gryllodes sigillatus. [3-13C]-D-Alanine was not metabolized. The metabolic rate of [1-13C]-D-glucose was found to be altered by prior injection of boric acid.

Tracing carbon fixation in phytoplankton—compound specific and total

NARCIS (Netherlands)

Grosse, J.; Van Breugel, P.; Boschker, H.T.S.

2015-01-01

Measurement of total primary production using 13C incorporation is a widely established tool. However, these bulk measurements lack information about the fate of fixed carbon: the production of major cellular compounds (carbohydrates, amino acids, fatty acids, and DNA/RNA) is affected by for

Metabolic pathways for ketone body production. 13C NMR spectroscopy of rat liver in vivo using 13C-multilabeled fatty acids

International Nuclear Information System (INIS)

Pahl-Wostl, C.; Seelig, J.

1986-01-01

The hormonal regulation of ketogenesis in the liver of living rat has been studied noninvasively with 13 C nuclear magnetic resonance. The spatial selection for the liver was better than 90%, with extrahepatic adipose tissue contribution only a very small amount of signal. The metabolic activities of the liver were investigated by infusion of 13 C-labeled butyrate in the jugular vein of the anesthetized rat. The rate of butyrate infusion was chosen to be close to the maximum oxidative capacity of the rat liver, and the 13 C signal intensities were enhanced by using doubly labeled [1,3- 13 C]butyrate as a substrate. Different 13 C NMR spectra and hence different metabolites were observed depending on the hormonal state of the animal. The 13 C NMR studies demonstrate that even when rate of acetyl-CoA production are high, the disposal of this compound is not identical in fasted and diabetic animals. This supports previous suggestions that the redox state of the mitochondrion represents the most important factor in regulation. For a given metabolic state of the animal, different signal intensities were obtained depending on whether butyrate was labeled at C-1, C-3, or C-1,3. From the ratios of incorporation of 13 C label into the carbons of 3-hydroxybutyrate, it could be estimated that a large fraction of butyrate evaded β-oxidation to acetyl-CoA but was converted directly to acetoacetyl-CoA. 13 C-labeled glucose could be detected in vivo in the liver of diabetic rats

Bacterial production of site specific {sup 13}C labeled phenylalanine and methodology for high level incorporation into bacterially expressed recombinant proteins

Energy Technology Data Exchange (ETDEWEB)

Ramaraju, Bhargavi; McFeeters, Hana; Vogler, Bernhard; McFeeters, Robert L., E-mail: robert.mcfeeters@uah.edu [University of Alabama in Huntsville, Department of Chemistry (United States)

2017-01-15

Nuclear magnetic resonance spectroscopy studies of ever larger systems have benefited from many different forms of isotope labeling, in particular, site specific isotopic labeling. Site specific {sup 13}C labeling of methyl groups has become an established means of probing systems not amenable to traditional methodology. However useful, methyl reporter sites can be limited in number and/or location. Therefore, new complementary site specific isotope labeling strategies are valuable. Aromatic amino acids make excellent probes since they are often found at important interaction interfaces and play significant structural roles. Aromatic side chains have many of the same advantages as methyl containing amino acids including distinct {sup 13}C chemical shifts and multiple magnetically equivalent {sup 1}H positions. Herein we report economical bacterial production and one-step purification of phenylalanine with {sup 13}C incorporation at the Cα, Cγ and Cε positions, resulting in two isolated {sup 1}H-{sup 13}C spin systems. We also present methodology to maximize incorporation of phenylalanine into recombinantly overexpressed proteins in bacteria and demonstrate compatibility with ILV-methyl labeling. Inexpensive, site specific isotope labeled phenylalanine adds another dimension to biomolecular NMR, opening new avenues of study.

Abnormal thermal expansion properties of cubic NaZn13-type La(Fe,Al)13 compounds.

Science.gov (United States)

Li, Wen; Huang, Rongjin; Wang, Wei; Zhao, Yuqiang; Li, Shaopeng; Huang, Chuanjun; Li, Laifeng

2015-02-28

The cubic NaZn13-type La(Fe,Al)13 compounds were synthesized, and their linear thermal expansion properties were investigated in the temperature range of 4.2-300 K. It was found that these compounds exhibit abnormal thermal expansion behavior, i.e., pronounced negative thermal expansion (NTE) or zero thermal expansion (ZTE) behavior, below the Curie temperature due to the magnetovolume effect (MVE). Moreover, in the La(Fe,Al)13 compounds, the modification of the coefficient of thermal expansion (CTE) as well as the abnormal thermal expansion (ATE) temperature-window is achieved through optimizing the proportion of Fe and Al. Typically, the average CTE of the LaFe13-xAlx compounds with x = 1.8 reaches as large as -10.47 × 10(-6) K(-1) between 100 and 225 K (ΔT = 125 K). Also, the ZTE temperature-window of the LaFe13-xAlx compounds with x = 2.5 and x = 2.7 could be broadened to 245 K (from 5 to 250 K). Besides, the magnetic properties of these compounds were measured and correlated with the abnormal thermal expansion behavior. The present results highlight the potential application of such La(Fe,Al)13 compounds with abnormal thermal expansion properties in cryogenic engineering.

Study for the charge symmetric systems, 12C+13N and 12C+13C with the orthogonalized coupled-reaction-channel method

International Nuclear Information System (INIS)

Imanishi, B.; Denisov, V.; Motobayashi, T.

1996-10-01

The charge-symmetric scattering systems, 12 C+ 13 N and 12 C+ 13 C have been investigated by using the orthogonalized coupled-reaction-channel (OCRC) method with the basis functions of the elastic, inelastic and transfer channels defined by the single-particle states, 1p1/2, 2s1/2, 1d5/2 and 1d3/2 of the valence nucleon in 13 N or 13 C. The data of the elastic scattering of 13 N on 12 C measured by Lienard et al. have been explained consistently with the data of the elastic and inelastic scattering of the 12 C+ 13 C system. The CRC effects both on the above systems are very strong, although those on the 12 C+ 13 N system are fairly weaker than the 12 C+ 13 C system. The role of the highly excited single-particle states 1d3/2 is particularly important in the formation of a specific CRC scheme, i.e., the formation of the covalent molecules due to the hybridization caused by the mixing of the different parity single-particle states. The fusion cross sections of the 12 C+ 13 C system at energies below the Coulomb barrier are strongly enhanced as a result of the strong CRC effects as compared with those of the 12 C+ 12 C system, while in 12 C+ 13 N system the enhancement of the sub-barrier fusion has not been observed. The above absorption mechanism for the 12 C+ 13 C system explains the lack of the molecular-resonance phenomena observed in the 12 C+ 12 C system. We check the effects of the dipole (E1) transition of the valence nucleon in 13 N (and also in 13 C) due to the core-core Coulomb interaction in the scattering at sub-barrier energies. The effects are not appreciable. (author)

Species specific and environment induced variation of δ13C and δ15N in alpine plants

Directory of Open Access Journals (Sweden)

Yang eYang

2015-06-01

Full Text Available Stable carbon and nitrogen isotope signals in plant tissues integrate plant-environment interactions over long periods. In this study, we hypothesized that humid alpine life conditions are narrowing the scope for significant deviations from common carbon, water and nitrogen relations as captured by stable isotope signals. We explored the variation in δ13C and δ15N in 32 plant species from tissue type to ecosystem scale across a suite of locations at c. 2500 m elevation in the Swiss Alps. Foliar δ13C and δ15N varied among species by about 3-4 ‰ and 7-8 ‰ respectively. However, there was no overall difference in means of δ13C and δ15N for species sampled in different plant communities or when bulk plant dry matter harvests of different plant communities were compared. δ13C was found to be highly species specific, so that the ranking among species was mostly maintained across 11 habitats. However, δ15N varied significantly from place to place in all species (a range of 2.7 ‰ except in Fabaceae (Trifolium alpinum and Juncaceae (Luzula lutea. There was also a substantial variation among individuals of the same species collected next to each other. No difference was found in foliar δ15N of non-legumes, which were either collected next to or away from the most common legume, T. alpinum. δ15N data place Cyperaceae and Juncaceae, just like Fabaceae, in a low discrimination category, well separated from other families. Soil δ15N was higher than in plants and increased with soil depth. The results indicate a high functional diversity in alpine plants that is similar to that reported for low elevation plants. We conclude that the surprisingly high variation in δ13C and δ15N signals in the studied high elevation plants is largely species specific (genetic and insensitive to obvious environmental cues.

Inter- and intra-specific variability in δ13C and δ18O values of freshwater gastropod shells from Lake Lednica, western Poland

Science.gov (United States)

Apolinarska, Karina; Pełechaty, Mariusz

2017-09-01

This study focuses on the inter- and intra-specific variability in δ13C and δ18O values of shells and opercula of gastropods sampled live from the littoral zone of Lake Lednica, western Poland. The δ13C and δ18O values were measured in individual opercula of Bithynia tentaculata and in shells of Bithynia tentaculata, Gyraulus albus, Gyraulus crista, Lymnaea sp., Physa fontinalis, Radix auricularia, Theodoxus fluviatilis and Valvata cristata. The gastropods selected for the study are among the species most commonly found in European Quaternary lacustrine sediments. The carbon isotope composition of the gastropod shells was species-specific and the same order of species from the most to the least 13C-depleted was observed at all sites sampled. Differences in shell δ13C values between species were similar at all sampling sites, thus the factors influencing shell isotopic composition were interpreted as species-specific. The δ18O values of shells were similar in all the species investigated. Significant intra-specific variability in shell δ13C and δ18O values was observed not only within the populations of Lake Lednica, which can be explained by heterogeneity of δ13C DIC, δ18O water and water temperature between the sites where macrophytes with snails attached were sampled, but also between individuals sampled from restricted areas of the lake's bottom. The latter points to the importance of factors related to the ontogeny of individual gastropods.

Synthesis of O- and C-glycosides derived from β-(1,3)-D-glucans.

Science.gov (United States)

Marca, Eduardo; Valero-Gonzalez, Jessika; Delso, Ignacio; Tejero, Tomás; Hurtado-Guerrero, Ramon; Merino, Pedro

2013-12-15

A series of β-(1,3)-d-glucans have been synthesized incorporating structural variations specifically on the reducing end of the oligomers. Both O- and C-glucosides derived from di- and trisaccharides have been obtained in good overall yields and with complete selectivity. Whereas the O-glycosides were obtained via a classical Koenigs-Knorr glycosylation, the corresponding C-glycosides were obtained through allylation of the anomeric carbon and further cross-metathesis reaction. Finally, the compounds were evaluated against two glycosidases and two endo-glucanases and no inhibitory activity was observed. Copyright © 2013 Elsevier Ltd. All rights reserved.

Compound-specific isotope analysis resolves the dietary origin of docosahexaenoic acid in the mouse brain.

Science.gov (United States)

Lacombe, R J Scott; Giuliano, Vanessa; Colombo, Stefanie M; Arts, Michael T; Bazinet, Richard P

2017-10-01

DHA (22:6n-3) may be derived from two dietary sources, preformed dietary DHA or through synthesis from α-linolenic acid (ALA; 18:3n-3). However, conventional methods cannot distinguish between DHA derived from either source without the use of costly labeled tracers. In the present study, we demonstrate the proof-of-concept that compound-specific isotope analysis (CSIA) by GC-isotope ratio mass spectrometry (IRMS) can differentiate between sources of brain DHA based on differences in natural 13 C enrichment. Mice were fed diets containing either purified ALA or DHA as the sole n-3 PUFA. Extracted lipids were analyzed by CSIA for natural abundance 13 C enrichment. Brain DHA from DHA-fed mice was significantly more enriched (-23.32‰ to -21.92‰) compared with mice on the ALA diet (-28.25‰ to -27.49‰). The measured 13 C enrichment of brain DHA closely resembled the dietary n-3 PUFA source, -21.86‰ and -28.22‰ for DHA and ALA, respectively. The dietary effect on DHA 13 C enrichment was similar in liver and blood fractions. Our results demonstrate the effectiveness of CSIA, at natural 13 C enrichment, to differentiate between the incorporation of preformed or synthesized DHA into the brain and other tissues without the need for tracers. Copyright © 2017 by the American Society for Biochemistry and Molecular Biology, Inc.

Achievement report on research and development of medical and welfare equipment technology. Unit {sup 13}C-MRS for noninvasive measurement of brain metabolism; Iryo fukushi kiki gijutsu kenkyu kaihatsu seika hokokusho. Mushinshuteki no taisha keisokuyo {sup 1}3C-MRS sochi

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-11-01

The effort is to develop technologies of conducting highly sensitive, uninterrupted observation of metabolism in the brain by use of the {sup 13}C-MRS unit, for which some carbon chain compounds (glucose, amino acids, etc.), which assume an important part in metabolism, are labelled by a stable isotope {sup 13}C and then administered to living things. A multi-slice HSQC (heteronuclear single quantum coherence) method is developed for the achievement of sensitivity enhanced 16 folds, excellent compound isolating capability, and high localizing capability, and these contribute to the specification of an optimum pulse sequence. A double tuning coil is developed for transmission, and a 6-channel multi-surface coil for reception, these two providing a 3-fold increase in detection probe sensitivity. The nonlinear least-square method is applied for the processing of spectral data, which enables excellent isolation of compounds. It also enables the generation of an inclined magnetic field quick to rise and of a sequence high in amplitude/phase accuracy. New methods are developed for the synthesis of {sup 13}C-labelled glucose, dopa, glutamine, glutamic acid, and GABA (gamma-aminobutyric acid) which are expected to be useful in brain metabolism measurement, and the products are administered to animals for evaluation. (NEDO)

NMR spectroscopy of organic compounds of selenium and tellurium. Communication 9. Chemical shifts of /sup 13/C in isological series of unsaturated ethers, sulfides, selenides and tellurides

Energy Technology Data Exchange (ETDEWEB)

Kalabin, G.A.; Bzhezovskii, V.M.; Kushnarev, D.F.; Proidakov, A.G. (Irkutskii Gosudarstvennyj Univ. (USSR))

1981-06-01

The effects of heteroatoms Eh(Eh=O, S, Se, Te) on /sup 13/C chemical shifts in eleven isological series of R/sup 1/-Eh-R/sup 2/ unsaturated compounds are compared. A linear relation between /sup 13/C nuclei screening and tEh electronegativity is observed. An assumption is suggested that both likeness of the effects of 6A and 7A group elements on /sup 13/C chemical shifts of R/sup 1/ and R/sup 2/ substituents and their difference for elements of the 4A group are caused by unbonded interactions of the substituents with unshared electron pairs of heteroatoms.

Applications of artificial intelligence techniques to organic chemistry. Study on sup 13 C NMR of steroids using computer. Aplicacoes de tecnicas de inteligencia artificial em quimica organica. Estudo, por computador, de RMN sup 13 C de esteroides

Energy Technology Data Exchange (ETDEWEB)

Lins, A P [Instituto Biologico, Sao Paulo, SP (Brazil). Secao de Farmacologia; Furlan, M [UNESP, Araraquara, SP (Brazil). Inst. de Quimica; Gastmans, G P [UNESP, Guaratingueta, SP (Brazil). Inst. de Quimica e Fisica; Emerenciano, V P [Sao Paulo Univ., SP (Brazil). Inst. de Quimica

1991-01-01

This work describes the utilization of two groups of programs in searching for characteristic signals of NMR {sup 13}C steroidal compounds. The first group of programs used data bases with the spectral data and a methodology that enables the choice and the search of substructures. The chemical shifts and multiplicities for each specific substructure are used as rules to identify different types and subtypes of steroidal compounds. The second one was built to apply the rules formulated by the first group of programs and to foresee any skeletal based on a spectral analysis. (author).

Compound-specific isotope analysis of light elements using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) and its application to geochemistry

International Nuclear Information System (INIS)

Naraoka, Hiroshi; Yamada, Keita; Matsumoto, Kohei; Ishiwatari, Ryoshi

1997-01-01

Compound-specific isotope analysis has been developed recently using gas chromatography/combustion/mass spectrometry (GC/C/IRMS). This paper summarizes principles and progress of GC/C/IRMS, and reviews recent some important works using this new method. GC/C/IRMS is a novel tool for (1) biomarker analysis in sediments and living matter, (2) paleoenvironment analysis including reconstruction of ancient biogeochemical processes, (3) geochemical cycle study of organic compounds in a terrestrial-marine system, (4) evaluation of maturity and diagenesis of organic matter including petroleum formation, (5) ecological analysis, (6) evaluation of anthropologenic pollution in environment, (7) detection of extraterrestrial organic compounds and the formation mechanism study, (8) tracer studies in environment. (author)

Clinical value of 13C-UBT diagnosing infection of the Hp

International Nuclear Information System (INIS)

Xu Changde; Chen Shaoliang; Liu Wenguan

2004-01-01

100 dyspeptic patients are performed an endoscopy with biopsy for histology, rapid urease test, 13 C-urea breath test( 13 C-UBT) and ASSURE TM Hp rapid Test(HpRT). Patients are considered to be infected if both histology and biopsies yield positive results, and not infected when both tests are negative. The pathology and persons responsible for endoscopy, urease test and 13 C-UBT are unaware of the results from the other diagnostic methods. The 13 C-UBT has the following results: sensitivity 96% ,specificity 95%; rapid urease test has the following results: sensitivity 79%, specificity 76%; HpRT has the following results: sensitivity 86%, specificity 88%. 13 C-UBT provides excellent sensitivity and specificity for the diagnosis of Hp. Pylori infected Hp, it can be the first choice for detecting the infection of the Hp. (authors)

Compound 13, an α1-selective small molecule activator of AMPK, inhibits Helicobacter pylori-induced oxidative stresses and gastric epithelial cell apoptosis

International Nuclear Information System (INIS)

Zhao, Hangyong; Zhu, Huanghuang; Lin, Zhou; Lin, Gang; Lv, Guoqiang

2015-01-01

Half of the world's population experiences Helicobacter pylori (H. pylori) infection, which is a main cause of gastritis, duodenal and gastric ulcer, and gastric cancers. In the current study, we investigated the potential role of compound 13 (C13), a novel α1-selective small molecule activator of AMP-activated protein kinase (AMPK), against H. pylori-induced cytotoxicity in cultured gastric epithelial cells (GECs). We found that C13 induced significant AMPK activation, evidenced by phosphorylation of AMPKα1 and ACC (acetyl-CoA carboxylase), in both primary and transformed GECs. Treatment of C13 inhibited H. pylori-induced GEC apoptosis. AMPK activation was required for C13-mediated GEC protection. Inhibition of AMPK kinase activity by the AMPK inhibitor Compound C, or silencing AMPKα1 expression by targeted-shRNAs, alleviated C13-induced GEC protective activities against H. pylori. Significantly, C13 inhibited H. pylori-induced reactive oxygen species (ROS) production in GECs. C13 induced AMPK-dependent expression of anti-oxidant gene heme oxygenase (HO-1) in GECs. Zinc protoporphyrin (ZnPP) and tin protoporphyrin (SnPP), two HO-1 inhibitors, not only suppressed C13-mediated ROS scavenging activity, but also alleviated its activity in GECs against H. pylori. Together, these results indicate that C13 inhibits H. pylori-induced ROS production and GEC apoptosis through activating AMPK–HO–1 signaling. - Highlights: • We synthesized compound 13 (C13), a α1-selective small molecule AMPK activator. • C13-induced AMPK activation requires α1 subunit in gastric epithelial cells (GECs). • C13 enhances Helicobacter pylori-induced pro-survival AMPK activation to inhibit GEC apoptosis. • C13 inhibits H. pylori-induced reactive oxygen species (ROS) production in GECs. • AMPK-heme oxygenase (HO-1) activation is required for C13-mediated anti-oxidant activity

Compound 13, an α1-selective small molecule activator of AMPK, inhibits Helicobacter pylori-induced oxidative stresses and gastric epithelial cell apoptosis

Energy Technology Data Exchange (ETDEWEB)

Zhao, Hangyong; Zhu, Huanghuang; Lin, Zhou; Lin, Gang; Lv, Guoqiang, E-mail: lvguoqiangwuxivip@163.com

2015-08-07

Half of the world's population experiences Helicobacter pylori (H. pylori) infection, which is a main cause of gastritis, duodenal and gastric ulcer, and gastric cancers. In the current study, we investigated the potential role of compound 13 (C13), a novel α1-selective small molecule activator of AMP-activated protein kinase (AMPK), against H. pylori-induced cytotoxicity in cultured gastric epithelial cells (GECs). We found that C13 induced significant AMPK activation, evidenced by phosphorylation of AMPKα1 and ACC (acetyl-CoA carboxylase), in both primary and transformed GECs. Treatment of C13 inhibited H. pylori-induced GEC apoptosis. AMPK activation was required for C13-mediated GEC protection. Inhibition of AMPK kinase activity by the AMPK inhibitor Compound C, or silencing AMPKα1 expression by targeted-shRNAs, alleviated C13-induced GEC protective activities against H. pylori. Significantly, C13 inhibited H. pylori-induced reactive oxygen species (ROS) production in GECs. C13 induced AMPK-dependent expression of anti-oxidant gene heme oxygenase (HO-1) in GECs. Zinc protoporphyrin (ZnPP) and tin protoporphyrin (SnPP), two HO-1 inhibitors, not only suppressed C13-mediated ROS scavenging activity, but also alleviated its activity in GECs against H. pylori. Together, these results indicate that C13 inhibits H. pylori-induced ROS production and GEC apoptosis through activating AMPK–HO–1 signaling. - Highlights: • We synthesized compound 13 (C13), a α1-selective small molecule AMPK activator. • C13-induced AMPK activation requires α1 subunit in gastric epithelial cells (GECs). • C13 enhances Helicobacter pylori-induced pro-survival AMPK activation to inhibit GEC apoptosis. • C13 inhibits H. pylori-induced reactive oxygen species (ROS) production in GECs. • AMPK-heme oxygenase (HO-1) activation is required for C13-mediated anti-oxidant activity.

A field-deployable compound-specific isotope analyzer based on quantum cascade laser and hollow waveguide

Science.gov (United States)

Wu, Sheng; Deev, Andrei

2013-01-01

A field deployable Compound Specific Isotope Analyzer (CSIA) coupled with capillary chromatogrpahy based on Quantum Cascade (QC) lasers and Hollow Waveguide (HWG) with precision and chemical resolution matching mature Mass Spectroscopy has been achieved in our laboratory. The system could realize 0.3 per mil accuracy for 12C/13C for a Gas Chromatography (GC) peak lasting as short as 5 seconds with carbon molar concentration in the GC peak less than 0.5%. Spectroscopic advantages of HWG when working with QC lasers, i.e. single mode transmission, noiseless measurement and small sample volume, are compared with traditional free space and multipass spectroscopy methods.

Applications of artificial intelligence techniques to organic chemistry. Study on 13C NMR of steroids using computer

International Nuclear Information System (INIS)

Lins, A.P.; Furlan, M.; Gastmans, G.P.; Emerenciano, V.P.

1991-01-01

This work describes the utilization of two groups of programs in searching for characteristic signals of NMR 13 C steroidal compounds. The first group of programs used data bases with the spectral data and a methodology that enables the choice and the search of substructures. The chemical shifts and multiplicities for each specific substructure are used as rules to identify different types and subtypes of steroidal compounds. The second one was built to apply the rules formulated by the first group of programs and to foresee any skeletal based on a spectral analysis. (author)

Recoveries of rat lymph FA after administration of specific structured C-13-TAG

DEFF Research Database (Denmark)

Vistisen, Bodil; Mu, Huiling; Høy, Carl-Erik

2003-01-01

of intragastrically administered L*L*L*, M*M*M*, ML*M, and ML*L* (where * = C-13-labeled FA) in rats. Lymph lipids were separated into lipid classes and analyzed by GC combustion isotope ratio MS. The recoveries of lymph TAG 18:2n-6 8 h after administration of L*L*L*, ML*M, and ML*L* were 38.6, 48.4, and 49...... rapid recovery of exogenous long-chain FA following administration of specific structured TAG compared with long-chain TAG was probably due to fast hydrolysis. The lymphatic recovery of 8:0 was 2.2% 24 h after administration of M*M*M*. This minor lymphatic recovery of exogenous 8:0 was probably due...... to low stimulation of chylomicron formation. These results demonstrate tendencies toward faster lymphatic recovery of long-chain FA after administration of specific structured TAG compared with long-chain TAG....

A new Schiff base compound N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone): synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, 1H NMR and 13C NMR spectra.

Science.gov (United States)

Saheb, Vahid; Sheikhshoaie, Iran

2011-10-15

The Schiff base compound, N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone) (NDHA) is synthesized through the condensation of 2-hydroxylacetophenone and 2,2-dimethyl 1,3-amino propane in methanol at ambient temperature. The yellow crystalline precipitate is used for X-ray single-crystal determination and measuring Fourier transform infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP, PBEPBE and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the FTIR, (1)H NMR and (13)C NMR spectra of the compound. Time-dependent density functional theory (TDDFT) method is used to calculate the UV-visible spectrum of NDHA. Vibrational frequencies are determined experimentally and compared with those obtained theoretically. Vibrational assignments and analysis of the fundamental modes of the compound are also performed. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR and (13)C NMR chemical shifts calculated by all DFT methods are consistent with the experimental data. However, the NMR shielding tensors computed at the B3LYP/6-31+G(d,p) level of theory are in better agreement with experimental (1)H NMR and (13)C NMR spectra. The electronic absorption spectrum calculated at the B3LYP/6-31+G(d,p) level by using TD-DFT method is in accordance with the observed UV-visible spectrum of NDHA. In addition, some quantum descriptors of the molecule are calculated and conformational analysis is performed and the results were compared with the crystallographic data. Copyright © 2011 Elsevier B.V. All rights reserved.

Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

Science.gov (United States)

Wu, Langping; Kümmel, Steffen; Richnow, Hans H

2017-04-01

Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

An improved synthesis of α-13C glycine and heteronuclear NMR studies of its incorporation into thioredoxin

International Nuclear Information System (INIS)

Wishart, D.S.; Sykes, B.D.; Richards, F.M.

1992-01-01

We present an improved method to easily prepare gram quantities of α- 13 C glycine beginning from K 13 CN. The four step synthesis involves the production of an N, N-diphenyl-cyanoformamidine intermediate through the coupling of cyanide to N, N-diphenylcarbodiimide. Subsequent reduction by LiAlH 4 and hydrolysis of the resulting amidine produces fully enriched α- 13 C labelled glycine with a 45-50% yield. This relatively fast and simple synthesis uses only commonly available compounds and requires no special equipment, making the process easy to perform in any well equipped biochemistry laboratory. We further demonstrate that the product may be used, without extensive purification, to specifically label bacterially expressed proteins (E. coli thioredoxin) through standard biosynthetic procedures. We also show that the 13 C glycine-labelled protein may be readily analyzed using commonly available heteronuclear NMR techniques. Complete assignments for all 9 glycines of native E. coli thoredoxin are presented. (Author)

Synthesis and applications of 13C glycerol

International Nuclear Information System (INIS)

Stocking, E.; Khalsa, O.; Martinez, R.; Silks, L.A. III

1994-01-01

The authors are currently developing new synthetic routes to the various isotopomers of glycerol. Labeled glycerol is useful for 13 C enrichment of biomolecules. However, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment or have poor overall yields (12-15%). In addition, the use of glycerol for enrichment can be prohibitively expensive and its availability depends on the level of demand. The authors have developed a short de novo synthesis of [U- 13 C]glycerol from carbon dioxide (∼53% overall yield for four steps) and are currently examining the feasibility of synthesizing site-specific 13 C labeled glycerol and dihydroxyacetone (DHA) from methanol and carbon dioxide. The authors have examined the enzymatic conversion of [U- 13 C]glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25-50% (as determined by NMR spectroscopy). The authors are also pursuing the chemical conversion of 13 C labeled DHA to DHAP and the results are presented. Labeled DHAP is a possible enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis.

Science.gov (United States)

Lojkasek-Lima, Paulo; Aravena, Ramon; Parker, Beth L; Cherry, John A

2012-01-01

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by

13C nuclear magnetic resonance study of the complexation of calcium by taurine

International Nuclear Information System (INIS)

Irving, C.S.; Hammer, B.E.; Danyluk, S.S.; Klein, P.D.

1980-01-01

13 C Nuclear magnetic resonance chemical shifts, 1 J/sub c-c/ scalar coupling constants, spin-lattice relaxation times, and nuclear Overhauser effects were determined for taurine-[1, 2 13 C] and a taurine-[1 13 C] and taurine-[2 13 C] mixture in the presence and absence of calcium. Comparison of taurine titration shifts to values for related compounds reveals some unusual electronic properties of the taurine molecule. Stability constants of 1:1 calcium complexes with taurine zwitterions and anions, as well as their 13 C chemical shifts, were obtained by least squares analysis of titration curves measured in the presence of calcium. The stability constants of calcium-taurine complexes were significantly lower than previous values and led to estimates that only approximately one percent of intracellular calcium of mammalian myocardial cells would exist in a taurine complex

Determination of the anomeric specificity of the Escherichia coli CTP:CMP-3-deoxy-D-manno-octulosonate cytidylyltransferase by 13C NMR spectroscopy

International Nuclear Information System (INIS)

Kohlbrenner, W.E.; Fesik, S.W.

1985-01-01

[99%, 1- 13 C]- and [90%, 2- 13 C]3-deoxy-D-manno-octulosonic acid (KDO) were prepared enzymatically and used to determine the anomeric specificity of the CTP:CMP-3-deoxy-D-manno-octulosonate cytidylyl transferase (CMP-KDO synthetase) by 13 C NMR spectroscopy. Addition of CMP-KDO synthetase to reaction mixtures containing either 1- 13 C- or 2- 13 C-labeled KDO resulted in rapid CMP-KDO formation which was accompanied by a substantial decrease in the 13 C-enriched resonances of the beta-pyranose form of KDO relative to the resonances of other KDO species in solution, demonstrating that the beta-pyranose is the preferred substrate. Concomitant with the production of CMP-KDO was the appearance of peaks at 174.3 and 101.4 ppm when [1- 13 C]- and [2- 13 C]KDO, respectively, were used as substrates. The correspondence of these resonances to the enriched carbons in CMP-KDO was confirmed by the expected 3-bond (3JP,C-1 = 6.9 Hz) and 2-bond coupling (2JP,C-2 = 8.3 Hz) between the labeled carbons and the ketosidically linked phosphoryl group. A large coupling (3J = 5.7 Hz) was observed in proton-coupled spectra of CMP-[1- 13 C]KDO between carbon 1 and the axial proton at carbon 3 of KDO. The magnitude of this coupling constant supports a diaxial relationship between these two groups and, along with chemical shift data, indicates that KDO retains the beta-configuration when linked in CMP-KDO

Synthesis and applications of 13C glycerol

International Nuclear Information System (INIS)

Stocking, E.; Khalsa, O.; Martinez, R.A.; Silks, L.A. III

1994-01-01

Due in part to the use of labeled glycerol for the 13 C enrichment of biomolecules, we are currently developing new synthetic routes to various isotopomers of glycerol. Judging from our experience, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment and/or have poor overall yields (12 to 15%). Furthermore, the use of glycerol for enrichment can be prohibitively expensive and its availability is limited by the level of demand. We are presently developing a short de novo synthesis of glycerol from carbon dioxide (∼53% overall yield for four steps) and are examining the feasibility of synthesizing site-specific 13 C-labeled glycerol and dihydroxyacetone (DHA) from labeled methanol and carbon dioxide. One application of 13 C glycerol we have examined is enzymatic conversion of glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25 to 50% (as determined by NMR spectroscopy). We are also pursuing the chemical conversion of 13 C-labeled DHA to DHAP. We are especially interested in 13 C-labeled DHAP because we are investigating its use as a chemo-enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

Science.gov (United States)

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high

Mictomagnetic, ferromagnetic, and antiferromagnetic transitions in La(FexAl1–x)13 intermetallic compounds

NARCIS (Netherlands)

Palstra, T.T.M.; Nieuwenhuys, G.J.; Mydosh, J.A.; Buschow, K.H.J.

