C-13 nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The C-13 NMR chemical shifts of graphite intercalation compounds have been calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about - 140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal-conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

Test of a new stable isotopic fingerprinting technique (i.e. Compound Specific Stable Isotope) in an Austrian sub-catchment to establish agricultural soil source contribution to deposited sediment

NASA Astrophysics Data System (ADS)

Mbaye, Modou; Mabit, Lionel; Gibbs, Max; Meusburger, Katrin; Toloza, Arsenio; Resch, Christian; Klik, Andreas; Swales, Andrew; Alewell, Christine

2017-04-01

In order to test and refine the use of compound-specific stable isotope (CSSI) as a fingerprinting technique, an innovative study was conducted in a sub-catchment dominated by C3 plants located 60 km north of Vienna. This experimental site consists of 4 different contributing sources (i.e. 3 agricultural fields and one grassed waterway) and one sediment mixture in which the δ13C values of the bulk soil carbon and of various fatty acids (FAs) were analysed after a cost effective sampling strategy. Bi-scatterplots of all possible combinations of δ13C FAs including the bulk soil carbon δ13C showed that bulk soil carbon δ13C is a strong discriminant among the other FAs. Moreover, bulk soil carbon δ13C values highlighted the highest difference between the four sources and the δ13C values of C24 indicated significant differences for all sources while δ13C of C22 did not exhibit a significant difference between the two first sources. An additional correlation analysis revealed that the highest significant linear dependencies are between δ13C16 & δ13C18 > δ13C18 & δ13C24 > δ13C16 & δ13C24. Among the variables, the bulk soil carbon δ13C was found to be the least correlated parameter, confirming that it is the most reliable discriminator to determine the sediment origins in the mixture. To summarize, only the long chain FAs (i.e. C22 and C24) as well as the bulk soil carbon δ13C succeeded in fulfilling our multivariate statistical tests. These findings were confirmed by the mixing polygon tests and Principal Component Analysis. Using three different mixing models (i.e. Iso-source, CSSIAR v1.0 and MIXSIAR), the contribution of the different sources to the mixture were evaluated. All models highlighted that the third source (field having C3 and C4 plants in rotation) and the grassed waterway were the main contributing agricultural area representing 25-31% and 50-57% of the deposited sediment constituting the mixture, respectively.

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

PubMed

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 (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/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.

Testing compound-specific δ13C of amino acids in mussels as a new approach to determine the average 13C values of primary production in littoral ecosystems

NASA Astrophysics Data System (ADS)

Vokhshoori, N. L.; Larsen, T.; McCarthy, M.

2012-12-01

Compound-specific isotope analysis of amino acids (CSI-AA) is a technique used to decouple trophic enrichment patterns from source changes at the base of the food web. With this new emerging tool, it is possible to precisely determine both trophic position and δ15N or δ13C source values in higher feeding organisms. While most work to date has focused on nitrogen (N) isotopic values, early work has suggested that δ13C CSI-AA has great potential as a new tracer both to a record δ13C values of primary production (unaltered by trophic transfers), and also to "fingerprint" specific carbon source organisms. Since essential amino acids (EAA) cannot be made de novo in metazoans but must be obtained from diet, the δ13C value of the primary producer is preserved through the food web. Therefore, the δ13C values of EAAs act as a unique signature of different primary producers and can be used to fingerprint the dominant carbon (C) source driving primary production at the base of the food web. In littoral ecosystems, such as the California Upwelling System (CUS), the likely dominant C sources of suspended particulate organic matter (POM) pool are kelp, upwelling phytoplankton or estuarine phytoplankton. While bulk isotopes of C and N are used extensively to resolve relative consumer hierarchy or shifting diet in a food web, we found that the δ13C bulk values in mussels cannot distinguish exact source in littoral ecosystems. Here we show 15 sites within the CUS, between Cape Blanco, OR and La Jolla, CA where mussels were sampled and analyzed for both bulk δ13C and CSI-AA. We found no latitudinal trends, but rather average bulk δ13C values for the entire coastal record were highly consistent (-15.7 ± 0.9‰). The bulk record would suggest either nutrient provisioning from kelp or upwelled phytoplankton, but 13C-AA fingerprinting confines these two sources to upwelling. This suggests that mussels are recording integrated coastal phytoplankton values, with the enriched δ13C values likely linked to nearshore processes in the CA upwelling zone. Overall, these results clearly demonstrate, for the first time, the dual potential of δ13C CSI-AA to simultaneously indicate δ13C values of primary production, as well as to narrow major primary production sources. Our results suggest that, when applied to littoral filter feeders or other bio or paleo-archives, δ13C CSI-AA represents a new tool for reconstructing past perturbations to the marine carbon cycle.

Latitudinal distribution of terrestrial lipid biomarkers and n-alkane compound-specific stable carbon isotope ratios in the atmosphere over the western Pacific and Southern Ocean

NASA Astrophysics Data System (ADS)

Bendle, James; Kawamura, Kimitaka; Yamazaki, Koji; Niwai, Takeji

2007-12-01

We investigated the latitudinal changes in atmospheric transport of organic matter to the western Pacific and Southern Ocean (27.58°N-64.70°S). Molecular distributions of lipid compound classes (homologous series of C 15 to C 35n-alkanes, C 8 to C 34n-alkanoic acids, C 12 to C 30n-alkanols) and compound-specific stable isotopes (δ 13C of C 29 and C 31n-alkanes) were measured in marine aerosol filter samples collected during a cruise by the R/V Hakuho Maru. The geographical source areas for each sample were estimated from air-mass back-trajectory computations. Concentrations of TC and lipid compound classes were several orders of magnitude lower than observations from urban sites in Asia. A stronger signature of terrestrial higher plant inputs was apparent in three samples collected under conditions of strong terrestrial winds. Unresolved complex mixtures (UCM) showed increasing values in the North Pacific, highlighting the influence of the plume of polluted air exported from East Asia. n-Alkane average chain length (ACL) distribution had two clusters, with samples showing a relation to latitude between 28°N and 47°S (highest ACL values in the tropics), whilst a subset of southern samples had anomalously high ACL values. Compound-specific carbon isotopic analysis of the C 29 (-25.6‰ to -34.5‰) and C 31n-alkanes (-28.3‰ to -37‰) revealed heavier δ 13C values in the northern latitudes with a transition to lighter values in the Southern Ocean. By comparing the isotopic measurements with back-trajectory analysis it was generally possible to discriminate between different source areas. The terrestrial vegetation source for a subset of the southernmost Southern Ocean is enigmatic; the back-trajectories indicate eastern Antarctica as the only intercepted terrestrial source area. These samples may represent a southern hemisphere background of well mixed and very long range transported higher plant organic material.

High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance

PubMed Central

Zare, Richard N.; Kuramoto, Douglas S.; Haase, Christa; Tan, Sze M.; Crosson, Eric R.; Saad, Nabil M. R.

2009-01-01

A continuous-flow cavity ring-down spectroscopy (CRDS) system integrating a chromatographic separation technique, a catalytic combustor, and an isotopic 13C/12C optical analyzer is described for the isotopic analysis of a mixture of organic compounds. A demonstration of its potential is made for the geochemically important class of short-chain hydrocarbons. The system proved to be linear over a 3-fold injection volume dynamic range with an average precision of 0.95‰ and 0.67‰ for ethane and propane, respectively. The calibrated accuracy for methane, ethane, and propane is within 3‰ of the values determined using isotope ratio mass spectrometry (IRMS), which is the current method of choice for compound-specific isotope analysis. With anticipated improvements, the low-cost, portable, and easy-to-use CRDS-based instrumental setup is poised to evolve into a credible challenge to the high-cost and complex IRMS-based technique. PMID:19564619

COMPOUND-SPECIFIC CARBON AND HYDROGEN ISOTOPE ANALYSIS-FIELD EVIDENCE OF MTBE BIOREMEDIATION

EPA Science Inventory

Chemical reactions (including bio- and abiotic degradation) tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), resulting in enrichment of the heavier isotopic species (13C, D) in the unreacted substrate, referred to as isotopic fractionation. On the other ...

Calibration and Data Processing in Gas Chromatography Combustion Isotope Ratio Mass Spectrometry

PubMed Central

Zhang, Ying; Tobias, Herbert J.; Sacks, Gavin L.; Brenna, J. Thomas

2013-01-01

Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis (13C/12C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the Δ13C = δ13CM – δ13CE difference measurements required for establishing adverse analytical findings for metabolites relative to endogenous reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

Gas chromatography and isotope ratio mass spectrometry of Pinot Noir wine volatile compounds (δ13C) and solid residues (δ13C, δ15N) for the reassessment of vineyard water-status.

PubMed

Spangenberg, Jorge E; Vogiatzaki, Maria; Zufferey, Vivian

2017-09-29

This paper describes a novel approach to reassess the water status in vineyards based on compound-specific isotope analysis (CSIA) of wine volatile organic compounds (δ 13 C VOC/VPDB ) and bulk carbon and nitrogen isotopes, and the C/N molar ratios of the wine solid residues (δ 13 C SR/VPDB , δ 15 N SR/Air-N2 ). These analyses link gas chromatography/combustion and elemental analysis to isotope ratio mass spectrometry (GC/C/IRMS, EA/IRMS). Field-grown cultivars of Pinot Noir grapevines were exposed during six growing seasons (2009-2014) to controlled soil water availability, while maintaining identical the other environmental variables and agricultural techniques. Wines were produced from the grapes by the same oenological protocol. This permitted for the assessment of the effects in the biochemistry of wines solely induced by the changes in the plant-soil water status. This mimicked the more recurrent and prolonged periods of soil water deficiency due to climate changes. Water stress in grapevine was assessed by the measurement of the predawn leaf water potential (Ψ pd ) and the stable carbon isotope composition of the berry sugars during harvest (must sugars). For quantitation purposes and the normalization of the measured stable carbon isotope ratios of the VOCs, the wine samples were spiked with three standard compounds with known concentration and δ 13 C VPDB values. VOCs were extracted by liquid-liquid extraction and analyzed by gas chromatography/flame ionization detection (GC/FID), gas chromatography/mass spectrometry (GC/MS), and GC/C/IRMS. δ 13 C values were obtained for eighteen VOCs. The solid residues were obtained by freeze-drying wine aliquots and were analyzed for their C and N content and isotope composition by EA/IRMS. All the isotopic ratios (δ 13 C SR , δ 15 N SR , δ 13 C VOC ) are highly correlated with the Ψ pd values, indicating that the proposed gas chromatography and isotope ratio mass spectrometry approach is a useful tool to assess the changes in the water status of grapevine cultivars in different terroirs. The combined analytical approach was used for the first time to complement the assessment of soil water availability effects on the grapevine. The δ 13 C values of the volatile compounds helped confirm (or establish) their main source(s) and biosynthetic pathway(s). Importantly, we also show for the first time that the combination of C/N and δ 15 N values of freeze-dried wines have an unexplored potential for the study of nitrogen dynamics in soil/grape/wine systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Non-statistical 13C Fractionation Distinguishes Co-incident and Divergent Steps in the Biosynthesis of the Alkaloids Nicotine and Tropine.

PubMed

Romek, Katarzyna M; Remaud, Gérald S; Silvestre, Virginie; Paneth, Piotr; Robins, Richard J

2016-08-05

During the biosynthesis of natural products, isotopic fractionation occurs due to the selectivity of enzymes for the heavier or lighter isotopomers. As only some of the positions in the molecule are implicated in a given reaction mechanism, position-specific fractionation occurs, leading to a non-statistical distribution of isotopes. This can be accessed by isotope ratio monitoring (13)C NMR spectrometry. The solanaceous alkaloids S-(-)-nicotine and hyoscyamine (atropine) are related in having a common intermediate, but downstream enzymatic steps diverge, providing a relevant test case to: (a) elucidate the isotopic affiliation between carbon atoms in the alkaloids and those in the precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, thus to make predictions as to their possible mechanism(s). We show that the position-specific (13)C/(12)C ratios in the different moieties of these compounds can satisfactorily be related to their known precursors and to the known kinetic isotope effects of enzymes involved in their biosynthesis, or to similar reaction mechanisms. Thus, the pathway to the common intermediate, N-methyl-Δ(1)-pyrrolinium, is seen to introduce similar isotope distribution patterns in the two alkaloids independent of plant species, whereas the remaining atoms of each target compound, which are of different origins, reflect their specific metabolic ancestry. We further demonstrate that the measured (13)C distribution pattern can be used to deduce aspects of the reaction mechanism of enzymes still to be identified. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Non-statistical 13C Fractionation Distinguishes Co-incident and Divergent Steps in the Biosynthesis of the Alkaloids Nicotine and Tropine*

PubMed Central

Romek, Katarzyna M.; Remaud, Gérald S.; Silvestre, Virginie; Paneth, Piotr; Robins, Richard J.

2016-01-01

During the biosynthesis of natural products, isotopic fractionation occurs due to the selectivity of enzymes for the heavier or lighter isotopomers. As only some of the positions in the molecule are implicated in a given reaction mechanism, position-specific fractionation occurs, leading to a non-statistical distribution of isotopes. This can be accessed by isotope ratio monitoring 13C NMR spectrometry. The solanaceous alkaloids S-(−)-nicotine and hyoscyamine (atropine) are related in having a common intermediate, but downstream enzymatic steps diverge, providing a relevant test case to: (a) elucidate the isotopic affiliation between carbon atoms in the alkaloids and those in the precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, thus to make predictions as to their possible mechanism(s). We show that the position-specific 13C/12C ratios in the different moieties of these compounds can satisfactorily be related to their known precursors and to the known kinetic isotope effects of enzymes involved in their biosynthesis, or to similar reaction mechanisms. Thus, the pathway to the common intermediate, N-methyl-Δ1-pyrrolinium, is seen to introduce similar isotope distribution patterns in the two alkaloids independent of plant species, whereas the remaining atoms of each target compound, which are of different origins, reflect their specific metabolic ancestry. We further demonstrate that the measured 13C distribution pattern can be used to deduce aspects of the reaction mechanism of enzymes still to be identified. PMID:27288405

An overview of methods using (13)C for improved compound identification in metabolomics and natural products.

PubMed

Clendinen, Chaevien S; Stupp, Gregory S; Ajredini, Ramadan; Lee-McMullen, Brittany; Beecher, Chris; Edison, Arthur S

2015-01-01

Compound identification is a major bottleneck in metabolomics studies. In nuclear magnetic resonance (NMR) investigations, resonance overlap often hinders unambiguous database matching or de novo compound identification. In liquid chromatography-mass spectrometry (LC-MS), discriminating between biological signals and background artifacts and reliable determination of molecular formulae are not always straightforward. We have designed and implemented several NMR and LC-MS approaches that utilize (13)C, either enriched or at natural abundance, in metabolomics applications. For LC-MS applications, we describe a technique called isotopic ratio outlier analysis (IROA), which utilizes samples that are isotopically labeled with 5% (test) and 95% (control) (13)C. This labeling strategy leads to characteristic isotopic patterns that allow the differentiation of biological signals from artifacts and yield the exact number of carbons, significantly reducing possible molecular formulae. The relative abundance between the test and control samples for every IROA feature can be determined simply by integrating the peaks that arise from the 5 and 95% channels. For NMR applications, we describe two (13)C-based approaches. For samples at natural abundance, we have developed a workflow to obtain (13)C-(13)C and (13)C-(1)H statistical correlations using 1D (13)C and (1)H NMR spectra. For samples that can be isotopically labeled, we describe another NMR approach to obtain direct (13)C-(13)C spectroscopic correlations. These methods both provide extensive information about the carbon framework of compounds in the mixture for either database matching or de novo compound identification. We also discuss strategies in which (13)C NMR can be used to identify unknown compounds from IROA experiments. By combining technologies with the same samples, we can identify important biomarkers and corresponding metabolites of interest.