1985-01-01

Cubic La(FexAl1–x)13 intermetallic compounds can be stabilized with iron concentration x between 0.46 and 0.92 in the NaZn13-type structure (D23) with Fm3c (Oh6) space-group symmetry. Here the Fe-Fe coordination number can increase up to 12. At low x values, a mictomagnetic regime occurs with

Defying c-Abl signaling circuits through small allosteric compounds

Directory of Open Access Journals (Sweden)

Stefania eGonfloni

2014-11-01

Full Text Available Many extracellular and intracellular signals promote the c-Abl tyrosine kinase activity. c-Abl in turn triggers a multitude of changes either in protein phosphorylation or in gene expression in the cell. Yet, c-Abl takes part in diverse signaling routes because of several domains linked to its catalytic core. Complex conformational changes turn on and off its kinase activity. These changes affect surface features of the c-Abl kinase and likely its capability to bind actin and/or DNA. Two specific inhibitors (ATP-competitive or allosteric compounds regulate the c-Abl kinase through different mechanisms. NMR studies show that a c-Abl fragment (SH3-SH2-linker-SH1 adopts different conformational states upon binding to each inhibitor. This supports an unconventional use for allosteric compounds to unraveling physiological c-Abl signaling circuits.

Fourier spectroscopy of the 12C2, 13C2, and 12C13C (0-0) swan bands

International Nuclear Information System (INIS)

Amiot, C.

1983-01-01

The (0-0) band of the C 2 Swan electronic system d 3 Pi/sub g/→a 3 Pi/sub u/ has been recorded by Fourier spectroscopy. The three isotopes species 12 C 2 , 13 C 2 , and 12 C 13 C were investigated. The observed wavenumbers were reduced to molecular parameters using a nonlinear least-square fitting procedure. Well-known perturbations at N' = 47 and N' = 51 again observed in the e 12 C 2 d 3 Pi/sub g/ (v = 0) level. Perturbations of the same kind are present in the 13 C 2 spectrum at N' = 34 and N' = 44,48,52. The 12 C 13 C spectrum exhibits in the observed spectral range a unique perturbation for N' = 41

Tracing carbon flow through coral reef food webs using a compound-specific stable isotope approach.

Science.gov (United States)

McMahon, Kelton W; Thorrold, Simon R; Houghton, Leah A; Berumen, Michael L

2016-03-01

Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world's oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column production, benthic primary production, and recycled detrital carbon (C). We coupled compound-specific stable C isotope ratio (δ(13)C) analyses with Bayesian mixing models to quantify C flow from primary producers to coral reef fishes across multiple feeding guilds and trophic positions in the Red Sea. Analyses of reef fishes with putative diets composed primarily of zooplankton (Amblyglyphidodon indicus), benthic macroalgae (Stegastes nigricans), reef-associated detritus (Ctenochaetus striatus), and coral tissue (Chaetodon trifascialis) confirmed that δ(13)C values of essential amino acids from all baseline C sources were both isotopically diagnostic and accurately recorded in consumer tissues. While all four source end-members contributed to the production of coral reef fishes in our study, a single-source end-member often dominated dietary C assimilation of a given species, even for highly mobile, generalist top predators. Microbially reworked detritus was an important secondary C source for most species. Seascape configuration played an important role in structuring resource utilization patterns. For instance, Lutjanus ehrenbergii showed a significant shift from a benthic macroalgal food web on shelf reefs (71 ± 13 % of dietary C) to a phytoplankton-based food web (72 ± 11 %) on oceanic reefs. Our work provides insights into the roles that diverse C sources play in the structure and function of coral reef ecosystems and illustrates a powerful fingerprinting method to develop and test nutritional frameworks for understanding resource utilization.

Tracing carbon flow through coral reef food webs using a compound-specific stable isotope approach

KAUST Repository

McMahon, Kelton

2015-11-21

Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world’s oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column production, benthic primary production, and recycled detrital carbon (C). We coupled compound-specific stable C isotope ratio (δ13C) analyses with Bayesian mixing models to quantify C flow from primary producers to coral reef fishes across multiple feeding guilds and trophic positions in the Red Sea. Analyses of reef fishes with putative diets composed primarily of zooplankton (Amblyglyphidodon indicus), benthic macroalgae (Stegastes nigricans), reef-associated detritus (Ctenochaetus striatus), and coral tissue (Chaetodon trifascialis) confirmed that δ13C values of essential amino acids from all baseline C sources were both isotopically diagnostic and accurately recorded in consumer tissues. While all four source end-members contributed to the production of coral reef fishes in our study, a single-source end-member often dominated dietary C assimilation of a given species, even for highly mobile, generalist top predators. Microbially reworked detritus was an important secondary C source for most species. Seascape configuration played an important role in structuring resource utilization patterns. For instance, Lutjanus ehrenbergii showed a significant shift from a benthic macroalgal food web on shelf reefs (71 ± 13 % of dietary C) to a phytoplankton-based food web (72 ± 11 %) on oceanic reefs. Our work provides insights into the roles that diverse C sources play in the structure and function of coral reef ecosystems and illustrates a powerful fingerprinting method to develop and test nutritional frameworks for understanding resource utilization.

Apportioning sources of organic matter in streambed sediments: An integrated molecular and compound-specific stable isotope approach

Energy Technology Data Exchange (ETDEWEB)

Cooper, Richard J., E-mail: Richard.J.Cooper@uea.ac.uk [School of Environmental Sciences, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ (United Kingdom); Pedentchouk, Nikolai; Hiscock, Kevin M.; Disdle, Paul [School of Environmental Sciences, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ (United Kingdom); Krueger, Tobias [IRI THESys, Humboldt University, 10099 Berlin (Germany); Rawlins, Barry G. [British Geological Survey, Keyworth, Nottingham NG12 5GG (United Kingdom)

2015-07-01

We present a novel application for quantitatively apportioning sources of organic matter in streambed sediments via a coupled molecular and compound-specific isotope analysis (CSIA) of long-chain leaf wax n-alkane biomarkers using a Bayesian mixing model. Leaf wax extracts of 13 plant species were collected from across two environments (aquatic and terrestrial) and four plant functional types (trees, herbaceous perennials, and C{sub 3} and C{sub 4} graminoids) from the agricultural River Wensum catchment, UK. Seven isotopic (δ{sup 13}C{sub 27}, δ{sup 13}C{sub 29}, δ{sup 13}C{sub 31}, δ{sup 13}C{sub 27–31}, δ{sup 2}H{sub 27}, δ{sup 2}H{sub 29}, and δ{sup 2}H{sub 27–29}) and two n-alkane ratio (average chain length (ACL), carbon preference index (CPI)) fingerprints were derived, which successfully differentiated 93% of individual plant specimens by plant functional type. The δ{sup 2}H values were the strongest discriminators of plants originating from different functional groups, with trees (δ{sup 2}H{sub 27–29} = − 208‰ to − 164‰) and C{sub 3} graminoids (δ{sup 2}H{sub 27–29} = − 259‰ to − 221‰) providing the largest contrasts. The δ{sup 13}C values provided strong discrimination between C{sub 3} (δ{sup 13}C{sub 27–31} = − 37.5‰ to − 33.8‰) and C{sub 4} (δ{sup 13}C{sub 27–31} = − 23.5‰ to − 23.1‰) plants, but neither δ{sup 13}C nor δ{sup 2}H values could uniquely differentiate aquatic and terrestrial species, emphasizing a stronger plant physiological/biochemical rather than environmental control over isotopic differences. ACL and CPI complemented isotopic discrimination, with significantly longer chain lengths recorded for trees and terrestrial plants compared with herbaceous perennials and aquatic species, respectively. Application of a comprehensive Bayesian mixing model for 18 streambed sediments collected between September 2013 and March 2014 revealed considerable temporal variability in the

Ecosystem differences in the trophic enrichment of 13C in aquatic food webs

International Nuclear Information System (INIS)

France, R.L.; Peters, R.H.

1997-01-01

Data from 35 published studies were collated to examine patterns in the trophic enrichment of 13 C of consumers. Because both δ 13 C and δ 14 N vary systematically across ecosystems, it was necessary to standardize for such differences before combining data from numerous sources. Relationships of these measures of ecosystem-standardized δ 13 C to ecosystem-standardized trophic position (Δδ 15 N) for freshwater, estuarine, coastal, and open-ocean and for all aquatic ecosystems yielded regression equations of low predictive capability (average of 20% explained variance in δ 13 C). However, differences were observed in the slopes between δ 13 C and standardized trophic position when data were examined study-specifically: the average trophic fractionation of 13 C was found to increase from +0.2micron for freshwater to +0.5micron for estuarine to +0.8micron for coastal, and to +1.1micron for open-ocean food webs. This ecosystem-specific gradient in 13 C enrichment for consumers supports previous findings of a similar continuum existing for zooplankton - particulate organic matter differences in δ 13 C. Possible mechanisms to explain these ecosystem-specific patterns in 13 C enrichment may be related to the relative importance of detritus, heterotrophic respiration, partial reliance on alternative food sources, and lipid influences in the different ecosystems. (author)

13 C analysis of aromas and perfumes by a coupled GC-IRMS technique. The case of vanillin and leaf alcohol extracts

International Nuclear Information System (INIS)

Breas, O.; Fourel, F.; Martin, G.J.

1994-01-01

The determination of stable isotope ratios is a precious tool to establish the natural status of flavors and fragrances. Results are presented concerning δ 13 C measurements using gas chromatography-combustion interface-isotope ratio mass spectrometry (GC-C- 13 C IRMS). This technique allows to measure carbon isotope ratios on pure compounds separated by capillary gas chromatography and injected on-line into an isotopic mass spectrometer. δ 13 C measurements carried out on vanilla extracts require only very small quantities of compounds ( 13 C measurements performed on cis-3-hexanol extracted from mint, the difference between natural and synthetic cis-3-hexanol is underlined and it is demonstrated that reproducible isotope ratios may be measured for cis-3-hexanol on mint extracts without purification even if this compound only represents 0.5% of the extract. (authors). 17 refs., 1 fig., 3 tabs

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

Science.gov (United States)

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

13C(α,n)16O reaction as the knock-out exchange process

International Nuclear Information System (INIS)

Kim, G.; Khajdarov, R.R.; Zaparov, Eh.A.

2000-01-01

S-factor for the 13 C(α,n) 16 O reaction is studied. In the framework of the simple phenomenological model this reaction is analysed as neutron knocked-out by α-particle exchange process. The analysis demonstrates the importance of taking into account 2p-state in 13 C. The 13 C(α,n) 16 O cross section is considered both as the knock-out exchange process and as it's combination with process through a compound nucleus. It was shown that for E α s value extrapolated to low energies is found to be noticeably larger that of R-matrix analysis. Different ways of improving the proposed model are discussed. (author)

Chiral effects on the 13C resonances of α-tocopherol and related compounds. A novel illustration of Newman's rule of six

International Nuclear Information System (INIS)

Brownstein, S.; Burton, G.W.; Hughes, L.; Ingold, K.U.

1989-01-01

The 100-MHz 13 C NMR spectrum of (2R,4'R,8'R)-α-tocopherol (natural vitamin E) has been completely assigned with the aid of a number of selectively deuteriated (2R,4'R,8'R)-α-tocopherols. The 13 C NMR spectrum of (2RS,4'RS,8'RS)-α-tocopherol (all-racemic, synthetic vitamin E) has also been measured. Many of the individual carbons in this all-racemic mixture of eight α-tocopherol stereoisomers give more than one resonance with eight of the carbons (2-CH 3 , 2',3',4',4'-CH 3 , 5', 8', and 9') giving the maximum number of four resonances from each of the four enantiomeric pairs; these resonances have also been assigned. The structurally related 5'-hydroxy-2-(4',8',12'-trimethyltridecyl)-2,4,6,7-tetramethyl-2,3,-dihydrobenzofuran (HTDBF) has been synthesized for the first time in the 2R,4'R,8'R and 2S,4'R,8'R configurations and their 13 C resonances have been assigned. In its all-racemic form this compound also shows up to four resonances from a single carbon. Related observations have been made with phytol and isophytol. A careful examination of these chirally induced chemical shift differences for the individual carbon atoms, Δ, reveals a bond-alternation effect with maxima at a separation of one, three, and five bonds from the closest chiral center and with the maximum at a five-bond separation being greater than that at a three-bond separation. 32 references, 2 figures, 4 tables

Assessment of MTBE biodegradation in contaminated groundwater using 13C and 14C analysis: Field and laboratory microcosm studies

International Nuclear Information System (INIS)

Thornton, Steven F.; Bottrell, Simon H.; Spence, Keith H.; Pickup, Roger; Spence, Michael J.; Shah, Nadeem; Mallinson, Helen E.H.; Richnow, Hans H.

2011-01-01

Highlights: → Carbon isotope fractionation for MTBE varies with dissolved oxygen concentration. → Carbon isotope fractionation can underestimate MTBE biodegradation at plume fringes. → Fractionation factors must be for specific biodegradation mechanisms and conditions. → Specific microbial populations influence carbon isotope fractionation in groundwater. - Abstract: Radiolabelled assays and compound-specific stable isotope analysis (CSIA) were used to assess methyl tert-butyl ether (MTBE) biodegradation in an unleaded fuel plume in a UK chalk aquifer, both in the field and in laboratory microcosm experiments. The 14 C-MTBE radiorespirometry studies demonstrated widespread potential for aerobic and anaerobic MTBE biodegradation in the aquifer. However, δ 13 C compositions of MTBE in groundwater samples from the plume showed no significant 13 C enrichment that would indicate MTBE biodegradation at the field scale. Carbon isotope enrichment during MTBE biodegradation was assessed in the microcosms when dissolved O 2 was not limiting, compared with low in situ concentrations (2 mg/L) in the aquifer, and in the absence of O 2 . The microcosm experiments showed ubiquitous potential for aerobic MTBE biodegradation in the aquifer within hundreds of days. Aerobic MTBE biodegradation in the microcosms produced an enrichment of 7 per mille in the MTBE δ 13 C composition and an isotope enrichment factor (ε) of -1.53 per mille when dissolved O 2 was not limiting. However, for the low dissolved O 2 concentration of up to 2 mg/L that characterizes most of the MTBE plume fringe, aerobic MTBE biodegradation produced an enrichment of 0.5-0.7 per mille, corresponding to an ε value of -0.22 per mille to -0.24 per mille. No anaerobic MTBE biodegradation occurred under these experimental conditions. These results suggest the existence of a complex MTBE-biodegrading community in the aquifer, which may consist of different aerobic species competing for MTBE and dissolved O 2

Quantitative evaluation of the biosynthetic pathways leading to δ-aminolevulinic acid from the Shemin precursor glycine via the C5 pathway in Arthrobacter hyalinus by analysis of 13C-labeled coproporphyrinogen III biosynthesized from [2-13C]glycine, [1-13C]acetate, and [2-13C]acetate using 13C NMR spectroscopy

International Nuclear Information System (INIS)

Katsumi Iida

2013-01-01

The biosynthetic pathways leading to δ-aminolevulinic acid (ALA) from the Shemin precursor glycine via the C5 pathway in Arthrobacter hyalinus were quantitatively evaluated by means of feeding experiments with [2- 13 C]glycine, sodium [1- 13 C]acetate, and sodium [2- 13 C]acetate, followed by analysis of the labeling patterns of coproporphyrinogen III (Copro'gen III) (biosynthesized from ALA) using 13 C NMR spectroscopy. Two biosynthetic pathways leading to ALA from glycine via the C5 pathway were identified: i.e., transformation of glycine to l-serine catalyzed by glycine hydroxymethyltransferase, and glycine synthase-catalyzed catabolism of glycine to N 5 , N 10 -methylene-tetrahydrofolic acid (THF), which reacts with another molecule of glycine to afford l-serine. l-Serine is transformed to acetyl-CoA via pyruvic acid. Acetyl-CoA enters the tricarboxylic acid cycle, affording 2-oxoglutaric acid, which in turn is transformed to l-glutamic acid. The l-glutamic acid enters the C5 pathway, affording ALA in A. hyalinus. A 13 C NMR spectroscopic comparison of the labeling patterns of Copro'gen III obtained after feeding of [2- 13 C]glycine, sodium [1- 13 C]acetate, and sodium [2- 13 C]acetate showed that [2- 13 C]glycine transformation and [2- 13 C]glycine catabolism in A. hyalinus proceed in the ratio of 52 and 48 %. The reaction of [2- 13 C]glycine and N 5 , N 10 -methylene-THF, that of glycine and N 5 , N 10 -[methylene- 13 C]methylene-THF generated from the [2- 13 C]glycine catabolism, and that of [2- 13 C]glycine and N 5 , N 10 -[methylene- 13 C]methylene-THF transformed the fed [2- 13 C]glycine to [1- 13 C]acetyl-CoA, [2- 13 C]acetyl-CoA, and [1,2- 13 C 2 ]acetyl-CoA in the ratios of 42, 37, and 21 %, respectively. These labeled acetyl-CoAs were then incorporated into ALA. Our results provide a quantitative picture of the pathways of biosynthetic transformation to ALA from glycine in A. hyalinus. (author)

Synthesis and applications of {sup 13}C glycerol

Energy Technology Data Exchange (ETDEWEB)

Stocking, E.; Khalsa, O.; Martinez, R.A.; Silks, L.A. III [Los Alamos National Laboratory, NM (United States)

1994-12-01

Due in part to the use of labeled glycerol for the {sup 13}C enrichment of biomolecules, we are currently developing new synthetic routes to various isotopomers of glycerol. Judging from our experience, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment and/or have poor overall yields (12 to 15%). Furthermore, the use of glycerol for enrichment can be prohibitively expensive and its availability is limited by the level of demand. We are presently developing a short de novo synthesis of glycerol from carbon dioxide ({approximately}53% overall yield for four steps) and are examining the feasibility of synthesizing site-specific {sup 13}C-labeled glycerol and dihydroxyacetone (DHA) from labeled methanol and carbon dioxide. One application of {sup 13}C glycerol we have examined is enzymatic conversion of glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25 to 50% (as determined by NMR spectroscopy). We are also pursuing the chemical conversion of {sup 13}C-labeled DHA to DHAP. We are especially interested in {sup 13}C-labeled DHAP because we are investigating its use as a chemo-enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids.

Complete 1H and 13C NMR assignments and anti fungal activity of two 8-hydroxy flavonoids in mixture

International Nuclear Information System (INIS)

Johann, Susana; Smania Junior, Artur; Branco, Alexsandro

2007-01-01

A mixture of the two new flavonols 8-hydroxy-3, 4', 5, 6, 7-pentamethoxyflavone (1) and 8-hydroxy-3, 3', 4', 5, 6, 7-hexamethoxyflavone (2) was isolated from a commercial sample of Citrus aurantifolia. An array of one- ( 1 H NMR, { 1 H} -13 C NMR, and APT -13 C NMR) and two-dimensional NMR techniques (COSY, NOESY, HMQC and HMBC) was used to achieve the structural elucidation and the complete 1 H and 13 C chemical shift assignments of these natural compounds. In addition, the antifungal activity of these compounds against phytopathogenic and human pathogenic fungi was investigated. (author)

Monitoring Cancer Response to Treatment with Hyperpolarized ¹³C MRS

DEFF Research Database (Denmark)

Eldirdiri, Abubakr

, and the patient is exposed to ionizing radiation. The introduction of hyperpolarized 13C MRS has opened completely new possibilities to study the biochemical changes in disease processes. Numerous 13C-labeled compounds were proposed to interrogate various aspects of cancer cell metabolism. The aim of this study......Monitoring the cancer response to treatment, non-invasively, by medical imaging is a key element in the management of cancer. For patients undergoing treatment, it is crucial to determine responders from non-responders in order to guide treatment decisions. Currently, PET is the most widely used...

13C Kinetic isotopic effect of polymerization on monomers with multiple bond

International Nuclear Information System (INIS)

Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

1988-01-01

13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

Inhibitors of the alpha-ketoglutarate dehydrogenase complex alter [1-13C]glucose and [U-13C]glutamate metabolism in cerebellar granule neurons.

Science.gov (United States)

Santos, Sónia Sá; Gibson, Gary E; Cooper, Arthur J L; Denton, Travis T; Thompson, Charles M; Bunik, Victoria I; Alves, Paula M; Sonnewald, Ursula

2006-02-15

Diminished activity of the alpha-ketoglutarate dehydrogenase complex (KGDHC), an important component of the tricarboxylic acid (TCA) cycle, occurs in several neurological diseases. The effect of specific KGDHC inhibitors [phosphonoethyl ester of succinyl phosphonate (PESP) and the carboxy ethyl ester of succinyl phosphonate (CESP)] on [1-13C]glucose and [U-13C]glutamate metabolism in intact cerebellar granule neurons was investigated. Both inhibitors decreased formation of [4-13C]glutamate from [1-13C]glucose, a reduction in label in glutamate derived from [1-13C]glucose/[U-13C]glutamate through a second turn of the TCA cycle and a decline in the amounts of gamma-aminobutyric acid (GABA), aspartate, and alanine. PESP decreased formation of [U-13C]aspartate and total glutathione, whereas CESP decreased concentrations of valine and leucine. The findings are consistent with decreased KGDHC activity; increased alpha-ketoglutarate formation; increased transamination of alpha-ketoglutarate with valine, leucine, and GABA; and new equilibrium position of the aspartate aminotransferase reaction. Overall, the findings also suggest that some carbon derived from alpha-ketoglutarate may bypass the block in the TCA cycle at KGDHC by means of the GABA shunt and/or conversion of valine to succinate. The results suggest the potential of succinyl phosphonate esters for modeling the biochemical and pathophysiological consequences of reduced KGDHC activity in brain diseases.

Synthesis of 13C-labeled vitamin E and interaction between vitamin E and phospholipid in liposome

International Nuclear Information System (INIS)

urano, S.; Matsuo, M.

1986-01-01

Vitamin E with a 13 C-labeled isoprenoid side chain, [4'a- 13 C], [6'- 13 C], [8'a- 13 C] and [12'a and 13'- 13 C]α-tocopherols were synthesized. These compounds were incorporated into three kinds of lecithin liposomes from dipalmitoyl phosphatidyl cholin, egg lecithin and rat liver lecithin, of which arachidonic acid contents are 0, 2.6 and 19.0%, respectively. T 1 values, which were measured by NMR for the labeled carbons, indicate that the segmental motion tends to increase with the increase of the distance from the chroman ring. This tendency is not affected with the arachidonic acid contents of phospholipids. This result can not be explained by Lucy's hypothesis. 1 figure; 1 table

Biosynthesis of quinolizidine alkaloids. Incorporation of [1-amino-15N, 1-13C] cadaverine into lupanine, 13-hydroxylupanine, and angustifoline

International Nuclear Information System (INIS)

Rana, J.; Robins, D.J.

1985-01-01

The labelling patterns in (+)-lupanine, (+)-13-hydroxylupanine, and (+)-angustifoline derived biosynthetically from [1-amino- 15 N,1- 13 C]-1,5-diaminopentane (cadaverine) have been established by 13 C n.m.r. spectroscopy. Three cadaverine units are incorporated to about the same extent into each of these three alkaloids. The presence of two doublets due to 13 C- 15 N coupling in the 13 C brace 1 H brace n.m.r. spectra associated with C-2 and C-15 of lupanine and 13-hydroxylupanine, and one 13 C- 15 N doublet at C-2 of angustifoline, indicate that two of the cadaverine units are converted into the outer rings of the tetracyclic quinolizidine alkaloids in a specific fashion. (author)

Site-selective 13C labeling of proteins using erythrose

International Nuclear Information System (INIS)

Weininger, Ulrich

2017-01-01

NMR-spectroscopy enables unique experimental studies on protein dynamics at atomic resolution. In order to obtain a full atom view on protein dynamics, and to study specific local processes like ring-flips, proton-transfer, or tautomerization, one has to perform studies on amino-acid side chains. A key requirement for these studies is site-selective labeling with 13 C and/or 1 H, which is achieved in the most general way by using site-selectively 13 C-enriched glucose (1- and 2- 13 C) as the carbon source in bacterial expression systems. Using this strategy, multiple sites in side chains, including aromatics, become site-selectively labeled and suitable for relaxation studies. Here we systematically investigate the use of site-selectively 13 C-enriched erythrose (1-, 2-, 3- and 4- 13 C) as a suitable precursor for 13 C labeled aromatic side chains. We quantify 13 C incorporation in nearly all sites in all 20 amino acids and compare the results to glucose based labeling. In general the erythrose approach results in more selective labeling. While there is only a minor gain for phenylalanine and tyrosine side-chains, the 13 C incorporation level for tryptophan is at least doubled. Additionally, the Phe ζ and Trp η2 positions become labeled. In the aliphatic side chains, labeling using erythrose yields isolated 13 C labels for certain positions, like Ile β and His β, making these sites suitable for dynamics studies. Using erythrose instead of glucose as a source for site-selective 13 C labeling enables unique or superior labeling for certain positions and is thereby expanding the toolbox for customized isotope labeling of amino-acid side-chains.

Zero thermal expansion in NaZn13-type La(Fe,Si)13 compounds.

Science.gov (United States)

Wang, Wei; Huang, Rongjin; Li, Wen; Tan, Jie; Zhao, Yuqiang; Li, Shaopeng; Huang, Chuanjun; Li, Laifeng

2015-01-28

A zero thermal expansion material in a pure form of NaZn13-type La(Fe,Si)13 was fabricated. Through optimizing the chemical composition, an isotropic zero thermal expansion material is achieved. The obtained materials exhibit a low expansion of |α| linear thermal expansion) over a broad temperature range (15-150 K). The present study indicates that the thermal expansion behavior of the NaZn13-type La(Fe,Si)13 compounds depends mainly on the content of Si element. This new material is desirable in many fields of industry as a reliable and low-cost zero thermal expansion material.

Microbial growth on C1 compounds: proceedings

International Nuclear Information System (INIS)

Crawford, R.L.; Hanson, R.S.

1984-01-01

This book contains individual papers prepared for the 4th International Symposium on Microbial Growth on One Carbon Compounds. Individual reports were abstracted and indexed for EDB. Topics presented were in the areas of the physiology and biochemistry of autotraps, physiology and biochemistry of methylotrophs and methanotrops, physiology and biochemistry of methanogens, genetics of microbes that use C 1 compounds, taxonomy and ecology of microbes tht grow on C 1 compounds, applied aspects of microbes that grow on C 1 compounds, and new directions in C 1 metabolism. (DT)

Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy.

Science.gov (United States)

Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

2018-07-01

We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 ). Copyright © 2018 Elsevier B.V. All rights reserved.

Evolution of E. coli on [U-13C] Glucose Reveals a Negligible Isotopic Influence on Metabolism and Physiology

DEFF Research Database (Denmark)

Sandberg, Troy E.; Long, Christopher P.; Gonzalez, Jacqueline E.

2016-01-01

13C-Metabolic flux analysis (13C-MFA) traditionally assumes that kinetic isotope effects from isotopically labeled compounds do not appreciably alter cellular growth or metabolism, despite indications that some biochemical reactions can be non-negligibly impacted. Here, populations of Escherichia...

Identification of solution products of lanthanoid (3) diethyldithiocarbamatohexamethyl phosphotriamide compounds from IR, electron and sup 1 H, sup 13 C, sup 31 P NMR absorption spectra. Identifikatsiya produktov rastvoreniya diehtilditiokarbamatogeksametil fosfotriamidnykh soedinenij lantanoidov (3) po IK, ehlektronnym i YaMR sup 1 H, sup 13 C, sup 31 P spektram pogloshcheniya

Energy Technology Data Exchange (ETDEWEB)

Skopenko, V V; Savost' yanova, A F; Trachevskij, V V; Gorbalyuk, A D; Sukhan, T A [Kievskij Gosudarstvennyj Univ., Kiev (Ukrainian SSR)

1991-01-01

By the methods of conductometry, IR, electron and {sup 1}H, {sup 13}C, {sup 31}P NMR spectroscopy nonaqueous solutions of the compounds (La(S{sub 2}CNEt{sub 2})Hmpa{sub 5})(BPh{sub 4}){sub 2}, Hmpa=OP(NMe{sub 2}){sub 3}; (Ln(S{sub 2}CNEt{sub 2}){sub 2}Hmpa{sub 3})BPh{sub 4}, Ln=Y, La-Lu; (Ln(S{sub 2}CNEt{sub 2}){sub 3}Hmpa{sub 2}), Ln=La-Gd, have been investigated. It is ascertained that bis-dithiocarbamate compounds are dissolved in all the studied solvents with preservation of composition and structure of lanthanide (3) inner coordination sphere. Tris-dithiocarbamates in nonaqueous solutions are subjected to reactions of ligand redistribution according to schemes depending on the solvent nature. In the process of dissolving of lanthanum monodithiocarbamate bond isomerization of dithiocarbamate groups occurs, which is pronounced in splitting of {sup 1}H and {sup 13}C NMR signals.

Study of lignin standard-substances type biphenyl by {sup 13} C NMR; Estudo de substancias-modelo de lignina do tipo bifenila, por RMN de {sup 13} C

Energy Technology Data Exchange (ETDEWEB)

Ferreira, Marcia Alves; Drumond, Mariza Guimaraes; Veloso, Dorila Pilo [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Quimica

1995-12-31

Lignins structural study by NMR has utilized standard-substances spectral comparative analysis. This work has present relaxation time studies for lignin standard-substance, and {sup 13} C NMR chemical shift values were also shown and compared for several compounds. NMR spectra were commented besides experimental data analysis 2 figs., 4 tabs.

/sup 13/C-/sup 13/C spin-spin coupling in structural investigations. VII. Substitution effects and direct carbon-carbon constants of the triple bond in acetyline derivatives

Energy Technology Data Exchange (ETDEWEB)

Krivdin, L.B.; Proidakov, A.G.; Bazhenov, B.N.; Zinchenko, S.V.; Kalabin, G.A.

1989-01-10

The effects of substitution on the direct /sup 13/C-/sup 13/C spin-spin coupling constants of the triple bond were studied in 100 derivatives of acetylene. It was established that these parameters exhibit increased sensitivity to the effect of substituents compared with other types of compounds. The main factor which determines their variation is the electronegativity of the substituting groups, and in individual cases the /pi/-electronic effects are appreciable. The effect of the substituents with an element of the silicon subgroup at the /alpha/ position simultaneously at the triple bond or substituent of the above-mentioned type and a halogen atom.

2,6-di-tert-butylphenylvinyl ether: effect of the unshared oxygen electron pair on the /sup 13/C-/sup 13/C spin-spin interaction constant

Energy Technology Data Exchange (ETDEWEB)

Krivdin, L.B.; Shcherbakov, V.V.; Glukhikh, N.G.; Sigalov, V.M.; Kalabin, G.A.

1987-07-10

Vinyl ethers were prepared by the well-known Favorskii-Shostakovskii method. The purity of the compounds was controlled by GLC and by the PMR and /sup 13/C NMR spectra. The proximity of sp/sup 7/-hybridized unshared pair of oxygen atoms result in a secondary, positive contribution in the constant of spin-spin interaction between neighboring carbon nuclei in the aromatic ring.

Degradation of linear alkylabenzene sulfonate (LAS) and its compounds in Donghu Lake (Hubei, P.R.C.) determined by high performance liquid chromatography (HPLC)

Science.gov (United States)

Ayfer, Yediler; Xu, Ying; Zhang, Yongyuan; Chen, Junjian

1990-06-01

Commercial linear alkylbenzene sulfonate (LAS), mixture of alkylchain lengths and phenyl position isomers (C10-C13), is widely used as a major constituent of household and industrial detergents in the People's Republic of China. Degradation process and behaviour of LAS compounds during an 82-hour lake water die-away study, with an added LAS concentration of 1.5mg·L-1, was quantified and accomplished by HPLO-UV after extractionon the SepPek C18 reversed-phase cartridges. The degradation rate became progressively faster with increasing chain length. The technique described in this study is fast, sensitive and specific, and can be used to determine low levels of LAS and for establishing water quality criteria and standards relating to LAS and its compounds.

Synthesis of 1-13C-1-indanone and 2-13C-1,2,3,4-tetrahydroquinoline

International Nuclear Information System (INIS)

Pickering, R.E.; Wysocki, M.A.; Eisenbraun, E.J.

1985-01-01

The synthesis of 2- 13 C-1,2,3,4-tetrahydroquinoline (5) via 1- 13 C-3-phenylpropanoic acid (1), 1- 13 C-1-indanone (2), 1- 13 C-1-indanone hydrazone (3) and 2- 13 C-3,4-dihydro-2(1H)-quinolinone (4) proceeded in 78, 96, 95, 79, and 85% individual yields respectively for 1, 2, 3, 4, 5 and 61% overall yield of the latter from 1. (author)

Re-evaluating the isotopic divide between angiosperms and gymnosperms using n-alkane δ13C values

Science.gov (United States)

Bush, R. T.; McInerney, F. A.

2009-12-01

Angiosperm δ13C values are typically 1-3‰ more negative than those of co-occurring gymnosperms. This is known for both bulk leaf and compound-specific values from n-alkanes, which are stable, straight-chain hydrocarbons (C23-C35) found in the epicuticular leaf wax of vascular plants. For n-alkanes, there is a second distinction between the δ13C values of angiosperms and gymnosperms—δ13C values generally decrease with increasing chain-length in angiosperms, while in gymnosperms they increase. These two distinctions have been used to support the ‘plant community change hypothesis’ explaining the difference between the terrestrial and marine carbon isotope excursions during the Paleocene-Eocene Thermal Maximum (PETM.) Preserved n-alkanes from terrestrial paleosols in the Bighorn Basin, Wyoming reveal a negative carbon isotope excursion during the PETM of 4-5‰, which is 1-2‰ greater than the excursion recorded by marine carbonates. The local plant community, known from macrofossils as well as palynoflora, shifted from a deciduous, mixed angiosperm/gymnosperm flora to a suite of evergreen angiosperm species during the PETM. At the end of the PETM, the community returned to a mixed deciduous flora very similar to the original. This change in the plant community could thus magnify the terrestrial negative carbon isotope excursion to the degree necessary to explain its divergence from the marine record. However, the comparison between modern angiosperms and gymnosperms has been made mostly between broadleaf, deciduous angiosperms and evergreen, coniferous gymnosperms. New data analyzing deciduous, coniferous gymnosperms, including Metasequoia glyptostroboides and Taxodium distichum, suggests that the division previously ascribed to taxonomy may actually be based on leaf habit and physiology, specifically broadleaf, deciduous versus needle-leaf, evergreen plants. If differences in n-alkane δ13C values can be described not as angiosperms versus gymnosperms

Synthesis of [13C6]-labelled phenethylamine derivatives for drug quantification in biological samples.

Science.gov (United States)

Karlsen, Morten; Liu, HuiLing; Berg, Thomas; Johansen, Jon Eigill; Hoff, Bård Helge

2014-05-15

The availability of high-quality (13)C-labelled internal standards will improve accurate quantification of narcotics and drugs in biological samples. Thus, the synthesis of 10 [(13)C6]-labelled phenethylamine derivatives, namely amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, 3,4-methylenedioxy-N-ethylamphetamine, 4-methoxyamphetamine, 4-methoxymethamphetamine, 3,5-dimethoxyphenethylamine 4-bromo-2,5-dimethoxyphenethylamine and 2,5-dimethoxy-4-iodophenethylamine, have been undertaken. [(13)C6]-Phenol proved to be an excellent starting material for making (13)C-labelled narcotic substances in the phenethylamine class, and a developed Stille-type coupling enabled an efficient synthesis of the 3,4-methylenedioxy and 4-methoxy derivatives. The pros and cons of alternative routes and transformations are also discussed. The [(13)C6]-labelled compounds are intended for use as internal standards in forensic analysis, health sciences and metabolomics studies by gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry. Copyright © 2014 John Wiley & Sons, Ltd.

Branched GDGTs in Lacustrine Environments: Tracing Allochthonous and Autochthonous Sources Using Compound-Specific Stable Carbon Isotope Analysis

Science.gov (United States)

Weber, Y.; S Sinninghe Damsté, J.; Lehmann, M. F.; Niemann, H.; Schubert, C. J.

2015-12-01

allochthonous (i.e., soil) source. Our data demonstrate the great potential of compound-specific C isotope analysis to constrain the origin of brGDGTs in lake sediments, possibly allowing the identification of freshwater environments that are particularly suited for brGDGT-based paleoenvironmental reconstructions.

Novel proxies for reconstructing paleohydrology from ombrotrophic peatlands: biomarker and compound-specific H and C stable isotope ratios

Science.gov (United States)

Wang, J.; Nichols, J. E.; Huang, Y.

2008-12-01

Ombrotrophic peatlands are excellent archives for paleohydrologic information because they are hydrologically isolated from their surroundings. However, quantitative proxies for deciphering peatland archives are lacking. Here, we present development and application of novel organic geochemical methods for quantitative reconstruction of paleohydrology from the ombrotrophic sediments, and comparison of organic geochemical data with conventional paleoecological proxies. Application of these methods to the sediments of several North American and European peatlands has revealed significant changes in the hydroclimate throughout the Holocene. The plant assemblage living at the surface of the peatland is tightly controlled by surface moisture. Under wet conditions, Sphagnum mosses, with no active mechanism for drawing water from below the surface of the peatland, are dominant. During dry conditions, vascular plants are more productive relative to Sphagnum. A ratio of the abundance of two biomarkers representing Sphagnum and vascular plants sensitively records changes in hydrologic balance (Nichols et al., 2006, Org. Geochem. 37, 1505-1513). We have further developed stable isotope models to compute climate parameters from compound-specific H and C isotope ratios of biomarkers to create a more comprehensive climate reconstruction. Vascular plant leaf waxes carry the D/H ratio signature of precipitation that is little affected by evaporation, whereas the Sphagnum biomarker records isotopic ratios of the water at the peatland surface, which is strongly enriched by evaporation. Evaporation amount can be calculated using the differences between D/H ratios of the two types of biomarkers. C isotope ratios of Sphagnum biomarkers can also be used to quantify surface wetness. Methanotrophic bacteria live symbiotically with Sphagnum, providing isotopically light carbon for photosynthesis. These bacteria are more active when the Sphagnum is wet, thus providing more 13C-depleted CO2

(1 H, 13 C and 31 P) NMR of phosphonic acid derivatives

International Nuclear Information System (INIS)

Campos, Valdevino; Costa, Valentim E. Uberti

1991-01-01

In the last years the development of phosphates analogues in the medical and agricultural pesticides has being very expressive. 1 H, 13 C and mainly 31 P NMR are used for stereochemical and conformational analysis, and reactivity studies on the compounds resulting from those chemical processes

Spin gap in heavy fermion compound UBe13

Science.gov (United States)

Storchak, V. G.; Brewer, J. H.; Eshchenko, D. G.; Mengyan, P. W.; Parfenov, O. E.; Tokmachev, A. M.; Dosanjh, P.; Fisk, Z.; Smith, J. L.

2016-08-01

Heavy fermion (HF) compounds are well known for their unique properties, such as narrow bandwidths, loss of coherence in a metal, non-Fermi-liquid behaviour, unconventional superconductivity, huge magnetoresistance etc. While these materials have been known since the 1970s, there is still considerable uncertainty regarding the fundamental mechanisms responsible for some of these features. Here we report transverse-field muon spin rotation (μ +SR) experiments on the canonical HF compound UBe13 in the temperature range from 0.025 to 300 K and in magnetic fields up to 7 T. The μ +SR spectra exhibit a sharp anomaly at 180 K. We present a simple explanation of the experimental findings identifying this anomaly with a gap in the spin excitation spectrum of f-electrons opening near 180 K. It is consistent with anomalies discovered in heat capacity, NMR and optical conductivity measurements of UBe13, as well as with the new resistivity data presented here. The proposed physical picture may explain several long-standing mysteries of UBe13 (as well as other HF systems).

Amino acid δ13C analysis of hair proteins and bone collagen using liquid chromatography/isotope ratio mass spectrometry

DEFF Research Database (Denmark)

Raghavan, Maanasa; McCullagh, James S. O.; Lynnerup, Niels

2010-01-01

We report a novel method for the chromatographic separation and measurement of stable carbon isotope ratios (delta(13)C) of individual amino acids in hair proteins and bone collagen using the LC-IsoLink system, which interfaces liquid chromatography (LC) with isotope ratio mass spectrometry (IRMS......). This paper provides baseline separation of 15 and 13 of the 18 amino acids in bone collagen and hair proteins, respectively. We also describe an approach to analysing small hair samples for compound-specific analysis of segmental hair sections. The LC/IRMS method is applied in a historical context...... by the delta(13)C analysis of hair proteins and bone collagen recovered from six individuals from Uummannaq in Greenland. The analysis of hair and bone amino acids from the same individual, compared for the first time in this study, is of importance in palaeodietary reconstruction. If hair proteins can be used...

Application of unsymmetrical indirect covariance NMR methods to the computation of the (13)C (15)N HSQC-IMPEACH and (13)C (15)N HMBC-IMPEACH correlation spectra.

Science.gov (United States)

Martin, Gary E; Hilton, Bruce D; Irish, Patrick A; Blinov, Kirill A; Williams, Antony J

2007-10-01

Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method. (c) 2007 John Wiley & Sons, Ltd.

Headspace solid phase microextraction--GC/C-IRMS for delta13CVPDB measurements of mono-aromatic hydrocarbons using EA-IRMS calibration.

Science.gov (United States)

Ebongué, Véronique Woule; Geypens, Benny; Berglund, Michael; Taylor, Philip

2009-03-01

This work aims at comparing the delta(13)C(VPDB) of mono-aromatic hydrocarbons benzene, toluene, ethylbenzene and xylene isomers (BTEX) measured by elemental analyser (EA)-isotope ratio mass spectrometer (IRMS) with the delta(13)C(VPDB) measured on the same compounds by headspace solid phase microextraction - GC/C-IRMS (hSPME - GC/C-IRMS) with the final goal of using these compounds as internal standards on the latter system. The EA-IRMS measurements were done using calcium and lithium carbonate isotopic reference materials: NBS19 and L-SVEC for establishing the delta(13)C(VPDB) scale. The EA-IRMS measurements with helium dilution of a set of five reference materials (USGS40, USGS41, IAEA-CH-6, IAEA-CH-3 and IAEA-601) show systematic bias of 1 per thousand relative to their assigned values. This bias due to the dilution mechanism in the used ConfloII interface device could not be avoided. As the selected hydrocarbons: BTEX could not be analysed by EA-IRMS without helium dilution, their delta(13)C(VPDB) must be corrected from this observed bias using an external calibration. The CO(2) gas calibrated using EA-IRMS without helium dilution, was used as an in-house reference for the delta(13)C(VPDB) measurements of the BTEX by the hSPME - GC/C-IRMS system. The comparison made between the delta(13)C(VPDB) measured on the same BTEX compounds by EA-IRMS (with external calibration) and by hSPME - GC/C-IRMS techniques showed good agreement.

Applications of stable isotopes of 2H, 13C and 15N to clinical problems

International Nuclear Information System (INIS)

Klein, P.D.; Szczepanik, P.A.; Hachey, D.L.

1974-01-01

The function of the Argonne Program is to provide synthetic, analytical instrumental capability in a core facility for the clinical investigator who needs to use 2 H, 13 C, or 15 N labelled compounds for metabolic or clinical research on pregnant women, newborn infants, young children, or for mass screening. To carry out such application development, there were six stages which were recurrent steps in every application. Five fundamental strategies should be adopted to establish the use of stable isotopes in clinical work. The instrument required for measurements was a combined gas chromatograph-mass spectrometer, and its use was schematically illustrated. Some of the successful experiences with compounds labelled by stable isotopes, such as deuterium labelled chenodeoxycholic acid, and respective 13 C and 15 N-labelled glycine were described. Deutrium labelled bile acid enabled easy and safe determination of the size of the bile acid pool and the replacement rate, providing clearer diagnoses for cholestatic liver disease and gallstones. 13 C and 15 N labelled compounds were used in clinical studies, of children with genetic disorders of amino acid metabolism, i.e., non ketotic hyperflycinemia, B 12 -responsive methyl malonic acidemia, and Lesch-Nyhan syndrome. 15 N-labelled glycine was also studied in a child with Lesch-Nyhan syndrome. (Mukohata, S.)

Determination of urea 13C in urea 13C mixed powder by HPLC

International Nuclear Information System (INIS)

Zhong Jianguo; Song Tianqi

2006-01-01

A HPLC method is developed for determination of Urea 13 C in Urea 13 C Mixed Powder. A Alltech Econosphere NH2 column (250 mm x 4.6 mm, 5 μm)is used as stationary phrase, a mixture of V(acetonitrile): V(methanol): V(water) = 900 : 100: 10 is used as mobile phase and the flow rate is l mL·min -1 , UV detection wavelength is performed at 200 nm. The calibration curve shows good linearity in the range of 0.2-1.0 g·L -1 of Urea 13 C, y=2.548 x 10 6 x + 4.005 x 10 4 , r=0.9999, and the averaged recovery is 100.6%. The method is simple and accurate, and can be used for the quality control of Urea 13C Mixed Powder. (authors)

Nitrogen Fertilizer and Straw Applications Affect Uptake of 13C,15N-Glycine by Soil Microorganisms in Wheat Growth Stages.

Directory of Open Access Journals (Sweden)

Lijie Yang

Full Text Available This study investigated the influence of nitrogen (N fertilizer and straw on intact amino acid N uptake by soil microorganisms and the relationship between amino acid turnover and soil properties during the wheat growing season. A wheat pot experiment was carried out with three treatments: control (CK, N fertilizer (NF and N fertilizer plus rice straw (NS. We used stable isotope compound-specific analysis to determine the uptake of 13C,15N-glycine by soil microorganisms. In the NF treatment, microbial 13C,15N-glycine uptake was lower compared with CK, suggesting that inorganic N was the preferred N source for soil microorganisms. However, The application of straw with N fertilizer (in NS treatment increased microbial 13C,15N-glycine uptake even with the same amount of N fertilizer application. In this treatment, enzyme activities, soil microbial biomass C and microbial biomass N increased simultaneously because more C was available. Soil mineral N and plant N contents all decreased substantially. The increased uptake of intact 13C,15N-glycine in the NS treatment can be attributed to direct assimilation by soil microorganisms to satisfy the demand for N when inorganic N was consumed.

Multisite Kinetic Modeling of 13C Metabolic MR Using [1-13C]Pyruvate

Directory of Open Access Journals (Sweden)

Pedro A. Gómez Damián

2014-01-01

Full Text Available Hyperpolarized 13C imaging allows real-time in vivo measurements of metabolite levels. Quantification of metabolite conversion between [1-13C]pyruvate and downstream metabolites [1-13C]alanine, [1-13C]lactate, and [13C]bicarbonate can be achieved through kinetic modeling. Since pyruvate interacts dynamically and simultaneously with its downstream metabolites, the purpose of this work is the determination of parameter values through a multisite, dynamic model involving possible biochemical pathways present in MR spectroscopy. Kinetic modeling parameters were determined by fitting the multisite model to time-domain dynamic metabolite data. The results for different pyruvate doses were compared with those of different two-site models to evaluate the hypothesis that for identical data the uncertainty of a model and the signal-to-noise ratio determine the sensitivity in detecting small physiological differences in the target metabolism. In comparison to the two-site exchange models, the multisite model yielded metabolic conversion rates with smaller bias and smaller standard deviation, as demonstrated in simulations with different signal-to-noise ratio. Pyruvate dose effects observed previously were confirmed and quantified through metabolic conversion rate values. Parameter interdependency allowed an accurate quantification and can therefore be useful for monitoring metabolic activity in different tissues.

Natural (13) C distribution in oil palm (Elaeis guineensis Jacq.) and consequences for allocation pattern.

Science.gov (United States)

Lamade, Emmanuelle; Tcherkez, Guillaume; Darlan, Nuzul Hijri; Rodrigues, Rosario Lobato; Fresneau, Chantal; Mauve, Caroline; Lamothe-Sibold, Marlène; Sketriené, Diana; Ghashghaie, Jaleh

2016-01-01

Oil palm has now become one of the most important crops, palm oil representing nearly 25% of global plant oil consumption. Many studies have thus addressed oil palm ecophysiology and photosynthesis-based models of carbon allocation have been used. However, there is a lack of experimental data on carbon fixation and redistribution within palm trees, and important C-sinks have not been fully characterized yet. Here, we carried out extensive measurement of natural (13) C-abundance (δ(13) C) in oil palm tissues, including fruits at different maturation stages. We find a (13) C-enrichment in heterotrophic organs compared to mature leaves, with roots being the most (13) C-enriched. The δ(13) C in fruits decreased during maturation, reflecting the accumulation in (13) C-depleted lipids. We further used observed δ(13) C values to compute plausible carbon fluxes using a steady-state model of (13) C-distribution including metabolic isotope effects ((12) v/(13) v). The results suggest that fruits represent a major respiratory loss (≈39% of total tree respiration) and that sink organs such as fruits are fed by sucrose from leaves. That is, glucose appears to be a quantitatively important compound in palm tissues, but computations indicate that it is involved in dynamic starch metabolism rather that C-exchange between organs. © 2015 John Wiley & Sons Ltd.

C-13 isotopic studies of the surface catalysed reactions of methane

International Nuclear Information System (INIS)

Long, M.A.; He, S.J.X.; Adebajo, M.

1997-01-01

The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

Carbon isotope analysis of carbonaceous compounds in Puget Sound and Lake Washington

International Nuclear Information System (INIS)

Swanson, J.R.

1980-01-01

A new method has been developed and tested for determining chronological profiles of organic pollutants. This method, Carbon Isotope Analysis (CIA), involves measurements of 12 C, 13 C and 14 C in carbonaceous compounds found in layers of sediment. Lipids, total aliphatic hydrocarbons (TAHs) and polycyclic aromatic hydrocarbons (PAHs) are separated from kg quantities of sediment. Large Soxhlet extractors are used to remove the extractable organics, using ultra-pure benzene-methanol solution and having an extraction efficiency of about 86% for compounds with boiling points higher than n-tetradecane (n-C 14 ). The basic steps in compound separation include freeze-drying, extraction, fractionation, column chromatography and evaporation. Isolating the TAH and PAH fractions is accomplished by eluting samples from Sephadex and alumina/silica-gel columns. The amount of each fraction recovered is determined by converting the hydrocarbons to carbon dioxide and measuring this gas manometrically. Variations in 12 C and 13 C abundances for carbonaceous compounds are primarily due to thermodynamic, photosynthetic and metabolic fractionation processes. Thus, the source of a particular organic compound can often be determined by measuring its 13 C/ 12 C ratio. Combining the information from both the 13 C analysis and 14 C analysis makes source identification more certain. In addition, this investigation reviews carbon isotopic data and carbon cycling and analyzes organic pollution in two limited ecosystems (Puget Sound and Lake Washington). Specifically, distinct carbonaceous species are analyzed for pollution in sediments of Lake Washington, Elliott Bay, Commencement Bay, central Puget Sound and northern Puget Sound near the Cherry Point oil refineries

Synthesis of selectively 13C-labelled benzoic acid for nuclear magnetic resonance spectroscopic measurement of glycine conjugation activity

International Nuclear Information System (INIS)

Akira, Kazuki; Hasegawa, Hiroshi; Baba, Shigeo

1995-01-01

The synthesis of [4- 13 C]benzoic acid (BA) labelled in a single protonated carbon, for use as a probe to measure glycine conjugation activity by nuclear magnetic resonance (NMR) spectroscopy, has been reported. The labelled compound was prepared by a seven-step synthetic scheme on a relatively small scale using [2- 13 C] acetone as the source of label in overall yield of 16%. The usefulness of [4- 13 C]BA was demonstrated by the NMR spectroscopic monitoring of urinary excretion of [4- 13 C]hippuric acid in the rat administered with the labelled BA. (Author)

In vivo dynamic turnover of cerebral 13C isotopomers from [U- 13C]glucose

Science.gov (United States)

Xu, Su; Shen, Jun

2006-10-01

An INEPT-based 13C MRS method and a cost-effective and widely available 11.7 Tesla 89-mm bore vertical magnet were used to detect dynamic 13C isotopomer turnover from intravenously infused [U- 13C]glucose in a 211 μL voxel located in the adult rat brain. The INEPT-based 1H → 13C polarization transfer method is mostly adiabatic and therefore minimizes signal loss due to B 1 inhomogeneity of the surface coils used. High quality and reproducible data were acquired as a result of combined use of outer volume suppression, ISIS, and the single-shot three-dimensional localization scheme built in the INEPT pulse sequence. Isotopomer patterns of both glutamate C4 at 34.00 ppm and glutamine C4 at 31.38 ppm are dominated first by a doublet originated from labeling at C4 and C5 but not at C3 (with 1JC4C5 = 51 Hz) and then by a quartet originated from labeling at C3, C4, and C5 (with 1JC3C4 = 35 Hz). A lag in the transition of glutamine C4 pattern from doublet-dominance to quartet dominance as compared to glutamate C4 was observed, which provides an independent verification of the precursor-product relationship between neuronal glutamate and glial glutamine and a significant intercompartmental cerebral glutamate-glutamine cycle between neurons and glial cells.

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

Science.gov (United States)

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

2007-03-15

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

Mn(III)-initiated facile oxygenation of heterocyclic 1,3-dicarbonyl compounds.

Science.gov (United States)

Rahman, Md Taifur; Haque, Md Aminul; Igarashi, Hikaru; Nishino, Hiroshi

2011-11-16

The Mn(III)-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

Sediment Origin Determination in the Sub-Catchment of Mistelbach (Austria) using Fatty Acids Biomarkers and Compound-Specific Stable Isotope Techniques

International Nuclear Information System (INIS)

Mabit, L.; Chen, X.; Resch, C.; Toloza, A.; Meusburger, K.; Alewell, C.; Gibbs, M.; Klik, A.; Eder, A.; Strauss, P.

2016-01-01

Compound-specific stable isotope (CSSI) signatures of inherent soil organic biomarkers allow discriminating and apportioning the source of soil contribution from different land uses. Plant communities label the soil where they grow by exuding organic biomarkers. Although all plants produce the same biomarkers, the stable isotopic signature of those biomarkers is different for each plant species. For agri-environmental investigations, the CSSI technique is based on the measurement of carbon-13 ( 13 C) natural abundance signatures of specific organic compounds such as natural fatty acids (FAs) in the soil. By linking fingerprints of land use to the sediment in deposition zones, this approach has been shown to be a useful technique for determining the source of eroded soil and thereby identifying areas prone to soil degradation. The authors have used this innovative technique to investigate a 3 hectares sub-catchment of Mistelbach situated 60 km north of Vienna. Using the 137 Cs technique, Mabit et al. (2009) reported a local maximum sedimentation rate reaching 20 to 50 t ha -1 yr -1 in the lowest part of this Austrian catchment. To test the ability of the CSSI technique to discriminate different sediment sources of these deposited sediments, representative soil samples from four main agricultural fields of the site were analyzed

Site-selective {sup 13}C labeling of proteins using erythrose

Energy Technology Data Exchange (ETDEWEB)

Weininger, Ulrich, E-mail: ulrich.weininger@physik.uni-halle.de [Lund University, Department of Biophysical Chemistry, Center for Molecular Protein Science (Sweden)

2017-03-15

NMR-spectroscopy enables unique experimental studies on protein dynamics at atomic resolution. In order to obtain a full atom view on protein dynamics, and to study specific local processes like ring-flips, proton-transfer, or tautomerization, one has to perform studies on amino-acid side chains. A key requirement for these studies is site-selective labeling with {sup 13}C and/or {sup 1}H, which is achieved in the most general way by using site-selectively {sup 13}C-enriched glucose (1- and 2-{sup 13}C) as the carbon source in bacterial expression systems. Using this strategy, multiple sites in side chains, including aromatics, become site-selectively labeled and suitable for relaxation studies. Here we systematically investigate the use of site-selectively {sup 13}C-enriched erythrose (1-, 2-, 3- and 4-{sup 13}C) as a suitable precursor for {sup 13}C labeled aromatic side chains. We quantify {sup 13}C incorporation in nearly all sites in all 20 amino acids and compare the results to glucose based labeling. In general the erythrose approach results in more selective labeling. While there is only a minor gain for phenylalanine and tyrosine side-chains, the {sup 13}C incorporation level for tryptophan is at least doubled. Additionally, the Phe ζ and Trp η2 positions become labeled. In the aliphatic side chains, labeling using erythrose yields isolated {sup 13}C labels for certain positions, like Ile β and His β, making these sites suitable for dynamics studies. Using erythrose instead of glucose as a source for site-selective {sup 13}C labeling enables unique or superior labeling for certain positions and is thereby expanding the toolbox for customized isotope labeling of amino-acid side-chains.

Application of backflush and micro-flow techniques to the analysis of C5-C13 hydrocarbons in crude oils and its geochemical significance

Institute of Scientific and Technical Information of China (English)

无

2007-01-01

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C5-C13 hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C5-C13 compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograrns (MID and full scan) could be obtained at the same time. The retension time differences of nC6-nC13 alkanes between GC and TIC were in the range of 0.02-0. 58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C6-C13 hydrocarbon group composition could be used in oil-oil correlation studies.

Critical contribution of aromatic rings to specific recognition of polyether rings. The case of ciguatoxin CTX3C-ABC and its specific antibody 1C49.

Science.gov (United States)

Tsumoto, Kouhei; Yokota, Akiko; Tanaka, Yoshikazu; Ui, Mihoko; Tsumuraya, Takeshi; Fujii, Ikuo; Kumagai, Izumi; Nagumo, Yoko; Oguri, Hiroki; Inoue, Masayuki; Hirama, Masahiro

2008-05-02

To address how proteins recognize polyether toxin compounds, we focused on the interaction between the ABC ring compound of ciguatoxin 3C and its specific antibody, 1C49. Surface plasmon resonance analyses indicated that Escherichia coli-expressed variable domain fragments (Fv) of 1C49 had the high affinity constants and slow dissociation constants typical of antigen-antibody interactions. Linear van't Hoff analyses suggested that the interaction is enthalpy-driven. We resolved the crystal structure of 1C49 Fv bound to ABC ring compound of ciguatoxin 3C at a resolution of 1.7A. The binding pocket of the antibody had many aromatic rings and bound the antigen by shape complementarity typical of hapten-antibody interactions. Three hydrogen bonds and many van der Waals interactions were present. We mutated several residues of the antibody to Ala, and we used surface plasmon resonance to analyze the interactions between the mutated antibodies and the antigen. This analysis identified Tyr-91 and Trp-96 in the light chain as hot spots for the interaction, and other residues made incremental contributions by conferring enthalpic advantages and reducing the dissociation rate constant. Systematic mutation of Tyr-91 indicated that CH-pi and pi-pi interactions between the aromatic ring at this site and the antigen made substantial contributions to the association, and van der Waals interactions inhibited dissociation, suggesting that aromaticity and bulkiness are critical for the specific recognition of polyether compounds by proteins.

Molecular Investigation of the Short-term Sequestration of Natural Abundance 13C -labelled Cow Dung in the Surface Horizons of a Temperate Grassland Soil

Science.gov (United States)

Dungait, J.; Bol, R.; Evershed, R. P.

2004-12-01

An adequate understanding of the carbon (C) sequestration potential of grasslands requires that the quantity and residence times of C inputs be measured. Herbivore dung is largely comprised of plant cell wall material, a significant source of stable C in intensively grazed temperate grassland ecosystems that contributes to the soil carbon budget. Our work uses compound-specific isotope analysis to identify the pattern of input of dung-derived compounds from natural abundance 13C/-labelled cow dung into the surface horizons of a temperate grassland soil over one year. C4 dung (δ 13C \\-12.6 ‰ ) from maize fed cows was applied to a temperate grassland surface (δ 13C \\-29.95 ‰ ) at IGER-North Wyke (Devon, UK), and dung remains and soil cores beneath the treatments collected at ŧ = 7, 14, 28, 56, 112, 224 and 372 days. Bulk dung carbon present in the 0\\-1 cm and 1\\-5 cm surface horizons of a grassland soil over one year was estimated using Δ 13C between C4 dung and C3 dung, after Bol {\\et al.} (2000). The major biochemical components of dung were quantified using proximate forage fibre analyses, after Goering and Van Soest (1970) and identified using `wet' chemical and GC-MS methods. Plant cell wall polysaccharides and lignin were found to account for up to 67 {%} of dung dry matter. Hydrolysed polysaccharides were prepared as alditol acetates for analyses (after Docherty {\\et al.}, 2001), and a novel application of an off-line pyrolysis method applied to measure lignin-derived phenolic compounds (after Poole & van Bergen, 2002). This paper focuses on major events in the incorporation of dung carbon, estimated using natural abundance 13C&-slash;labelling technique. This revealed a major bulk input of dung carbon after a period of significant rainfall with a consequent decline in bulk soil δ 13C values until the end of the experiment (Dungait {\\et al.}, submitted). Findings will be presented revealing contribution of plant cell wall polysaccharides and

A facile synthesis of δ-aminolevulinic acid (ALA) regio-selectively labeled with 13C and direct observation of enzymatic transformation from ALA to porphobilinogen (PBG)

International Nuclear Information System (INIS)

Kurumaya, Katsuyuki; Okazaki, Takeo; Seido, Nobuo; Akasaka, Yuzuru; Kawajiri, Yoshiki; Kajiwara, Masahiro; Kondo, Masao

1989-01-01

δ-Aminolevulinic acid (ALA), labeled with 13 C at position 1, 2, 3, 4, or 5, was synthesized from 13 C-labeled glycine, Meldrum's acid, or bromoacetate. The latter compounds were prepared from 13 C-sodium acetate or 13 C-acetic acid. Enzymatic transformation from ALA to porphobilinogen (PBG) was directly observed by 13 C-NMR. (author)

Carbon-13 composition of bulk dry wines by irm-EA/MS and irm-13C NMR: An indicator of vine water status

Directory of Open Access Journals (Sweden)

Guyon Francois

2017-01-01

Full Text Available Measurements performed on a set of 32 authentic wines (not submitted to any oenological treatment and their ethanol, recovered by distillation, show high correlation between δ13C of bulk wine and its ethanol. These measurements were performed by isotope ratio monitoring by mass spectrometry coupled to an elemental analyzer (irm-EA/MS. Then a series of wines produced by vines of which water status was assessed during the growing season with predawn leaf water potential measurements, was studied by irm-EA/MS. As expected δ13C is correlated to vine water status conditions, as a result of stomatal closure. The ethanol of these specific wines was also analyzed by isotope ratio monitoring and by nuclear magnetic resonance (irm-13C NMR to determine carbon-13 composition on the two specific sites of the ethanol skeleton. If these measurements confirm the correlation between 13C composition and vine growth conditions, the 13C stereospecific information does not make vine water status assessment more precise.