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

PubMed

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.

Effect of 13C enrichment and sugar type on analysis of sugars by gas chromatography/combustion/isotope ratio mass spectrometry.

PubMed

Baumann, Karen; Dignac, Marie-France; Bardoux, Gérard; Rumpel, Cornelia

2012-09-15

The objective of this investigation was to test gas-chromatographic compound-specific analysis for studies on the isotopic composition of (13)C-enriched sugar molecules. The effects of (13)C enrichment and type of sugar (C5, C6) will provide valuable information on isotopic correction for future studies employing (13)C-enriched sugars. Five sugar solutions of xylose, mannose and glucose with (13)C enrichments ranging between 1.1 and 1.5 atom-% were prepared. The (13)C enrichments of the initial sugars were measured by elemental analyser/isotope ratio mass spectrometry (EA/IRMS); (13)C enrichments for derivatised sugars were obtained by gas chromatography/combustion/IRMS (GC/C/IRMS). The linear relationships between the (13)C enrichments of the initial sugars and the values for the derivatised sugars were sugar-type dependent. Corrections for GC/C/IRMS values took into account the kinetic isotope effect (KIE) of the derivatising agent associated with the coefficient (K(d)) and a newly introduced second coefficient (K(c)) associated with the KIE of the sugar. While K(d) was constant, K(c) varied with sugar type. During derivatisation acetate groups with (12)C and sugars with more (13)C reacted faster. Coefficients for the specific ranges of (13)C enrichments under study have to be assessed and the reactions of different sugar types have to be taken into account to avoid underestimation of (13)C enrichment of up to 9% (C5) or overestimation of up to 4% (C6). Copyright © 2012 John Wiley & Sons, Ltd.

Review: Current applications and challenges for liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS).

PubMed

Godin, Jean-Philippe; McCullagh, James S O

2011-10-30

High-precision isotope analysis is recognized as an essential research tool in many fields of study. Until recently, continuous flow isotope ratio mass spectrometry (CF-IRMS) was available via an elemental analyzer or a gas chromatography inlet system for compound-specific analysis of light stable isotopes. In 2004, however, an interface that coupled liquid chromatography with IRMS (LC/IRMS) became commercially available for the first time. This brought the capability for new areas of application, in particular enabling compound-specific δ(13)C analysis of non-volatile, aqueous soluble, compounds from complex mixtures. The interface design brought with it several analytical constraints, however, in particular a lack of compatibility with certain types of chromatography as well as limited flow rates and mobile phase compositions. Routine LC/IRMS methods have, however, been established for measuring the δ(13)C isotopic ratios of underivatized individual compounds for application in archeology, nutrition and physiology, geochemistry, hydrology, soil science and food authenticity. Seven years after its introduction, we review the technical advances and constraints, methodological developments and new applications of liquid chromatography coupled to isotope ratio mass spectrometry. Copyright © 2011 John Wiley & Sons, Ltd.

Preliminary use of compound-specific stable isotope (CSSI) technique to identify and apportion sediment origin in a small Austrian catchment

NASA Astrophysics Data System (ADS)

Mabit, Lionel; Gibbs, Max; Chen, Xu; Meusburger, Katrin; Toloza, Arsenio; Resch, Christian; Klik, Andreas; Eder, Alexander; Strauss, Peter; Alewell, Christine

2015-04-01

The overall impacts of climate change on agriculture are expected to be negative, threatening global food security. In the agricultural areas of the European Union, water erosion risk is expected to increase by about 80% by the year 2050. Reducing soil erosion and sedimentation-related environmental problems represent a key requirement for mitigating the impact of climate change. A new forensic stable isotope technique, using the compound specific stable isotope (CSSI) signatures of inherent soil organic biomarkers, can discriminate and apportion the source 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 investigation, 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 tested this innovative stable isotopic approach in a small Austrian agricultural catchment located 60 km north of Vienna. A previous fallout radionuclide (i.e. 137-Cs) based investigation established a sedimentation rate of 4 mm/yr in the lowest part of the study site. To gain knowledge about the origin of these sediments, the CSSI technique was then tested using representative samples from the different land-uses of the catchment as source material. Values of 13-C signatures of specific FAs (i.e. C22:0 = Behenic Acid ; C24:0 = Lignoceric Acid) and the bulk 13-C of the sediment mixture and potential landscape sources were analyzed with the mixing models IsoSource and CSSIAR v1.00. Using both mixing models, preliminary results highlighted that about 50-55% of the sediment located in the deposition area originated from the main grassed waterway of the catchment.

Compound-specific isotope analysis: Questioning the origins of a trichloroethene plume

USGS Publications Warehouse

Eberts, S.M.; Braun, C.; Jones, S.

2008-01-01

Stable carbon isotope ratios of trichloroethene (TCE), cis-1,2- dichloroethene, and trans-1,2-dichloroethene were determined by use of gas chromatography-combustion-isotope ratio mass spectroscopy to determine whether compound-specific stable carbon isotopes could be used to help understand the origin and history of a TCE groundwater plume in Fort Worth, TX. Calculated ??13C values for total chlorinated ethenes in groundwater samples, which can approximate the ??13C of a spilled solvent if all degradation products are accounted for, were useful for determining whether separate lobes of the plume resulted from different sources. Most notably, values for one lobe, where tetrachloroethene (PCE) has been detected periodically, were outside the range for manufactured TCE but within the range for manufactured PCE, whereas values for a separate lobe, which is downgradient of reported TCE spills, were within the range for manufactured TCE. Copyright ?? Taylor & Francis Group, LLC.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Shiguang; Mao, Li; Ji, Feng, E-mail: huaiaifengjidr@163.com

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 othermore » 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.« less

Theoretical DFT, vibrational and NMR studies of benzimidazole and alkyl derivatives

NASA Astrophysics Data System (ADS)

Infante-Castillo, Ricardo; Rivera-Montalvo, Luis A.; Hernández-Rivera, Samuel P.

2008-04-01

Benzimidazoles are heterocyclic compounds that have awaked great interest during the last few years because of their proven biological activity as antiviral, antimicrobial, and antitumoral agents. For this reason, the development of a systematic FT-IR, FT-Raman and NMR study of 1-substituted compounds in 2-methylbenzimidazole constitutes a significant tool in understanding the molecular dynamics and the structural parameters that govern their behavior. Two new 1-alkyl-2-methylbenzimidazoles compounds were synthesized from reaction of 2-methylbenzimidazole with primary and secondary alkyl halides using a strong base as a catalyst. These compounds were purified and characterized by elemental analysis and different spectroscopic methods. The comparative analysis of vibrational modes of benzimidazole and its alkyl derivatives show that regions of absorption are very similar in all of them. However, changes are produced at low frequencies specifically in the C-H out of plane deformations, ring breathing and ring skeletal vibrations. The ring out-of plane bending modes shift by 10-15 cm -1 in some cases as results of alkyl substitution. The theoretical calculated spectra, using Density Functional Theory (DFT) approximation, and experimental results were consistent with each other. The GIAO method was used to calculate absolute shieldings, which agree consistently with those measured by 1H and 13C NMR. The consistency and efficiency of the GIAO 13C and 1H NMR calculations were thoroughly checked by the analysis of statistical parameters concerning computed and experimental 13C and 1H NMR chemical shift values of the studied compounds.

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

NASA Technical Reports Server (NTRS)

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.

An estimation of Central Iberian Peninsula atmospheric δ13C and water δD in the Upper Cretaceous using pyrolysis compound specific isotopic analysis (Py-CSIA) of a fossil conifer.

NASA Astrophysics Data System (ADS)

González-Pérez, José A.; Jiménez-Morillo, Nicasio T.; De la Rosa, José M.; Almendros, Gonzalo; González-Vila, Francisco J.

2015-04-01

Frenelopsis is a frequently found genus of the Cretaceous floras adapted to dry, saline and in general to environmental conditions marked by severe water stress [1]. Stable isotope analysis of fossil organic materials can be used to infer palaeoenvironmental variables helpful to reconstruct plant paleohabitats [2]. In this study stable isotope analysis of organic fossil remains (FR) and humic fractions (FA, HA and humin) of Frenelopsis oligiostomata are studied in bulk (C, H, O, N IRMS) and in specific compounds released by pyrolysis (C, H, Py-CSIA). Well preserved F. oligiostomata fossils were handpicked from a limestone included in compacted marls from Upper Cretaceous (Senonian c. 72 Mya) in Guadalix de la Sierra (Madrid, Spain) [3]. The fossils were decarbonated with 6M HCl. Humic substances were extracted from finely ground fossil remains (FR) by successive treatments with 0.1M Na4P2O7 + NaOH [4]. The extract was acidified resulting into insoluble HA and soluble FA fractions. The HA and FA were purified as in [5] and [6] respectively. Bulk stable isotopic analysis (δ13C, δD, δ18O, δ15N IRMS) was done in an elemental micro-analyser coupled to a continuous flow Delta V Advantage isotope ratio mass spectrometer (IRMS). Pyrolysis compound specific isotopic analysis Py-CSIA (δ13C, δD): was done by coupling a double-shot pyrolyzer to a chromatograph connected to an IRMS. Structural features of specific peaks were inferred by comparing/matching mass spectra from conventional Py-GC/MS (data not shown) with Py-GC/IRMS chromatograms obtained using the same chromatographic conditions. Bulk C isotopic signature found for FR (-20.5±0.02 ‰) was in accordance with previous studies [2, 7-9]. This heavy isotopic δ13C signature indicates a depleted stomatal conductance and paleoenvironmental growth conditions of water and salt stress. This is in line with the morphological and depositional characteristics [3] confirming that F. oligostomata was adapted to highly xeric and saline habitats being a component of salt-marsh vegetation. The values obtained for δD (-101.9±2.2 ‰), δ15N (10.7±0.2 ‰) and δ18O (20.9±0.39 ‰) lay within those previously reported for fossil floras [10] growing in warm environment and probably with very high evaporation rates. δ13C Py-CSIA was recorded for biogenic compound; polysaccharides, lipid series, lignin and degraded lignin compounds (alkyl benzenes and alkyl phenols) and for a S containing compounds probably with a diagenetic origin. In general δ13C Py-CSIA values were more depleted that the bulk ones and can be considered a better approach to the real plant δ13C value (c. -22 ‰). Considering that plant-air C fractionation in degraded lignin compounds for a C4 photosystem plant is c. Δ13C≈ 20.0 ‰ [11] and a an extra fractionation (Δ13C≈ -3.0 ‰) due to the plant depleted stomatal conductance growing in extreme warm, saline and dry conditions, we estimate atmospheric δ13C value in the area during the Upper Cretaceous in c. δ13C = -5.3±0.2 ‰. This indicates that our F.oligostomata probably grew on a 13C enriched atmosphere, more enriched than preindustrial one (δ13C ≈ -6.5 ‰; [12]). This could be caused by a combination of reasons i.e. emissions of heavy 13C isotope to the atmosphere by an increase in ocean's temperature and acidification by volcanic S depositions during this geologically active and warm period, and/or an increase of primary production and net terrestrial C uptake with selective removal of light 12C isotope by plants. Values for δD CSIA of lipid compounds such as n-alkanes with C chain lengths, C23-C31 are believed to derive exclusively from leaf waxes of higher plants. Plant δD carries isotope information of environmental water that is particularly preserved during the geological record in n-alkyl structures, whereas other structures i.e. isoprenoids, are most prone to hydrogen exchange [13-14]. We were able to measure δD for long chain alkane/alkene series in the range C24-C29 (δD = -124.44±5.2‰). This was taken as a proxy to infer the original H isotopic signal of water in the area in the Upper Cretaceous. Poole et al. (2004) proposed that δDpalaeowarter= δDC24-C29 n-alkanes + 100 giving a value for plaeowater δD = -24.44±5.2‰. This indicates that 75 Mya our plant probably uptake deuterium enriched rain water that again points to warm growing environmental conditions. (1) Gómez, B.; Martín-Closas C.; Brale G.; Solé de Porta N.; Thévenard F.; Guignard G. Paleontology 2002 45, 997-1036. (2) Nguyen Tu, T.T.; Kvaček, J.; Uličnỷ, D.; Bocherens, H.; Mariotti, A.; Broutin, J. Palaeogeogr. Palaeoclimatol. Palaeoecol. 2002 183, 43-70. (3) Almendros, G.; Álvarez-Ramis, C.; Polo, A. Revista de la Real Academia de Ciencias Exactas, Físicas y Naturales 1982 76, 285-302. (4) Dabin, B. Chah. ORSTOM Ser. Pedol. 1976 4, 287-297. (5) Schnitzer, M.; Khan, S.U. Humic Substances in the Environment. Marcel Dekker Inc. 1972, New York, N.Y. (6) Dorado, E.; Polo. A. An. Edafol. Agrobiol. 1976 55, 723-732. (7) Bocherens, H.; Friis, E.M.; Mariotti, A.; Pedersen, K.R. Lethaia 1993 26, 347-358. (8) Nguyen Tu, T.T.; Bocherens, H.; Mariotti, A.; Baudin, F.; Pons, D.; Broutin, J.; Derenne, S.; Largeau C. Palaeogeogr. Palaeoclimatol. Palaeoecol. 1999 145, 79-93. (9) Aucour, A-.M.; Gomez, B.; Sheppard, S.M.F., Thévenard, F. Palaeogeogr. Palaeoclimatol. Palaeoecol. 2008 257, 462-473. (10) Michener, N.; Lajtha K. (Eds). Stable Isotopes in Ecology and Environmental Science (2nd Ed) 2007 Blackwell Publishing. (11) Poole, I., van Bergen, P.F.; Kool, K.; Schouten , S.; Cantrill, D. J. Org. Geochem. 2004 35, 1261-1274. (12) Gerber, S.; Joos, F.; Brügger, P.; Stocker, T.F.; Mann, M.E.; Sitch, S.; Scholze, M. Clim. Dyn. 2003 20, 281-299, 2003 (13) Pedentchouk, N.; Freeman, K.H.; Harris, N.B. Geochim. Cosmochim. Acta 2006 70, 2063-2072. (14) Radke, J.; Bechtel, A.; Gaupp, R.; Püttmann, W.; Schwark, L.; Sachse D.; Gleixner, G. Geochim. Cosmochim. Acta 2005 69, 5517-5530. Acknowledgements Projects CGL2012-38655-C04-01 and CGL2008-04296 and fellowship BES-2013-062573 given by the Spanish Ministry for Economy and Competitiveness to N.T.J.M. Dr. J.M. R. is the recipient of a fellowship from the JAE-Doc subprogram financed by the CSIC and the European Social Fund.