Compound-Specific Isotope Analysis (CSIA Application for Source Apportionment and Natural Attenuation Assessment of Chlorinated Benzenes

Directory of Open Access Journals (Sweden)

Luca Alberti

2017-11-01

Full Text Available In light of the complex management of chlorobenzene (CB contaminated sites, at which a hydraulic barrier (HB for plumes containment is emplaced, compound-specific stable isotope analysis (CSIA has been applied for source apportionment, for investigating the relation between the upgradient and downgradient of the HB, and to target potential CB biodegradation processes. The isotope signature of all the components potentially involved in the degradation processes has been expressed using the concentration-weighted average δ13C of CBs + benzene (δ13Csum. Upgradient of the HB, the average δ13Csum of −25.6‰ and −29.4‰ were measured for plumes within the eastern and western sectors, respectively. Similar values were observed for the potential sources, with δ13Csum values of −26.5‰ for contaminated soils and −29.8‰ for the processing water pipeline in the eastern and western sectors, respectively, allowing for apportioning of these potential sources to the respective contaminant plumes. For the downgradient of the HB, similar CB concentrations but enriched δ13Csum values between −24.5‰ and −25.9‰ were measured. Moreover, contaminated soils showed a similar δ13Csum signature of −24.5‰, thus suggesting that the plumes likely originate from past activities located in the downgradient of the HB. Within the industrial property, significant δ13C enrichments were measured for 1,2,4-trichlorobenzene (TCB, 1,2-dichlorobenzene (DCB, 1,3-DCB, and 1,4-DCBs, thus suggesting an important role for anaerobic biodegradation. Further degradation of monochlorobenzene (MCB and benzene was also demonstrated. CSIA was confirmed to be an effective approach for site characterization, revealing the proper functioning of the HB and demonstrating the important role of natural attenuation processes in reducing the contamination upgradient of the HB.

Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

Science.gov (United States)

Muhammad, Syahidah; Frew, Russell; Hayman, Alan

2015-02-01

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

Directory of Open Access Journals (Sweden)

Syahidah Akmal Muhammad

2015-02-01

Full Text Available Compound-specific isotope analysis (CSIA offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

Compound-specific isotope analysis of diesel fuels in a forensic investigation.

Science.gov (United States)

Muhammad, Syahidah A; Frew, Russell D; Hayman, Alan R

2015-01-01

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ(13)C and δ(2)H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples.

Crystallographic characterization of divalent organosamarium compound (C5H5)2Sm(THF)2

International Nuclear Information System (INIS)

Jagannatha Swamy, S.

2002-01-01

The single pot reaction between SmX 2 (X = Cl - , I - ) and BuLi in THF at -40 degC, followed by the addition of C 5 H 5 - Na + results in a dark red solution. Leaving the concentrated reaction mixture at -25 degC for two days in a deep freezer results in the formation of the crystals of the compound, (C 5 H 5 ) 2 ; Sm(THF) 2 . The compound is insoluble in any solvent and it has been characterized by conventional methods. The crystals are monoclinic with space group C2/c, and a = 13.416(1), b = 9.644(1), c = 14.129(2) pm, β109.873(9) 0 and z = 4 for ρcalcd = 1.64 g cm -3 . Least squares refinement on the basis of 1804 observed reflections has led to a final R value of 0.037 and R w = 0.054. (author)

Mn(III-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

Directory of Open Access Journals (Sweden)

Md. Aminul Haque

2011-11-01

Full Text Available The Mn(III-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

7-epi-griffonilide, a new lactone from Bauhinia pentandra: complete 1H and 13C chemical shift assignments.

Science.gov (United States)

Almeida, Macia C S DE; Souza, Luciana G S; Ferreira, Daniele A; Pinto, Francisco C L; Oliveira, Débora R DE; Santiago, Gilvandete M P; Monte, Francisco J Q; Braz-Filho, Raimundo; Lemos, Telma L G DE

2017-01-01

A new lactone, 7-epi-griffonilide (1), and six known compounds, 2, 3a - 3c, 4a and 4b, were isolated from the leaves of Bauhinia pentandra (Fabaceae). The structures elucidation of 1 and 2 were based on detailed 2D NMR techniques and spectral comparison with related compounds, leading to complete assignment of the 1H and 13C NMR spectra.

Multi site Kinetic Modeling of 13C Metabolic MR Using [1-13C]Pyruvate

International Nuclear Information System (INIS)

Damian, P.A.G.; Sperl, J.I.; Janich, M.A.; Wiesinger, F.; Schulte, R.F.; Menzel, M.I.; Damian, P.A.G.; Damian, P.A.G.; Haase, A.; Janich, M.A.; Schwaiger, M.; Janich, M.A.; Khegai, O.; Glaser, S.J.

2014-01-01

Hyperpolarized 13 C imaging allows real-time in vivo measurements of metabolite levels. Quantification of metabolite conversion between [1- 13 C]pyruvate and downstream metabolites [1- 13 C]alanine, [1- 13 C]lactate, and [ 13 C] bicarbonate can be achieved through kinetic modeling. Since pyruvate interacts dynamically and simultaneously with its downstream metabolites, the purpose of this work is the determination of parameter values through a multi site, dynamic model involving possible biochemical pathways present in MR spectroscopy. Kinetic modeling parameters were determined by fitting the multi site model to time-domain dynamic metabolite data. The results for different pyruvate doses were compared with those of different two-site models to evaluate the hypothesis that for identical data the uncertainty of a model and the signal-to-noise ratio determine the sensitivity in detecting small physiological differences in the target metabolism. In comparison to the two-site exchange models, the multi site model yielded metabolic conversion rates with smaller bias and smaller standard deviation, as demonstrated in simulations with different signal-to-noise ratio. Pyruvate dose effects observed previously were confirmed and quantified through metabolic conversion rate values. Parameter interdependency allowed an accurate quantification and can therefore be useful for monitoring metabolic activity in different tissues

Biosynthetic Studies of 13-Desmethylspirolide C Produced by Alexandrium ostenfeldii (= A. peruvianum): Rationalization of the Biosynthetic Pathway Following Incorporation of (13)C-Labeled Methionine and Application of the Odd-Even Rule of Methylation.

Science.gov (United States)

Anttila, Matthew; Strangman, Wendy; York, Robert; Tomas, Carmelo; Wright, Jeffrey L C

2016-03-25

Understanding the biosynthesis of dinoflagellate polyketides presents many unique challenges. Because of the remaining hurdles to dinoflagellate genome sequencing, precursor labeling studies remain the only viable way to investigate dinoflagellate biosynthesis. However, prior studies have shown that polyketide chain assembly does not follow any of the established processes. Additionally, acetate, the common precursor for polyketides, is frequently scrambled, thus compromising interpretation. These factors are further compounded by low production yields of the compounds of interest. A recent report on the biosynthesis of spirolides, a group belonging to the growing class of toxic spiroimines, provided some insight into the polyketide assembly process based on acetate labeling studies, but many details were left uncertain. By feeding (13)C methyl-labeled methionine to cultures of Alexandrium ostenfeldii, the producing organism of 13-desmethylspirolide C, and application of the odd-even methylation rule, the complete biosynthetic pathway has been established.

Complete {sup 1}H and {sup 13}C NMR assignments and anti fungal activity of two 8-hydroxy flavonoids in mixture

Energy Technology Data Exchange (ETDEWEB)

Johann, Susana; Smania Junior, Artur [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Microbiologia e Parasitologia. Lab. de Antibioticos; Pizzolatti, Moacir G. [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica; Schripsema, Jan; Braz-Filho, Raimundo [Universidade Estadual do Norte Fluminense (UENF), Campos dos Goytacazes, RJ (Brazil). Setor de Quimica de Produtos Naturais. Lab. de Quimica e Funcao de Proteinas e Peptideos (LQFPP); Branco, Alexsandro [Universidade Estadual de Feira de Santana, BA (Brazil). Dept. de Saude. Lab. de Fitoquimica]. E-mail: branco@uefs.br

2007-06-15

A mixture of the two new flavonols 8-hydroxy-3, 4', 5, 6, 7-pentamethoxyflavone (1) and 8-hydroxy-3, 3', 4', 5, 6, 7-hexamethoxyflavone (2) was isolated from a commercial sample of Citrus aurantifolia. An array of one- ({sup 1}H NMR, {l_brace}{sup 1}H{r_brace} {sup -13}C NMR, and APT{sup -13}C NMR) and two-dimensional NMR techniques (COSY, NOESY, HMQC and HMBC) was used to achieve the structural elucidation and the complete {sup 1}H and {sup 13}C chemical shift assignments of these natural compounds. In addition, the antifungal activity of these compounds against phytopathogenic and human pathogenic fungi was investigated. (author)

Occurrence, biological activities and 13C NMR data of amides from Piper (Piperaceae)

International Nuclear Information System (INIS)

Nascimento, Jeferson C. do; Paula, Vanderlucia F. de; David, Jorge M.; David, Juceni P.

2012-01-01

This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae). Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled 13 C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts. (author)

HSQC-1,n-ADEQUATE: a new approach to long-range 13C-13C correlation by covariance processing.

Science.gov (United States)

Martin, Gary E; Hilton, Bruce D; Willcott, M Robert; Blinov, Kirill A

2011-10-01

Long-range, two-dimensional heteronuclear shift correlation NMR methods play a pivotal role in the assembly of novel molecular structures. The well-established GHMBC method is a high-sensitivity mainstay technique, affording connectivity information via (n)J(CH) coupling pathways. Unfortunately, there is no simple way of determining the value of n and hence no way of differentiating two-bond from three- and occasionally four-bond correlations. Three-bond correlations, however, generally predominate. Recent work has shown that the unsymmetrical indirect covariance or generalized indirect covariance processing of multiplicity edited GHSQC and 1,1-ADEQUATE spectra provides high-sensitivity access to a (13)C-(13) C connectivity map in the form of an HSQC-1,1-ADEQUATE spectrum. Covariance processing of these data allows the 1,1-ADEQUATE connectivity information to be exploited with the inherent sensitivity of the GHSQC spectrum rather than the intrinsically lower sensitivity of the 1,1-ADEQUATE spectrum itself. Data acquisition times and/or sample size can be substantially reduced when covariance processing is to be employed. In an extension of that work, 1,n-ADEQUATE spectra can likewise be subjected to covariance processing to afford high-sensitivity access to the equivalent of (4)J(CH) GHMBC connectivity information. The method is illustrated using strychnine as a model compound. Copyright © 2011 John Wiley & Sons, Ltd.

Structure and magnetic transition of LaFe13-xSix compounds

International Nuclear Information System (INIS)

Bo Liuxu; Altounian, Z; Ryan, D H

2003-01-01

Structure and magnetic transitions were investigated by x-ray diffraction and Moessbauer spectroscopy in LaFe 13-x Si x compounds with x = 1.6, 2.0 and 2.6. With increasing Si content, the La-Fe interatomic distance decreased while the average Fe-Fe distance increased. These changes affect the structural stability and the magnetic properties of the compounds. The temperature dependence of the hyperfine field for the compound with x = 2.6 can be fitted very well using a mean field model with a Brillouin function (BF) while that for the compounds with x = 1.6 and 2.0 changes more sharply than that predicted by the BF relation near the Curie temperature. The different nature of the magnetic transition with different Si content originates from the spatial distribution of the Si atoms and related variation of the La-(Fe, Si) and the Fe-Fe distances in the cubic NaZn 13 structure

Tracing fresh assimilates through Larix decidua exposed to elevated CO₂ and soil warming at the alpine treeline using compound-specific stable isotope analysis.

Science.gov (United States)

Streit, Kathrin; Rinne, Katja T; Hagedorn, Frank; Dawes, Melissa A; Saurer, Matthias; Hoch, Günter; Werner, Roland A; Buchmann, Nina; Siegwolf, Rolf T W

2013-02-01

How will carbon source-sink relations of 35-yr-old larch trees (Larix decidua) at the alpine treeline respond to changes in atmospheric CO(2) and climate? We evaluated the effects of previously elevated CO(2) concentrations (9 yr, 580 ppm, ended the previous season) and ongoing soil warming (4 yr, + 4°C). Larch branches were pulse labeled (50 at% (13)CO(2)) in July 2010 to trace fresh assimilates through tissues (buds, needles, bark and wood) and non-structural carbon compounds (NCC; starch, lipids, individual sugars) using compound-specific isotope analysis. Nine years of elevated CO(2) did not lead to increased NCC concentrations, nor did soil warming increase NCC transfer velocities. By contrast, we found slower transfer velocities and higher NCC concentrations than reported in the literature for lowland larch. As a result of low dilution with older carbon, sucrose and glucose showed the highest maximum (13)C labels, whereas labels were lower for starch, lipids and pinitol. Label residence times in needles were shorter for sucrose and starch (c. 2 d) than for glucose (c. 6 d). Although our treatments showed no persistent effect on larch carbon relations, low temperature at high altitudes clearly induced a limitation of sink activities (growth, respiration, root exudation), expressed in slower carbon transfer and higher NCC concentrations. © 2012 The Authors. New Phytologist © 2012 New Phytologist Trust.

Intramolecular 13C analysis of tree rings provides multiple plant ecophysiology signals covering decades.

Science.gov (United States)

Wieloch, Thomas; Ehlers, Ina; Yu, Jun; Frank, David; Grabner, Michael; Gessler, Arthur; Schleucher, Jürgen

2018-03-22

Measurements of carbon isotope contents of plant organic matter provide important information in diverse fields such as plant breeding, ecophysiology, biogeochemistry and paleoclimatology. They are currently based on 13 C/ 12 C ratios of specific, whole metabolites, but we show here that intramolecular ratios provide higher resolution information. In the glucose units of tree-ring cellulose of 12 tree species, we detected large differences in 13 C/ 12 C ratios (>10‰) among carbon atoms, which provide isotopically distinct inputs to major global C pools, including wood and soil organic matter. Thus, considering position-specific differences can improve characterisation of soil-to-atmosphere carbon fluxes and soil metabolism. In a Pinus nigra tree-ring archive formed from 1961 to 1995, we found novel 13 C signals, and show that intramolecular analysis enables more comprehensive and precise signal extraction from tree rings, and thus higher resolution reconstruction of plants' responses to climate change. Moreover, we propose an ecophysiological mechanism for the introduction of a 13 C signal, which links an environmental shift to the triggered metabolic shift and its intramolecular 13 C signature. In conclusion, intramolecular 13 C analyses can provide valuable new information about long-term metabolic dynamics for numerous applications.

Synthesis of [21-13C]-cholesterol

International Nuclear Information System (INIS)

Caballero, G.M.; Gros, E.G.

1994-01-01

The synthesis of [21- 13 C]-cholesterol from 3β-O-(t-butyldimethylsilyl)-17β-cyano-androst-5-ene is described. Labelled carbon-atom was introduced by Grignard reaction of nitrile derivative with [ 13 C]-methylmagnesium iodide. Location of label was confirmed by 13 C-NMR spectroscopy. (author)

IRMS detection of testosterone manipulated with 13C labeled standards in human urine by removing the labeled 13C

International Nuclear Information System (INIS)

Wang, Jingzhu; Yang, Rui; Yang, Wenning; Liu, Xin; Xing, Yanyi; Xu, Youxuan

2014-01-01

Highlights: • 13 C labeled testosterone can be used to adjust the isotope ratio of testosterone. • The novel testosterone cannot be detected by the regular IRMS method in doping test. • A method was explored to remove the labeled 13 C. • The established method can be used to detect the manipulated testosterone. - Abstract: Isotope ratio mass spectrometry (IRMS) is applied to confirm testosterone (T) abuse by determining the carbon isotope ratios (δ 13 C value). However, 13 C labeled standards can be used to control the δ 13 C value and produce manipulated T which cannot be detected by the current method. A method was explored to remove the 13 C labeled atom at C-3 from the molecule of androsterone (Andro), the metabolite of T in urine, to produce the resultant (A-nor-5α-androstane-2,17-dione, ANAD). The difference in δ 13 C values between Andro and ANAD (Δδ 13 C Andro–ANAD , ‰) would change significantly in case manipulated T is abused. Twenty-one volunteers administered T manipulated with different 13 C labeled standards. The collected urine samples were analyzed with the established method, and the maximum value of Δδ 13 C Andro–ANAD post ingestion ranged from 3.0‰ to 8.8‰. Based on the population reference, the cut-off value of Δδ 13 C Andro–ANAD for positive result was suggested as 1.2‰. The developed method could be used to detect T manipulated with 3- 13 C labeled standards

13C NMR for the assessment of human brain glucose metabolism in vivo

International Nuclear Information System (INIS)

Beckman, N.; Seelig, J.; Turkalj, I.; Keller, U.

1991-01-01

Proton-decoupled 13 C NMR spectra of the human head were obtained during hyperglycemic glucose clamping using intravenous infusions of [1- 13 C]glucose in normal volunteers. In addition to 13 C signals of mobile lipids, a variety of new metabolite resonances could be resolved for the first time in the human brain. At an enrichment level of 20% [1- 13 C]glucose, the signals of α- and β-glucose at 92.7 and 96.6 ppm, respectively, could be detected in the human brain after only an infusion period of 15 minutes. The spatial localization of the different regions of interest was confirmed by 13 C NMR spectroscopic imaging with a time resolution of 9 minutes. Increasing the enrichment level to 99% [1- 13 C]glucose not only improved the time resolution but allowed the detection of metabolic breakdown products of [1- 13 C]glucose. The time course of 13 C label incorporation into the C 2 , C 3 , and C 4 resonances of glutamate/glutamine and into lactate could be recorded in the human brain. These results suggest the possibility of obtaining time-resolved, spatially selective, and chemically specific information on the human body

Mono and dinuclear arene ruthenium(II) triazoles by 1,3-dipolar cycloadditions to a coordinated azide in ruthenium(II) compounds

Digital Repository Service at National Institute of Oceanography (India)

Singh, K.S.; Svitlyk, V.; Mozharivskyj, Y.

= Me, 3 or Et, 4). In contrast, a similar 1,3-dipolar cycloaddition reaction of (((Eta sup(6)-C sub(6)Me sub(6))Ru(L sub(2))N sub(3))) (2) (where; L sub(2) = tropolone) with acetylene yielded the monomeric triazole compound ((Eta sup(6)-C sub(6)Me sub(6...

Whole-core analysis by 13C NMR

International Nuclear Information System (INIS)

Vinegar, H.J.; Tutunjian, P.N.; Edelstein, W.A.; Roemer, P.B.

1991-01-01

This paper reports on a whole-core nuclear magnetic resonance (NMR) system that was used to obtain natural abundance 13 C spectra. The system enables rapid, nondestructive measurements of bulk volume of movable oil, aliphatic/aromatic ratio, oil viscosity, and organic vs. carbonate carbon. 13 C NMR can be used in cores where the 1 H NMR spectrum is too broad to resolve oil and water resonances separately. A 5 1/4-in. 13 C/ 1 H NMR coil was installed on a General Electric (GE) CSI-2T NMR imager/spectrometer. With a 4-in.-OD whole core, good 13 C signal/noise ratio (SNR) is obtained within minutes, while 1 H spectra are obtained in seconds. NMR measurements have been made of the 13 C and 1 H density of crude oils with a wide range of API gravities. For light- and medium-gravity oils, the 13 C and 1 H signal per unit volume is constant within about 3.5%. For heavy crudes, the 13 C and 1 H density measured by NMR is reduced by the shortening of spin-spin relaxation time. 13 C and 1 H NMR spin-lattice relaxation times were measured on a suite of Cannon viscosity standards, crude oils (4 to 60 degrees API), and alkanes (C 5 through C 16 ) with viscosities at 77 degrees F ranging from 0.5 cp to 2.5 x 10 7 cp. The 13 C and 1 H relaxation times show a similar correlation with viscosity from which oil viscosity can be estimated accurately for viscosities up to 100 cp. The 13 C surface relaxation rate for oils on water-wet rocks is very low. Nonproton decoupled 13 C NMR is shown to be insensitive to kerogen; thus, 13 C NMR measures only the movable hydrocarbon content of the cores. In carbonates, the 13 C spectrum also contains a carbonate powder pattern useful in quantifying inorganic carbon and distinguishing organic from carbonate carbon

Occurrence, biological activities and 13C NMR data of amides from Piper (Piperaceae

Directory of Open Access Journals (Sweden)

Jeferson C. do Nascimento

2012-01-01

Full Text Available This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae. Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled 13C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts.

Carbon isotope discrimination during litter decomposition can be explained by selective use of substrate with differing δ13C

Science.gov (United States)

Ngao, J.; Cotrufo, M. F.

2011-01-01

Temporal dynamics of C isotopic composition (δ13C) of CO2 and leaf litter was monitored during a litter decomposition experiment using Arbutus unedo L., as a slow decomposing model substrate. This allowed us (1) to quantify isotopic discrimination variation during litter decomposition, and (2) to test whether selective substrate use or kinetic fractionation could explain the observed isotopic discrimination. Total cumulative CO2-C loss (CL) comprised 27% of initial litter C. Temporal evolution of CL was simulated following a three-C-pool model. Isotopic composition of respired CO2 (δRL) was higher with respect to that of the bulk litter. The isotopic discrimination Δ(L/R) varied from -2‰ to 0‰ and it is mostly attributed to the variations of δRL. A three-pool model, with the three pools differing in their δ13C, described well the dynamic of Δ(L/R), in the intermediate stage of the process. This suggests that the observed isotopic discrimination between respired CO2 and bulk litter is in good agreement with the hypothesis of successive consumption of C compounds differing in δ13C during decomposition. However, to explain also 13C-CO2 dynamics at the beginning and end of the incubation the model had to be modified, with discrimination factors ranging from -1‰ to -4.6‰ attributed to the labile and the recalcitrance pool, respectively. We propose that this discrimination is also the result of further selective use of specific substrates within the two pools, likely being both the labile and recalcitrant pool of composite nature. In fact, the 2‰ 13C enrichment of the α-cellulose observed by the end of the experiment, and potentially attributable to kinetic fractionation, could not explain the measured Δ(L/R) dynamics.

Skeletal and chlorine effects on 13C-NMR chemical shifts of chlorinated polycyclic systems

Directory of Open Access Journals (Sweden)

Costa V.E.U.

1999-01-01

Full Text Available In order to establish a comparative analysis of chemical shifts caused by ring compression effects or by the presence of a chlorine atom on strained chlorinated carbons, a series of the chlorinated and dechlorinated polycyclic structures derived from "aldrin" (5 and "isodrin" (14 was studied. Compounds were classified in four different groups, according to their conformation and number of ring such as: endo-exo and endo-endo tetracyclics, pentacyclics and hexacyclics. The 13C chemical shift comparison between the chlorinated and dechlorinated compounds showed that when C-9 and C-10 are olefinic carbons, it occurs a shielding of 0.5-2.4 ppm for endo-endo tetracyclics and of 4.7-7.6 ppm for endo-exo tetracyclic. The chemical shift variation for C-11 reaches 49-53 ppm for endo-exo and endo-endo tetracyclics, 54 ppm for pentacyclic and 56-59 ppm for hexacyclic compounds. From these data, it was possible to observe the influence of ring compression on the chemical shifts.

7-epi-griffonilide, a new lactone from Bauhinia pentandra: complete "1H and "1"3C chemical shift assignments

International Nuclear Information System (INIS)

Almeida, Macia C.S. de; Souza, Luciana G.S.; Ferreira, Daniele A.; Pinto, Francisco C.L.; Santiago, Gilvandete M.P.; Monte, Francisco J.Q.; Lemos, Telma L.G.; Oliveira, Debora R. de; Braz-Filho, Raimundo

2017-01-01

A new lactone, 7-epi-griffonilide (1), and six known compounds, 2, 3a - 3c, 4a and 4b, were isolated from the leaves of Bauhinia pentandra (Fabaceae). The structures elucidation of 1 and 2 were based on detailed 2D NMR techniques and spectral comparison with related compounds, leading to complete assignment of the "1H and "1"3C NMR spectra. (author)

13C CPMAS NMR Studies of Anthocyanidins and their Glucosides

International Nuclear Information System (INIS)

Wolniak, M.; Wawer, I.

2005-01-01

Anthocyanins are responsible for red, purple or blue colours of flower petals and can be found in red or black fruits and berries. Many foods, especially red grapes and wines, aronia or blueberries contain large amounts of anthocyanins. Their health beneficial effects are related to antioxidant and radical scavenging properties. Structural analysis of anthocyanins by NMR are few, owing to the difficulty in obtaining analysable spectra for unstable, interconverting compounds, available in small amounts. Compounds studied by us were isolated from fruits and berries. 13 C CPMAS NMR spectra were recorded on a Bruker DSX-400 spectrometer for solid chlorides of: cyanidin, cyanidin 3-O-glucoside, cyanidin 3,5-O-diglucoside, pelargonidin and pelargonidin 3-O-glucoside. Dipolar dephased and short contact pulse sequences were used as an aid in the assignment of resonances in CPMAS spectra of solids. Inspection of the spectra indicates that anthocyanidins are in the form of flavylium (cationic) and not in form of the chalcone.: the resonance of C2 appears at ca. 160 ppm and C3 at ca. 135 ppm, whereas C ring opening produces C2 = O, for which chemical shift of ca. 180 ppm can be expected. A comparison of experimental (CPMAS) and predicted (GIAO DFT) shielding constants for cyanidin provided information about the orientation of OH groups, twist angle of aromatic ring B and the localization of the chloride anion.(author)

A facile synthesis of. delta. -aminolevulinic acid (ALA) regio-selectively labeled with sup 13 C and direct observation of enzymatic transformation from ALA to porphobilinogen (PBG)

Energy Technology Data Exchange (ETDEWEB)

Kurumaya, Katsuyuki; Okazaki, Takeo; Seido, Nobuo; Akasaka, Yuzuru; Kawajiri, Yoshiki; Kajiwara, Masahiro (Meiji College of Pharmacy, Tokyo (Japan)); Kondo, Masao (Institute of Public Health, Tokyo (Japan))

1989-02-01

{delta}-Aminolevulinic acid (ALA), labeled with {sup 13}C at position 1, 2, 3, 4, or 5, was synthesized from {sup 13}C-labeled glycine, Meldrum's acid, or bromoacetate. The latter compounds were prepared from {sup 13}C-sodium acetate or {sup 13}C-acetic acid. Enzymatic transformation from ALA to porphobilinogen (PBG) was directly observed by {sup 13}C-NMR. (author).

Study of the direct detection of crosslinking in hydrocarbons by 13C-NMR. II. Identification of crosslink in model compound and application to irradiate paraffins

International Nuclear Information System (INIS)

Bennett, R.L.; Keller, A.; Stejny, H.H.; Murray, M.

1976-01-01

A 13 C-NMR investigation was carried out in aid of direct detection of crosslinks in hydrocarbons with the future objective of studying radiation-induced crosslinking in polyethylene by a direct method. The resonance signal due to a tertiary carbon atom appropriate to a crosslink far remote from molecular ends has been identified in a definitive manner with the aid of the H-shaped model compound 1,1,2,2-tetra(tridecyl)ethane synthetized in Part I of this study. This identification was then put to use in the examination of the irradiated linear paraffins n-hexadecane and n-eicosane, where it enabled the detection of radiation-induced crosslinks. This crosslinking could then be associated with corresponding changes in molecular weight (dimer, trimer formation) as revealed by discrete peaks in the gel-permeation chromatograms of the same samples and randomness of the crosslinking process in the liquid state of these compounds being inferred

IRMS detection of testosterone manipulated with 13C labeled standards in human urine by removing the labeled 13C.

Science.gov (United States)

Wang, Jingzhu; Yang, Rui; Yang, Wenning; Liu, Xin; Xing, Yanyi; Xu, Youxuan

2014-12-10

Isotope ratio mass spectrometry (IRMS) is applied to confirm testosterone (T) abuse by determining the carbon isotope ratios (δ(13)C value). However, (13)C labeled standards can be used to control the δ(13)C value and produce manipulated T which cannot be detected by the current method. A method was explored to remove the (13)C labeled atom at C-3 from the molecule of androsterone (Andro), the metabolite of T in urine, to produce the resultant (A-nor-5α-androstane-2,17-dione, ANAD). The difference in δ(13)C values between Andro and ANAD (Δδ(13)CAndro-ANAD, ‰) would change significantly in case manipulated T is abused. Twenty-one volunteers administered T manipulated with different (13)C labeled standards. The collected urine samples were analyzed with the established method, and the maximum value of Δδ(13)CAndro-ANAD post ingestion ranged from 3.0‰ to 8.8‰. Based on the population reference, the cut-off value of Δδ(13)CAndro-ANAD for positive result was suggested as 1.2‰. The developed method could be used to detect T manipulated with 3-(13)C labeled standards. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of hepatic ischemia-reperfusion injury on the blood-brain barrier permeability to [14C] and [13C]sucrose.

Science.gov (United States)

Miah, Mohammad K; Bickel, Ulrich; Mehvar, Reza

2017-12-01

Hepatic encephalopathy that is associated with severe liver failure may compromise the blood-brain barrier (BBB) integrity. However, the effects of less severe liver diseases, in the absence of overt encephalopathy, on the BBB are not well understood. The goal of the current study was to investigate the effects of hepatic ischemia-reperfusion (IR) injury on the BBB tight junction permeability to small, hydrophilic molecules using the widely used [ 14 C]sucrose and recently-proposed alternative [ 13 C]sucrose as markers. Rats were subjected to 20 min of hepatic ischemia or sham surgery, followed by 8 h of reperfusion before administration of a single bolus dose of [ 14 C] or [ 13 C]sucrose and collection of serial (0-30 min) blood and plasma and terminal brain samples. The concentrations of [ 14 C] and [ 13 C]sucrose in the samples were determined by measurement of total radioactivity (nonspecific) and LC-MS/MS (specific), respectively. IR injury significantly increased the blood, plasma, and brain concentrations of both [ 14 C] and [ 13 C]sucrose. However, when the brain concentrations were corrected for their respective area under the blood concentration-time curve, only [ 14 C]sucrose showed significantly higher (30%) BBB permeability values in the IR animals. Because [ 13 C]sucrose is a more specific BBB permeability marker, these data indicate that our animal model of hepatic IR injury does not affect the BBB tight junction permeability to small, hydrophilic molecules. Methodological differences among studies of the effects of liver diseases on the BBB permeability may confound the conclusions of such studies.

Trace level detection of compounds related to the chemical weapons convention by 1H-detected 13C NMR spectroscopy executed with a sensitivity-enhanced, cryogenic probehead.

Science.gov (United States)

Cullinan, David B; Hondrogiannis, George; Henderson, Terry J

2008-04-15

Two-dimensional 1H-13C HSQC (heteronuclear single quantum correlation) and fast-HMQC (heteronuclear multiple quantum correlation) pulse sequences were implemented using a sensitivity-enhanced, cryogenic probehead for detecting compounds relevant to the Chemical Weapons Convention present in complex mixtures. The resulting methods demonstrated exceptional sensitivity for detecting the analytes at trace level concentrations. 1H-13C correlations of target analytes at chemical shift information could be derived quickly and simultaneously from the resulting spectra. The fast-HMQC pulse sequences generated magnitude mode spectra suitable for detailed analysis in approximately 4.5 h and can be used in experiments to efficiently screen a large number of samples. The HSQC pulse sequences, on the other hand, required roughly twice the data acquisition time to produce suitable spectra. These spectra, however, were phase-sensitive, contained considerably more resolution in both dimensions, and proved to be superior for detecting analyte 1H-13C correlations. Furthermore, a HSQC spectrum collected with a multiplicity-edited pulse sequence provided additional structural information valuable for identifying target analytes. The HSQC pulse sequences are ideal for collecting high-quality data sets with overnight acquisitions and logically follow the use of fast-HMQC pulse sequences to rapidly screen samples for potential target analytes. Use of the pulse sequences considerably improves the performance of NMR spectroscopy as a complimentary technique for the screening, identification, and validation of chemical warfare agents and other small-molecule analytes present in complex mixtures and environmental samples.

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

Science.gov (United States)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-09-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

Occurrence, biological activities and {sup 13}C NMR data of amides from Piper (Piperaceae)

Energy Technology Data Exchange (ETDEWEB)

Nascimento, Jeferson C. do; Paula, Vanderlucia F. de [Universidade Estadual do Sudoeste da Bahia, Jequie, BA (Brazil). Dept. de Quimica e Exatas; David, Jorge M. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Quimica; David, Juceni P., E-mail: jmdavid@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Fac. de Farmacia

2012-07-01

This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae). Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled {sup 13}C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts. (author)

Electric dipole moment of 13C

Science.gov (United States)

Yamanaka, Nodoka; Yamada, Taiichi; Hiyama, Emiko; Funaki, Yasuro

2017-06-01

We calculate for the first time the electric dipole moment (EDM) of 13C generated by the isovector charge conjugation-parity (CP)-odd pion exchange nuclear force in the α -cluster model, which describes well the structures of low-lying states of the 13C nucleus. The linear dependence of the EDM of 13C on the neutron EDM and the isovector CP-odd nuclear coupling is found to be d13C=-0.33 dn-0.0020 G¯π(1 ) . The linear enhancement factor of the CP-odd nuclear coupling is smaller than that of the deuteron, due to the difference of the structure between the 1 /21- state and the opposite-parity (1 /2+ ) states. We clarify the role of the structure played in the enhancement of the EDM. This result provides good guiding principles to search for other nuclei with large enhancement factor. We also mention the role of the EDM of 13C in determining the new physics beyond the standard model.

Characterization of methacetin-methoxy-"1"3C

International Nuclear Information System (INIS)

Lu Weijing; Lu Hao; Yang Weicheng; Liu Weixia; Li Shuai; Xu Zhongjie; Guan Liang; Zhu Chengmo; Chen Suyun; Jiang Lei

2010-01-01

Methacetin-methoxy-"1"3C was synthesized by using methanol-"1"3C with a novel method, and the characterization of it was performed using HPLC, LC-MS and "1HMNR. The results indicated that the synthetic was right. And the yield of methacetin-methoxy-"1"3C was 70.0% with 99% "1"3C abundance and 99.8% purity. Compared with the classical method, there was more benefit. The methacetin "1"3C-breath test was performed with the synthetic on the live mice, which showed a precise reflection of alteration of liver function in liver injury and functional recovery. (authors)

13C/12C ratios in human urine concrementes

International Nuclear Information System (INIS)

Hoefs, J.; Armbruster, T.

1978-01-01

Oxalate, uric acid, and phosphate stones have been analyzed for their carbon isotope composition. The oxalate stones show delta 13 C values between -17.0 and -19.5 pro mille, the uric acid stones between -14.9 and -19.4 pro mille, and the phosphate stones between -13.0 and -23.9 pro mille. It is proposed that endogenic rather than exogenic sources are responsible for the 13 C/ 12 C ratios of the stones. The isotopic composition of the phosphate stones seems to be influenced primarily by bacterial activity. (orig.) [de

Two-Scale 13C Metabolic Flux Analysis for Metabolic Engineering.

Science.gov (United States)

Ando, David; Garcia Martin, Hector

2018-01-01

Accelerating the Design-Build-Test-Learn (DBTL) cycle in synthetic biology is critical to achieving rapid and facile bioengineering of organisms for the production of, e.g., biofuels and other chemicals. The Learn phase involves using data obtained from the Test phase to inform the next Design phase. As part of the Learn phase, mathematical models of metabolic fluxes give a mechanistic level of comprehension to cellular metabolism, isolating the principle drivers of metabolic behavior from the peripheral ones, and directing future experimental designs and engineering methodologies. Furthermore, the measurement of intracellular metabolic fluxes is specifically noteworthy as providing a rapid and easy-to-understand picture of how carbon and energy flow throughout the cell. Here, we present a detailed guide to performing metabolic flux analysis in the Learn phase of the DBTL cycle, where we show how one can take the isotope labeling data from a 13 C labeling experiment and immediately turn it into a determination of cellular fluxes that points in the direction of genetic engineering strategies that will advance the metabolic engineering process.For our modeling purposes we use the Joint BioEnergy Institute (JBEI) Quantitative Metabolic Modeling (jQMM) library, which provides an open-source, python-based framework for modeling internal metabolic fluxes and making actionable predictions on how to modify cellular metabolism for specific bioengineering goals. It presents a complete toolbox for performing different types of flux analysis such as Flux Balance Analysis, 13 C Metabolic Flux Analysis, and it introduces the capability to use 13 C labeling experimental data to constrain comprehensive genome-scale models through a technique called two-scale 13 C Metabolic Flux Analysis (2S- 13 C MFA) [1]. In addition to several other capabilities, the jQMM is also able to predict the effects of knockouts using the MoMA and ROOM methodologies. The use of the jQMM library is

({sup 1} H, {sup 13} C and {sup 31} P) NMR of phosphonic acid derivatives; Ressonancia magnetica nuclear ({sup 1} H, {sup 13} C, {sup 31} P) de derivados do acido fosfonico

Energy Technology Data Exchange (ETDEWEB)

Campos, Valdevino; Costa, Valentim E. Uberti [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica

1992-12-31

In the last years the development of phosphates analogues in the medical and agricultural pesticides has being very expressive. {sup 1} H, {sup 13} C and mainly {sup 31} P NMR are used for stereochemical and conformational analysis, and reactivity studies on the compounds resulting from those chemical processes 2 refs., 4 figs., 1 tab.

Investigating tumor perfusion and metabolism using multiple hyperpolarized 13C compounds: HP001, pyruvate and urea

DEFF Research Database (Denmark)

von Morze, Cornelius; Larson, Peder E.Z.; Hu, Simon

2012-01-01

The metabolically inactive hyperpolarized agents HP001 (bis-1,1-(hydroxymethyl)-[1-13C]cyclopropane-d8) and urea enable a new type of perfusion magnetic resonance imaging based on a direct signal source that is background-free. The addition of perfusion information to metabolic information obtained...... (T1=95 s ex vivo, 32 s in vivo at 3 T) using a pulse sequence with balanced steady-state free precession and ramped flip angle over time for efficient utilization of the hyperpolarized magnetization and three-dimensional echo-planar spectroscopic imaging of urea copolarized with [1-13C...... of separate dynamic HP001 imaging and copolarized pyruvate/urea imaging were compared. A strong and significant correlation (R=0.73, P=.02) detected between the urea and HP001 data confirmed the value of copolarizing urea with pyruvate for simultaneous assessment of perfusion and metabolism....

Stereoselective synthesis of L-[4-13C]carnitine

International Nuclear Information System (INIS)

Unkefer, C.J.; Ehler, D.S.

1991-01-01

The stereoselective synthesis of L-[4- 13 C]carnitine was achieved in 5 steps. The label was introduced from K 13 CN into an easily separated diastereomeric pair of 3-deoxy-D-[1- 13 C]aldohexoses. Reductive amination of the labeled aldohexose yielded the corresponding D-1-(dimethylamino)[1- 13 C]alditol which was oxidized in two steps and alkylated with iodomethane to yield L-[4- 13 C]carnitine. The stereochemical integrity at C-2 of the 3-deoxy-D-[1- 13 C]glucose precursor was maintained throughout the synthesis of L-[4- 13 C]carnitine. (author)

Synthesis of deuterium labeled perillyl alcohol and dual C-13 and deuterium labeled perillic acid, major metabolites of d-limonene

International Nuclear Information System (INIS)

Chen, Haitao; Chan, K.C.

1997-01-01

Dual C-13 and deuterium labeled perillic acid, [(1,1-dideuterio-1- 13 C-2-methyl)ethenyl]-1-cyclohexene -1-carboxylic acid (6) and deuterated perillyl alcohol, [(2,2-dideuterio-1-methyl)ethenyl]-1-deuteriohydroxymethyl-1-cyclo -hexene (9) were synthesized from commercially available (4S)-(-)-perillaidehyde (1). Compound 1 was first protected with ethylene glycol to yield the ethylene ketal followed by oxidation with OsO 4 /NalO 4 to cleave the terminal double bond to afford the key intermediate ketone, 4-acetyl-1-cyclohexene-1-carboxaldehyde ethylene ketal (3). 3 was then converted to the labeled perillyl aldehyde by Wittig reaction with prepared Ph 3 P 13 CD 3 l or Ph 3 PCD 3 l. Followed by deprotection to give the labeled perillaldehydes, [(2,2-dideuterio-2- 13 C-1-methyl)ethenyl] -1-cyclohexene-1-carboxaldehyde-1-carboxaldehyde (5) or [(2,2-dideuterio-1-methyl)ethenyl] -1-cyclohexene-1-carboxaldehyde (8). 5 was further oxidized by freshly prepared Ag 2 O to give the desired compound 6. 8 was reduced by LiAID 4 to afford the desired compound 9. The same synthetic procedure may be adopted to synthesize the radioactive isotope labeled perillic acid and perilly alcohol. (author)

A polymer-based magnetic resonance tracer for visualization of solid tumors by 13C spectroscopic imaging.

Directory of Open Access Journals (Sweden)

Yoshikazu Suzuki

Full Text Available Morphological imaging precedes lesion-specific visualization in magnetic resonance imaging (MRI because of the superior ability of this technique to depict tissue morphology with excellent spatial and temporal resolutions. To achieve lesion-specific visualization of tumors by MRI, we investigated the availability of a novel polymer-based tracer. Although the 13C nucleus is a candidate for a detection nucleus because of its low background signal in the body, the low magnetic resonance sensitivity of the nucleus needs to be resolved before developing a 13C-based tracer. In order to overcome this problem, we enriched polyethylene glycol (PEG, a biocompatible polymer, with 13C atoms. 13C-PEG40,000 (13C-PEG with an average molecular weight of 40 kDa emitted a single 13C signal with a high signal-to-noise ratio due to its ability to maintain signal sharpness, as was confirmed by in vivo investigation, and displayed a chemical shift sufficiently distinct from that of endogenous fat. 13C-PEG40,000 intravenously injected into mice showed long retention in circulation, leading to its effective accumulation in tumors reflecting the well-known phenomenon that macromolecules accumulate in tumors because of leaky tumor capillaries. These properties of 13C-PEG40,000 allowed visualization of tumors in mice by 13C spectroscopic imaging. These findings suggest that a technique based on 13C-PEG is a promising strategy for tumor detection.

7-epi-griffonilide, a new lactone from Bauhinia pentandra: complete {sup 1}H and {sup 13}C chemical shift assignments

Energy Technology Data Exchange (ETDEWEB)

Almeida, Macia C.S. de; Souza, Luciana G.S.; Ferreira, Daniele A.; Pinto, Francisco C.L.; Santiago, Gilvandete M.P.; Monte, Francisco J.Q.; Lemos, Telma L.G., E-mail: fmonte@dqoi.ufc.br [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil); Oliveira, Debora R. de; Braz-Filho, Raimundo [Universidade Federal Rural do Rio de Janeiro (UFRRJ), Seropedica, RJ (Brazil). Departamento de Quimica

2017-09-01

A new lactone, 7-epi-griffonilide (1), and six known compounds, 2, 3a - 3c, 4a and 4b, were isolated from the leaves of Bauhinia pentandra (Fabaceae). The structures elucidation of 1 and 2 were based on detailed 2D NMR techniques and spectral comparison with related compounds, leading to complete assignment of the {sup 1}H and {sup 13}C NMR spectra. (author)

13C- and 15N-labelled non-biogenic compounds used as stable isotope drugs for human liver function tests

International Nuclear Information System (INIS)

Krumbiegel, P.

1989-01-01

As a result of liver diseases, the elimination of certain drugs is retarded. After labelling a suitable drug with 13 C, the 13 CO 2 elimination rate serves as a liver function parameter. Current contributions to the 13 CO 2 breath test method are reviewed and related to the 14 CO 2 breath test proposals. In spite of several advantages of 13 C-labelled agents, some dissatisfaction has remained with the tests, especially at using them with infants. It is the necessity of face masks and the uncertainty to consider endogeneous CO 2 contributions diluting the exhaled 13 CO 2 . The problems are avoided if the other molecule site of the drug is labelled which is known to be eliminated via urine. With 15 N as a tracer, a suitable urine test using [ 15 N]-methacetin as agent has been proposed and put into practice. (author)

Conformational study of C8 diazocine turn mimics using {sup 3}J{sub CH} coupling constants with {sup 13}C in natural abundance

Energy Technology Data Exchange (ETDEWEB)

Bean, J.W.; Briand, J.; Burgess, J.L.; Callahan, J.F. [SmithKline Beecham Pharmaceuticals, King of Prussia, PA (United States)

1994-12-01

The conformations of two diazocine turn mimics, which were later incorporated into GPIIb/IIIa peptide antagonists, were investigated using nuclear magnetic resonance techniques. The two compounds, methyl (2,5-dioxo-3-(S)-(3-{omega}-tosylguanidino-propyl)-4-methyl-octahydro-1,4-dazocin-1-yl)acetate (1) and methyl (2,5-dioxo-3-(S)-(3-{omega}-tosyl-guanidino-propyl)-octahydro-1,5-diazocin-1-yl)acetate (2), differ only in their substituent at the diazocine position 4 nitrogen, yet this substitution results in a marked difference in the affinity of the resulting analogs for the GPIIb/IIIa receptor. It was of interest to determine if the difference observed in the antagonistic potency between these analogs was related to constitutional or, perhaps, conformational differences. The backbone conformations of these two molecules can be determined by measuring vicinal coupling constants along the trimethylene portion of the C8 ring backbone and by measuring interproton NOE intensities between the diazocine methine proton and the protons of the trimethylene group. For compound 1, {sup 3}J{sub HH} values measured from a P.E.COSY spectrum and interproton distances calculated from ROESY buildup curves indicated the presence of a single C8 ring backbone conformation where the trimethylene bridge adopted a staggered conformation and the H{alpha}1 and H{gamma}1 protons of the trimethylene group were 2.2 A from the methine proton. For compound 2, however, partial overlap of the central H{beta}1 and H{beta}2 protons made it impossible to measure {sup 3}J{sub HH} values from the P.E.COSY spectrum. We therefore used a {sup 13}C-filtered TOCSY experiment to measure the {sup 3}J{sub CH} values in both compounds 1 and 2. These heteronuclear vicinal coupling constants measured with {sup 13}C in natural abundance in conjunction with measured interproton NOE intensities indicate that these compounds share a common C8 ring backbone conformation.

[13C] GC-C-IRMS analysis of methylboronic acid derivatives of glucose from liver glycogen after the ingestion of [13C] labeled tracers in rats.

Science.gov (United States)

Luengo, Catherine; Azzout-Marniche, Dalila; Fromentin, Claire; Piedcoq, Julien; Lemosquet, Sophie; Tomé, Daniel; Gaudichon, Claire

2009-11-01

We developed a complete method to measure low [(13)C] enrichments in glycogen. Fourteen rats were fed a control diet. Six of them also ingested either [U-(13)C] glucose (n=2) or a mixture of 20 [U-(13)C] amino acids (n=4). Hepatic glycogen was extracted, digested to glucose and purified on anion-cation exchange resins. After the optimization of methylboronic acid derivatization using GC-MS, [(13)C] enrichment of extracted glucose was measured by GC-C-IRMS. The accuracy was addressed by measuring the enrichment excess of a calibration curve, which observed values were in good agreement with the expected values (R=0.9979). Corrected delta values were -15.6+/-1.6 delta(13)C (per thousand) for control rats (n=8) and increased to -5 to 8 delta(13)C (per thousand) per thousand and 12-14 delta(13)C (per thousand) per thousand after the ingestion of [U-(13)C] amino acids or [U-(13)C] glucose as oral tracers, respectively. The method enabled the determination of dietary substrate transfer into glycogen. The sequestration of dietary glucose in liver glycogen 4 h after the meal was 35% of the ingested dose whereas the transfer of carbon skeletons from amino acids was only 0.25 to 1%.

Evidence for in situ degradation of mono-and polyaromatic hydrocarbons in alluvial sediments based on microcosm experiments with 13C-labeled contaminants

International Nuclear Information System (INIS)

Morasch, B.; Hoehener, P.; Hunkeler, D.

2007-01-01

A microcosm study was conducted to investigate the degradation of mono- and polyaromatic hydrocarbons under in situ-like conditions using alluvial sediments from the site of a former cokery. Benzene, naphthalene, or acenaphthene were added to the sediments as 13 C-labeled substrates. Based on the evolution of 13 C-CO 2 determined by gas chromatography isotope-ratio mass spectrometry (GC-IRMS) it was possible to prove mineralization of the compound of interest in the presence of other unknown organic substances of the sediment material. This new approach was suitable to give evidence for the intrinsic biodegradation of benzene, naphthalene, and acenaphthene under oxic and also under anoxic conditions, due to the high sensitivity and reproducibility of 13 C/ 12 C stable isotope analysis. This semi-quantitative method can be used to screen for biodegradation of any slowly degrading, strongly sorbing compound in long-term experiments. - A method based on 13 C-labeled substrates was developed to determine the intrinsic biodegradation potential of aromatic pollutants under oxic and under anoxic conditions

/sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk

Energy Technology Data Exchange (ETDEWEB)

Bzhezovskii, V.M.; Valeev, R.B.; Kalabin, G.A.; Aliev, I.A.

1987-06-20

The /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk were obtained. The changes in the screening of the /sup 13/C, /sup 17/O, and /sup 33/S nuclei in these compounds are determined by the effect of the alkyl substituents, which alternates in sign and decreases along the chain of atoms in the order: CH/sub 3/, C/sub 2/H/sub 5/, iso-C/sub 3/H/sub 7/, and tert-C/sub 4/H/sub 9/. In the alkyl phenyl sulfides C/sub 6/H/sub 5/SAlk the additional effect of disruption in the p,..pi.. interaction between the sulfur atom and the benzene ring as a result of conformational changes is superimposed on the screening of the /sup 13/C/sup ortho/ nuclei. For the changes in the screening of the /sup 13/C/sup para/ nuclei in C/sub 6/H/sub 5/SAlk the steric disruption of the p,..pi.. conjugation by the alkyl substituents is determining.

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

Science.gov (United States)

Clark, Justin A; Stotler, Randy L; Frape, Shaun K; Illman, Walter A

2017-01-01

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ 37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵ Cl /ϵ C ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume. © 2016, National Ground Water Association.

Radical C-H functionalization to construct heterocyclic compounds.

Science.gov (United States)

Yu, Jin-Tao; Pan, Changduo

2016-02-07

Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

Dynamics of growth/mature-related substances in vegetables using specific triple labeled compound

International Nuclear Information System (INIS)

Yamato, Yoichi; Hamano, Megumi; Yamazaki, Hiroko; Miura, Hiroyuki

2000-01-01

To progress physiological studies of vegetables, development of biosynthetic method for production of triple labeled compounds was attempted in this study and such method for vegetables using specifically labeled sugars was examined. As a sugar compound, 6-C 14 -glucose (14-CG) and 1-H 3 -glucose (3-HG) were given to culture medium for cells derived from tomato embryonic axis and the changes of these compounds were monitored. Tomato embryonic cells were harvested 20 and 44 hours after the addition of 14-CG or 3-CG into the culture medium the cells. The cells were homogenized and the supernatant after centrifugation was applied onto HPLC. Radio analyzer revealed major two peaks in the chromatography of the sugar fraction from the cells after 20 hours from the addition of 14-CG. One was the peak of glucose, itself and the other was estimated to be that of fructose based on the retention time. Whereas in the elution pattern of the sugar fraction after 44 hours from the addition, a peak of sucrose was found along with the peak of glucose. These results indicate that C 14 in 14-CG but not H 3 in 3-HG was transferred into fructose after the metabolism in tomato. Moreover, in both elution patterns, there was a peak positioned at the same retention time, indicating that the compound in this peak was produced from either of 14-CG or 3-HG. Therefore, it is thought that H 3 and C 14 double-labeled compound could be produced from the cell culture added with both labeled compounds; 14-CG and 3-HG. (M.N.)

Intrinsic ratios of glucose, fructose, glycerol and ethanol 13C/12C isotopic ratio determined by HPLC-co-IRMS: toward determining constants for wine authentication.

Science.gov (United States)

Guyon, François; Gaillard, Laetitia; Salagoïty, Marie-Hélène; Médina, Bernard

2011-09-01

High-performance liquid chromatography linked to isotope ratio mass spectrometry (HPLC-co-IRMS) via a Liquiface© interface has been used to simultaneously determine (13)C isotope ratios of glucose (G), fructose (F), glycerol (Gly) and ethanol (Eth) in sweet and semi-sweet wines. The data has been used the study of wine authenticity. For this purpose, 20 authentic wines from various French production areas and various vintages have been analyzed after dilution in pure water from 20 to 200 times according to sugar content. If the (13)C isotope ratios vary according to the production area and the vintage, it appears that internal ratios of (13)C isotope ratios (R((13)C)) of the four compounds studied can be considered as a constant. Thus, ratios of isotope ratios are found to be 1.00 ± 0.04 and 1.02 ± 0.08 for R((13)C(G/F)) and R((13)C(Gly/Eth)), respectively. Moreover, R((13)C(Eth/Sugar)) is found to be 1.15 ± 0.10 and 1.16 ± 0.08 for R((13)C(Gly/Sugar)). Additions of glucose, fructose and glycerol to a reference wine show a variation of the R((13)C) value for a single product addition as low as 2.5 g/L(-1). Eighteen commercial wines and 17 concentrated musts have been analyzed. Three wine samples are suspicious as the R((13)C) values are out of range indicating a sweetening treatment. Moreover, concentrated must analysis shows that (13)C isotope ratio can be also used directly to determine the authenticity of the matrix.

Facile determination of the specific activity of carbonyl compounds reduced by tritiated borohydride

Energy Technology Data Exchange (ETDEWEB)

Avigad, G [Rutgers--the State Univ., Piscataway, NJ (USA)

1979-12-01

Three procedures are described for microliter samples of glucose 6-phosphate or lactose as model compounds. After the reduction with (/sup 3/H)-NaBH/sub 4/ and suitable treatment, specific activity is calculated from the ratios /sup 3/H activity/total phosphorus, /sup 3/H//sup 14/C activity, or /sup 3/H activity/galactoside concentration.

Synthesis of labeled compounds

International Nuclear Information System (INIS)

Whaley, T.W.

1977-01-01

Intermediate compounds labeled with 13 C included methane, sodium cyanide, methanol, ethanol, and acetonitrile. A new method for synthesizing 15 N-labeled 4-ethylsulfonyl-1-naphthalene-sulfonamide was developed. Studies were conducted on pathways to oleic-1- 13 C acid and a second pathway investigated was based on carbonation of 8-heptadecynylmagnesium bromide with CO 2 to prepare sterolic acid. Biosynthetic preparations included glucose- 13 C from starch isolated from tobacco leaves following photosynthetic incubation with 13 CO 2 and galactose- 13 C from galactosylglycerol- 13 C from kelp. Research on growth of organisms emphasized photosynthetic growth of algae in which all cellular carbon is labeled. Preliminary experiments were performed to optimize the growth of Escherichia coli on sodium acetate- 13 C

Synthesis of edatrexate (2-13C-glutamate)

International Nuclear Information System (INIS)

DeGraw, J.I.; Colwell, W.T.; Jue, Thomas

1997-01-01

The experimental antitumor drug Edatrexate, labeled with 99% 13 C at the 2-position of the glutamate acid group was required for 13 C-magnetic resonance spectroscopy studies in biological media. Coupling of 2,4-diamino-4-deoxy-10-ethyl-10-deazapteroic acid with diethyl L-2- 13 C-glutamate as promoted by BOP reagent afforded Edatrexate (2- 13 C-glu) diethyl ester in 60% yield following purification by column chromatography. Saponification by aqueous NaOH in 2-methoxyethanol gave the target molecule in 44% yield or 26% overall. (author)

The C-12/C-13 abundance ratio in Comet Halley

International Nuclear Information System (INIS)

Wyckoff, S.; Lindholm, E.; Wehinger, P.A.; Peterson, B.A.; Zucconi, J.M.

1989-01-01

The individual (C-13)N rotational lines in Comet Halley are resolved using high-resolution spectra of the CN B2Sigma(+)-X2Sigma(+) (0,0) band. The observe C-12/C-13 abundance ratio excludes a site of origin for the comet near Uranus and Neptune and suggests a condensation environment quite distinct from other solar system bodies. Two theories are presented for the origin of Comet Halley. One theory suggest that the comet originated 4.5 Gyr ago in an inner Oort cloud at a heliocentric distance greater than 100 AU where chemical fractionation led to the C-13 enrichment in the CN parent molecule prior to condensation of the comet nucleus. According to the other, more plausible theory, the comet nucleus condensed relatively recently from the interstellar medium which has become enriches in C-13 and was subsequently gravitationally captured by the solar system. 107 refs

IRMS detection of testosterone manipulated with {sup 13}C labeled standards in human urine by removing the labeled {sup 13}C

Energy Technology Data Exchange (ETDEWEB)

Wang, Jingzhu, E-mail: wangjingzhu@chinada.cn [National Anti-Doping Laboratory, China Anti-Doping Agency, Beijing (China); Yang, Rui [Sport Science College, Beijing Sport University Beijing, Beijing (China); Yang, Wenning [School of Pharmacy, Beijing University of Chinese Medicine, Beijing (China); Liu, Xin; Xing, Yanyi; Xu, Youxuan [National Anti-Doping Laboratory, China Anti-Doping Agency, Beijing (China)

2014-12-10

Highlights: • {sup 13}C labeled testosterone can be used to adjust the isotope ratio of testosterone. • The novel testosterone cannot be detected by the regular IRMS method in doping test. • A method was explored to remove the labeled {sup 13}C. • The established method can be used to detect the manipulated testosterone. - Abstract: Isotope ratio mass spectrometry (IRMS) is applied to confirm testosterone (T) abuse by determining the carbon isotope ratios (δ{sup 13}C value). However, {sup 13}C labeled standards can be used to control the δ{sup 13}C value and produce manipulated T which cannot be detected by the current method. A method was explored to remove the {sup 13}C labeled atom at C-3 from the molecule of androsterone (Andro), the metabolite of T in urine, to produce the resultant (A-nor-5α-androstane-2,17-dione, ANAD). The difference in δ{sup 13}C values between Andro and ANAD (Δδ{sup 13}C{sub Andro–ANAD}, ‰) would change significantly in case manipulated T is abused. Twenty-one volunteers administered T manipulated with different {sup 13}C labeled standards. The collected urine samples were analyzed with the established method, and the maximum value of Δδ{sup 13}C{sub Andro–ANAD} post ingestion ranged from 3.0‰ to 8.8‰. Based on the population reference, the cut-off value of Δδ{sup 13}C{sub Andro–ANAD} for positive result was suggested as 1.2‰. The developed method could be used to detect T manipulated with 3-{sup 13}C labeled standards.

Synthesis of deuterium-labelled compounds for FOTEK project

International Nuclear Information System (INIS)

Joergensen, O.; Egsgaard, H.; Larsen, E.

1996-01-01

In the FoTech project there have been utilized labelled compounds of stable isotopes as internal standards. Some of these compounds are commercially available ( 13 C-labelled PCB congeners, 13 C-labelled diethylstilbestrol for determination of anabolic steroids). Others, like D 9 -clenbuterol, D 3 -clenbuterol, D 3 -zeramol and D 3 -dimetridazol have been synthesized. General aspects of deuterium compounds labelling are considered. (EG)

Comparison of liquid chromatography-isotope ratio mass spectrometry (LC/IRMS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) for the determination of collagen amino acid δ13C values for palaeodietary and palaeoecological reconstruction.

Science.gov (United States)

Dunn, Philip J H; Honch, Noah V; Evershed, Richard P

2011-10-30

Results are presented of a comparison of the amino acid (AA) δ(13)C values obtained by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) and liquid chromatography-isotope ratio mass spectrometry (LC/IRMS). Although the primary focus was the compound-specific stable carbon isotope analysis of bone collagen AAs, because of its growing application for palaeodietary and palaeoecological reconstruction, the results are relevant to any field where AA δ(13)C values are required. We compare LC/IRMS with the most up-to-date GC/C/IRMS method using N-acetyl methyl ester (NACME) AA derivatives. This comparison involves the analysis of standard AAs and hydrolysates of archaeological human bone collagen, which have been previously investigated as N-trifluoroacetyl isopropyl esters (TFA/IP). It was observed that, although GC/C/IRMS analyses required less sample, LC/IRMS permitted the analysis of a wider range of AAs, particularly those not amenable to GC analysis (e.g. arginine). Accordingly, reconstructed bulk δ(13)C values based on LC/IRMS-derived δ(13)C values were closer to the EA/IRMS-derived δ(13)C values than those based on GC/C/IRMS values. The analytical errors for LC/IRMS AA δ(13)C values were lower than GC/C/IRMS determinations. Inconsistencies in the δ(13)C values of the TFA/IP derivatives compared with the NACME- and LC/IRMS-derived δ(13)C values suggest inherent problems with the use of TFA/IP derivatives, resulting from: (i) inefficient sample combustion, and/or (ii) differences in the intra-molecular distribution of δ(13)C values between AAs, which are manifested by incomplete combustion. Close similarities between the NACME AA δ(13)C values and the LC/IRMS-derived δ(13)C values suggest that the TFA/IP derivatives should be abandoned for the natural abundance determinations of AA δ(13)C values. Copyright © 2011 John Wiley & Sons, Ltd.

How Energy Metabolism Supports Cerebral Function: Insights from 13C Magnetic Resonance Studies In vivo

Directory of Open Access Journals (Sweden)

Sarah Sonnay

2017-05-01

Full Text Available Cerebral function is associated with exceptionally high metabolic activity, and requires continuous supply of oxygen and nutrients from the blood stream. Since the mid-twentieth century the idea that brain energy metabolism is coupled to neuronal activity has emerged, and a number of studies supported this hypothesis. Moreover, brain energy metabolism was demonstrated to be compartmentalized in neurons and astrocytes, and astrocytic glycolysis was proposed to serve the energetic demands of glutamatergic activity. Shedding light on the role of astrocytes in brain metabolism, the earlier picture of astrocytes being restricted to a scaffold-associated function in the brain is now out of date. With the development and optimization of non-invasive techniques, such as nuclear magnetic resonance spectroscopy (MRS, several groups have worked on assessing cerebral metabolism in vivo. In this context, 1H MRS has allowed the measurements of energy metabolism-related compounds, whose concentrations can vary under different brain activation states. 1H-[13C] MRS, i.e., indirect detection of signals from 13C-coupled 1H, together with infusion of 13C-enriched glucose has provided insights into the coupling between neurotransmission and glucose oxidation. Although these techniques tackle the coupling between neuronal activity and metabolism, they lack chemical specificity and fail in providing information on neuronal and glial metabolic pathways underlying those processes. Currently, the improvement of detection modalities (i.e., direct detection of 13C isotopomers, the progress in building adequate mathematical models along with the increase in magnetic field strength now available render possible detailed compartmentalized metabolic flux characterization. In particular, direct 13C MRS offers more detailed dataset acquisitions and provides information on metabolic interactions between neurons and astrocytes, and their role in supporting neurotransmission. Here

Accurate determination of 13C/12C in CO2 of past atmospheres from 13C/12C in tree rings by removal of climatic interferences. Final technical progress report

International Nuclear Information System (INIS)

Long, A.; Leavitt, S.W.