The Fate of Crude Oil during Photooxidation under Natural Sunlight

NASA Astrophysics Data System (ADS)

Wang, Q.; Evans, M.; Bacosa, H. P.; Hu, X.; Liu, Z.

2016-02-01

Photooxidation plays an important role in removing spilled crude oil, particularly the aromatic fraction, in surface seawater. Even though much research has been done regarding the changes of different oil fractions by photooxidation, including saturate, aromatic, resin and asphaltene (SARA), we know little about how specific aromatic compounds change in the SARA fractions during photooxidation. In this study, we amended 13C-labled phenanthrene in slightly weathered Louisiana light sweet crude, and followed the fates of 13C values of the SARA fractions during a 44-d incubation experiment under the natural sunlight in south Texas. Our results showed that the aromatic fraction of the crude decreased from 25.4% at time zero to 13.5% at the 44th d, while the resin increased from 12.2% to 16.5% and asphaltene from 2.4% to 13.3%, respectively. This result indicates the aromatic was transformed mostly into asphaltene by photooxidation, and most of the changes took place within the first 10 d. In contrast, no significant difference was observed in the SARA fractions in the dark controls. Analyses of 13C values and phenanthrene concentrations in the SARA fractions are currently on going and will be presented. Results from this experiment provide insights into changes of specific aromatic compounds within oil fractions by photochemical oxidation during oil weathering in the ocean.

Effect of glucose on the fatty acid composition of Cupriavidus necator JMP134 during 2,4-dichlorophenoxyacetic acid degradation: implications for lipid-based stable isotope probing methods.

PubMed

Lerch, Thomas Z; Dignac, Marie-France; Barriuso, Enrique; Mariotti, André

2011-10-01

Combining lipid biomarker profiling with stable isotope probing (SIP) is a powerful technique for studying specific microbial populations responsible for the degradation of organic pollutants in various natural environments. However, the presence of other easily degradable substrates may induce significant physiological changes by altering both the rate of incorporation of the target compound into the biomass and the microbial lipid profiles. In order to test this hypothesis, Cupriavidus necator JMP134, a 2,4-dichlorophenoxyacetic acid (2,4-D)-degrading bacterium, was incubated with [(13)C]2,4-D, [(13)C]glucose, or mixtures of both substrates alternatively labeled with (13)C. C. necator JMP134 exhibited a preferential use of 2,4-D over glucose. The isotopic analysis showed that glucose had only a small effect on the incorporation of the acetic chain of 2,4-D into the biomass (at days 2 and 3) and no effect on that of the benzenic ring. The addition of glucose did change the fatty acid methyl ester (FAME) composition. However, the overall FAME isotopic signature reflected that of the entire biomass. Compound-specific individual isotopic analyses of FAME composition showed that the (13)C-enriched FAME profiles were slightly or not affected when tracing the 2,4-D acetic chain or 2,4-D benzenic ring, respectively. This batch study is a necessary step for validating the use of lipid-based SIP methods in complex environments.

Comparative study of ¹³C composition in ethanol and bulk dry wine using isotope ratio monitoring by mass spectrometry and by nuclear magnetic resonance as an indicator of vine water status.

PubMed

Guyon, Francois; van Leeuwen, Cornelis; Gaillard, Laetitia; Grand, Mathilde; Akoka, Serge; Remaud, Gérald S; Sabathié, Nathalie; Salagoïty, Marie-Hélène

2015-12-01

The potential of wine (13)C isotope composition (δ(13)C) is presented to assess vine water status during grape ripening. Measurements of δ(13)C have been performed on a set of 32 authentic wines and their ethanol recovered after distillation. The data, obtained by isotope ratio monitoring by mass spectrometry coupled to an elemental analyser (irm-EA/MS), show a high correlation between δ(13)C of the bulk wine and its ethanol, indicating that the distillation step is not necessary when the wine has not been submitted to any oenological treatment. Therefore, the ethanol/wine δ(13)C correlation can be used as an indicator of possible enrichment of the grape must or the wine with exogenous organic compounds. Wine ethanol δ(13)C is correlated to predawn leaf water potential (R(2) = 0.69), indicating that this parameter can be used as an indicator of vine water status. Position-specific (13)C analysis (PSIA) of ethanol extracted from wine, performed by isotope ratio monitoring by nuclear magnetic resonance (irm-(13)C NMR), confirmed the non-homogenous repartition of (13)C on ethanol skeleton. It is the δ(13)C of the methylene group of ethanol, compared to the methyl moiety, which is the most correlated to predawn leaf water potential, indicating that a phase of photorespiration of the vine during water stress period is most probably occurring due to stomata closure. However, position-specific (13)C analysis by irm-(13)C NMR does not offer a greater precision in the assessment of vine water status compared to direct measurement of δ(13)C on bulk wine by irm-EA/MS.

Position-specific 13C distributions within propane from experiments and natural gas samples

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Position-specific 13C distributions within propane from experiments and natural gas samples

USGS Publications Warehouse

Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Compound-Specific Amino Acid Isotopic Analysis of Benthic Food Webs in the Chukchi Sea

NASA Astrophysics Data System (ADS)

Zhang, M.; Cooper, L. W.; Biasatti, D. M.; Grebmeier, J. M.

2014-12-01

The Chukchi Sea is known for locally high standing stocks of benthic macrofauna and strong coupling between pelagic-benthic components of the ecosystem. However, benthic food structure is not fully understood, due to varied sources of particulate organic matter (POM) and the high diversity of benthic invertebrates. We provide the first demonstration of the application of compound-specific amino acid isotope analysis to study the dietary sources and trophic structure for this Arctic marginal sea. About 20 stations in Chukchi Sea were sampled during cruises in August of 2012 and 2013. At each station, phytoplankton, POM and benthic fauna were collected, processed and analyzed using GC-C-IRMS (gas chromatography-combustion-isotope ratio mass spectrometry). Among benthic fauna, dominant species included the following taxonomic groups: Ophiuroidea, Amphipoda, Polychaeta, Gastropoda, Bivalvia, and Cnidaria. The benthic fauna showed similar patterns of individual amino acid δ13C, with glycine the most enriched in 13C and leucine the most depleted in 13C. Specific amino acids including phenylalanine showed spatial variability in δ13C and δ15N values within the sampled area, indicating contributions of different dietary sources including phytoplankton, sea ice algae, benthic algae and terrestrial organic materials. δ15N values of individual amino acids such as the difference between glutamic acid and phenylalanine, i.e. Δ15Nglu-phe (δ15Nglu - δ15Nphe), were also used to identify trophic levels of benthic invertebrates relative to estimates available from bulk δ15N values. These data will ultimately be used to evaluate the spatial variability of organic carbon sources and trophic level interactions of dominant benthic species in the Chukchi Sea.

Synthesis of 2H- and 13C-substituted dithanes

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2003-01-01

The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

Synthesis Of 2h- And 13c-Substituted Dithanes

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2004-05-04

The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

Hydrocarbons identified in extracts from estuarine water accommodated no. 2 fuel oil by gas chromatography-mass spectrometry

NASA Technical Reports Server (NTRS)

Lewis, B. W.; Walker, A. L.; Bieri, R. H.

1974-01-01

Results are presented on a computerized gas chromatograph-mass spectrometer analysis of methylene chloride and n-heptane extracts of a No. 2 fuel oil accommodated estuarine water sample. The analytical method is briefly described, and the limitations on the identifications are categorized. Some attempt was made to determine major and trace constituents in the water accommodate. Altogether 66 hydrocarbon compounds were identified specifically, and 75 compounds were partially identified. Seven compounds could be recognized as major constituents of the water accommodated oil and ten were present only as traces. The aromatic compounds found were alkyl benzenes, naphthalene, tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl substituted isomers in the range of carbon numbers C7 to C15. Four n-alkanes, C10 to C13, were found along with four other assorted hydrocarbons.

Synthesis of three novel fluorine-18 labeled analogues of L-deprenyl for positron emission tomography (PET) studies of monoamine oxidase B (MAO-B).

PubMed

Nag, Sangram; Lehmann, Lutz; Heinrich, Tobias; Thiele, Andrea; Kettschau, Georg; Nakao, Ryuji; Gulyás, Balázs; Halldin, Christer

2011-10-27

The aim in this project was to synthesize and to study fluorine-18 labeled analogues of l-deprenyl which bind selectively to the enzyme monoamine oxidase B (MAO-B). Three fluorinated l-deprenyl analogues have been generated in multistep organic syntheses. The most promising fluorine-18 compound N-[(2S)-1-[(18)F]fluoro-3-phenylpropan-2-yl]-N-methylprop-2-yn-1-amine (4c) was synthesized by a one-step fluorine-18 nucleophilic substitution reaction. Autoradiography on human brain tissue sections demonstrated specific binding for compound 4c to brain regions known to have a high content of MAO-B. In addition, the corresponding nonradioactive fluorine-19 compound (13) inhibited recombinant human MAO-B with an IC(50) of 170.5 ± 29 nM but did not inhibit recombinant human MAO-A (IC(50) > 2000 nM), demonstrating its specificity. Biodistribution of 4c in mice showed high initial brain uptake leveling at 5.2 ± 0.04%ID/g after 2 min post injection. In conclusion, compound 4c is a specific inhibitor of MAO-B with high initial brain uptake in mice and is, therefore, a candidate for further investigation in PET.

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

NASA Astrophysics Data System (ADS)

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.

Can Small Chemical Modifications of Natural Pan-inhibitors Modulate the Biological Selectivity? The Case of Curcumin Prenylated Derivatives Acting as HDAC or mPGES-1 Inhibitors.

PubMed

Iranshahi, Mehrdad; Chini, Maria Giovanna; Masullo, Milena; Sahebkar, Amirhossein; Javidnia, Azita; Chitsazian Yazdi, Mahsa; Pergola, Carlo; Koeberle, Andreas; Werz, Oliver; Pizza, Cosimo; Terracciano, Stefania; Piacente, Sonia; Bifulco, Giuseppe

2015-12-24

Curcumin, or diferuloylmethane, a polyphenolic molecule isolated from the rhizome of Curcuma longa, is reported to modulate multiple molecular targets involved in cancer and inflammatory processes. On the basis of its pan-inhibitory characteristics, here we show that simple chemical modifications of the curcumin scaffold can regulate its biological selectivity. In particular, the curcumin scaffold was modified with three types of substituents at positions C-1, C-8, and/or C-8' [C5 (isopentenyl, 5-8), C10 (geranyl, 9-12), and C15 (farnesyl, 13, 14)] in order to make these molecules more selective than the parent compound toward two specific targets: histone deacetylase (HDAC) and microsomal prostaglandin E2 synthase-1 (mPGES-1). From combined in silico and in vitro analyses, three selective inhibitors by proper substitution at position 8 were revealed. Compound 13 has improved HDAC inhibitory activity and selectivity with respect to the parent compound, while 5 and 9 block the mPGES-1 enzyme. We hypothesize about the covalent interaction of curcumin, 5, and 9 with the mPGES-1 binding site.

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

PubMed

Can, Nafiz Öncü; Can, Özgür Devrim; Osmaniye, Derya; Demir Özkay, Ümide

2018-03-21

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), 13 C Nuclear Magnetic Resonance Spectroscopy ( 13 C-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.

Preparation of 7-hydroxy-2-oxoindolin-3-ylacetic acid and its [13C2], [5-n-3H], and [5-n-3H]-7-O-glucosyl analogues for use in the study of indol-3-ylacetic acid catabolism

NASA Technical Reports Server (NTRS)

Lewer, P.; Bandurski, R. S. (Principal Investigator)

1987-01-01

An improved synthesis of 7-hydroxy-2-oxoindolin-3-ylacetic acid via the base-induced condensation reaction between oxalate esters and 7-benzyloxyindolin-2-one is described. 7-Benzyloxyindolin-2-one was prepared in four steps and 50% overall yield from 3-hydroxy-2-nitrotoluene. The yield of the title compound from 7-benzyloxyindolin-2-one was 56%. This route was used to prepare 7-hydroxy-2-oxoindolin-3-yl[13C2]acetic acid in 30% yield from [13C2]oxalic acid dihydrate. The method could not be extended to the preparation of the corresponding [14C2]-compound. However, an enzyme preparation from Zea mays roots catalysed the conversion of carrier-free [5-n-3H]indol-3-ylacetic acid with a specific activity of 16.7 Ci mmol-1 to a mixture of 7-hydroxy-2-oxo[5-n-3H]indolin-3-ylacetic acid and its [5-n-3H]-7-O-glucoside in ca. 3 and 40% radiochemical yield respectively. The glucoside was converted into the 7-hydroxy compound in 80% yield by means of beta-glucosidase.

Using stable isotope analysis to discriminate gasoline on the basis of its origin.

PubMed

Heo, Su-Young; Shin, Woo-Jin; Lee, Sin-Woo; Bong, Yeon-Sik; Lee, Kwang-Sik

2012-03-15

Leakage of gasoline and diesel from underground tanks has led to a severe environmental problem in many countries. Tracing the production origin of gasoline and diesel is required to enable the development of dispute resolution and appropriate remediation strategies for the oil-contaminated sites. We investigated the bulk and compound-specific isotopic compositions of gasoline produced by four oil companies in South Korea: S-Oil, SK, GS and Hyundai. The relative abundance of several compounds in gasoline was determined by the peak height of the major ion (m/z 44). The δ(13)C(Bulk) and δD(Bulk) values of gasoline produced by S-Oil were significantly different from those of SK, GS and Hyundai. In particular, the compound-specific isotopic value (δ(13)C(CSIA)) of methyl tert-butyl ether (MTBE) in S-Oil gasoline was significantly lower than that of gasoline produced by other oil companies. The abundance of several compounds in gasoline, such as n-pentane, MTBE, n-hexane, toluene, ethylbenzene and o-xylene, differed widely among gasoline from different oil companies. This study shows that gasoline can be forensically discriminated according to the oil company responsible for its manufacture using stable isotope analysis combined with multivariate statistical analysis. Copyright © 2012 John Wiley & Sons, Ltd.

Isotopic 13C NMR spectrometry to assess counterfeiting of active pharmaceutical ingredients: site-specific 13C content of aspirin and paracetamol.

PubMed

Silvestre, Virginie; Mboula, Vanessa Maroga; Jouitteau, Catherine; Akoka, Serge; Robins, Richard J; Remaud, Gérald S

2009-10-15

Isotope profiling is a well-established technique to obtain information about the chemical history of a given compound. However, the current methodology using IRMS can only determine the global (13)C content, leading to the loss of much valuable data. The development of quantitative isotopic (13)C NMR spectrometry at natural abundance enables the measurement of the (13)C content of each carbon within a molecule, thus giving simultaneous access to a number of isotopic parameters. When it is applied to active pharmaceutical ingredients, each manufactured batch can be characterized better than by IRMS. Here, quantitative isotopic (13)C NMR is shown to be a very promising and effective tool for assessing the counterfeiting of medicines, as exemplified by an analysis of aspirin (acetylsalicylic acid) and paracetamol (acetaminophen) samples collected from pharmacies in different countries. It is proposed as an essential complement to (2)H NMR and IRMS.