1982-07-01

Analysis of delta 13 C in tree rings offers the potential for reconstructing changes in delta 13 C of atmospheric CO 2 , which combined with 14 C trends will be important in evaluating the past and present role of the biosphere as a net carbon dioxide source or sink. One problem with such tree-ring delta 13 C records is that in addition to changes in atmospheric delta 13 C, climatic factors may influence the isotopic composition of the rings. This study examines delta 13 C in cellulose of five-year intervals of juniper tree rings. The sampling sites were near weather stations for which climate data are readily available. delta 13 C vs winter climate relationships were derived from those sites not under the influence of local pollution sources. These relationships facilitated development of a delta 13 C record from which climate effects have been factored out. The resulting 1930-1979 delta 13 C reconstruction shows a pronounced delta 13 C decrease from 1930 to 1960 and then a post-1960 flattening of the curve. We interpret this trend as representing an increasing role of biospheric CO 2 sinks relative to sources, although other interpretations may be possible within the limits of precision of data analysis. Research with this technique is continuing with pinyon pine and dendroclimatological reconstructions to verify these results and to develop a climate-free delta 13 C chronology back to pre-industrial time

Pressure-dependent {sup 13}C chemical shifts in proteins: origins and applications

Energy Technology Data Exchange (ETDEWEB)

Wilton, David J. [University of Sheffield, Department of Molecular Biology and Biotechnology (United Kingdom); Kitahara, Ryo [Ritsumeikan University, College of Pharmaceutical Sciences (Japan); Akasaka, Kazuyuki [Kinki University, Department of Biotechnological Science, School of Biology-Oriented Science and Technology (Japan); Williamson, Mike P. [University of Sheffield, Department of Molecular Biology and Biotechnology (United Kingdom)], E-mail: m.williamson@sheffield.ac.uk

2009-05-15

Pressure-dependent {sup 13}C chemical shifts have been measured for aliphatic carbons in barnase and Protein G. Up to 200 MPa (2 kbar), most shift changes are linear, demonstrating pressure-independent compressibilities. CH{sub 3}, CH{sub 2} and CH carbon shifts change on average by +0.23, -0.09 and -0.18 ppm, respectively, due to a combination of bond shortening and changes in bond angles, the latter matching one explanation for the {gamma}-gauche effect. In addition, there is a residue-specific component, arising from both local compression and conformational change. To assess the relative magnitudes of these effects, residue-specific shift changes for protein G were converted into structural restraints and used to calculate the change in structure with pressure, using a genetic algorithm to convert shift changes into dihedral angle restraints. The results demonstrate that residual {sup 13}C{alpha} shifts are dominated by dihedral angle changes and can be used to calculate structural change, whereas {sup 13}C{beta} shifts retain significant dependence on local compression, making them less useful as structural restraints.

Tricarboxylic acid cycle activity measured by 13C magnetic resonance spectroscopy in rats subjected to the kaolin model of obstructed hydrocephalus

DEFF Research Database (Denmark)

Melø, Torun M; Håberg, Asta K; Risa, Øystein

2011-01-01

in the amounts of glutamate, alanine and taurine. In addition, the concentration of the neuronal marker N-acetyl aspartate was decreased. (13)C Labelling of most amino acids derived from [1,6-(13)C]glucose was unchanged 2 weeks after hydrocephalus induction. The only indication of astrocyte impairment......Evaluating early changes in cerebral metabolism in hydrocephalus can help in the decision making and the timing of surgical intervention. This study was aimed at examining the tricarboxylic acid (TCA) cycle rate and (13)C label incorporation into neurotransmitter amino acids and other compounds 2...

Asymmetric 1,8/13,2,x-M2C2B10 14-vertex metallacarboranes by direct electrophilic insertion reactions; the VCD and BHD methods in critical analysis of cage C atom positions.

Science.gov (United States)

McAnaw, Amelia; Lopez, Maria Elena; Ellis, David; Rosair, Georgina M; Welch, Alan J

2014-04-07

The isolation of six isomeric, low-symmetry, dicobaltacarboranes with bicapped hexagonal antiprismatic cage structures, always in low yield, is described from reactions in which 13-vertex cobaltacarborane anions and sources of cobalt-containing cations were present. The vertex-to-centroid distance (VCD) and boron-H distance (BHD) methods are used to locate the correct C atom positions in the cages, thus allowing the compounds to be identified as 1,13-Cp2-1,13,2,10-closo-Co2C2B10H12 (1), 1,8-Cp2-3-OEt-1,8,2,10-closo-Co2C2B10H11 (2), 1,13-Cp2-1,13,2,9-closo-Co2C2B10H12 (3), 1,8-Cp2-1,8,2,4-closo-Co2C2B10H12 (4), 1,13-Cp2-1,13,2,4-closo-Co2C2B10H12 (5) and 1,8-Cp2-1,8,2,5-closo-Co2C2B10H12 (6). It is shown that a common alternative method of cage C atom identification, using refined (as B) U(eq) values, does not work well, at least in these cases. Having identified the correct isomeric forms of the six dicobaltacarboranes, their syntheses are tentatively rationalised in terms of the direct electrophilic insertion of a {CpCo(+)} fragment into [CpCoC2B10](-) anions and it is demonstrated that compounds 1, 4, 5 and 6 can be successfully prepared by deliberately performing such reactions.

Determination of fructose metabolic pathways in normal and fructose-intolerant children: A 13C NMR study using [U-13C]fructose

International Nuclear Information System (INIS)

Gopher, A.; Lapidot, A.; Vaisman, N.; Mandel, H.

1990-01-01

An inborn deficiency in the ability of aldolase B to split fructose 1-phosphate is found in humans with hereditary fructose intolerance (HFI). A stable isotope procedure to elucidate the mechanism of conversion of fructose to glucose in normal children and in HFI children has been developed. A constant infusion of D-[U- 13 C]fructose was given nasogastrically to control and to HFI children. Hepatic fructose conversion to glucose was estimated by examination of 13 C NMR spectra of plasma glucose. Significantly lower values (∼3-fold) for fructose conversion to glucose were obtained for the HFI patients as compared to the controls. A quantitative determination of the metabolic pathways of fructose conversion to glucose was derived from 13 C NMR measurement of plasma [ 13 C]glucose isotopomer populations. The finding of isotopomer populations of three adjacent 13 C atoms at glucose C-4 ( 13 C 3 - 13 C 4 - 13 C 5 ) suggests that there is a direct pathway from fructose, by-passing fructose-1-phosphate aldolase, to fructose 1,6-bisphosphate. The metabolism of fructose by fructose-1-phosphate aldolase activity accounts for only ∼50% of the total amount of hepatic fructose conversion to glucose. In view of the marked decline by 67% in synthesis of glucose from fructose in HFI subjects found in this study, the extent of [ 13 C]glucose formation from a trace amount of [U- 13 C]fructose infused into the patient can be used as a safe and noninvasive diagnostic test for inherent faulty fructose metabolism

Non-stationary (13)C-metabolic flux ratio analysis.

Science.gov (United States)

Hörl, Manuel; Schnidder, Julian; Sauer, Uwe; Zamboni, Nicola

2013-12-01

(13)C-metabolic flux analysis ((13)C-MFA) has become a key method for metabolic engineering and systems biology. In the most common methodology, fluxes are calculated by global isotopomer balancing and iterative fitting to stationary (13)C-labeling data. This approach requires a closed carbon balance, long-lasting metabolic steady state, and the detection of (13)C-patterns in a large number of metabolites. These restrictions mostly reduced the application of (13)C-MFA to the central carbon metabolism of well-studied model organisms grown in minimal media with a single carbon source. Here we introduce non-stationary (13)C-metabolic flux ratio analysis as a novel method for (13)C-MFA to allow estimating local, relative fluxes from ultra-short (13)C-labeling experiments and without the need for global isotopomer balancing. The approach relies on the acquisition of non-stationary (13)C-labeling data exclusively for metabolites in the proximity of a node of converging fluxes and a local parameter estimation with a system of ordinary differential equations. We developed a generalized workflow that takes into account reaction types and the availability of mass spectrometric data on molecular ions or fragments for data processing, modeling, parameter and error estimation. We demonstrated the approach by analyzing three key nodes of converging fluxes in central metabolism of Bacillus subtilis. We obtained flux estimates that are in agreement with published results obtained from steady state experiments, but reduced the duration of the necessary (13)C-labeling experiment to less than a minute. These results show that our strategy enables to formally estimate relative pathway fluxes on extremely short time scale, neglecting cellular carbon balancing. Hence this approach paves the road to targeted (13)C-MFA in dynamic systems with multiple carbon sources and towards rich media. © 2013 Wiley Periodicals, Inc.

Characterization of phenols biodegradation by compound specific stable isotope analysis

Science.gov (United States)

Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

2015-04-01

-cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

Biokinetics of 13C in the human body after oral administration of 13C-labeled glucose as an index for the biokinetics of 14C.

Science.gov (United States)

Masuda, Tsuyoshi; Tako, Yasuhiro; Matsushita, Kensaku; Takeda, Hiroshi; Endo, Masahiro; Nakamura, Yuji; Hisamatsu, Shun'ichi

2016-09-01

The retention of 13 C in the human body after oral administration of 13 C-labeled glucose was studied in three healthy volunteer subjects to estimate the 50 year cumulative body burden for 13 C as an index of the committed dose of the radioisotope 14 C. After administration of 13 C-labeled glucose, the volunteers ingested controlled diets with a fixed number of calories for 112 d. Samples of breath and urine were collected up to 112 d after administration. Samples of feces were collected up to 14 d after administration. Hair samples were obtained at 119 d after administration and analyzed as a representative index of the rate of excretion of organic 13 C via pathways such as skin cell exfoliation and mucus secretion. All samples were analyzed for 13 C/ 12 C atomic ratio to determine the rate of excretion via each pathway. We then constructed a metabolic model with a total of four pathways (breath, urine, feces, and other) comprising seven compartments. We determined the values of the biokinetic parameters in the model by using the obtained excretion data. From 74% to 94% of the 13 C administered was excreted in breath, whereas    0.1). In addition, the dataset for one of the three subjects was markedly different from those of the other two. When we estimated the 50 year cumulative body burden for 13 C by using our model and we included non-statistically significant parameters, a considerable cumulative body burden was found in the compartments excreting to the other pathway. Although our results on the cumulative body burden of 13 C from orally administered carbon as glucose were inconclusive, we found that the compartments excreting to the other pathway had a markedly long residence time and therefore should be studied further to clarify the fate of carbon in the human body. In addition to excreta, data for serum and blood cell samples were also collected from the subjects to examine the metabolism of 13 C in human body.

12C(d,p) 13C reaction at Esub(d) = 30 MeV to the positive-parity states in 13C

International Nuclear Information System (INIS)

Ohnuma, H.; Hoshino, N.; Mikoshiba, O.

1985-07-01

The 12 C(d, p) 13 C reaction has been studied at Esub(d) = 30 MeV. All the known positive-parity states of 13 C below 10 MeV in excitation energy, including the 7/2 + and 9/2 + states, are observed in this reaction. The angular distributions for these positive-parity bound and unbound states are analyzed in CCBA frame work. The 13 C wave functions, which reproduce the resonant and non-resonant scattering of neutrons from 12 C, also give good accounts of the experimentally observed angular distributions and energy spectra of outgoing protons in the 12 C(d, p) 13 C reaction. In most cases the cross section magnitude and the angular distribution shape are primarily determined by the 0 + x j component, even if it is only a small fraction of the total wave function. An exception is the 7/2 + state, where the main contribution comes from the 2 + x dsub(5/2) component. The inclusion of the 4 + state in 12 C and the gsub(9/2) and gsub(7/2) neutron components in the n + 12 C system has very small effects on the low-spin states, but is indispensable for a good fit to the 7/2 + and 9/2 + angular distributions. The transitions to the negative-parity states, 1/2 1 - , 3/2 1 - , 5/2 - , 7/2 - and 1/2 3 - , are also observed experimentally, and analyzed by DWBA. (author)

Distribution of 14C-activity among the organic acids in the Satsuma mandarin fruits fed with 14C-compounds

International Nuclear Information System (INIS)

Kubota, Shuji; Akao, Shoichiro; Hayashida, Michito.

1978-01-01

1. Twenty four hours after 14 CO 2 feeding to the leaves, malic acid had the highest level of total and specific radioactivity among the organic acids extracted from the juice vesicles, and citric acid had the second highest total activity. An unidentified acid compound had a relatively high activity. 2. Pyruvic acid-2- 14 C was fed as a substrate for acid formation to the one young fruit on a shoot, and NaH 14 CO 3 was fed as a source of carbon-dioxide to the other young fruit through the pedicel. After three hours of pyruvic acid feeding, malic acid, citric acid and aspartic acid were the major labelled compounds in the vesicles. Then, a marked increase and redistribution of activity in acids took place with time, and the levels of total and specific activity in citric acid increased steadily. The sorts of labelled compounds into which activity was incorporated from NaH 14 CO 3 were essentially similar to those in pyruvic acid-2- 14 C feeding. 3. These results seem to support the theory that the dark fixation of carbon-dioxide plays an important role in the synthesis of the organic acids in citrus fruit vesicles. (auth.)

The CSSIAR v.1.00 Software: A new tool based on SIAR to assess soil redistribution using Compound Specific Stable Isotopes

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de los Santos-Villalobos Sergio

2017-01-01

Full Text Available Soil erosion is one of the biggest challenges for food production around the world. Many techniques have been used to evaluate and mitigate soil degradation. Nowadays isotopic techniques are becoming a powerful tool to assess soil apportionment. One of the innovative techniques used is the Compound Specific Stable Isotopes (CSSI analysis, which has been used to track down sediments and specify their sources by the isotopic signature of δ13C in specific fatty acids. The application of this technique on soil apportionment has been recently developed, however there is a lack of user-friendly Software for data processing and interpretation. The aim of this article is to introduce a new open source tool for working with data sets generated by the use of the CSSI technique to assess soil apportionment, called the CSSIARv1.00 Software

The CSSIAR v.1.00 Software: A new tool based on SIAR to assess soil redistribution using Compound Specific Stable Isotopes

Science.gov (United States)

Sergio, de los Santos-Villalobos; Claudio, Bravo-Linares; dos Anjos Roberto, Meigikos; Renan, Cardoso; Max, Gibbs; Andrew, Swales; Lionel, Mabit; Gerd, Dercon

Soil erosion is one of the biggest challenges for food production around the world. Many techniques have been used to evaluate and mitigate soil degradation. Nowadays isotopic techniques are becoming a powerful tool to assess soil apportionment. One of the innovative techniques used is the Compound Specific Stable Isotopes (CSSI) analysis, which has been used to track down sediments and specify their sources by the isotopic signature of δ13 C in specific fatty acids. The application of this technique on soil apportionment has been recently developed, however there is a lack of user-friendly Software for data processing and interpretation. The aim of this article is to introduce a new open source tool for working with data sets generated by the use of the CSSI technique to assess soil apportionment, called the CSSIARv1.00 Software

RhII -Catalyzed β-C(sp2 )-H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds.

Science.gov (United States)

McLarney, Brett D; Cavitt, Marchello A; Donnell, Theodore M; Musaev, Djamaladdin G; France, Stefan

2017-01-23

A Rh II -catalyzed method for intermolecular alkylation of the β-C(sp 2 )-H bond of enol ethers, enamides, and enecarbamates with α-diazo-1,3-dicarbonyl compounds is reported. The products are formed in up to 99 % yield and can be readily derivatized under a variety of conditions. By utilizing a combination of experimental and computational studies, the presumptive addition-elimination reaction mechanism was investigated and found to proceed under thermodynamic control at higher temperature. The acquired fundamental knowledge was translated into a strategic reaction design and yielded the first example of the β-C-H functionalizations of acyclic enol ethers using α-diazo-1,3-dicarbonyl compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of deleobuvir, a potent hepatitis C virus polymerase inhibitor, and its major metabolites labeled with carbon-13 and carbon-14.

Science.gov (United States)

Latli, Bachir; Hrapchak, Matt; Chevliakov, Maxim; Li, Guisheng; Campbell, Scot; Busacca, Carl A; Senanayake, Chris H

2015-05-30

Deleobuvir, (2E)-3-(2-{1-[2-(5-bromopyrimidin-2-yl)-3-cyclopentyl-1-methyl-1H-indole-6-carboxamido]cyclobutyl}-1-methyl-1H-benzimidazol-6-yl)prop-2-enoic acid (1), is a non-nucleoside, potent, and selective inhibitor of hepatitis C virus NS5B polymerase. Herein, we describe the detailed synthesis of this compound labeled with carbon-13 and carbon-14. The synthesis of its three major metabolites, namely, the reduced double bond metabolite (2) and the acyl glucuronide derivatives of (1) and (2), is also reported. Aniline-(13) C6 was the starting material to prepare butyl (E)-3-(3-methylamino-4-nitrophenyl-(13) C6 )acrylate [(13) C6 ]-(11) in six steps. This intermediate was then used to obtain [(13) C6 ]-(1) and [(13) C6 ]-(2) in five and four more steps, respectively. For the radioactive synthesis, potassium cyanide-(14) C was used to prepare 1-cylobutylaminoacid [(14) C]-(23) via Buchrer-Bergs reaction. The carbonyl chloride of this acid was then used to access both [(14) C]-(1) and [(14) C]-(2) in four steps. The acyl glucuronide derivatives [(13) C6 ]-(3), [(13) C6 ]-(4) and [(14) C]-(3) were synthesized in three steps from the acids [(13) C6 ]-(1), [(13) C6 ]-(2) and [(14) C]-(1) using known procedures. Copyright © 2015 John Wiley & Sons, Ltd.

Excitation functions of the systems 12C+14C and 13C+12C

International Nuclear Information System (INIS)

Haindl, E.

1975-01-01

The excitation functions of the systems 12 C+ 14 C and 13 C+ 12 C are investigated for different exit channels. The excitation functions measured do not show correlated structures as in the system 12 C+ 12 C. (WL/AK) [de

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

Directory of Open Access Journals (Sweden)

R. J. Sheesley

2009-05-01

Full Text Available Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (¹⁴C "alive" versus fossil fuel (¹⁴C "dead" combustion. Here, the first compound-specific radiocarbon analysis (CSRA of atmospheric polycyclic aromatic hydrocarbons (PAHs was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ¹⁴C for PAHs spanned from −138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (f_biomass contribution, which was constrained to 71–87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an f_biomass of 71%, while fluoranthene and phenanthrene (gas phase had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon f_biomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.

Residue-specific membrane location of peptides and proteins using specifically and extensively deuterated lipids and {sup 13}C-{sup 2}H rotational-echo double-resonance solid-state NMR

Energy Technology Data Exchange (ETDEWEB)

Xie Li; Ghosh, Ujjayini; Schmick, Scott D.; Weliky, David P., E-mail: weliky@chemistry.msu.edu [Michigan State University, Department of Chemistry (United States)

2013-01-15

Residue-specific location of peptides in the hydrophobic core of membranes was examined using {sup 13}C-{sup 2}H REDOR and samples in which the lipids were selectively deuterated. The transmembrane topology of the KALP peptide was validated with this approach with substantial dephasing observed for deuteration in the bilayer center and reduced or no dephasing for deuteration closer to the headgroups. Insertion of {beta} sheet HIV and helical and {beta} sheet influenza virus fusion peptides into the hydrophobic core of the membrane was validated in samples with extensively deuterated lipids.

Antifungal chemical compounds identified using a C. elegans pathogenicity assay.

Directory of Open Access Journals (Sweden)

Julia Breger

2007-02-01

Full Text Available There is an urgent need for the development of new antifungal agents. A facile in vivo model that evaluates libraries of chemical compounds could solve some of the main obstacles in current antifungal discovery. We show that Candida albicans, as well as other Candida species, are ingested by Caenorhabditis elegans and establish a persistent lethal infection in the C. elegans intestinal track. Importantly, key components of Candida pathogenesis in mammals, such as filament formation, are also involved in nematode killing. We devised a Candida-mediated C. elegans assay that allows high-throughput in vivo screening of chemical libraries for antifungal activities, while synchronously screening against toxic compounds. The assay is performed in liquid media using standard 96-well plate technology and allows the study of C. albicans in non-planktonic form. A screen of 1,266 compounds with known pharmaceutical activities identified 15 (approximately 1.2% that prolonged survival of C. albicans-infected nematodes and inhibited in vivo filamentation of C. albicans. Two compounds identified in the screen, caffeic acid phenethyl ester, a major active component of honeybee propolis, and the fluoroquinolone agent enoxacin exhibited antifungal activity in a murine model of candidiasis. The whole-animal C. elegans assay may help to study the molecular basis of C. albicans pathogenesis and identify antifungal compounds that most likely would not be identified by in vitro screens that target fungal growth. Compounds identified in the screen that affect the virulence of Candida in vivo can potentially be used as "probe compounds" and may have antifungal activity against other fungi.

Inference of past atmospheric delta13C and P/sub CO2/ from 13C/12C measurements in tree rings

International Nuclear Information System (INIS)

Leavitt, S.W.

1982-01-01

Carbon dioxide release from fossil-fuel burning is significant enough that we may soon experience perceptible changes in climate with important human consequences. An accurate reconstruction of past 13 C/ 12 C ratios of atmospheric CO 2 may provide key constraints on the historical activity of the biosphere as CO 2 source or sink. Tree rings appear to be a repository of this information but there is much noise in the collection of previous reconstructions, presumably associated with site selection, radial variability, choice of representative wood chemical constituent, and subtle effects of climate on fractionation. This study attempts to avoid these pitfalls and develop a 50-yr delta 13 C/sub ATM/ record from juniper trees (genus Juniperus), in fact, by taking advantage of the influence of climate on fractionation. Trees were harvested from suitable sites in close proximity to weather stations with monthly records of temperature and precipitation. The most useful relationships for at most 7 of the 10 sites were delta 13 C with December temperature or precipitation, because the coefficients were nearly constant from one interval to the next and the intercepts differed. Local pollution effects are believed responsible for the three anomalous sites. The separation of these regression lines of different intervals is interpreted as the response of the trees to the changing delta 13 C of atmospheric CO 2 so that delta 13 C/sub ATM/ curves are constructed from this spacing. The shape of the best-fit reconstruction suggests the biosphere has acted as CO 2 source to about 1965 and may now be a net sink

Lewis base catalyzed 1,3-dithiane addition to carbonyl and imino compounds using 2-trimethylsilyl-1,3-dithiane.

Science.gov (United States)

Michida, Makoto; Mukaiyama, Teruaki

2008-09-01

Lewis base-catalyzed 1,3-dithiane addition to electrophiles such as carbonyl compounds and N-substituted aldimines with 2-trimethylsilyl-1,3-dithiane (TMS-dithiane) is described. By the activation of the carbon-silicon bond in the presence of a Lewis base catalyst such as tetrabutylammonium phenoxide (PhONnBu(4)), a 1,3-dithiane addition reaction proceeded smoothly to afford the corresponding adducts in good to high yields under mild conditions. This synthesis is also applied to the reactions of ketones having alpha-protons, and of N-substituted aldimines.

Computer-aided structure analysis. Structure identification by infrared and /sup 13/C NMR measurements

Energy Technology Data Exchange (ETDEWEB)

Szalontai, G; Simon, Z; Csapo, Z; Farkas, M; Pfeifer, Gy [Nehezvegyipari Kutato Intezet, Veszprem (Hungary)

1980-01-01

The results obtained from the computer-aided interpretation of /sup 13/C NMR and IR spectra using the artificial intelligence approach are presented. In its present state the output of the system is a list of functional groups which are resonable candidates for the final structural isomers. The input requires empirical formula, /sup 13/C NMR data (off resonance data also) and IR spectral data. The confirmation of the presence of a functional group is based on comparison of the experimental data with the spectral properties of functional groups stored in a property matrix. If the molecular weight of the compounds studied is less or equal 500, the output contains usually 1.5-2.5 times more groups than really present, in most cases without the loss of the real ones.

Comparison of the Quantitative Values of C-14 and C-13 UBT to Reflect the Presence and Degree of Ongoing Helicobacter pylori Infection

International Nuclear Information System (INIS)

Lim, Seok Tae; Kim, Dong Wook; Jeong, Hwan Jeong; Sohn, Myung Hee

2008-01-01

A urea breath test (UBT) using C-14 or C-13 has been developed for identifying Helicobacter (H) pylori infection on the basis of urease production with release of labeled CO 2 . We investigated if the C-14 and C-13 UBT have the difference to reflect the presence and degree of H. pylori infection detected by gastroduodenoscopic biopsies (GBx) in the same patients. Thirty eight patients (M:F=28:10, age 53.4±13.0 yrs) with upper gastrointestinal symptoms such as indigestion, gastric fullness or pain consecutively underwent C-14 UBT, GBx and C-13 UBT within one week before medications. For the C-14 UBT, a single breath sample was collected at 10 minutes after ingestion of C-14 urea (37 KBq) capsule and counting was done in a liquid scintillation counter for 1 minute, and the results were classified as positive (≥200 dpm), intermediate (50∼199 dpm) or negative (<50 dpm). For the C-13 UBT, the results were classified as positive (≥2.5) or negative (<2.5). The results of GBx with Giemsa stain were graded 0 (normal) to 4 (diffuse) according to the distribution of H. pylori by the Wyatt method. We compared C-14 UBT and C-13 UBT results with GBx grade as a gold standard. The prevalence of H. pylori infection by GBx with Giemsa stain was 25/38 (65.8%). In the assessment of the presence of H. pylori infection, the C-14 UBT global performance yielded sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV) and accuracy of 92.0%, 92.3%, 95.8%, 91.7% and 92.1%, respectively. However, the C-13 UBT had sensitivity, specificity, PPV, NPV and accuracy of 96.0%, 84.6%, 92.3%, 91.7% and 92.1%, respectively. The more significant correlation in C-14 than C-13 UBT (r=0.948 vs r=0.819, p<0.001) was found between the value of UBT and the grade of distribution of H. pylori infection. We conclude that the diagnostic performance between C-14 and C-13 UBT to detect H. pylori infection is not significantly different, but the value of C-14 UBT more

Comparison of the Quantitative Values of C-14 and C-13 UBT to Reflect the Presence and Degree of Ongoing Helicobacter pylori Infection

Energy Technology Data Exchange (ETDEWEB)

Lim, Seok Tae; Kim, Dong Wook; Jeong, Hwan Jeong; Sohn, Myung Hee [Chonbuk National University Medical School, Jeonju (Korea, Republic of)

2008-06-15

A urea breath test (UBT) using C-14 or C-13 has been developed for identifying Helicobacter (H) pylori infection on the basis of urease production with release of labeled CO{sub 2}. We investigated if the C-14 and C-13 UBT have the difference to reflect the presence and degree of H. pylori infection detected by gastroduodenoscopic biopsies (GBx) in the same patients. Thirty eight patients (M:F=28:10, age 53.4{+-}13.0 yrs) with upper gastrointestinal symptoms such as indigestion, gastric fullness or pain consecutively underwent C-14 UBT, GBx and C-13 UBT within one week before medications. For the C-14 UBT, a single breath sample was collected at 10 minutes after ingestion of C-14 urea (37 KBq) capsule and counting was done in a liquid scintillation counter for 1 minute, and the results were classified as positive ({>=}200 dpm), intermediate (50{approx}199 dpm) or negative (<50 dpm). For the C-13 UBT, the results were classified as positive ({>=}2.5) or negative (<2.5). The results of GBx with Giemsa stain were graded 0 (normal) to 4 (diffuse) according to the distribution of H. pylori by the Wyatt method. We compared C-14 UBT and C-13 UBT results with GBx grade as a gold standard. The prevalence of H. pylori infection by GBx with Giemsa stain was 25/38 (65.8%). In the assessment of the presence of H. pylori infection, the C-14 UBT global performance yielded sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV) and accuracy of 92.0%, 92.3%, 95.8%, 91.7% and 92.1%, respectively. However, the C-13 UBT had sensitivity, specificity, PPV, NPV and accuracy of 96.0%, 84.6%, 92.3%, 91.7% and 92.1%, respectively. The more significant correlation in C-14 than C-13 UBT (r=0.948 vs r=0.819, p<0.001) was found between the value of UBT and the grade of distribution of H. pylori infection. We conclude that the diagnostic performance between C-14 and C-13 UBT to detect H. pylori infection is not significantly different, but the value of C-14 UBT

Measuring soil organic matter turn over and carbon stabilisation in pasture soils using 13C enrichment methodology.

Science.gov (United States)

Robinson, J. M.; Barker, S.; Schipper, L. A.

2017-12-01

Carbon storage in soil is a balance between photosynthesis and respiration, however, not all C compounds decompose equally in soil. Soil C consists of several fractions of C ranging from, accessible C (rapidly cycling) to stored or protected C (slow cycling). The key to increasing C storage is through the transfer of soil C from this accessible fraction, where it can be easily lost through microbial degradation, into the more stable fraction. With the increasing use of isotope enrichment techniques, 13C may be used to trace the movement of newly incorporated carbon in soil and examine how land management practises affect carbon storage. A laboratory method was developed to rapidly analyse soil respired CO2 for δ13C to determine the temperature sensitivity of newly incorporated 13C enriched carbon. A Horotiu silt loam (2 mm sieved, 60% MWHC) was mixed with 13C enriched ryegrass/clover plant matter in Hungate tubes and incubated for 5 hours at 20 temperatures( 4 - 50 °C) using a temperature gradient method (Robinson J. M., et al, (2017) Biogeochemistry, 13, 101-112). The respired CO2 was analysed using a modified Los Gatos, Off-axis ICOS carbon dioxide analyser. This method was able to analyse the δ13C signature of respired CO2 as long as a minimum concentration of CO2 was produced per tube. Further analysis used a two-component mixing model to separate the CO2 into source components to determine the contribution of added C and soil to total respiration. Preliminary data showed the decomposition of the two sources of C were both temperature dependant. Overall this method is a relatively quick and easy way to analyse δ13C of respired soil CO2 samples, and will allow for the testing of the effects of multiple variables on the decomposition of carbon fractions in future use.

Simultaneous determination of wine sugars, glycerol and organic acids 13C/12C isotopic ratio by ion chromatography-co-IRMS

Directory of Open Access Journals (Sweden)

Guyon Francois

2014-01-01

Full Text Available Ion chromatography (IC isotope ratio mass spectrometry (IRMS coupling is possible using a liquid interface allowing chemical oxidation (co of organic compounds. Synthetic solutions containing a mixture of glycerol, sugars (sucrose, glucose and fructose and organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric were elaborated to estimate analytical applications of two different IC systems. It appears that the use of carbonated solution in the eluting phase is a perturbation for 13C isotope measurements as it creates a δ13C deviation from the expected values. A sample of authentic sweet wine was analyzed by IC-co-IRMS using KOH gradient. Ratios of isotopic, ratios of organic acids and glycerol was found to be, in average, equal 1.01 ± 0.04 that is in accordance with our previous results.

Origin of Xylitol in Chewing Gum: A Compound-Specific Isotope Technique for the Differentiation of Corn- and Wood-Based Xylitol by LC-IRMS.