Diel variations in carbon isotopic composition and concentration of organic acids and their impact on plant dark respiration in different species.

PubMed

Lehmann, M M; Wegener, F; Werner, R A; Werner, C

2016-09-01

Leaf respiration in the dark and its C isotopic composition (δ(13) CR ) contain information about internal metabolic processes and respiratory substrates. δ(13) CR is known to be less negative compared to potential respiratory substrates, in particular shortly after darkening during light enhanced dark respiration (LEDR). This phenomenon might be driven by respiration of accumulated (13) C-enriched organic acids, however, studies simultaneously measuring δ(13) CR during LEDR and potential respiratory substrates are rare. We determined δ(13) CR and respiration rates (R) during LEDR, as well as δ(13) C and concentrations of potential respiratory substrates using compound-specific isotope analyses. The measurements were conducted throughout the diel cycle in several plant species under different environmental conditions. δ(13) CR and R patterns during LEDR were strongly species-specific and showed an initial peak, which was followed by a progressive decrease in both values. The species-specific differences in δ(13) CR and R during LEDR may be partially explained by the isotopic composition of organic acids (e.g., oxalate, isocitrate, quinate, shikimate, malate), which were (13) C-enriched compared to other respiratory substrates (e.g., sugars and amino acids). However, the diel variations in both δ(13) C and concentrations of the organic acids were generally low. Thus, additional factors such as the heterogeneous isotope distribution in organic acids and the relative contribution of the organic acids to respiration are required to explain the strong (13) C enrichment in leaf dark-respired CO2 . © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Hangyong; Zhu, Huanghuang; Lin, Zhou

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 ofmore » 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.« less

Analysis of Active Methylotrophic Communities: When DNA-SIP Meets High-Throughput Technologies.

PubMed

Taubert, Martin; Grob, Carolina; Howat, Alexandra M; Burns, Oliver J; Chen, Yin; Neufeld, Josh D; Murrell, J Colin

2016-01-01

Methylotrophs are microorganisms ubiquitous in the environment that can metabolize one-carbon (C1) compounds as carbon and/or energy sources. The activity of these prokaryotes impacts biogeochemical cycles within their respective habitats and can determine whether these habitats act as sources or sinks of C1 compounds. Due to the high importance of C1 compounds, not only in biogeochemical cycles, but also for climatic processes, it is vital to understand the contributions of these microorganisms to carbon cycling in different environments. One of the most challenging questions when investigating methylotrophs, but also in environmental microbiology in general, is which species contribute to the environmental processes of interest, or "who does what, where and when?" Metabolic labeling with C1 compounds substituted with (13)C, a technique called stable isotope probing, is a key method to trace carbon fluxes within methylotrophic communities. The incorporation of (13)C into the biomass of active methylotrophs leads to an increase in the molecular mass of their biomolecules. For DNA-based stable isotope probing (DNA-SIP), labeled and unlabeled DNA is separated by isopycnic ultracentrifugation. The ability to specifically analyze DNA of active methylotrophs from a complex background community by high-throughput sequencing techniques, i.e. targeted metagenomics, is the hallmark strength of DNA-SIP for elucidating ecosystem functioning, and a protocol is detailed in this chapter.

Design, synthesis, anticancer screening, docking studies and in silico ADME prediction of some β-carboline derivatives.

PubMed

Abdelsalam, Mohamed A; AboulWafa, Omaima M; M Badawey, El-Sayed A; El-Shoukrofy, Mai S; El-Miligy, Mostafa M; Gouda, Noha; Elaasser, Mahmoud M

2018-05-22

Medicinal interest has focused on β-carbolines as anticancer agents. Several β-carbolines were designed, synthesized and evaluated for their cytotoxic activity against MCF-7 and A-549 cancer cell lines using MTT assay. Compounds 13a, 13c, 13d and 20a were the most promising showing high selectivity indices. Compounds 13c and 20a showed potent inhibition of topoisomerase (topo-I) and kinesin spindle protein (KSP/Eg5 ATPase) which was confirmed by their docking results into the active site of both enzymes. In silico physicochemical calculations predicted that compounds 13a, 13d and 20a obeyed Lipinski's rule of five. Compounds 13c and 20a are multitarget anticancer leads that act as potent inhibitors for both topo-I and/or KSP ATPase.

Monitoring Microbial Mineralization Using Reverse Stable Isotope Labeling Analysis by Mid-Infrared Laser Spectroscopy

PubMed Central

2017-01-01

Assessing the biodegradation of organic compounds is a frequent question in environmental science. Here, we present a sensitive, inexpensive, and simple approach to monitor microbial mineralization using reverse stable isotope labeling analysis (RIL) of dissolved inorganic carbon (DIC). The medium for the biodegradation assay contains regular organic compounds and 13C-labeled DIC with 13C atom fractions (x(13C)DIC) higher than natural abundance (typically 2–50%). The produced CO2 (x(13C) ≈ 1.11%) gradually dilutes the initial x(13C)DIC allowing to quantify microbial mineralization using mass-balance calculations. For 13C-enriched CO2 samples, a newly developed isotope ratio mid-infrared spectrometer was introduced with a precision of x(13C) < 0.006%. As an example for extremely difficult and slowly degradable compounds, CO2 production was close to the theoretical stoichiometry for anaerobic naphthalene degradation by a sulfate-reducing enrichment culture. Furthermore, we could measure the aerobic degradation of dissolved organic carbon (DOC) adsorbed to granular activated carbon in a drinking water production plant, which cannot be labeled with 13C. Thus, the RIL approach can be applied to sensitively monitor biodegradation of various organic compounds under anoxic or oxic conditions. PMID:28903553

A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

NASA Astrophysics Data System (ADS)

Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2015-04-01

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects. This bodes well for the use of CSIA to identify and monitor transformation in the field as any isotopic effects due to volatile loss would only result in a conservative estimate of transformation but not confuse the degradation signal. As a result, enrichment factors in field samples might be underestimated and lead to a more conservative estimate of degradation at contaminated sites. CFCs from several suppliers were characterized to investigate δ13C variation between sources and between different CFC compounds. Significant differences were observed between all measured compounds. However for each compound, δ13C values determined in this study were similar to ranges reported previously for other pure phase CFCs - suggesting a consistent range of source signatures may exist for each compound. As a last step of method evaluation, water samples from a contaminated industrial site were measured. This first preliminary field data will be discussed in comparison to pure phase compounds and with respect to potential degradation.

Nuclear Magnetic Resonance (NMR) as a tool for the study of the metabolism of Rickettsia slovaca.

PubMed

García-Álvarez, Lara; Busto, Jesús H; Peregrina, Jesús M; Santibáñez, Sonia; Portillo, Aránzazu; Avenoza, Alberto; Oteo, José A

2015-01-01

Rickettsial infections are caused by intracellular bacteria. They do not grow in standard culture media so there are limitations in routine practice to study their metabolism. Nuclear Magnetic Resonance (NMR) spectroscopy is used for identification of metabolites in biological samples. Vero cells infected with Rickettsia slovaca as well as uninfected cells were monitored by (1)H NMR showing the presence of ethanol and lactic acid. As no differences were observed, labeled compounds were added into cultures. When D-[1-13C]glucose was monitored by (13)C NMR no differences among infected and uninfected cells were observed in metabolic profiles. Glucose was transformed into ethanol in all cultures. Monitored experiments carried out with [2-13C]glycine showed differences between infected and uninfected cell cultures spectra. Glycine was partially transformed into serine, but the amount of the serine formed was larger in those infected. Moreover, L-[2-13C]leucine, L-[1-13C]isoleucine and L-[15N]tyrosine were evaluated. No differences among infected and uninfected cells were observed in the metabolic profiles when tyrosine and leucine were monitored. The amino acid L-[1-13C]isoleucine exhibited different metabolism in presence of the R. slovaca, showing a promising behavior as biomarker. In this work we focused on finding one or more compounds that could be metabolized specifically by R. slovaca and could be used as an indicator of its activity. Copyright © 2015 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

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

PubMed

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.

Effect of Glucose on the Fatty Acid Composition of Cupriavidus necator JMP134 during 2,4-Dichlorophenoxyacetic Acid Degradation: Implications for Lipid-Based Stable Isotope Probing Methods▿†

PubMed Central

Lerch, Thomas Z.; Dignac, Marie-France; Barriuso, Enrique; Mariotti, André

2011-01-01

Combining lipid biomarker profiling with stable isotope probing (SIP) is a powerful technique for studying specific microbial populations responsible for the degradation of organic pollutants in various natural environments. However, the presence of other easily degradable substrates may induce significant physiological changes by altering both the rate of incorporation of the target compound into the biomass and the microbial lipid profiles. In order to test this hypothesis, Cupriavidus necator JMP134, a 2,4-dichlorophenoxyacetic acid (2,4-D)-degrading bacterium, was incubated with [13C]2,4-D, [13C]glucose, or mixtures of both substrates alternatively labeled with 13C. C. necator JMP134 exhibited a preferential use of 2,4-D over glucose. The isotopic analysis showed that glucose had only a small effect on the incorporation of the acetic chain of 2,4-D into the biomass (at days 2 and 3) and no effect on that of the benzenic ring. The addition of glucose did change the fatty acid methyl ester (FAME) composition. However, the overall FAME isotopic signature reflected that of the entire biomass. Compound-specific individual isotopic analyses of FAME composition showed that the 13C-enriched FAME profiles were slightly or not affected when tracing the 2,4-D acetic chain or 2,4-D benzenic ring, respectively. This batch study is a necessary step for validating the use of lipid-based SIP methods in complex environments. PMID:21856833

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

NASA Astrophysics Data System (ADS)

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.

Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

PubMed

Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

2018-05-08

A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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 relaxing agent concentrations, leading to a strong reduction of the overall experiment time.

Molecular DYNAmics of Soil Organic carbon (DYNAMOS ): a project focusing on soils and carbon through data and modeling

NASA Astrophysics Data System (ADS)

Mendez-Millan, Mercedes

2010-05-01

Here we present the first results of the DynaMOS project whose main issue is the build-up of a new generation of soil carbon model. The modeling will describe together soil organic geochemistry and soil carbon dynamics in a generalized, quantitative representation. The carbon dynamics time scale envisaged here will cover the 1 to 1000 yr range and describe molecule behaviours (i.e.)carbohydrate, peptide, amino acid, lignin, lipids, their products of biodegradation and uncharacterized carbonaceous species of biological origin. Three main characteristics define DYNAMOS model originalities: it will consider organic matter at the molecular scale, integrate back to global scale and account for component vertical movements. In a first step, specific data acquisition will concern the production, fate and age of carbon of individual organic compounds. Dynamic parameters will be acquired by compound-specific carbon isotope analysis of both 13C and 14C, by GC/C/IR-MS and AMS. Sites for data acquisition, model calibration and model validation will be chosen on the base of their isotopic history and environmental constraints: 13C natural labeling (with and without C3/C4 vegetation changes), 13C/15N-labelled litter application in both forest and cropland. They include some long-term experiments owned by the partners themselves plus a worldwide panel of sites. In a second step the depth distribution of organic species, isotopes and ages in soils (1D representation) will be modeled by coupling carbon dynamics and vertical movement. Besides the main objective of providing a robust soil carbon dynamics model, DYNAMOS will assess and model the alteration of the isotopic signature of molecules throughout decay and create a shared database of both already published and new data of compound specific information. Issues of the project will concern different scientific fields: global geochemical cycles by refining the description of the terrestrial carbon cycle and entering the chemical composition of organic matter in carbon models; forestry or agriculture by offering a chemical frame for the management of crop residues or organic wastes; geochronology, paleoecology and paleo climatology by modeling the alteration of isotope signature and the preservation of terrestrial biomarkers.

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

PubMed

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 (<1.3 per thousand). Limits of detection (LODs) for delta13C analysis by SPME-GC/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 <0.8 per thousand) for all NACs except for TNT. delta15N signatures matched the reference values obtained by EA-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.

Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

NASA Astrophysics Data System (ADS)

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

2012-09-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) 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 indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent-body chemistry.

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

PubMed

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.

Preparation of Mo-Re-C samples containing Mo7Re13C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

NASA Astrophysics Data System (ADS)

Oh-ishi, Katsuyoshi; Nagumo, Kenta; Tateishi, Kazuya; Takafumi, Ohnishi; Yoshikane, Kenta; Sugiyama, Machiko; Oka, Kengo; Kobayashi, Ryota

2017-01-01

Mo-Re-C compounds containing Mo7Re13C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo7Re13C with the β-Mn structure using the solid state method. Almost single-phase Mo7Re13C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with a pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K.

Food residue fatty acid δ13C and δD values as proxies for evaluating cultural and climatic change at Çatalhöyük, Turkey

NASA Astrophysics Data System (ADS)

Pitter, S.; Evershed, R. P.; Hodder, I.

2012-12-01

Compound specific δ13C stable isotope analysis via gas chromatography-combustion-isotope ratio mass spectrometry (GC-C- IRMS) of C16:0 and C18:0 fatty acids from archaeological pottery has been used previously to probe the organic residue record to identify specific animal origins of fats. By following previously established methods (Evershed et al. 2008) a more comprehensive record of the domestic animal-based subsistence practices of the Neolithic site Çatalhöyük has now been established. Furthermore, a new palaeoenvironmental proxy was also established through δD analysis of C16:0 and C18:0 fatty acids using GC-thermal conversion-IRMS (GC-TC-IRMS). This novel approach has demonstrated a means of observing changes in relative humidity associated with specific pottery types at archaeological sites, creating a proxy that may address several limitations in the field of archaeology with regards to understanding links between humans and their changing environments.

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

PubMed

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.

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

PubMed

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.

To Covary or Not to Covary, That is the Question

NASA Astrophysics Data System (ADS)

Oehlert, A. M.; Swart, P. K.

2016-12-01

The meaning of covariation between the δ13C values of carbonate carbon and that of organic material is classically interpreted as reflecting original variations in the δ13C values of the dissolved inorganic carbon in the depositional environment. However, recently it has been shown by the examination of a core from Great Bahama Bank (Clino) that during exposure not only do the rocks become altered acquiring a negative δ13C value, but at the same time terrestrial vegetation adds organic carbon to the system masking the original marine values. These processes yield a strong positive covariation between δ13Corg and δ13Ccar values even though the signals are clearly not original and unrelated to the marine δ13C values. Examining the correlation between the organic and inorganic system in a stratigraphic sense at Clino and in a second more proximally located core (Unda) using a windowed correlation coefficient technique reveals that the correlation is even more complex. Changes in slope and the magnitude of the correlation are associated with exposure surfaces, facies changes, dolomitized bodies, and non-depositional surfaces. Finally other isotopic systems such as the δ13C value of specific organic compounds as well as δ15N values of bulk and individual compounds can provide additional information. In the case of δ15N values, decreases reflect a changes in the influence of terrestrial organic material and an increase contribution of organic material from the platform surface where the main source of nitrogen is derived from the activities of cyanobacteria.

Preparative chromatography for specific δ13C isotopic analysis of individual carbohydrates in environmental samples

NASA Astrophysics Data System (ADS)

Nouara, Amel; Panagiotopoulos, Christos; Balesdent, Jérôme; Sempéré, Richard

2017-04-01

Carbohydrates are among the most abundant organic molecules on the Earth and are present in all geochemical systems. Despite their high abundance in the environment, very few studies assessed their origin using molecular carbohydrate isotopic analyses. In contrast with bulk stable isotope analysis (BSIA), which gives the isotopic signature of the entire sample without any specification about its chemical composition, compound specific 13C isotopic analysis of individual sugars (CSIA) offers valuable information about the origin of single molecules. Previous investigations used gas or liquid chromatography coupled with isotope ratio mass spectroscopy (GC-IRMS; HPLC-IRMS) for CSIA of sugars however the former requires δ13C corrections due to the carbon added to the sugar (derivatization) while the later does not provide always adequate separations among monosaccharides. Here we used cation preparative chromatography (Ca2+, Pb2+ and Na+) with refractive index detection in order to produce pure monosaccharide targets for subsequent EA-IRMS analyses. Milli-Q water was used as eluant at a flow rate 0.6 ml min-1. In general, three successive purifications (Ca2+, Pb2+, Ca2+) were sufficient to produce pure compounds. Pure monosaccharides were compared with authentic monosaccharide standards using 1H NMR and/or mass spectroscopy. The detection limit of our technique was about 1µM/sugar with a precision of 10% (n=6). Blanks run with Milli-Q water after three successive purifications resulted in carbon content of 0.13 to 2.77 µgC per collected sugar. These values are much lower than the minimum required amount (5 µgC) of the EA-IRSMS system with a precision of ± 0.35 ‰. Application of our method to environmental samples resulted in δ13C values of glucose, fructose, and levoglucosan in the range of -24 to -26 ‰ (PM10 atmospheric particles), and -15‰ to -22 ‰ for arabinose, glucose, and xylose (marine high molecular dissolved organic matter). These results fall in the range of previous reported values for terrestrial and aquatic ecosystems.

Impact of feeding and short-term temperature stress on the content and isotopic signature of fatty acids, sterols, and alcohols in the scleractinian coral Turbinaria reniformis

NASA Astrophysics Data System (ADS)

Tolosa, I.; Treignier, C.; Grover, R.; Ferrier-Pagès, C.

2011-09-01

This study assesses the combined effect of feeding and short-term thermal stress on various physiological parameters and on the fatty acid, sterol, and alcohol composition of the scleractinian coral Turbinaria reniformis. The compound-specific carbon isotope composition of the lipids was also measured. Under control conditions (26°C), feeding with Artemia salina significantly increased the symbiont density and chlorophyll content and the growth rates of the corals. It also doubled the concentrations of almost all fatty acid (FA) compounds and increased the n-alcohol and sterol contents. δ13C results showed that the feeding enhancement of FA concentrations occurred either via a direct pathway, for one of the major polyunsaturated fatty acid (PUFA) compounds of the food (18:3n-3 FA), or via an enhancement of photosynthate transfer (indirect pathway), for the other coral FAs. Cholesterol (C27Δ5) was also directly acquired from the food. Thermal stress (31°C) affected corals, but differently according to their feeding status. Chlorophyll, protein content, and maximal photosynthetic efficiency of photosystem II (PSII) decreased to a greater extent in starved corals. In such corals, FA concentrations were reduced by 33%, (especially C16, C18 FAs, and n-3 PUFA) and the sterol content by 27% (especially the C28∆5,22 and C28∆5). The enrichment in the δ13C signature of the storage and structural FAs suggests that they were the main compounds respired during the stress to maintain the coral metabolism. Thermal stress had less effect on the lipid concentrations of fed corals, as only FA levels were reduced by 13%, with no major changes in their isotope carbon signatures. In conclusion, feeding plays an essential role in sustaining T. reniformis metabolism during the thermal stress.

Compound-specific carbon isotope analysis of instantaneous gas generated from shaly coal during hydrous pyrolysis

NASA Astrophysics Data System (ADS)

Tsai, Wen-Yu; Sun, Chih-Hsien; Huang, Wuu-Liang

2010-05-01

Isotopes of natural gases have provided important information for indicating their maturation, origins and influencing factors during the generation processes. In order to distinguish compositions of gas generated at different intervals of maturities, the present study investigates the variation of compound-specific carbon isotope (CSI) ratios of hydrocarbon gases from a shaly coal by instantaneous hydrous pyrolysis, during which the earlier generated gas was evacuated before the start of next maturation stage. The experiments were conducted at ten different maturity stages (0.65 to 2.02 % Ro) from a terrestrial shaly coal with 0.48 % Ro. The gas products were analyzed by GC-IR-MS. The results show that, in general, the δ13C values of methane (C1), ethane (C2), propane (C3) slightly increase, then decrease and finally increase with increasing maturities. This reverse phenomenon indicates the heterogeneous and complex compositions of the kerogen. The isotope compositions of gases exhibit three distinct clusters in natural gas plot of δ13C values versus 1/n (where n is carbon number of the gaseous molecule), corresponding to three different groups of maturity stages. By linking the same maturity stage of δ13C values, all lines show nearly parallel in each group with consistently reverse trend of δ13C3 < δ13C2 > δ13C1. These three distinct clusters were also observed in the cross plotting of iC4/nC4 versus iC5/nC5 isomer ratios. This may imply that the kerogen is composed of three discrete structural domains which were progressively cracked at three major groups of maturity stages. The reverse trend was inconsistent with data for gas collected cumulatively in most prior pyrolysis experiments and the linear relationship predicted from kinetic isotope effect (KIE) model. Although the non-linear relationship or reverse trend, δ13C3 < δ13C2, was also reported for some natural gases, it was interpreted as a result of mixing from different source rocks or other processes. Our results, however, suggest that this non-linear relationship or reverse phenomenon can also be attributed to the mixing of gases generated from different maturity stages solely from a single source formation. Therefore, our results provide a new interpretation for the variation of isotope data of the cumulative and instantaneous gases in hydrous pyrolysis experiments and isotope variation in natural gas.

Relationship between Trophic Status and Methanogenic Pathways in Alaskan Peatlands

NASA Astrophysics Data System (ADS)

Zhang, L.; Liu, X.; Sidelinger, W.; Wang, Y.; Hines, M. E.; Langford, L.; Chanton, J.

2015-12-01

To improve predictions of naturally emitted CH4 from northern wetlands, it is necessary to further examine the methanogenic pathways in these wetlands. Stable isotope C ratios (δ13C) have been used as a robust tool to distinguish different pathways, but different sources of parent compounds (acetate and CO2) with unique δ13C may add complexity to previously established criteria. Large portions of peatlands accommodate a mixture of different sphagna and sedges. Plant species may look very similar and belong to the same genus but are different morphologically and physiologically. To better understand the relationships between surface vegetation patterns and methanogenic pathways, 26 peatland sites were studied in Fairbanks and Anchorage, Alaska in summers of 2014 and 2015. These sites were ordinated using multiple factor analysis into 3 clusters based on pH, temp, CH4 and volatile fatty acids production rates, δ13C values, and surface vegetation species/pattern. In the low-pH trophic cluster (pH~3.5), non-vascular/vascular plant ratios (NV/V) were ~ 0.87 and dominated by diverse Sphagnum species and specific sedges (Eriophorum vaginatum), and fermentation was the dominant end-point in decomposition with no CH4 detected. Although NV/V is about the same in the intermediate cluster (0.74) (pH~4.5), and Sphagnum squarrosum was largely present, both hydrogenotrophic (HM) and acetoclastic methanogenesis (AM) were very active. Syntrophy was present at certain sites, which may provide CO2 with unique δ13C for CH4 production. At the highest pH trophic cluster examined in this study (pH~5), non-vascular plants were almost not existent and Carex aquatilis dominated. CH4 production rates (mainly HM) were slower than those in the intermediate cluster and the apparent fractionation factor a was lower than in the sites with syntrophy, which warrants further investigation of the position and compound specific δ13C analysis of volatile fatty acids.

Hyperpolarized 13C NMR lifetimes in the liquid-state: relating structures and T1 relaxation times

NASA Astrophysics Data System (ADS)

Parish, Christopher; Niedbalski, Peter; Hashami, Zohreh; Fidelino, Leila; Kovacs, Zoltan; Lumata, Lloyd

Among the various attempts to solve the insensitivity problem in nuclear magnetic resonance (NMR), the physics-based technique dissolution dynamic nuclear polarization (DNP) is probably the most successful method of hyperpolarization or amplifying NMR signals. Using this technique, liquid-state NMR signal enhancements of several thousand-fold are expected for low-gamma nuclei such as carbon-13. The lifetimes of these hyperpolarized 13C NMR signals are directly related to their 13C spin-lattice relaxation times T1. Depending upon the 13C isotopic location, the lifetimes of hyperpolarized 13C compounds can range from a few seconds to minutes. In this study, we have investigated the hyperpolarized 13C NMR lifetimes of several 13C compounds with various chemical structures from glucose, acetate, citric acid, naphthalene to tetramethylallene and their deuterated analogs at 9.4 T and 25 deg C. Our results show that the 13C T1s of these compounds can range from a few seconds to more than 60 s at this field. Correlations between the chemical structures and T1 relaxation times will be discussed and corresponding implications of these results on 13C DNP experiments will be revealed. US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

Nature and kinetic analysis of carbon-carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds.

PubMed

Cho, Dae Won; Parthasarathi, Ramakrishnan; Pimentel, Adam S; Maestas, Gabriel D; Park, Hea Jung; Yoon, Ung Chan; Dunaway-Mariano, Debra; Gnanakaran, S; Langan, Paul; Mariano, Patrick S

2010-10-01

Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C-C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(β-1) and 1-aryl-2-aryloxy-(β-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the β-1 models take place more rapidly than those of the β-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the β-1 lignin model compounds are significantly lower than those of the β-O-4 models, providing clear evidence for the source of the rate differences.

Biomarker Evidence for Widespread Anaerobic Methane Oxidation in Mediterranean Sediments by a Consortium of Methanogenic Archaea and Bacteria†

PubMed Central

Pancost, Richard D.; Sinninghe Damsté, Jaap S.; de Lint, Saskia; van der Maarel, Marc J. E. C.; Gottschal, Jan C.

2000-01-01

Although abundant geochemical data indicate that anaerobic methane oxidation occurs in marine sediments, the linkage to specific microorganisms remains unclear. In order to examine processes of methane consumption and oxidation, sediment samples from mud volcanoes at two distinct sites on the Mediterranean Ridge were collected via the submersible Nautile. Geochemical data strongly indicate that methane is oxidized under anaerobic conditions, and compound-specific carbon isotope analyses indicate that this reaction is facilitated by a consortium of archaea and bacteria. Specifically, these methane-rich sediments contain high abundances of methanogen-specific biomarkers that are significantly depleted in 13C (δ13C values are as low as −95‰). Biomarkers inferred to derive from sulfate-reducing bacteria and other heterotrophic bacteria are similarly depleted. Consistent with previous work, such depletion can be explained by consumption of 13C-depleted methane by methanogens operating in reverse and as part a consortium of organisms in which sulfate serves as the terminal electron acceptor. Moreover, our results indicate that this process is widespread in Mediterranean mud volcanoes and in some localized settings is the predominant microbiological process. PMID:10698781

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

PubMed

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.

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

PubMed

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

2018-04-01

Isotope ratio monitoring by 13 C NMR spectrometry (irm- 13 C NMR) provides the complete 13 C 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 13 C natural abundance values (50‰), irm- 13 C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13 C NMR. Until now, the conventional strategy to determine the position-specific abundance x i relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13 C 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 13 C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1 H NMR pulse sequence (named DWET) with a 13 C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T 1 , which forms a serious limitation for irm- 13 C 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 T 1 variations. Their performance is evaluated on the determination of the 13 C 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- 13 C NMR since it is now possible to perform isotopic analysis with high relaxing agent concentrations, leading to a strong reduction of the overall experiment time. Copyright © 2018 Elsevier Inc. All rights reserved.

Catenanes: A molecular mechanics analysis of the (C13H26)2 Structure 13-13 D2.

PubMed

Lii, Jenn-Huei; Allinger, Norman L; Hu, Ching-Han; Schaefer, Henry F

2016-01-05

Molecular mechanics (MM4) studies have been carried out on the catenane (C13H26)2, specifically 13-13D2. The structure obtained is in general agreement with second-order perturbation theory. More importantly, the MM4 structure allows a breakdown of the energy of the molecule into its component classical parts. This allows an understanding of why the structure is so distorted, in terms of C-C bonding and nonbonding interactions, van der Waals repulsion, C-C-C and C-C-H angle bending, torsional energies, stretch-bend, torsion-stretch, and bend-torsion-bend interactions. Clearly, the hole in 113-membered ring is too small for the other ring to fit through comfortably. There are too many atoms trying to fit into the limited space at the same time, leading to large van der Waals repulsions. The rings distort in such a way as to enlarge this available space, and lower the total energy of the molecule. While the distortions are spread around the rings, one of the nominally tetrahedral C-C-C bond angles in each ring is opened to 147.9° by MM4 (146.8° by MP2). The stability of the compound is discussed in terms of the strain energy. © 2015 Wiley Periodicals, Inc.

Gas chromatographic/mass spectrometric determination of carbon isotope composition in unpurified samples: methamphetamine example.

PubMed

Low, I A; Liu, R H; Legendre, M G; Piotrowski, E G; Furner, R L

1986-10-01

A gas chromatograph/quadrupole mass spectrometer system, operated in electron impact/selected ion monitoring mode, is used to determine the intensity ratio of the m/z 59 and the m/z 58 ions of the [C3H8N]+ fragment derived from methamphetamine samples synthesized with varying amounts of 13C-labeled methylamine. Crude products are introduced into the gas chromatograph without prior cleanup. The ratios measured were in excellent agreement with those calculated. A change in 0.25% use of 13C-methylamine is sufficient for product differentiation. The feasibility of using isotope labeling and subsequent mass spectrometric isotope ratio measurement as the basis of a compound tracing mechanism is discussed. Specifically, if methamphetamine samples manufactured from legal sources are asked to incorporate distinct 13C compositions, their sources can be traced when samples are diverted into illegal channels. Samples derived from illicit preparations can also be traced if the manufacturers of a precursor (methylamine in this case) incorporate distinct 13C compositions in their products.

Analysis of polycyclic aromatic hydrocarbons extracted from air particulate matter using a temperature programmable injector coupled to GC-C-IRMS.