Science.gov (United States)

Köster, Daniel; Wolbert, Jens-Benjamin; Schulte, Marcel S; Jochmann, Maik A; Schmidt, Torsten C

2018-02-28

The sugar replacement compound xylitol has gained increasing attention because of its use in many commercial food products, dental-hygiene articles, and pharmaceuticals. It can be classified by the origin of the raw material used for its production. The traditional "birch xylitol" is considered a premium product, in contrast to xylitol produced from agriculture byproducts such as corn husks or sugar-cane straw. Bulk stable-isotope analysis (BSIA) and compound-specific stable-isotope analysis (CSIA) by liquid-chromatography isotope-ratio mass spectrometry (LC-IRMS) of chewing-gum extracts were used to determine the δ 13 C isotope signatures for xylitol. These were applied to elucidate the original plant type the xylitol was produced from on the basis of differences in isotope-fractionation processes of photosynthetic CO 2 fixation. For the LC-IRMS analysis, an organic-solvent-free extraction protocol and HPLC method for the separation of xylitol from different artificial sweeteners and sugar-replacement compounds was successfully developed and applied to the analysis of 21 samples of chewing gum, from which 18 could be clearly related to the raw-material plant class.

Laboratory spectra of C-13 ethane

Science.gov (United States)

Kurtz, Joe; Reuter, Dennis C.; Jennings, Donald E.; Hillman, John J.

1991-01-01

The laboratory infrared spectrum of C-13 monosubstituted ethane has been obtained at high resolution (0.0025/cm) using the McMath Fourier transform spectrometer at Kitt Peak National Observatory in May 1990. A preliminary analysis of the nu12 rQ0 branch (substituted species) suggests that its intensity is 1.15 + or - 0.05 times stronger than the equivalent nu9 branch in the normal (C-12)2H6 species. This result leads to a correction of a previously published estimate for the C-12/C-13 ratio in the atmosphere of Jupiter from about 94 to about 106.

Identifying inter-residue resonances in crowded 2D {sup 13}C-{sup 13}C chemical shift correlation spectra of membrane proteins by solid-state MAS NMR difference spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Miao Yimin; Cross, Timothy A. [Florida State University, Department of Chemistry and Biochemistry (United States); Fu Riqiang, E-mail: rfu@magnet.fsu.edu [National High Magnet Field Lab (United States)

2013-07-15

The feasibility of using difference spectroscopy, i.e. subtraction of two correlation spectra at different mixing times, for substantially enhanced resolution in crowded two-dimensional {sup 13}C-{sup 13}C chemical shift correlation spectra is presented. With the analyses of {sup 13}C-{sup 13}C spin diffusion in simple spin systems, difference spectroscopy is proposed to partially separate the spin diffusion resonances of relatively short intra-residue distances from the longer inter-residue distances, leading to a better identification of the inter-residue resonances. Here solid-state magic-angle-spinning NMR spectra of the full length M2 protein embedded in synthetic lipid bilayers have been used to illustrate the resolution enhancement in the difference spectra. The integral membrane M2 protein of Influenza A virus assembles as a tetrameric bundle to form a proton-conducting channel that is activated by low pH and is essential for the viral lifecycle. Based on known amino acid resonance assignments from amino acid specific labeled samples of truncated M2 sequences or from time-consuming 3D experiments of uniformly labeled samples, some inter-residue resonances of the full length M2 protein can be identified in the difference spectra of uniformly {sup 13}C labeled protein that are consistent with the high resolution structure of the M2 (22-62) protein (Sharma et al., Science 330(6003):509-512, 2010)

Elastic scattering of lithium by 9Be, 10B, 12C, 13C, 16O, and 28Si from 4 to 63 MeV

International Nuclear Information System (INIS)

Poling, J.E.; Norbeck, E.; Carlson, R.R.

1976-01-01

Elastic scattering angular distributions have been measured at energies between 4.0 and 13.0 MeV for 6 Li and 7 Li beams and targets of 10 B, 12 C, 13 C, 16 O, and 28 Si. Yield curves have been measured for energies from 3.0 to 13.0 MeV for 6 Li beams and targets of 9 Be, 12 C, 13 C, 16 O, and 28 Si, and for 7 Li and 12 C. The angular distributions, supplemented by published angular distributions, have been fitted with optical-model potentials. For 6 Li+ 12 C, angular distributions were available at energies from 4.5 to 63.0 MeV. Potentials which gave fits to the data across the entire available energy range were obtained for each elastic scattering reaction. The usual ambiguities were observed in the optical-model potentials. In certain cases the back angles were not well fitted by parameter sets which were useful for all energies. The quality of the fits did not seem to be limited by experimental errors, which were generally better than 10% for our data; compound nucleus effects are presumed to be the cause of rapid energy variations in the angular distributions

Preparation of [13C3]-melamine and [13C3]-cyanuric acid and their application to the analysis of melamine and cyanuric acid in meat and pet food using liquid chromatography-tandem mass spectrometry.

Science.gov (United States)

Varelis, P; Jeskelis, R

2008-10-01

For the determination of melamine and cyanuric acid the labelled internal standards [(13)C(3)]-melamine and [(13)C(3)]-cyanuric acid were synthesized using the common substrate [(13)C(3)]-cyanuric chloride by reaction with ammonia and acidified water, respectively. Standards with excellent isotopic and chemical purities were obtained in acceptable yields. These compounds were used to develop an isotope dilution liquid chromatography/mass spectrometry (LC/MS) method to determine melamine and cyanuric acid in catfish, pork, chicken, and pet food. The method involved extraction into aqueous methanol, liquid-liquid extraction and ion exchange solid phase clean-up, with normal phase high-performance liquid chromatography (HPLC) in the so-called hydrophilic interaction mode. The method had a limit of detection (LOD) of 10 microg kg(-1) for both melamine and cyanuric acid in the four foods with a percentage coefficient of variation (CV) of less than 10%. The recovery of the method at this level was in the range of 87-110% and 96-110% for melamine and cyanuric acid, respectively.

Probing the possibility of a C-12/C-13 galactic abundance gradient

International Nuclear Information System (INIS)

Hawkins, I.

1990-01-01

High S/N (equal to or greater than 500) observations of interstellar CH+ with the 3.0 m telescope were performed at Lick Observatory and with the 4.0 m telescope at CTIO, of the reddened, early-type stars HD 183143, HD 24432, and HD 157038 in an effort to probe the existence of a C-12/C-13 abundance gradient in our Galaxy. Previous very high quality optical observations of interstellar CH+ toward five stars within 1 kpc of the Sun have yielded a precise weighted mean C-12/C-13 isotope ratio of 43 plus or minus 4 (1 sigma) (Hawkins, Jura, and Meyer 1985; Hawkins and Jura 1987). The isotope ratios derived toward four lines of sight in the local ISM are uniform within 12 percent. The similarity among these carbon isotope ratios determined in diffuse clouds possessing different physical conditions precludes the possibility that the CH+ molecule is suffering from isotope selective effects in these regions. The precise C-12/C-13 derivable from high quality observations of (12)CH+ and (13)CH+ provide the unique opportunity to probe the homogeneity of the ISM in a large scale and the history of nucleosynthesis in our Galaxy. Since CH+ seems to be the most sensitive probe of C-12/C-13 in the diffuse ISM, observations toward more distant stars located up to 2.5 kpc from the Sun are the best way to study the possibility of a Galactic (C-12/C-13) abundance gradient. The researcher obtained 4232 angstrom data toward all three of the stars mentioned above, 3957 angstrom data toward HD 183143 and HD 157038, and 3745 angstrom data toward HD 157038. Because of the poorer quality of the HD 24432 spectrum, and its weaker CH+ absorption lines, the satellite (13)CH+ line was not detected, and thus only a lower limit on the C-12/C-13 ratio toward this star was obtained. The results obtained from careful reduction and analysis of the data toward these stars in the Northern and Southern Hemispheres are presented

Molecular and compound-specific hydrogen isotope analyses of insoluble organic matter from different carbonaceous chondrite groups

Science.gov (United States)

Wang, Yi; Huang, Yongsong; Alexander, Conel M. O.'D.; Fogel, Marilyn; Cody, George

2005-07-01

We have conducted the first systematic analyses of molecular distribution and δD values of individual compounds in pyrolysates of insoluble organic matter (IOM) from different carbonaceous chondrite groups, using flash pyrolysis coupled to gas chromatography-mass spectrometry and compound-specific D/H analysis. IOM samples from six meteorites of different classifications, Elephant Moraine (EET) 92042 (CR2), Orgueil (CI1), Allan Hills (ALH) 83100 (CM1/2), Murchison (CM2), ALH 85013 (CM2), and Tagish Lake (C2) were isolated and studied. Except for the pyrolysate of Tagish Lake IOM, pyrolysates of all five meteorite IOM samples were dominated by an extensive series of aromatic (C 1 to C 7 alkyl-substituted benzenes, C 0 to C 2 alkyl-substituted naphthalenes), with aliphatic (straight chain and branched C 10 to C 15 alkanes) hydrocarbons and several S- and O- containing compounds (C 1 to C 2 alkylthiophenes, benzothiophene, benzaldehyde) being also present. The strong similarity in the pyrolysates of different carbonaceous chondrites suggests certain common characteristics in the formation mechanisms of IOM from different meteorites. The Tagish Lake IOM sample is unique in that its pyrolysate lacks most of the alkyl-substituted aromatic hydrocarbons detected in other meteorite IOM samples, suggesting distinctively different formation processes. Both bulk δD values of meteorite IOMs and weighted-average δD values of individual compounds in pyrolysates show a decreasing trend: CR2 > CI1 > CM2 > C2 (Tagish Lake), with the EET 92042 (CR2) IOM having the highest δD values (˜2000‰ higher than other samples). We attribute the high D contents in the IOM to primitive interstellar organic sources.

SRS-sensor 13C/12C isotops measurements for detecting Helicobacter Pylori

Science.gov (United States)

Grishkanich, Aleksandr; Chubchenko, Yan; Elizarov, Valentin; Zhevlakov, Aleksandr; Konopelko, Leonid

2018-02-01

We developed SRS-sensor 13C/12C isotops measurements detecting Helicobacter Pylori for medical diagnostics of human health. Measuring of absolute 13C/12C isotope amount ratios allows to explore the topical problems of the modern world, alcoholic beverages and tobacco, medical diagnostics of human health. SRS method is used to measure the ratio of carbon isotopes in the exhaled carbon dioxide, which is used to diagnose the human infection of Helicobacter pylori and the influence of the Helicobacter pylori bacterium on the occurrence of gastritis, gastric and duodenal ulcers. A method for the analysis of human infection with Helicobacter pylori was developed on the basis of measurements of the ratio of 13C / 12C carbon isotopes in human exhaled air with a high level of measurement accuracy. The article reviews the work in the field of provision comparability of absolute 13C/12C isotope amount ratios in the environment and food. The analysis of the technical and metrological characteristics of traditional and perspective instruments for measuring isotope ratios is presented. The provision of comparability of absolute 13C/12C isotope amount ratios is carried by gravimetrically prepared reference standards. The key features and emerging issues are discussed.

An ab initio investigation of vibrational, thermodynamic, and optical properties of Sc2AlC MAX compound

International Nuclear Information System (INIS)

Ali, M A; Nasir, M T; Khatun, M R; Naqib, S H; Islam, A K M A

2016-01-01

The structural vibrational, thermodynamical, and optical properties of potentially technologically important, weakly coupled MAX compound, Sc 2 AlC are calculated using density functional theory (DFT). The structural properties of Sc 2 AlC are compared with the results reported earlier. The vibrational, thermodynamical, and optical properties are theoretically estimated for the first time. The phonon dispersion curve is calculated and the dynamical stability of this compound is investigated. The optical and acoustic modes are observed clearly. We calculate the Helmholtz free energy ( F ), internal energy ( E ), entropy ( S ), and specific heat capacity ( C v ) from the phonon density of states. Various optical parameters are also calculated. The reflectance spectrum shows that this compound has the potential to be used as an efficient solar reflector. (paper)

Identification of natural metabolites in mixture: a pattern recognition strategy based on (13)C NMR.

Science.gov (United States)

Hubert, Jane; Nuzillard, Jean-Marc; Purson, Sylvain; Hamzaoui, Mahmoud; Borie, Nicolas; Reynaud, Romain; Renault, Jean-Hugues

2014-03-18

Because of their highly complex metabolite profile, the chemical characterization of bioactive natural extracts usually requires time-consuming multistep purification procedures to achieve the structural elucidation of pure individual metabolites. The aim of the present work was to develop a dereplication strategy for the identification of natural metabolites directly within mixtures. Exploiting the polarity range of metabolites, the principle was to rapidly fractionate a multigram quantity of a crude extract by centrifugal partition extraction (CPE). The obtained fractions of simplified chemical composition were subsequently analyzed by (13)C NMR. After automatic collection and alignment of (13)C signals across spectra, hierarchical clustering analysis (HCA) was performed for pattern recognition. As a result, strong correlations between (13)C signals of a single structure within the mixtures of the fraction series were visualized as chemical shift clusters. Each cluster was finally assigned to a molecular structure with the help of a locally built (13)C NMR chemical shift database. The proof of principle of this strategy was achieved on a simple model mixture of commercially available plant secondary metabolites and then applied to a bark extract of the African tree Anogeissus leiocarpus Guill. & Perr. (Combretaceae). Starting from 5 g of this genuine extract, the fraction series was generated by CPE in only 95 min. (13)C NMR analyses of all fractions followed by pattern recognition of (13)C chemical shifts resulted in the unambiguous identification of seven major compounds, namely, sericoside, trachelosperogenin E, ellagic acid, an epimer mixture of (+)-gallocatechin and (-)-epigallocatechin, 3,3'-di-O-methylellagic acid 4'-O-xylopyranoside, and 3,4,3'-tri-O-methylflavellagic acid 4'-O-glucopyranoside.

Neutron orbital radii in {sup 13} C; Radios orbitales neutronicos en {sup 13} C

Energy Technology Data Exchange (ETDEWEB)

Aguilera R, E.F.; Murillo, G.; Ramirez, J.J.; Avila, O.L. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

1988-01-15

In this work its were carried out experimental measurements of the reaction {sup 12}C(d,p) {sup 13}C at low energy. Preliminary results of a DWBA analysis of the data are presented, and the possibility of using this reaction to obtain the orbital radius of the transferred neutron is investigated. (Author)

Soil fertilization leads to a decline in between-samples variability of microbial community δ13C profiles in a grassland fertilization experiment.

Directory of Open Access Journals (Sweden)

Stavros D Veresoglou

Full Text Available Gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS was used to measure the (13C/(12C ratios of PLFAs at natural abundance levels from a temperate grassland nitrogen (N and phosphorus (P factorial fertilization experiment in northern Greece. In each plot two rhizosphere samples were derived centred around individual Agrostis capillaris and Prunella vulgaris plants. It was hypothesized that the isotopic signal of microbes that preferentially feed on recalcitrant litter such as fungi would be modified by fertilization more strongly than that of opportunistic microbes using labile C. Microbial community δ(13C was affected by both P and N fertilization regime and plant species identity. However, we have been unable to detect significant nutrient effects on individual groups of microbes when analyzed separately in contrast to our original hypothesis. Intra-treatment variability, as evaluated from Hartley's F(max tests in the five first PCA components axes as well as the size of the convex hulls in PCA scoreplots and Mahalanobis distances, was considerably higher in the non-fertilized controls. Moreover, a significant relationship was established between the change in PLFA abundances and their respective changes in δ(13C for the aggregate of samples and those simultaneously fertilized with N and P. We conclude that use of compound specific isotope analysis in the absence of labelling represents a valuable and overlooked tool in obtaining an insight of microbial community functioning.

Foliar δ13C Showed No Altitudinal Trend in an Arid Region and Atmospheric Pressure Exerted a Negative Effect on Plant δ13C

Directory of Open Access Journals (Sweden)

Zixun Chen

2017-07-01

Full Text Available Previous studies have suggested foliar δ13C generally increases with altitude. However, some observations reported no changes or even decreased trends in foliar δ13C. We noted that all the studies in which δ13C increased with elevation were conducted in the human regions, whereas those investigations in which δ13C did not vary or decreased were conducted in areas with water stress. Thus, we proposed that the pattern of increasing δ13C with elevation is not a general one, and that δ13C may remain unchanged or decrease in plants grown in arid environments. To test the hypothesis, we sampled plants along altitude gradients on the shady and sunny slopes of Mount Tianshan characterized by arid and semiarid climates. The measurements of foliar δ13C showed no altitudinal trends for the plants grown on either of the slopes. Therefore, this study supported our hypothesis. In addition, the present study addressed the effect of atmospheric pressure on plant δ13C by accounting for the effects of temperature and precipitation on δ13C. This study found that the residual foliar δ13C increased with increasing altitude, suggesting that atmospheric pressure played a negative role in foliar δ13C.

Physical properties of layered homologous RE-B-C(N) compounds

International Nuclear Information System (INIS)

Mori, Takao; Zhang Fuxiang; Leithe-Jasper, Andreas

2004-01-01

Physical properties of a series of homologous RE-B-C(N) B 12 cluster compounds REB 17 CN, REB 22 C 2 N, and REB 28.5 C 4 (RE=Er,Ho) were investigated. The structures of the compounds are layer-like along the c-axis, with rare earth and B 6 octahedral layers separated by B 12 icosahedral and C-B-C chain layers whose number increases successively from two B 12 layers for the REB 17 CN compound to four for the REB 28.5 C 4 compound. The rare earth atoms are configured in two triangular flat layers which are stacked on top of one another in AB stacking where the nearest-neighbor rare earth directions are the three atoms forming a triangle in the adjacent layer. The series of homologous compounds exhibit a spin glass transition with T f shifting in correspondence with variations of the basal plane lattice constants, consistent with the magnetic interaction being effective in the basal planes. The isothermal remanent magnetization shows a stretched exponential decay I m (t)∝ exp[-Ct -(1-n) ]. Exponents determined for the different homologous compounds were scaled as a function of T r =T/T f and found to follow the empirical dependency determined for typical spin glasses. It is indicated that a mixture of disorder originating from the partial occupancy of the rare earth sites and frustration of interactions due to the unique configuration is responsible for the manifestation of spin glass transitions in these homologous systems

Effect of alcohol consumption on the liver detoxication capacity as measured by [13C]methacetin- and [methyl-13C]methionine-breath tests.

Science.gov (United States)

Wutzke, Klaus D; Forberger, Anke; Wigger, Marianne

2008-06-01

The aim of this study was to investigate the hepatic microsomal and mitochondrial functions by using the 13CO2-breath test in healthy subjects either before or after the consumption of red wine. Fourteen adults received [13C]methacetin and [methyl-13C]methionine together with a standardised dinner. Expired air samples were taken over 6 h. After a wash-out period, the subjects consumed 0.4 ml ethanol/kg/day together with dinner over a 10-day period. Thereafter, 13C-tracer administration was repeated under identical conditions. The 13CO2-enrichments were measured by isotope ratio mass spectrometry. The mean cumulative percentage 13C-dose recovery (CPDR) after administration of [13C]methacetin and [methyl-13C]methionine either without or with red wine consumption amounted to 38.2+/-6.3 vs. 36.3+/-6.7% (p=0.363) and 9.5+/-3.3 vs. 8.8+/-2.5% (p=0.47), respectively. Moderate alcohol consumption does not induce significant short-term changes of the microsomal and the mitochondrial functions of the human liver in healthy subjects.

Quantifying the Contribution of Grape Hexoses to Wine Volatiles by High-Precision [U13C]-Glucose Tracer Studies

Science.gov (United States)

Nisbet, Mark A.; Tobias, Herbert J.; Brenna, J. Thomas; Sacks, Gavin L.; Mansfield, Anna Katharine

2016-01-01

Many fermentation volatiles important to wine aroma potentially arise from yeast metabolism of hexose sugars, but assessing the relative importance of these pathways is challenging due to high endogenous hexose substrate concentrations. To overcome this problem, gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) was used to measure high-precision 13C/12C isotope ratios of volatiles in wines produced from juices spiked with tracer levels (0.01–1 APE) of uniformly labeled [U-13C]-glucose. The contribution of hexose to individual volatiles was determined from the degree of 13C enrichment. As expected, straight-chain fatty acids and their corresponding ethyl esters were derived almost exclusively from hexoses. Most fusel alcohols and their acetate esters were also majority hexose-derived, indicating the importance of anabolic pathways for their formation. Only two compounds were not derived primarily from hexoses (hexanol and isobutyric acid). This approach can be extended to other food systems or substrates for studying precursor–product relationships. PMID:24960193

Ethane's 12C/13C Ratio in Titan: Implications for Methane Replenishment

Science.gov (United States)

Jennings, Donald E.; Nixon, C. A.; Romani, P. N.; Bjoraker, G. L.; Sada, P. V.; Lunsford, A. W.; Boyle, R. J.; Hesman, B. E.; McCabe, G. H.

2009-01-01

As the .main destination of carbon in the destruction of methane in the atmosphere of Titan, ethane provides information about the carbon isotopic composition of the reservoir from which methane is replenished. If the amount of methane entering the atmosphere is presently equal to the amount converted to ethane, the 12C/13C ratio in ethane should be close to the ratio in the reservoir. We have measured the 12C/13C ratio in ethane both with Cassini CIRS(exp 1) and from the ground and find that it is very close to the telluric standard and outer planet values (89), consistent with a primordial origin for the methane reservoir. The lower 12C/13C ratio measured for methane by Huygens GCMS (82.3) can be explained if the conversion of CH4 to CH3 (and C2H6) favors 12C over 13C with a carbon kinetic isotope effect of 1.08. The time required for the atmospheric methane to reach equilibrium, i.e., for replenishment to equal destruction, is approximately 5 methane atmospheric lifetimes.

Optical hyperpolarization of 13C nuclear spins in nanodiamond ensembles

Science.gov (United States)

Chen, Q.; Schwarz, I.; Jelezko, F.; Retzker, A.; Plenio, M. B.

2015-11-01

Dynamical nuclear polarization holds the key for orders of magnitude enhancements of nuclear magnetic resonance signals which, in turn, would enable a wide range of novel applications in biomedical sciences. However, current implementations of DNP require cryogenic temperatures and long times for achieving high polarization. Here we propose and analyze in detail protocols that can achieve rapid hyperpolarization of 13C nuclear spins in randomly oriented ensembles of nanodiamonds at room temperature. Our protocols exploit a combination of optical polarization of electron spins in nitrogen-vacancy centers and the transfer of this polarization to 13C nuclei by means of microwave control to overcome the severe challenges that are posed by the random orientation of the nanodiamonds and their nitrogen-vacancy centers. Specifically, these random orientations result in exceedingly large energy variations of the electron spin levels that render the polarization and coherent control of the nitrogen-vacancy center electron spins as well as the control of their coherent interaction with the surrounding 13C nuclear spins highly inefficient. We address these challenges by a combination of an off-resonant microwave double resonance scheme in conjunction with a realization of the integrated solid effect which, together with adiabatic rotations of external magnetic fields or rotations of nanodiamonds, leads to a protocol that achieves high levels of hyperpolarization of the entire nuclear-spin bath in a randomly oriented ensemble of nanodiamonds even at room temperature. This hyperpolarization together with the long nuclear-spin polarization lifetimes in nanodiamonds and the relatively high density of 13C nuclei has the potential to result in a major signal enhancement in 13C nuclear magnetic resonance imaging and suggests functionalized and hyperpolarized nanodiamonds as a unique probe for molecular imaging both in vitro and in vivo.

Task-specific ionic liquids for solubilizing metal compounds

OpenAIRE

Thijs, Ben

2007-01-01

The main goal of this PhD thesis was to design new task-specific ionic liquids with the ability to dissolve metal compounds. Despite the large quantity of papers published on ionic liquids, not much is known about the mechanisms of dissolving metals in ionic liquids or about metal-containing ionic liquids. Additionally, many of the commercially available ionic liquids exhibit a very limited solubilizing power for metal compounds, although this is for many applications like electrodeposition a...

Succession after fire: variation in \\delta13C of organic tissues and respired CO2 in boreal forests

Science.gov (United States)

Fessenden, J. E.; Li, H.; Mack, M.; Schuur, T.; Warren, S.; Randerson, J. T.

2001-12-01

Isotope ratios of carbon dioxide and leaf organic matter were measured in 5 neighboring forests of varying ages: 7, 14, 45, 140, and 160 years. These forests are composed primarily of black spruce (Picea Mariana) and quaking aspen (Populus tremuloides) with a shift in species dominance from aspen to spruce 50 years after fire disturbance. Research on the carbon isotope ratios of leaf material and CO2 was conducted to look for influences from species composition, forest age, and time after most recent burn. Samples of organic \\delta13C in whole leaf tissue were collected from the dominant species of each forest. Concurrent aboveground NPP measurements allowed us to estimate total ecosystem \\delta13C by providing a method for weighting \\delta13C of individual species and plant tissues. \\delta13CO2 and [CO2] were measured on canopy CO2 to determine the isotopic ratio of ecosystem respiration. The atmospheric results indicated that the \\delta13C of ecosystem respiration changes with successional stage. Specifically, the aspen dominating forests showed 13C depleted values relative to the spruce dominated forests. Organic results showed more 13C-enriched values with increased forest age and vegetation functional type. Specifically, oldest trees within the coniferous species had the most 13C-enriched values in leaf tissues. These results suggest that increases in the disturbance regime of northern boreal forests will lead to a decrease in the \\delta13C of ecosystem carbon with consequences for the atmospheric \\delta13C budget.

IMPROVED LINE DATA FOR THE SWAN SYSTEM 12C13C ISOTOPOLOGUE

International Nuclear Information System (INIS)

Ram, Ram S.; Brooke, James S. A.; Bernath, Peter F.; Sneden, Christopher; Lucatello, Sara

2014-01-01

We present new, accurate predictions for rotational line positions, excitation energies, and transition probabilities of the 12 C 13 C isotopologue Swan d 3 Π-a 3 Π system 0-0, 0–1, 0–2, 1–0, 1–1, 1–2, 2–0, 2–1, and 2–2 vibrational bands. The line positions and energy levels were predicted through new analyses of published laboratory data for the 12 C 13 C lines. Transition probabilities were derived from recent computations of transition dipole moments and related quantities. The 12 C 13 C line data were combined with similar data for 12 C 2, reported in a companion paper, and applied to produce synthetic spectra of carbon-rich metal-poor stars that have strong C 2 Swan bands. The matches between synthesized and observed spectra were used to estimate band head positions for a few of the 12 C 13 C vibrational bands and to verify that the new computed line data match observed spectra. The much weaker C 2 lines of the bright red giant Arcturus were also synthesized in the band head regions

Biosynthesis of highly enriched 13C-lycopene for human metabolic studies using repeated batch tomato cell culturing with 13C-glucose

Science.gov (United States)

Moran, Nancy E.; Rogers, Randy B.; Lu, Chi-Hua; Conlon, Lauren E.; Lila, Mary Ann; Clinton, Steven K.; Erdman, John W.

2013-01-01

While putative disease-preventing lycopene metabolites are found in both tomato (Solanum lycopersicum) products and in their consumers, mammalian lycopene metabolism is poorly understood. Advances in tomato cell culturing techniques offer an economical tool for generation of highly-enriched 13C-lycopene for human bioavailability and metabolism studies. To enhance the 13C-enrichment and yields of labeled lycopene from the hp-1 tomato cell line, cultures were first grown in 13C-glucose media for three serial batches and produced increasing proportions of uniformly labeled lycopene (14.3 +/− 1.2 %, 39.6 +/− 0.5 %, and 48.9 +/− 1.5% with consistent yields (from 5.8 to 9 mg/L). An optimized 9-day-long 13C-loading and 18-day-long labeling strategy developed based on glucose utilization and lycopene yields, yielded 13C-lycopene with 93% 13C isotopic purity, and 55% of isotopomers were uniformly labeled. Furthermore, an optimized acetone and hexane extraction led to a four-fold increase in lycopene recovery from cultures compared to a standard extraction. PMID:23561155

Regioselectivity of tributyltin ether mediated alkylations. A 119Sn and 13C NMR study

International Nuclear Information System (INIS)

Cruzado, C.; Bernabe, M.; Martin-Lomas, M.

1989-01-01

The 119 Sn and 13 C NMR spectra of the stannylated species resulting from the treatment of conformationally rigid polyhydroxylated compounds with bis(tributyltin) oxide have been determined and the effect of N-methylimidazole, added as catalyst in tributyltin ether mediated regioselective alkylations, has been investigated. The observed signal intensity changes, upfield shifts, signal broadenings, and the results of variable temperature experiments have been interpreted as indicative of the selective formation of pentacoordinated tin species, involving conveniently disposed adjacent hydroxyl groups, on addition of the catalyst. On these bases, a mechanistic hypothesis for the observed regioselectivity of N-methylimidazole-catalyzed tributyltin ether mediated benzylations is proposed. 13 references, 5 tables

Noninvasive brain metabolism measurement using carbon-13 magnetic resonance spectroscopy ({sup 13}C-MRS); Tanso 13 jiki kyomei spectroscopy ({sup 13}C-MRS) ni yoru mushinshuteki notaisha keisoku

Energy Technology Data Exchange (ETDEWEB)

Okamoto, K.; Tsukada, Y. [Toshiba Corp., Tokyo (Japan)

1998-10-10

Carbon-13 magnetic resonance spectroscopy ({sup 13}C-MRS) and research and development efforts for brain metabolism measurement are described. Brain metabolism is a process characterized in that it not only extracts energy by disintegrating grape sugar that is the practically sole source of energy into H2O, CO2, etc., but also vigorously synthesizes amino acids that perform important functions in neural transmission, such as glutamic acid, glutamine, and {gamma}-amino acid. MRS is a technique that utilizes the magnetic resonance, which is generated when an atomic nucleus with a spin is placed in a magnetic field, for the isolation and identification of chemicals in a living body through examining the delicate difference in the magnetic resonance frequencies of the nuclei under observation. Since the signals from {sup 13}C are low in intensity as compared with those from other nuclides, a method was contrived around 1980, which observes {sup 1}H combined with {sup 13}C in grape sugar and amino acids, named the HSQC (heteronuclear single quantum coherence) method. The author et al., combining gradient magnetic pulses with HSQC, actually measure Homo sapiens brain metabolism using {sup 13}C-MRS, and now believe that the technology will be put to practical application. 7 refs., 10 figs., 1 tab.

Automated 13CO2 analyzing system for the 13C breath test

International Nuclear Information System (INIS)

Suehiro, Makiko; Kuroda, Akira; Maeda, Masahiro; Hinaga, Kou; Watanabe, Hiroyuki.

1987-01-01

An automated 13 CO 2 analyzing system for the 13 C breath test was designed, built and evaluated. The system, which was designed to be controlled by a micro-computer, includes CO 2 purification, 13 CO 2 abundance measurement, data processing and data filing. This article gives the description of the whole system with flow charts. This system has proved to work well and it has become feasible to dispose of 5 to 6 CO 2 samples per hour. With such a system, the 13 C breath test will be carried out much more easily and will obtain much greater popularity. (author)

Analysis of 14C-bearing compounds released by the corrosion of irradiated steel using accelerator mass spectrometry.

Science.gov (United States)

Cvetković, B Z; Salazar, G; Kunz, D; Szidat, S; Wieland, E

2018-06-25

The combination of ion chromatography (IC) with accelerator mass spectrometry (AMS) was developed to determine the speciation of 14C-(radiocarbon) bearing organic compounds in the femto to pico molar concentration range. The development of this compound-specific radiocarbon analysis (CSRA) of carboxylic acids is reported and the application of the method on a leaching solution from neutron-irradiated steel is demonstrated. The background and the dynamic range of the AMS-based method were quantified. On using 14C-labelled standards, the measurements demonstrate the repeatability of the analytical method and the reproducible recovery of the main target carboxylic acids (i.e., acetate, formate, malonate, and oxalate). The detection limit was determined to be in the mid fmol 14C per L level while the dynamic range of the analytical method covers three orders of magnitude from the low fmol to the mid pmol 14C per L level. Cross contamination was found to be negligible during IC fractionation and was accounted for during eluate processing and 14C detection by AMS. The 14C-bearing carboxylates released from an irradiated steel nut into an alkaline leaching solution were analysed using the CSRA-based analytical method with the aim to check the applicability of the approach and develop appropriate sample preparation. The concentrations of 14C-bearing formate and acetate, the main organic corrosion products, were at a low pmol 14C per L level for convenient dimensions of the alkaline leaching experiment which demonstrates that compound-specific 14C AMS is an extremely sensitive analytical method for analysing 14C-bearing compounds. The content of total organic 14C in solution (TO14C) determined by the direct measurement of an aliquot of the leaching solution agrees well with the sum of the 14C concentrations of the individual carboxylates within the uncertainty of the data. Furthermore, the TO14C content is in good agreement with the calculated value using the corrosion rate

Probing ADAMTS13 substrate specificity using phage display.