PubMed

Mikolajczuk, Agnieszka; Przyk, Elzbieta Perez; Geypens, Benny; Berglund, Michael; Taylor, Philip

2010-03-01

Compound specific isotopic analysis (CSIA) can provide information about the origin of analysed compounds - in this case, polycyclic aromatic hydrocarbons (PAHs). In the study, PAHs were extracted from three dust samples: winter and summer filter dust and tunnel dust. The measurement was performed using the method validated in our laboratory using pure, solid compounds and EPA 610 reference assortment. CSIA required an appropriate clean-up method to avoid an unresolved complex in the gas chromatographic analysis usually found in the chromatography of PAHs. Extensive sample clean-up for this particular matrix was found to be necessary to obtain good gas chromatography-combustion-isotope ratio mass spectrometry analysis results. The sample purification method included two steps in which the sample is cleaned up and the aliphatic and aromatic hydrocarbons are separated. The concentration of PAHs in the measured samples was low; so a large volume injection technique (100 microl) was applied. The delta(VPDB)(13)C was measured with a final uncertainty smaller than 1 per thousand. Comparison of the delta(VPDB)(13)C signatures of PAHs extracted from different dust samples was feasible with this method and, doing so, significant differences were observed.

Interaction of CO2 concentrations and water stress in semiarid plants causes diverging response in instantaneous water use efficiency and carbon isotope composition

NASA Astrophysics Data System (ADS)

Zhao, Na; Meng, Ping; He, Yabing; Yu, Xinxiao

2017-07-01

In the context of global warming attributable to the increasing levels of CO2, severe drought may be more frequent in areas that already experience chronic water shortages (semiarid areas). This necessitates research on the interactions between increased levels of CO2 and drought and their effect on plant photosynthesis. It is commonly reported that 13C fractionation occurs as CO2 gas diffuses from the atmosphere to the substomatal cavity. Few researchers have investigated 13C fractionation at the site of carboxylation to cytoplasm before sugars are exported outward from the leaf. This process typically progresses in response to variations in environmental conditions (i.e., CO2 concentrations and water stress), including in their interaction. Therefore, saplings of two typical plant species (Platycladus orientalis and Quercus variabilis) from semiarid areas of northern China were selected and cultivated in growth chambers with orthogonal treatments (four CO2 concentration ([CO2]) × five soil volumetric water content (SWC)). The δ13C of water-soluble compounds extracted from leaves of saplings was determined for an assessment of instantaneous water use efficiency (WUEcp) after cultivation. Instantaneous water use efficiency derived from gas-exchange measurements (WUEge) was integrated to estimate differences in δ13C signal variation before leaf-level translocation of primary assimilates. The WUEge values in P. orientalis and Q. variabilis both decreased with increased soil moisture at 35-80 % of field capacity (FC) and increased with elevated [CO2] by increasing photosynthetic capacity and reducing transpiration. Instantaneous water use efficiency (iWUE) according to environmental changes differed between the two species. The WUEge in P. orientalis was significantly greater than that in Q. variabilis, while an opposite tendency was observed when comparing WUEcp between the two species. Total 13C fractionation at the site of carboxylation to cytoplasm before sugar export (total 13C fractionation) was species-specific, as demonstrated in the interaction of [CO2] and SWC. Rising [CO2] coupled with moistened soil generated increasing disparities in δ13C between water-soluble compounds (δ13CWSC) and estimates based on gas-exchange observations (δ13Cobs) in P. orientalis, ranging between 0.0328 and 0.0472 ‰. Differences between δ13CWSC and δ13Cobs in Q. variabilis increased as [CO2] and SWC increased (0.0384-0.0466 ‰). The 13C fractionation from mesophyll conductance (gm) and post-carboxylation both contributed to the total 13C fractionation that was determined by δ13C of water-soluble compounds and gas-exchange measurements. Total 13C fractionation was linearly dependent on stomatal conductance, indicating that post-carboxylation fractionation could be attributed to environmental variation. The magnitude and environmental dependence of apparent post-carboxylation fractionation is worth our attention when addressing photosynthetic fractionation.

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

NASA Astrophysics Data System (ADS)

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 lignin to these bulk δ 13C values, and their potential for sequestration considered. References: Bol, R., Amelung, W., Friedrich, C. Ostle, N. (2000). Tracing dung-derived carbon in temperate grassland using 13C natural abundance measurements. Soil Biology and Biochemistry, 32, 1337-1343. Goering and Van Soest (1970). Forage fibre analysis (apparatus, reagents, procedures and some applications). In: USDA-ARS Agricultural Handbook, 379. U. S. Government Printing Office, Washington D.C. Docherty, G., Jones, V. and Evershed, R.P. (2001). Practical and theoretical considerations in the gas chromatography/combustion/isotope ratio mass spectrometry δ 13C analysis of small polyfunctional compounds. Rapid Communications in Mass Spectrometry, 15, 730-738. Poole, I. & van Bergen, P. F. (2002). Carbon isotope ratio analysis of organic moieties from fossil mummified wood: establishing optimum conditions for off-line pyrolysis extraction using gas chromatography/mass spectrometry. Rapid Communications in Mass Spectrometry, 16, 1976-1981. Dungait, J. A. J., Bol, R. and Evershed, R.P. (submitted). The Fate of Dung Carbon in Temperate Grassland Soil: 1. Preliminary Findings Based on Bulk Stable Carbon Isotope Determinations. Isotopes in Health and Environmental Studies

Molecular DYNAmics of Soil Organic carbon (DYNAMOS *): a project focusing on soils and carbon through data and modeling

NASA Astrophysics Data System (ADS)

Hatté, C.; Balesdent, J.; Derenne, S.; Derrien, D.; Dignac, M.; Egasse, C.; Ezat, U.; Gauthier, C.; Mendez-Millan, M.; Nguyen Tu, T.; Rumpel, C.; Sicre, M.; Zeller, B.

2009-12-01

Here we present the first results of the DynaMOS project whose main issue is the build-up of a new generation of soil carbon model. The modeling will describe together soil organic geochemistry and soil carbon dynamics in a generalized, quantitative representation. The carbon dynamics time scale envisaged here will cover the 1 to 1000 yr range and described molecules will be carbohydrate, peptide, amino acid, lignin, lipids, their products of biodegradation and uncharacterized carbonaceous species of biological origin. Three main characteristics define DYNAMOS model originalities: it will consider organic matter at the molecular scale, integrate back to global scale and account for component vertical movements. In a first step, specific data acquisition will concern the production, fate and age of carbon of individual organic compounds. Dynamic parameters will be acquired by compound-specific carbon isotope analysis of both 13C and 14C, by GC/C/IR-MS and AMS. Sites for data acquisition, model calibration and model validation will be chosen on the base of their isotopic history and environmental constraints: 13C natural labeling (with and without C3/C4 vegetation changes), 13C/15N-labelled litter application in both forest and cropland. They include some long-term experiments owned by the partners themselves plus a worldwide panel of sites. In a second step the depth distribution of organic species, isotopes and ages in soils (1D representation) will be modeled by coupling carbon dynamics and vertical movement. Besides the main objective of providing a robust soil carbon dynamics model, DYNAMOS will assess and model the alteration of the isotopic signature of molecules throughout decay and create a shared database of both already published and new data of compound specific information. Issues of the project will concern different scientific fields: global geochemical cycles by refining the description of the terrestrial carbon cycle and entering the chemical composition of organic matter in carbon models; forestry or agriculture by offering a chemical frame for the management of crop residues or organic wastes; geochronology, paleoecology and paleo climatology by modeling the alteration of isotope signature and the preservation of terrestrial biomarkers. (*) funded by the French National Agency of Research (ANR): ANR-07-Blan-0222-01, http://dynamos.lsce.ipsl.fr

Short-term dynamics and partitioning of newly assimilated carbon in the foliage of adult beech and pine are driven by seasonal variations

NASA Astrophysics Data System (ADS)

Desalme, Dorine; Priault, Pierrick; Gérant, Dominique; Dannoura, Masako; Maillard, Pascale; Plain, Caroline; Epron, Daniel

2017-04-01

Carbon (C) allocation is a key process determining C cycling in forest ecosystems. However, the mechanisms underlying the annual patterns of C partitioning in trees, influenced by tree phenology and environmental conditions, are not well identified yet. This study aimed to characterize the short-term dynamics and partitioning of newly assimilated carbon in the foliage of adult European beeches (Fagus sylvatica) and maritime pines (Pinus pinaster) across the seasons. We hypothesized that residence times of recently assimilated C in C compounds should change according to the seasons and that seasonal pattern should differ between deciduous and evergreen tree species, since they have different phenology. 13CO2 pulse-labelling experiments were performed in situ at different dates corresponding to different phenological stages. In beech leaves and pine needles, C contents, isotopic compositions, and 13C dynamics parameters were determined in total organic matter (bulk foliage), in polar fraction (PF, including soluble sugars, amino acids, organic acids) and in starch. For both species and at each phenological stage, 13C amount in bulk foliage decreased following a two-pool exponential model, highlighting the partitioning of newly assimilated C between 'mobile' and 'stable' pools. The relative proportion of the stable pool was maximal in beech leaves in May, when leaves were still growing and could incorporate newly assimilated C in structural C compounds. Young pine needles were still receiving C from previous-year needles in June (two months after budburst) although they are already photosynthesizing, acting as a strong C sink. In summer, short mean residence times of 13C (MRT) in foliage of both tree species reflected the fast respiration and exportation of recent photosynthates to support the whole tree C demand (e.g., supplying perennial organ growth). At the end of the growing season, pre-senescing beech leaves were supplying 13C to perennial organs, whereas overwintering pine needles accumulated labelled PF, probably to acclimate to colder winter temperatures. Results of this experiment revealed that the dynamics and the in-leaf partitioning of newly assimilated C varied seasonally according to the phenology of the two species. In the future, coupling 13C pulse labelling with compound-specific isotope analysis will be promising for tracing the allocation of newly assimilated C to various physiological functions such as growth, export, osmoregulation and defence in trees submitted to global changes.

Development of new method of δ13C measurement for trace hydrocarbons in natural gas using solid phase micro-extraction coupled to gas chromatography isotope ratio mass spectrometry.

PubMed

Li, Zhongping; Wang, Xibin; Li, Liwu; Zhang, Mingjie; Tao, Mingxin; Xing, Lantian; Cao, Chunhui; Xia, Yanqing

2014-11-01

Compound specific isotope analysis (CSIA) of normal-level hydrocarbons (C 1 -C 4 ) in natural gas is often successfully used in natural gas origin identification and classification, but little progress so far has been made for trace level hydrocarbons (C 5 -C 14 ) in natural gas. In this study, we developed a method for rapid analysis of carbon isotopic ratios for trace hydrocarbons in natural gas samples. This method can be described as a combined approach characterized by solid phase micro-extraction (SPME) technique coupled to gas chromatography isotope ratio mass spectrometry (GC/IRMS). In this study, the CAR-PDMS fiber was chosen as the SPME adsorptive material after comparative experiments with other four fibers, and the parameters, including equilibration time, extraction temperature and desorption time, for efficient extraction of trace hydrocarbons were systematically optimized. The results showed the carbon isotopic fractionation was not observed as a function of equilibration time and extraction temperature. And the δ 13 C signatures determined by SPME-GC/IRMS were in good agreement with the known δ 13 C values of C 5 -C 14 measured by GC-IRMS, and the accuracy is generally within ±0.5‰. Five natural gas samples were analyzed using this method, and the δ 13 C values for C 5 -C 14 components were obtained with satisfied repeatability. The SPME-GC/IRMS approach fitted with CAR-PDMS fiber is well suited for the preconcentration of trace hydrocarbons and provides so far the most reliable carbon isotopic analysis for trace compounds in natural gas. Published by Elsevier B.V.

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.

PubMed

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.

Synthesis of 13 C-labeled 5-Aminoimidazole-4-carboxamide-1-β-D-[13 C5 ] ribofuranosyl 5'-monophosphate.

PubMed

Zarkin, Allison K; Elkins, Phyllis D; Gilbert, Amanda; Jester, Teresa L; Seltzman, Herbert H

2018-06-14

5-Aminoimidazole-4-carboxamide-1-β-D-[ 13 C 5 ] ribofuranosyl 5'-monophosphate ([ 13 C 5 ribose] AICAR-PO 3 H 2 ) (6) has been synthesized from [ 13 C 5 ]adenosine. Incorporation of the mass-label into [ 13 C 5 ribose] AICAR-PO 3 H 2 provides a useful standard to aid in metabolite identification and quantification in monitoring metabolic pathways. A synthetic route to the 13 C-labeled compound has not been previously reported. Our method employs a hybrid enzymatic and chemical synthesis approach that applies an enzymatic conversion from adenosine to inosine followed by a ring-cleavage of the protected inosine. A direct phosphorylation of the resulting 2',3'-isopropylidine acadesine (5) was developed to yield the title compound in 99% purity following ion exchange chromatography. This article is protected by copyright. All rights reserved.

21 CFR 700.13 - Use of mercury compounds in cosmetics including use as skinbleaching agents in cosmetic...

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 7 2012-04-01 2012-04-01 false Use of mercury compounds in cosmetics including use as skinbleaching agents in cosmetic preparations also regarded as drugs. 700.13 Section 700.13...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.13 Use of mercury compounds in cosmetics...

21 CFR 700.13 - Use of mercury compounds in cosmetics including use as skinbleaching agents in cosmetic...

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 7 2013-04-01 2013-04-01 false Use of mercury compounds in cosmetics including use as skinbleaching agents in cosmetic preparations also regarded as drugs. 700.13 Section 700.13...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.13 Use of mercury compounds in cosmetics...

21 CFR 700.13 - Use of mercury compounds in cosmetics including use as skinbleaching agents in cosmetic...

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 7 2014-04-01 2014-04-01 false Use of mercury compounds in cosmetics including use as skinbleaching agents in cosmetic preparations also regarded as drugs. 700.13 Section 700.13...) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.13 Use of mercury compounds in cosmetics...

High-Precision Measurement of 13C/12C Isotopic Ratio Using Gas Chromatography-Combustion-Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Saad, N.; Kuramoto, D. S.; Haase, C.; Crosson, E.; Tan, S.; Zare, R. N.

2009-12-01

Light stable isotope analysis, and in particular, compound specific isotopic analysis (CSIA), is a valuable tool to elucidate pathways and provide a better insight into biological, ecological, and geological systems. We present here the results of compound-specific isotopic carbon analysis of short chain hydrocarbons using the world’s first combination of gas chromatography, combustion interface, and cavity ring-down spectroscopy (GC-C-CRDS). Cavity ring-down spectroscopy (CRDS) is a highly sensitive optical spectroscopy, one application of which is to measure the stable isotopic ratios in small molecules. Because it uses a highly reflective optical cavity with many kilometers effective path length, CRDS provides some of the most sensitive and precise optical absorption measurements. Most optical spectroscopy isotopic analysis measures the quantities of each isotopologue independently using their distinct ro-vibrational spectra. The most common isotopes measured with optical spectroscopy are 13C and 12C in carbon dioxide. However, the isotopes of hydrogen, oxygen, and sulfur have also been measured. Unlike isotope ratio mass spectrometry (IRMS), optical spectroscopy can distinguish among isobars, which have essentially identical m/z ratios. The combination of chemical separation, chemical conversion, and CRDS makes a nearly universal tool for isotopic analysis of mixtures. In addition, CRDS can tolerate a variety of compounds mixed with the target. For example, CRDS can measure carbon dioxide and its isotopic 13C/12C ratio in the presence of oxygen. Using the novel GC-C-CRDS system, we injected a 75-microliter mixture of approximately equal quantities of methane, ethane, and propane into a gas chromatograph using helium as carrier gas. The methane, ethane, and propane were separated in time by 100 to 200 seconds after the chromatograph. Oxygen gas was added, and the hydrocarbons were combusted in a catalytic combustor with platinum and nickel, held at 1150oC. The combusted products were combined with dry nitrogen gas to provide sufficient gas flow for the CRDS analyzer, which measured the 13C/12C isotopic ratio of the separated methane, ethane, and propane, obtaining a precision of 0.95 permil or better. The calibration accuracy was within 3 permil of the values determined using IRMS. The current CRDS-based system is less expensive, does not require highly trained personnel to operate, and is portable, compared with IRMS. We anticipate that advances in spectroscopic analysis will improve the precision and accuracy of the CRDS isotopic measurement, making it comparable with IRMS.

Malate as a key carbon source of leaf dark-respired CO2 across different environmental conditions in potato plants

PubMed Central

Lehmann, Marco M.; Rinne, Katja T.; Blessing, Carola; Siegwolf, Rolf T. W.; Buchmann, Nina; Werner, Roland A.

2015-01-01

Dissimilation of carbon sources during plant respiration in support of metabolic processes results in the continuous release of CO2. The carbon isotopic composition of leaf dark-respired CO2 (i.e. δ 13 C R) shows daily enrichments up to 14.8‰ under different environmental conditions. However, the reasons for this 13C enrichment in leaf dark-respired CO2 are not fully understood, since daily changes in δ13C of putative leaf respiratory carbon sources (δ 13 C RS) are not yet clear. Thus, we exposed potato plants (Solanum tuberosum) to different temperature and soil moisture treatments. We determined δ 13 C R with an in-tube incubation technique and δ 13 C RS with compound-specific isotope analysis during a daily cycle. The highest δ 13 C RS values were found in the organic acid malate under different environmental conditions, showing less negative values compared to δ 13 C R (up to 5.2‰) and compared to δ 13 C RS of soluble carbohydrates, citrate and starch (up to 8.8‰). Moreover, linear relationships between δ 13 C R and δ 13 C RS among different putative carbon sources were strongest for malate during daytime (r2=0.69, P≤0.001) and nighttime (r2=0.36, P≤0.001) under all environmental conditions. A multiple linear regression analysis revealed δ 13 C RS of malate as the most important carbon source influencing δ 13 C R. Thus, our results strongly indicate malate as a key carbon source of 13C enriched dark-respired CO2 in potato plants, probably driven by an anapleurotic flux replenishing intermediates of the Krebs cycle. PMID:26139821

Molecular Dynamics Simulations to Determine the Structure and Dynamics of Hepatitis B Virus Capsid Bound to a Novel Anti-viral Drug.

PubMed

Watanabe, Go; Sato, Shunsuke; Iwadate, Mitsuo; Umeyama, Hideaki; Hayakawa, Michiyo; Murakami, Yoshiki; Yoneda, Shigetaka

2016-01-01

Hepatitis B virus (HBV) chronically infects millions of people worldwide and is a major cause of serious liver diseases, including liver cirrhosis and liver cancer. In our previous study, in silico screening was used to isolate new anti-viral compounds predicted to bind to the HBV capsid. Four of the isolated compounds have been reported to suppress the cellular multiplication of HBV experimentally. In the present study, molecular dynamics simulations of the HBV capsid were performed under rotational symmetry boundary conditions, to clarify how the structure and dynamics of the capsid are affected at the atomic level by the binding of one of the isolated compounds, C13. Two simulations of the free HBV capsid, two further simulations of the capsid-C13 complex, and one simulation of the capsid-AT-130 complex were performed. For statistical confidence, each set of simulations was repeated by five times, changing the simulation conditions. C13 continued to bind at the predicted binding site during the simulations, supporting the hypothesis that C13 is a capsid-binding compound. The structure and dynamics of the HBV capsid were greatly influenced by the binding and release of C13, and these effects were essentially identical to those seen for AT-130, indicating that C13 likely inhibits the function of the HBV capsid.

From Position-Specific Labeling to Environmental Fluxomics: Elucidating Biogeochemical Cycles from the Metabolic Perspective (BG Division Outstanding ECS Award Lecture)

NASA Astrophysics Data System (ADS)

Dippold, Michaela; Apostel, Carolin; Dijkstra, Paul; Kuzyakov, Yakov

2017-04-01

Understanding soil and sedimentary organic matter (SOM) dynamics is one of the most important challenges in biogeoscience. To disentangle the fluxes and transformations of C in soils a detailed knowledge on the biochemical pathways and its controlling factors is required. Biogeochemists' view on the C transformation of microorganisms in soil has rarely exceed a strongly simplified concept assuming that C gets either oxidized to CO2 via the microbial catabolism or incorporated into biomass via the microbial anabolism. Biochemists, however, thoroughly identified in the past decades the individual reactions of glycolysis, pentose-phosphate pathway and citric acid cycle underlying the microbial catabolism. At various points within that metabolic network the anabolic fluxes feeding biomass formation branch off. Recent studies on metabolic flux tracing by position-specific isotope labeling allowed tracing these C transformations in soils in situ, an approach which is qunatitatively complemented by metabolic flux modeling. This approach has reached new impact by the cutting-edge combination of position-specific 13C labeling with compound-specific isotope analysis of microbial biomarkers and metabolites which allows 1) tracing specific anabolic pathways in diverse microbial communities in soils and 2) identification of specific pathways of individual functional microbial groups. Thus, the combination of position-specific labeling, compound-specific isotope incorporation in biomarkers and quantitative metabolic flux modelling provide the toolbox for quantitative soil fluxomics. Our studies combining position-specific labeled glucose with amino sugar 13C analysis showed that up to 55% of glucose, incorporated into the glucose derivative glucosamine, first passed glycolysis before allocated back via gluconeogenesis. Similarly, glutamate-derived C is allocated via anaplerotic pathways towards fatty acid synthesis and in parallel to its oxidation in citric acid cycle. Thus, oxidizing catabolic pathways and anabolic pathways, i.e. building-up new cellular compounds, occurred in soils simultaneously, a combination unlikely to occur in pure cultures, where constant growth conditions under high C supply allow a straight unidirectional regulation of C metabolism. However, unstable environmental conditions, C scarcity and interactions between a still unknown diversity of microorganisms in soils are likely to induce the observed metabolic diversity. Coupling these results with the position-specific fingerprint of microbial biomarkers revealed that microbial groups show deviating adaptation strategies and that they react on environmental changes by activation or deactivation of specific metabolic pathways such as anaplerotic fluxes. To understand how microorganisms catalyze the biogeochemical fluxes in soil a profound understanding of their metabolic adaptation strategies such as recycling or switching between pathways is crucial. Metabolic flux models adapted to soil microbial communities and their regulatory strategies will not only deepen our understanding on the microorganims' reactions to environmental changes but also create the prerequisits for a quantitative prediction of biogeochemical fluxes based on the underlying microbial processes.

Quinone-based stable isotope probing for assessment of 13C substrate-utilizing bacteria

NASA Astrophysics Data System (ADS)

Kunihiro, Tadao; Katayama, Arata; Demachi, Toyoko; Veuger, Bart; Boschker, Henricus T. S.; van Oevelen, Dick

2015-04-01

In this study, we attempted to establish quinone-stable-isotope probing (SIP) technique to link substrate-utilizing bacterial group to chemotaxonomic group in bacterial community. To identify metabolically active bacterial group in various environments, SIP techniques combined with biomarkers have been widely utilized as an attractive method for environmental study. Quantitative approaches of the SIP technique have unique advantage to assess substrate-incorporation into bacteria. As a most major quantitative approach, SIP technique based on phospholipid-derived fatty acids (PLFA) have been applied to simultaneously assess substrate-incorporation rate into bacteria and microbial community structure. This approach is powerful to estimate the incorporation rate because of the high sensitivity due to the detection by a gas chromatograph-combustion interface-isotope ratio mass spectrometer (GC-c-IRMS). However, its phylogenetic resolution is limited by specificity of a compound-specific marker. We focused on respiratory quinone as a biomarker. Our previous study found a good correlation between concentrations of bacteria-specific PLFAs and quinones over several orders of magnitude in various marine sediments, and the quinone method has a higher resolution (bacterial phylum level) for resolving differences in bacterial community composition more than that of bacterial PLFA. Therefore, respiratory quinones are potentially good biomarkers for quantitative approaches of the SIP technique. The LC-APCI-MS method as molecular-mass based detection method for quinone was developed and provides useful structural information for identifying quinone molecular species in environmental samples. LC-MS/MS on hybrid triple quadrupole/linear ion trap, which enables to simultaneously identify and quantify compounds in a single analysis, can detect high molecular compounds with their isotope ions. Use of LC-MS/MS allows us to develop quinone-SIP based on molecular mass differences due to 13C abundance in the quinone. In this study, we verified carbon stable isotope of quinone compared with bulk carbon stable isotope of bacterial culture. Results indicated a good correlation between carbon stable isotope of quinone compared with bulk carbon stable isotope. However, our measurement conditions for detection of quinone isotope-ions incurred underestimation of 13C abundance in the quinone. The quinone-SIP technique needs further optimization for measurement conditions of LC-MS/MS.

Contribution of microorganisms to non-extractable residue formation from biodegradable organic contaminants in soil

NASA Astrophysics Data System (ADS)

Nowak, K. M.; Girardi, C.; Miltner, A.; Schäffer, A.; Kästner, M.

2012-04-01

Biodegradation of organic contaminants in soil is actually understood as their transformation into various primary metabolites, microbial biomass, mineralisation products and non-extractable residues (NER). NER are generally considered to be composed of parent compounds or primary metabolites with hazardous potential. Up to date, however, their chemical composition remains still unclear. Studies on NER formation are limited to quantitative analyses in soils or to simple humic acids-contaminant systems. However, in the case of biodegradable organic compounds, NER may also contain microbial biomass components, e.g. fatty acids (FA) and amino acids (AA). After cell death, these biomolecules are incorporated into soil organic matter (SOM) and stabilised, ultimately forming biogenic residues which are not any more extractable. We investigated the incorporation of the 13C-label into FA and AA and their fate during biodegradation experiments in soil with isotope-labelled 2,4-dichlorophenoxyacetic acid (13C6-2,4-D) and ibuprofen (13C6-ibu) as model organic contaminants. Our study proved for the first time that nearly all NER formed from 13C6-2,4-D and 13C6-ibu in soil derived from harmless microbial biomass components stabilised in SOM. 13C-FA and 13C-AA contents in the living microbial biomass fraction decreased over time and these components were continuously incorporated into the non-living SOM pool in biotic experiments with 13C6-2,4-D and 13C6-ibu. The 13C-AA in the non-living SOM were surprisingly stable from day 32 (13C6-2,4-D) and 58 (13C6-ibu) until the end of incubation. We also studied the transformation of 13C6-2,4-D and 13C6-ibu into NER in the abiotic soil experiments. In these experiments, the total NER contents were much lower than in the corresponding biotic experiments. The absence of labelled biomolecules in the NER fraction in abiotic soils demonstrated that they consist of the potentially hazardous parent compounds and / or their metabolites. Biogenic residue formation is relevant during biodegradation of organic contaminants, whereas abiotic NER are formed from the non-biodegraded residual contaminants. Abiotic NER and biogenic residue formation are competitive processes and do not occur in a similar extent. In the biotic treatment, the rapid mineralisation of an organic compound reduces the extent of abiotic NER formation via physico-chemical interactions between a parent compound and / or its primary metabolites with SOM. Therefore, in order to properly assess the potential risks of a target contaminant in soil to humans and the environment, it is necessary to distinguish between abiotic NER and biogenic residue formation in the mass balances of contaminants.

Chemical and isotopic composition of secondary organic aerosol generated by α-pinene ozonolysis

NASA Astrophysics Data System (ADS)

Meusinger, Carl; Dusek, Ulrike; King, Stephanie M.; Holzinger, Rupert; Rosenørn, Thomas; Sperlich, Peter; Julien, Maxime; Remaud, Gerald S.; Bilde, Merete; Röckmann, Thomas; Johnson, Matthew S.

2017-05-01

Secondary organic aerosol (SOA) plays a central role in air pollution and climate. However, the description of the sources and mechanisms leading to SOA is elusive despite decades of research. While stable isotope analysis is increasingly used to constrain sources of ambient aerosol, in many cases it is difficult to apply because neither the isotopic composition of aerosol precursors nor the fractionation of aerosol forming processes is well characterised. In this paper, SOA formation from ozonolysis of α-pinene - an important precursor and perhaps the best-known model system used in laboratory studies - was investigated using position-dependent and average determinations of 13C in α-pinene and advanced analysis of reaction products using thermal-desorption proton-transfer-reaction mass spectrometry (PTR-MS). The total carbon (TC) isotopic composition δ13C of the initial α-pinene was measured, and the δ13C of the specific carbon atom sites was determined using position-specific isotope analysis (PSIA). The PSIA analysis showed variations at individual positions from -6.9 to +10. 5 ‰ relative to the bulk composition. SOA was formed from α-pinene and ozone in a constant-flow chamber under dark, dry, and low-NOx conditions, with OH scavengers and in the absence of seed particles. The excess of ozone and long residence time in the flow chamber ensured that virtually all α-pinene had reacted. Product SOA was collected on two sequential quartz filters. The filters were analysed offline by heating them stepwise from 100 to 400 °C to desorb organic compounds that were (i) detected using PTR-MS for chemical analysis and to determine the O : C ratio, and (ii) converted to CO2 for 13C analysis. More than 400 ions in the mass range 39-800 Da were detected from the desorbed material and quantified using a PTR-MS. The largest amount desorbed at 150 °C. The O : C ratio of material from the front filter increased from 0.18 to 0.25 as the desorption temperature was raised from 100 to 250 °C. At temperatures above 250 °C, the O : C ratio of thermally desorbed material, presumably from oligomeric precursors, was constant. The observation of a number of components that occurred across the full range of desorption temperatures suggests that they are generated by thermal decomposition of oligomers. The isotopic composition of SOA was more or less independent of desorption temperature above 100 °C. TC analysis showed that SOA was enriched in 13C by 0.6-1.2 ‰ relative to the initial α-pinene. According to mass balance, gas-phase products will be depleted relative to the initial α-pinene. Accordingly, organic material on the back filters, which contain adsorbed gas-phase compounds, is depleted in 13C in TC by 0.7 ‰ relative to the initial α-pinene, and by 1.3 ‰ compared to SOA collected on the front filter. The observed difference in 13C between the gas and particle phases may arise from isotope-dependent changes in the branching ratios in the α-pinene + O3 reaction. Alternatively, some gas-phase products involve carbon atoms from highly enriched and depleted sites, as shown in the PSIA analysis, giving a non-kinetic origin to the observed fractionations. In either case, the present study suggests that the site-specific distribution of 13C in the source material itself governs the abundance of 13C in SOA.