Directory of Open Access Journals (Sweden)

Karl C Desch

Full Text Available Von Willebrand factor (VWF is a large, multimeric protein that regulates hemostasis by tethering platelets to the subendothelial matrix at sites of vascular damage. The procoagulant activity of plasma VWF correlates with the length of VWF multimers, which is proteolytically controlled by the metalloprotease ADAMTS13. To probe ADAMTS13 substrate specificity, we created phage display libraries containing randomly mutated residues of a minimal ADAMTS13 substrate fragment of VWF, termed VWF73. The libraries were screened for phage particles displaying VWF73 mutant peptides that were resistant to proteolysis by ADAMTS13. These peptides exhibited the greatest mutation frequency near the ADAMTS13 scissile residues. Kinetic assays using mutant and wild-type substrates demonstrated excellent agreement between rates of cleavage for mutant phage particles and the corresponding mutant peptides. Cleavage resistance of selected mutations was tested in vivo using hydrodynamic injection of corresponding full-length expression plasmids into VWF-deficient mice. These studies confirmed the resistance to cleavage resulting from select amino acid substitutions and uncovered evidence of alternate cleavage sites and recognition by other proteases in the circulation of ADAMTS13 deficient mice. Taken together, these studies demonstrate the key role of specific amino acids residues including P3-P2' and P11', for substrate specificity and emphasize the importance in flowing blood of other ADAMTS13-VWF exosite interactions outside of VWF73.

Implementation of a Novel Laser System for Simultaneous Measurement of 13C/12C and D/H to Food Provenance

Science.gov (United States)

Saad, N.; Hoffnagle, J.

2012-04-01

Olive oil samples were analyzed using the world's first simultaneous δ13C + δD instrument, the 13C+D Combustion Module-Cavity Ringdown Spectroscopy (CM-CRDS) Isotope Analyzer. Simultaneous measurements of δ13C and δD of the whole oil have been performed on commercially available olive oils produced in Greece, Spain, Italy, California, Lebanon, Israel, Australia and Turkey. Together, the measurements of isotopic ratios of carbon (13C/12C) and hydrogen (D/H) produce statistically significant differentiation between olive oils from different locations around the globe. Stable isotope ratios are exquisitely sensitive to the biochemistry of plant species and the nutrients available to them in a particular geographical location. Isotope ratios provide detailed knowledge useful for forensic applications through a combination of stable-isotope measurements of carbon (13C/12C) and hydrogen (D/H) isotopes of organic matter and can help the associations among specific geographic areas through the measurement of these dual isotopes. We report here on the development of a novel laser spectroscopy based system for the simultaneous analysis of the stable isotope ratios of carbon (13C/12C) and hydrogen (D/H) that is robust, easy-to-use, and is the first stable isotope ratio analysis system to combine the measurement of 13C/12C and D/H in one simple analysis from a bulk organic sample. The system comprises a combustion module to convert the organic sample into CO2 and H2O and a Cavity Ring-Down Spectrometer (CRDS) that analyzes the combustion species inside an optical cavity based on the molecular absorption of individual isotopomers. The CRDS uses dual lasers to target the four isotpomers of interest: 12CO2, 13CO2, H2O and HDO. The system delivers a typical precision of 0.1permil for δ13C and 1.5 permil for δD that parallels that achieved by IRMS, but with an unprecedented simplicity that allows scientists to leverage the science and map out the provenance of the analyzed

Overexpression of a homogeneous oligosaccharide with {sup 13}C labeling by genetically engineered yeast strain

Energy Technology Data Exchange (ETDEWEB)

Kamiya, Yukiko; Yamamoto, Sayoko [National Institutes of Natural Sciences, Okazaki Institute for Integrative Bioscience and Institute for Molecular Science (Japan); Chiba, Yasunori; Jigami, Yoshifumi [National Institute of Advanced Industrial Science and Technology, Research Center for Medical Glycoscience (Japan); Kato, Koichi, E-mail: kkatonmr@ims.ac.jp [National Institutes of Natural Sciences, Okazaki Institute for Integrative Bioscience and Institute for Molecular Science (Japan)

2011-08-15

This report describes a novel method for overexpression of {sup 13}C-labeled oligosaccharides using genetically engineered Saccharomyces cerevisiae cells, in which a homogeneous high-mannose-type oligosaccharide accumulates because of deletions of genes encoding three enzymes involved in the processing pathway of asparagine-linked oligosaccharides in the Golgi complex. Using uniformly {sup 13}C-labeled glucose as the sole carbon source in the culture medium of these engineered yeast cells, high yields of the isotopically labeled Man{sub 8}GlcNAc{sub 2} oligosaccharide could be successfully harvested from glycoprotein extracts of the cells. Furthermore, {sup 13}C labeling at selected positions of the sugar residues in the oligosaccharide could be achieved using a site-specific {sup 13}C-enriched glucose as the metabolic precursor, facilitating NMR spectral assignments. The {sup 13}C-labeling method presented provides the technical basis for NMR analyses of structures, dynamics, and interactions of larger, branched oligosaccharides.

Selective and extensive 13C labeling of a membrane protein for solid-state NMR investigations

International Nuclear Information System (INIS)

Hong, M.; Jakes, K.

1999-01-01

The selective and extensive 13C labeling of mostly hydrophobic amino acid residues in a 25 kDa membrane protein, the colicin Ia channel domain, is reported. The novel 13C labeling approach takes advantage of the amino acid biosynthetic pathways in bacteria and suppresses the synthesis of the amino acid products of the citric acid cycle. The selectivity and extensiveness of labeling significantly simplify the solid-state NMR spectra, reduce line broadening, and should permit the simultaneous measurement of multiple structural constraints. We show the assignment of most 13C resonances to specific amino acid types based on the characteristic chemical shifts, the 13C labeling pattern, and the amino acid composition of the protein. The assignment is partly confirmed by a 2D homonuclear double-quantum-filter experiment under magic-angle spinning. The high sensitivity and spectral resolution attained with this 13C-labeling protocol, which is termed TEASE for ten-amino acid selective and extensive labeling, are demonstrated

(13)C MRS of human brain at 7 Tesla using [2-(13)C]glucose infusion and low power broadband stochastic proton decoupling.

Science.gov (United States)

Li, Shizhe; An, Li; Yu, Shao; Ferraris Araneta, Maria; Johnson, Christopher S; Wang, Shumin; Shen, Jun

2016-03-01

Carbon-13 ((13)C) MR spectroscopy (MRS) of the human brain at 7 Tesla (T) may pose patient safety issues due to high radiofrequency (RF) power deposition for proton decoupling. The purpose of present work is to study the feasibility of in vivo (13)C MRS of human brain at 7 T using broadband low RF power proton decoupling. Carboxylic/amide (13)C MRS of human brain by broadband stochastic proton decoupling was demonstrated on a 7 T scanner. RF safety was evaluated using the finite-difference time-domain method. (13)C signal enhancement by nuclear Overhauser effect (NOE) and proton decoupling was evaluated in both phantoms and in vivo. At 7 T, the peak amplitude of carboxylic/amide (13)C signals was increased by a factor of greater than 4 due to the combined effects of NOE and proton decoupling. The 7 T (13)C MRS technique used decoupling power and average transmit power of less than 35 watts (W) and 3.6 W, respectively. In vivo (13)C MRS studies of human brain can be performed at 7 T, well below the RF safety threshold, by detecting carboxylic/amide carbons with broadband stochastic proton decoupling. © 2015 Wiley Periodicals, Inc.

Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

Science.gov (United States)

Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

2008-09-01

The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

Synthesis of Some Novel Thiadiazole Derivative Compounds and Screening Their Antidepressant-Like Activities

Directory of Open Access Journals (Sweden)

Nafiz Öncü Can

2018-03-01

Full Text Available Novel thiadiazole derivatives were synthesized through the reaction of acetylated 2-aminothiadiazole and piperazine derivatives. The chemical structures of the compounds were clarified by Infrared Spectroscopy (IR, 1H Nuclear Magnetic Resonance Spectroscopy (1H-NMR, 13C Nuclear Magnetic Resonance Spectroscopy (13C-NMR and Electronspray Ionisation Mass Spectroscopy (ESI-MS spectroscopic methods. Antidepressant-like activities were evaluated by the tail-suspension (TST and modified forced swimming (MFST methods. Besides, possible influence of the test compounds on motor activities of the animals were examined by activity cage tests. In the TST, administration of the compounds 2c, 2d, 2e, 2f, 2g and 2h significantly decreased the immobility time of mice regarding the control values. Further, in the MFST, the same compounds reduced the total number of immobility behaviors while increasing swimming performance. However, no change was observed in the total number of climbing behaviors. These data suggested that compounds 2c, 2d, 2e, 2f, 2g and 2h possess notable antidepressant-like activities. Reference drug fluoxetine (10 mg/kg was also exhibited its antidepressant activity, as expected. No significant difference was seen between the locomotor activity values of the test groups signifying that observed antidepressant-like activities are specific. Theoretical calculation of absorption, distribution, metabolism, excretion (ADME properties for the obtained compounds were performed and obtained data supported the antidepressant-like potential of these novel thiadiazole derivatives.

13C-NMR assignment, structure, and dynamics of deoxyoligonucleotides

International Nuclear Information System (INIS)

Zanatta, N.; Borer, P.N.; Levy, G.C.

1986-01-01

The unique spectral properties of 13 C-NMR for studying nucleic acids and some of the important features of 13 C-NMR in oligonucleotide studies are demostrated. The main difficulty in studying oligonucleotides by 13 C-NMR and recent improvements in NMR instrumentation and advances in oligonucleotide synthesis are presented. The high resolution 13 C-NMR spectra, T 1 relaxation times and NOEs were measured for duplex of the self-complementary oligo-DNAs: d(CG) 3 and d(GGTATACC) are studied. The target of this study is to developed a systematic 13 C-NMR spectral assignment and to investigate the structure and dynamics of these two sequences by this techniques. (M.J.C.) [pt

Rb-intercalated C60 compounds studied by Inverse Photoemission Spectroscopy

International Nuclear Information System (INIS)

Finazzi, M.; Brambilla, A; Biagioni, P.; Cattoni, A.; Duo, L.; Ciccacci, F.; Braicovich, L.; Giovanelli, L.; Goldoni, A.

2004-01-01

Full text: Since the discovery of superconductivity in alkali-doped solid C 60 , the electronic structure of the host material (C 60 ) and the doped compounds (A x C 60 , where A is an alkali metal), has been the subject of a considerable amount of work, both theoretical and experimental. The spectroscopic investigations of the alkali-doped C 60 compounds has been mainly focussed on the valence states, while much less information is available on the unoccupied states. In particular, inverse photoemission data on the complete set of stable Rb x C 60 compounds was, so far, still missing. We have performed Inverse Photoemission (IPE) spectroscopy on Rb x C 60 compounds (x = 1, 3, 4, 6). IPE spectra were obtained using a band-pass photon detector (hv = 9.4 eV, FWHM = 0.7 eV) and scanning the kinetic energy of the electrons impinging on the sample. Rb was evaporated on C 60 films (thickness = 6-12 atomic layers) grown in situ on a Cu(100) substrate. The temperature of the substrate was kept equal to T = 100 deg C, which is lower than the C 60 sublimation temperature. The amount of Rb was checked by measuring the intensity of the C1s and Rb3d photoemission lines. After the required amount of Rb had been deposited, the samples were annealed to distillate the desired stable phase

Synthesis of {sup 14}C-labeled levamisole and {sup 13}C-labeled tetramisole

Energy Technology Data Exchange (ETDEWEB)

Feil, V.J. [US Department of Agriculture, Agricultural Research Service, Biosciences Research Lab., Fargo, ND (United States)

1996-12-01

The syntheses of {sup 14}C-ring labeled levamisole ([-]-2,3,5,6-tetrahydro-6-phenyl [{sup 14}C]-UL imidazo[2,1-b]thiazole) from acetophenone-ring-UL-{sup 14}C in 5 steps plus resolution with a 7.5% overall yield, and {sup 13}C{sub 6}-ring labeled tetramisole ([{+-}]-2,3,5,6-tetrahydro-6-phenyl [{sup 13}C{sub 6}]imidazo[2,1-b]thiazole) from benzene-{sup 13}C{sub 6} in 6 steps with a 9.0% overall yield are described. (author).

Compound-Specific Radiocarbon Dating Reveals the Age Distribution of Plant-Wax Biomarkers Exported to the Bengal Fan

Science.gov (United States)

Galy, V.; French, K. L.; Hein, C. J.; Haghipour, N.; Wacker, L.; Kudrass, H.; Eglinton, T. I.

2017-12-01

The stable isotope composition of leaf-wax compounds preserved in lacustrine and marine sediments has been widely used to reconstruct terrestrial paleo-environments. However, the timescales of plant-wax storage in continental reservoirs before riverine export are not well known, representing a key uncertainty in paleo-environment studies. We couple numerical models with bulk and leaf-wax fatty acid organic 13C and 14C signatures hosted in a high-deposition-rate sediment core from the Bengal shelf canyon in order to estimate storage timescales within the Ganges-Brahmaputra catchment area. The fatty acid 14C record reveals a muted nuclear weapons bomb spike, requiring that the Ganges-Brahmaputra river system exports a mixture of young and old (pre-aged) leaf-wax compounds. According to numerical simulations, 79-83% of the leaf-wax fatty acids in this core are sourced from continental reservoirs that store organic carbon on an average of 1000-1200 calendar years, while the remainder has an average age of 15 years. These results demonstrate that a majority of the leaf-wax compounds produced in the Ganges-Brahmaputra river basin was stored in soils, floodplains, and wetlands prior to its export to the Bengal Fan. We will discuss the implications of these findings for plant-wax based paleoenvironmental records.

Synthesis and characterization of "1"3C_3-tristearin

International Nuclear Information System (INIS)

Wu Hangyu; Lin Lin; Li Lei; Chen Dazhou

2011-01-01

A highly efficient synthesis of "1"3C_3 labeled triglycerides of stearic acids from "1"3C_3-glycerol and stearic acids, by immobilized lipase-catalyzed in solvent-free medium was described. The structure of the product were characterized by fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), mass spectra (MS). The results showed that triglycerides of stearic acids contained three "1"3C atoms. The isotope abundance of "1"3C_3-tristearin was more than 99% and the yield was 80% of "1"3C_3-tristearin through calculation. Chemical purity (> 98%) was obtained by differential scanning calorimetry (DSC). (authors)

Carbon-13 isotope effects on 199Hg nuclear shielding

International Nuclear Information System (INIS)

Sebald, Angelika; Wrackmeyer, Bernd

1985-01-01

Secondary 13 C/ 12 C isotope effects on 199 Hg nuclear shielding (Δdeltasup(i)( 199 Hg)) are of interest because of the unusual shift to high frequency which has been observed for a few alkyl mercury compounds. Continuing interest in the NMR parameters of mercury compounds prompted a search for the values Δdeltasup(i)( 199 Hg) in a greater variety of organomercurials. This should help to find out about the range of Δdeltasup(i)( 199 Hg) and to obtain a firmer basis for the discussion of the high-frequency shifts. The data and experimental conditions are given for chemical shifts delta 199 Hg, coupling constants sup(n)J( 199 Hg 13 C) and 13 C/ 12 C isotope shifts Δdeltasup(i)( 199 Hg) of fourteen 199 Hg organomercury compounds. The results are discussed. (author)

Recent Developments in Carbonylation Chemistry Using [13 C]CO, [11 C]CO and [14 C]CO.

Science.gov (United States)

Nielsen, Dennis U; Neumann, Karoline T; Lindhardt, Anders T; Skrydstrup, Troels

2018-06-01

Carbon monoxide represents the most important C1-building block for the chemical industry, both for the production of bulk and fine chemicals, but also for synthetic fuels. Yet, its toxicity and subsequently its cautious handling has limited its applications in medicinal chemistry research and in particular for the synthesis of pharmaceutically relevant molecules. Recent years have nevertheless witnessed a considerable headway on the development of carbon monoxide surrogates and reactor systems, which provide an ideal setting for performing carbonylation chemistry with stoichiometric and sub-stoichiometric carbon monoxide. Such set-ups are particularly ideal for the introduction of isotope labels such as carbon-11, carbon-13 and carbon-14 into bioactive compounds. This review summarizes this growing field and examines the large number of carbonylation reactions that can be exploited for the introduction of a carbon isotope. This article is protected by copyright. All rights reserved.

Incorporation of 13C labeled Pinus ponderosa needle and fine root litter into soil organic matter measured by Py-GC/MS-C-IRMS

Science.gov (United States)

Mambelli, S.; Gleixner, G.; Dawson, T. E.; Bird, J. A.; Torn, M. S.

2006-12-01

Developing effective strategies for enhancing C storage in soils requires understanding the influence of plant C quality. In turn, plant C quality impacts the decay continuum between plant residue and humified, stable SOM. This remains one of the least understood aspects of soil biogeochemistry. We investigated the initial phase of incorporation of 13C labeled Pinus ponderosa needle and fine root litter into SOM. The two litter types were placed in separate microcosms in the A horizon in a temperate conifer soil. Curie-point pyrolysis-gas chromatography coupled with on-line mass spectrometry and isotope ratio mass spectrometry (Py-GC/MS-C- IRMS) were used to determine the identity and the 13C enrichment of pyrolysis products (fragments of carbohydrates, lignin, proteins and lipids). We compared the two initial litter types, needles and fine roots, to samples of the bulk soil (A horizon, < 2mm) and soil humin fraction (from chemical solubility) obtained from each microcosm 1.5y after litter addition. Pyrolysis of plant material and SOM produced 56 suitable products for isotopic analysis; of them, 15 occurred in both the litter and bulk soil, 7 in both the litter and the humin fraction and 9 in both bulk soil and the humin fraction. The pyrolysis products found in common in the plant and soil were related either to polysaccharides or were non-specific and could have originated from various precursors. The data suggest that the majority of plant inputs, both from needles or fine roots, were degraded very rapidly. In the humin fraction, the most recalcitrant pool of C in soil, with a measured turnover time of 260y (this soil), only products from the fragmentation of polysaccharides and alkyl-benzene compounds were found. Comparisons of the enrichment normalized by input level suggest little difference between the incorporation of C from needles versus fine roots into SOM. The most enriched fragments in the humin fraction were products from polysaccharides degradation

13C and 31P NMR [Nuclear Magnetic Resonance] studies of prostate tumor metabolism

International Nuclear Information System (INIS)

Sillerud, L.O.; Halliday, K.R.; Freyer, J.P; Griffey, R.H.; Fenoglio-Preiser, C.

1989-01-01

The current research on prostate cancer by NMR spectroscopy and microscopy will most significantly contribute to tumor diagnosis and characterization only if sound biochemical models of tumor metabolism are established and tested. Prior searches focused on universal markers of malignancy, have to date, revealed no universal markers by any method. It is unlikely that NMRS will succeed where other methods have failed, however, NMR spectroscopy does provide a non-invasive means to analyze multiple compounds simultaneously in vivo. In order to fully evaluate the ability of NMRS to differentiate non-malignant from malignant tissues it is necessary to determine sufficient multiple parameters from specific, well-diagnosed, histological tumor types that, in comparison to normal tissue and non-neoplastic, non-normal pathologies from which the given neoplasm must be differentiated, one has enough degrees of freedom to make a mathematically and statistically significant determination. Confounding factors may consist of tumor heterogeneity arising from regional variations in differentiation, ischemia, necrosis, hemorrhage, inflammation and the presence of intermingled normal tissue. One related aspect of our work is the development of { 13 C}- 1 H metabolic imaging of 13 C for metabolic characterization, with enhanced spatial localization (46). This should markedly extend the range of potential clinical NMR uses because the spatial variation in prostate metabolism may prove to be just as important in tumor diagnoses as bulk (volume-averaged) properties themselves. It is our hope that NMRS and spectroscopic imaging will reveal a sound correlation between prostate metabolism and tumor properties that will be clinically straightforward and useful for diagnosis

Probing ADAMTS13 Substrate Specificity using Phage Display

Science.gov (United States)

Desch, Karl C.; Kretz, Colin; Yee, Andrew; Gildersleeve, Robert; Metzger, Kristin; Agrawal, Nidhi; Cheng, Jane; Ginsburg, David

2015-01-01

Von Willebrand factor (VWF) is a large, multimeric protein that regulates hemostasis by tethering platelets to the subendothelial matrix at sites of vascular damage. The procoagulant activity of plasma VWF correlates with the length of VWF multimers, which is proteolytically controlled by the metalloprotease ADAMTS13. To probe ADAMTS13 substrate specificity, we created phage display libraries containing randomly mutated residues of a minimal ADAMTS13 substrate fragment of VWF, termed VWF73. The libraries were screened for phage particles displaying VWF73 mutant peptides that were resistant to proteolysis by ADAMTS13. These peptides exhibited the greatest mutation frequency near the ADAMTS13 scissile residues. Kinetic assays using mutant and wild-type substrates demonstrated excellent agreement between rates of cleavage for mutant phage particles and the corresponding mutant peptides. Cleavage resistance of selected mutations was tested in vivo using hydrodynamic injection of corresponding full-length expression plasmids into VWF-deficient mice. These studies confirmed the resistance to cleavage resulting from select amino acid substitutions and uncovered evidence of alternate cleavage sites and recognition by other proteases in the circulation of ADAMTS13 deficient mice. Taken together, these studies demonstrate the key role of specific amino acids residues including P3-P2’ and P11’, for substrate specificity and emphasize the importance in flowing blood of other ADAMTS13–VWF exosite interactions outside of VWF73. PMID:25849793

13C and 31P NMR study of gluconeogenesis: utilization of 13C-labeled substrates by perfused liver from streptozotocin-diabetic and untreated rats

International Nuclear Information System (INIS)

Cohen, S.M.

1987-01-01

The metabolism of 13 C-labeled substrates was followed by 13 C and 31 P NMR in perfused liver from the streptozotocin-treated rat model of insulin-dependent diabetes. Comparison was made with perfused liver from untreated littermates, fasted either 24 or 12 h. The major routes of pyruvate metabolism were followed by a 13 C NMR approach that provided for the determination of the metabolic fate of several substances simultaneously. The rate of gluconeogenesis was 2-4-fold greater and β-hydroxybutyrate production was 50% greater in liver from the chronically diabetic rats as compared with the control groups. Large differences in the distribution of 13 C label in hepatic alanine were measured between diabetic and control groups. The biosyntheses of 13 C-labeled glutathione and N-carbamoylaspartate were monitored in time-resolved 13 C NMR spectra of perfused liver. Assignments for the resonances of glutathione and N-carbamoylaspartate were made with the aid of 13 C NMR studies of perchloric acid extracts of the freeze-clamped livers. 13 C NMR spectroscopy of the perfusates provided a convenient, rapid assay of the rate of oxidation of [2- 13 C]ethanol, the hepatic output of [2- 13 ]acetaldehyde, and the accumulation of [2- 13 C]acetate in the perfusate. By 31 P NMR spectroscopy, carbamoyl phosphate was measured in all diabetic livers and an unusual P,P'-diesterified pyrophosphate was observed in one-fourth of the diabetic livers examined. Neither of these phosphorylated metabolites was detected in control liver. Both 13 C and 31 P NMR were useful in defining changes in hepatic metabolism in experimental diabetes

SUMOFLUX: A Generalized Method for Targeted 13C Metabolic Flux Ratio Analysis

Science.gov (United States)

Kogadeeva, Maria

2016-01-01

Metabolic fluxes are a cornerstone of cellular physiology that emerge from a complex interplay of enzymes, carriers, and nutrients. The experimental assessment of in vivo intracellular fluxes using stable isotopic tracers is essential if we are to understand metabolic function and regulation. Flux estimation based on 13C or 2H labeling relies on complex simulation and iterative fitting; processes that necessitate a level of expertise that ordinarily preclude the non-expert user. To overcome this, we have developed SUMOFLUX, a methodology that is broadly applicable to the targeted analysis of 13C-metabolic fluxes. By combining surrogate modeling and machine learning, we trained a predictor to specialize in estimating flux ratios from measurable 13C-data. SUMOFLUX targets specific flux features individually, which makes it fast, user-friendly, applicable to experimental design and robust in terms of experimental noise and exchange flux magnitude. Collectively, we predict that SUMOFLUX's properties realistically pave the way to high-throughput flux analyses. PMID:27626798

The ¹³C bicarbonate method

DEFF Research Database (Denmark)

Junghans, Peter; Larsson, Caroline; Jensen, Rasmus Bovbjerg

2015-01-01

2 production calculated by the (13)C-BM, RaCO2((13)C) is compared to the result from the indirect calorimetry, RCO2(IC). In an interspecies comparison (dog, goat, horse, cattle, children, adult human; body mass ranging from 15 to 350 kg, resting and fasting conditions) we found an excellent...

The carbon isotopic compositions of individual compounds from ancient and modern depositional environments

Energy Technology Data Exchange (ETDEWEB)

Freeman, K.H.

1991-01-01

This work examines factors influencing the isotopic compositions of individual compounds and, consequently, that of preserved sedimentary organic matter. Specifically, isotope effects associated with reactions resulting in the production and degradation of organic matter in the water column and reactions affecting preservation during diagenesis are considered in three projects. The first documents the preservation of the isotopic compositions of hydrocarbons altered by diagenetic reaction. Isotopic compositions of structurally-related polycyclic aromatic hydrocarbons (PAH) from the Messel Shale show little variation with increased unsaturation. The influence of environmental conditions on the isotopic composition of sedimentary organic carbon is documented by a comparison of the {delta}{sup 13}C of hydrocarbons in the marine Julia Creek Oil Shale and the lacustrine Condor Oil Shale. A model is proposed for identifying relative degrees of oxygenation and productivity within a paleoenvironment based on the observed {sup 13}C contents of biomarkers. Effects of processes proposed in the environmental model are documented by an examination of hydrocarbons from the waters and sediments of the Black Sea and of the Cariaco Trench. Sources of individual compounds are identified by comparison of their {sup 13}C content with that predicted for autotrophic biomass calculated from the concentration and {sup 13}C content of CO{sub 2}(aq) in the surface waters.

The 12C/ 13C isotopic ratio in Titan hydrocarbons from Cassini/CIRS infrared spectra

Science.gov (United States)

Nixon, C. A.; Achterberg, R. K.; Vinatier, S.; Bézard, B.; Coustenis, A.; Irwin, P. G. J.; Teanby, N. A.; de Kok, R.; Romani, P. N.; Jennings, D. E.; Bjoraker, G. L.; Flasar, F. M.

2008-06-01

We have analyzed infrared spectra of Titan recorded by the Cassini Composite Infrared Spectrometer (CIRS) to measure the isotopic ratio 12C/ 13C in each of three chemical species in Titan's stratosphere: CH 4, C 2H 2 and C 2H 6. This is the first measurement of 12C/ 13C in any C 2 molecule on Titan, and the first measurement of 12CH 4/ 13CH 4 (non-deuterated) on Titan by remote sensing. Our spectra cover five widely-spaced latitudes, 65° S to 71° N and we have searched for both latitude variability of 12C/ 13C within a given species, and also for differences between the 12C/ 13C in the three gases. For CH 4 alone, we find C12/C13=76.6±2.7 (1- σ), essentially in agreement with the 12CH 4/ 13CH 4 measured by the Huygens Gas Chromatograph/Mass Spectrometer instrument (GCMS) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784]: 82.3±1.0, and also with measured values in H 13CN and 13CH 3D by CIRS at lower precision [Bézard, B., Nixon, C., Kleiner, I., Jennings, D., 2007. Icarus 191, 397-400; Vinatier, S., Bézard, B., Nixon, C., 2007. Icarus 191, 712-721]. For the C 2 species, we find C12/C13=84.8±3.2 in C 2H 2 and 89.8±7.3 in C 2H 6, a possible trend of increasingly value with molecular mass, although these values are both compatible with the Huygens GCMS value to within error bars. There are no convincing trends in latitude. Combining all fifteen measurements, we obtain a value of C12/C13=80.8±2.0, also compatible with GCMS. Therefore, the evidence is mounting that 12C/ 13C is some 8% lower on Titan than on the Earth (88.9, inorganic standard), and lower than typical for the outer planets ( 88±7 [Sada, P.V., McCabe, G.H., Bjoraker, G.L., Jennings, D.E., Reuter, D.C., 1996. Astrophys. J. 472, 903-907]). There is no current model for this enrichment, and we discuss several mechanisms that may be at work.

CACA-TOCSY with alternate {sup 13}C-{sup 12}C labeling: a {sup 13}C{sup {alpha}} direct detection experiment for mainchain resonance assignment, dihedral angle information, and amino acid type identification

Energy Technology Data Exchange (ETDEWEB)

Takeuchi, Koh [National Institute of Advanced Industrial Science and Technology (AIST), Biomedicinal Information Research Center (BIRC) (Japan); Frueh, Dominique P.; Sun, Zhen-Yu J.; Hiller, Sebastian; Wagner, Gerhard, E-mail: gerhard_wagner@hms.harvard.ed [Harvard Medical School, Department of Biological Chemistry and Molecular Pharmacology (United States)

2010-05-15

We present a {sup 13}C direct detection CACA-TOCSY experiment for samples with alternate {sup 13}C-{sup 12}C labeling. It provides inter-residue correlations between {sup 13}C{sup {alpha}} resonances of residue i and adjacent C{sup {alpha}s} at positions i - 1 and i + 1. Furthermore, longer mixing times yield correlations to C{sup {alpha}} nuclei separated by more than one residue. The experiment also provides C{sup {alpha}}-to-side chain correlations, some amino acid type identifications and estimates for {psi} dihedral angles. The power of the experiment derives from the alternate {sup 13}C-{sup 12}C labeling with [1,3-{sup 13}C] glycerol or [2-{sup 13}C] glycerol, which allows utilizing the small scalar {sup 3}J{sub CC} couplings that are masked by strong {sup 1}J{sub CC} couplings in uniformly {sup 13}C labeled samples.

Direct 13C-1H coupling constants in the vinyl group of 1-vinylpyrazoles

International Nuclear Information System (INIS)

Afonin, A.V.; Voronov, V.K.; Es'kova, L.A.; Domnina, E.S.; Petrova, E.V.; Zasyad'ko, O.V.

1987-01-01

In a continuation of a study of the rotational isomerism of 1-vinylpyrazoles, they studied the direct 13 C- 1 H coupling constants in the vinyl group of 1-vinylpyrazole, 1-vinyl-4-bromopyrazole, 1-vinyl-3-methylpyrazole, 1-vinyl-5-methylpyrazole, 1-vinyl-3,5-dimethylpyrazole, and 1-vinyl-4-nitro-3,5-dimethylpyrazole. The 13 C- 1 H direct coupling constants in the vinyl group of 1-vinylpyrazoles are stereo-specific and vary with change in the conformer ratio

10 CFR 34.13 - Specific license for industrial radiography.

Science.gov (United States)

2010-01-01