Production of isotopically labeled standards from a uniformly labeled precursor for quantitative volatile metabolomic studies.

PubMed

Gómez-Cortés, Pilar; Brenna, J Thomas; Sacks, Gavin L

2012-06-19

Optimal accuracy and precision in small-molecule profiling by mass spectrometry generally requires isotopically labeled standards chemically representative of all compounds of interest. However, preparation of mixed standards from commercially available pure compounds is often prohibitively expensive and time-consuming, and many labeled compounds are not available in pure form. We used a single-prototype uniformly labeled [U-(13)C]compound to generate [U-(13)C]-labeled volatile standards for use in subsequent experimental profiling studies. [U-(13)C]-α-Linolenic acid (18:3n-3, ALA) was thermally oxidized to produce labeled lipid degradation volatiles which were subsequently characterized qualitatively and quantitatively. Twenty-five [U-(13)C]-labeled volatiles were identified by headspace solid-phase microextraction-gas chromatography/time-of-flight mass spectrometry (HS-SPME-GC/TOF-MS) by comparison of spectra with unlabeled volatiles. Labeled volatiles were quantified by a reverse isotope dilution procedure. Using the [U-(13)C]-labeled standards, limits of detection comparable to or better than those of previous HS-SPME reports were achieved, 0.010-1.04 ng/g. The performance of the [U-(13)C]-labeled volatile standards was evaluated using a commodity soybean oil (CSO) oxidized at 60 °C from 0 to 15 d. Relative responses of n-decane, an unlabeled internal standard otherwise absent from the mixture, and [U-(13)C]-labeled oxidation products changed by up to 8-fold as the CSO matrix was oxidized, demonstrating that reliance on a single standard in volatile profiling studies yields inaccurate results due to changing matrix effects. The [U-(13)C]-labeled standard mixture was used to quantify 25 volatiles in oxidized CSO and low-ALA soybean oil with an average relative standard deviation of 8.5%. Extension of this approach to other labeled substrates, e.g., [U-(13)C]-labeled sugars and amino acids, for profiling studies should be feasible and can dramatically improve quantitative results compared to use of a single standard.

Isolation of furocoumarins from bergamot fruits as HL-60 differentiation-inducing compounds.

PubMed

Kawaii, S; Tomono, Y; Katase, E; Ogawa, K; Yano, M

1999-10-01

The HL-60 differentiation-inducing compounds in bergamot fruits were isolated with column chromatography and identified as bergamottin, bergapten, and citropten by (1)H and (13)C NMR. Their HL-60 differentiation-inducing activity was measured by examining nitro blue tetrazolium (NBT) reducing, nonspecific acid esterase (NSE), specific esterase (SE), and phagocytic activities, and bergamottin showed the strongest activity among the coumarins isolated from bergamot fruits. The structure-activity relationship obtained from HL-60 differentiation assay suggests that hydrophobicity of furocoumarins is correlated with their activity.

Quantitative sediment source attribution with compound-specific isotope analysis in a C3 plant-dominated catchment (central Switzerland)

NASA Astrophysics Data System (ADS)

Alewell, Christine; Birkholz, Axel; Meusburger, Katrin; Schindler Wildhaber, Yael; Mabit, Lionel

2016-03-01

As sediment loads impact freshwater systems and infrastructure, their origin in complex landscape systems is of crucial importance for sustainable management of agricultural catchments. We differentiated the sediment source contribution to a lowland river in central Switzerland by using compound-specific isotope analysis (CSIA). We found a clear distinction of sediment sources originating from forest and agricultural land use. Our results demonstrate that it is possible to reduce the uncertainty of sediment source attribution in: (i) using compound content (in our case, long-chain fatty acids; FAs) rather than soil organic matter content to transfer δ13C signal of FAs to soil contribution and (ii) restricting the investigation to the long-chain FAs (> C22 : 0) not to introduce errors due to aquatic contributions from algae and microorganisms. Results showed unambiguously that during base flow, agricultural land contributed up to 65 % of the suspended sediments, while forest was the dominant sediment source during high flow. This indicates that connectivity of sediment source areas within the river changes between base and high flow conditions. Uncertainty, which might occur in complex, large-scale studies due to undetected source attribution and/or CSSI signature degradation, is low because of limited data complexity in our study (i.e., two-three sources and two tracers). Our findings are the first published results highlighting (i) significant differences in compound-specific stable isotope (CSSI) signature of sediment sources from land uses dominated by C3 plant cultivation and (ii) the use of these differences to quantify sediment contribution to a small river.

Structural relationship of curcumin derivatives binding to the BRCT domain of human DNA polymerase lambda.

PubMed

Takeuchi, Toshifumi; Ishidoh, Tomomi; Iijima, Hiroshi; Kuriyama, Isoko; Shimazaki, Noriko; Koiwai, Osamu; Kuramochi, Kouji; Kobayashi, Susumu; Sugawara, Fumio; Sakaguchi, Kengo; Yoshida, Hiromi; Mizushina, Yoshiyuki

2006-03-01

We previously reported that phenolic compounds, petasiphenol and curcumin (diferuloylmethane), were a selective inhibitor of DNA polymerase lambda (pol lambda) in vitro. The purpose of this study was to investigate the molecular structural relationship of curcumin and 13 chemically synthesized derivatives of curcumin. The inhibitory effect on pol lambda (full-length, i.e. intact pol lambda including the BRCA1 C- terminal [BRCT] domain) by some derivatives was stronger than that by curcumin, and monoacetylcurcumin (compound 13) was the strongest pol lambda inhibitor of all the compounds tested, achieving 50% inhibition at a concentration of 3.9 microm. The compound did not influence the activities of replicative pols such as alpha, delta, and epsilon. It had no effect on pol beta activity either, although the three-dimensional structure of pol beta is thought to be highly similar to that of pol lambda. Compound 13 did not inhibit the activity of the C-terminal catalytic domain of pol lambda including the pol beta-like core, in which the BRCT motif was deleted from its N-terminal region. MALDI-TOF MS analysis demonstrated that compound 13 bound selectively to the N-terminal domain of pol lambda, but did not bind to the C-terminal region. Based on these results, the pol lambda-inhibitory mechanism of compound 13 is discussed.

Preparation of Mo-Re-C samples containing Mo{sub 7}Re{sub 13}C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oh-ishi, Katsuyoshi, E-mail: oh-ishi@kc.chuo-u.ac.jp; Nagumo, Kenta; Tateishi, Kazuya

Mo-Re-C compounds containing Mo{sub 7}Re{sub 13}C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo{sub 7}Re{sub 13}C with the β-Mn structure using the solid state method. Almost single-phase Mo{sub 7}Re{sub 13}C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with amore » pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K. - Graphical abstract: Temperature dependence of the magnetic susceptibility measured under 10 Oe for the superconducting PBM-T samples without Fe element and non-superconducting PBM-S with Fe element. The inset is the enlarged view of the data for the PBM-S sample.« less

X-ray study of the hetero ring flexibility in 5,6-tri-, 5,6-tetra- and 5,6-penta-methylene-2,3,5,6-tetrahydro-1,3-oxazin-4-ones. The structures of 2-spiropentamethylene- cis-5,6-tetramethylene-2,3,5,6-tetrahydro-1,3-oxazin-4-one (I), 2-spiropentamethylene- cis-5,6-pentamethylene-2,3,5,6-tetrahydro-1,3-oxazin-4-one ( c-II) and 2-spiropentamethylene- trans-5,6-pentamethylene-2,3,5,6-tetrahydro-1,3-oxazin-4-one ( t-II)

NASA Astrophysics Data System (ADS)

Ribár, B.; Kapor, Á.; Kálmán, A.; Argay, Gy.; Fülöp, F.; Bernáth, G.

1989-01-01

The structures of the title compounds were established by X-ray crystallography by means of direct methods. Crystals of compound I (C 12H 19NO 2) are monoclinic, space group P2 1/ n, with a = 11.365(3), b = 10.343(4), c = 10.343(2) Å, β = 110.25(3)°, Z = 4 and Dc = 1.218 g cm -3. Crystals of compound c- II (C 13H 21NO 2) are monoclinic, space group C2/ c, with a = 20.830(8), b = 6.594(4), c = 17.944(8) Å, β = 95.83(2)°, Z = 8 and Dc = 1.209 g cm -3. Crystals of t- II (C 13H 21NO 2) are also monoclinic, space group P2 1/ n, with a = 14.268(4), b = 6.112(3), c = 14.041(7) Å, β = 93.63(3)°, Z = 4 and Dc = 1.210 g cm -3. The structures were refined to R = 0.059 for 1697 reflections of I, R = 0.052 for 1718 reflections of c- II, and R = 0.057 for 2178 reflections of t- II. The conformations of the 1,3-oxazin-4-one moieties in the title compounds were compared with those found earlier in related compounds. As shown by an analysis of the puckering parameters (D. Cremer and J.A. Pople, J. Am. Chem. Soc., 97 (1975) 1354), they cluster in a random distribution around the 1H 6 half-chair form. Marked deviation from this canonical form towards the 1E envelope was observed only under the influence of the cyclopentane ring.

Olive oil or lard?: distinguishing plant oils from animal fats in the archeological record of the eastern Mediterranean using gas chromatography/combustion/isotope ratio mass spectrometry.

PubMed

Steele, Valerie J; Stern, Ben; Stott, Andy W

2010-12-15

Distinguishing animal fats from plant oils in archaeological residues is not straightforward. Characteristic plant sterols, such as β-sitosterol, are often missing in archaeological samples and specific biomarkers do not exist for most plant fats. Identification is usually based on a range of characteristics such as fatty acid ratios, all of which indicate that a plant oil may be present, none of which uniquely distinguish plant oils from other fats. Degradation and dissolution during burial alter fatty acid ratios and remove short-chain fatty acids, resulting in degraded plant oils with similar fatty acid profiles to other degraded fats. Compound-specific stable isotope analysis of δ(13)C(18:0) and δ(13)C(16:0), carried out by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), has provided a means of distinguishing fish oils, dairy fats, ruminant and non-ruminant adipose fats, but plant oils are rarely included in these analyses. For modern plant oils where C(18:1) is abundant, δ(13)C(18:1) and δ(13)C(16:0) are usually measured. These results cannot be compared with archaeological data or data from other modern reference fats where δ(13)C(18:0) and δ(13)C(16:0) are measured, as C(18:0) and C(18:1) are formed by different processes resulting in different isotopic values. Eight samples of six modern plant oils were saponified, releasing sufficient C(18:0) to measure the isotopic values, which were plotted against δ(13)C(16:0). The isotopic values for these oils, with one exception, formed a tight cluster between ruminant and non-ruminant animal fats. This result complicates the interpretation of mixed fatty residues in geographical areas where both animal fats and plant oils were in use. Copyright © 2010 John Wiley & Sons, Ltd.

Synthesis of chiral chloroquine and its analogues as antimalarial agents.

PubMed

Sinha, Manish; Dola, Vasanth R; Soni, Awakash; Agarwal, Pooja; Srivastava, Kumkum; Haq, Wahajul; Puri, Sunil K; Katti, Seturam B

2014-11-01

In this investigation, we describe a new approach to chiral synthesis of chloroquine and its analogues. All tested compounds displayed potent activity against chloroquine sensitive as well as chloroquine resistant strains of Plasmodium falciparum in vitro and Plasmodium yoelii in vivo. Compounds S-13 b, S-13c, S-13 d and S-13 i displayed excellent in vitro antimalarial activity with an IC50 value of 56.82, 60.41, 21.82 and 7.94 nM, respectively, in the case of resistant strain. Furthermore, compounds S-13a, S-13c and S-13 d showed in vivo suppression of 100% parasitaemia on day 4 in the mouse model against Plasmodium yoelii when administered orally. These results underscore the application of synthetic methodology and need for further lead optimization. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

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.

Synthesis and biological evaluation of novel 6-hydroxy-benzo[d][1,3]oxathiol-2-one Schiff bases as potential anticancer agents.

PubMed

Chazin, Eliza de Lucas; Sanches, Paola de Souza; Lindgren, Eric Brazil; Vellasco Júnior, Walcimar Trindade; Pinto, Laine Celestino; Burbano, Rommel Mario Rodríguez; Yoneda, Julliane Diniz; Leal, Kátia Zaccur; Gomes, Claudia Regina Brandão; Wardell, James Lewis; Wardell, Solange Maria Silva Veloso; Montenegro, Raquel Carvalho; Vasconcelos, Thatyana Rocha Alves

2015-01-27

With the aim of discovering new anticancer agents, we have designed and synthesized novel 6-hydroxy-benzo[d][1,3]oxathiol-2-one Schiff bases. The synthesis started with the selective nitration at 5-position of 6-hydroxybenzo[d][1,3]oxathiol-2-one (1) leading to the nitro derivative 2. The nitro group of 2 was reduced to give the amino intermediate 3. Schiff bases 4a-r were obtained from coupling reactions between 3 and various benzaldehydes and heteroaromatic aldehydes. All the new compounds were fully identified and characterized by NMR (1H and 13C) and specifically for 4q by X-ray crystallography. The in vitro cytotoxicity of the compounds was evaluated against cancer cell lines (ACP-03, SKMEL-19 and HCT-116) by using MTT assay. Schiff bases 4b and 4o exhibited promising cytotoxicity against ACP-03 and SKMEL-19, respectively, with IC50 values lower than 5 μM. This class of compounds can be considered as a good starting point for the development of new lead molecules in the fight against cancer.

Tree-ring cellulose exhibits several distinct intramolecular 13C signals

NASA Astrophysics Data System (ADS)

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

2017-04-01

Stable carbon isotopes are a key tool in biogeosciences. Present applications including compound-specific isotope analysis measure 13C/12C ratios (δ13C) of bulk material or of whole molecules. However, it is well known that primary metabolites also show large intramolecular 13C variation - also called isotopomer variation. This variation reflects 13C fractionation by enzyme reactions and therefore encodes metabolic information. Furthermore, δ13C must be considered an average of the intramolecular 13C distribution. Here we will present (1) methodology to analyse intramolecular 13C distributions of tree-ring cellulose by quantitative 13C NMR (Chaintreau et al., 2013, Anal Chim Acta, 788, 108-113); (2) intramolecular 13C distributions of an annually-resolved tree ring chronology (Pinus nigra, 1961-1995); (3) isotope parameters and terminology for analysis of intramolecular isotope time series; (4) a method for correcting for heterotrophic C redistribution. We will show that the intramolecular 13C distribution of tree-ring cellulose shows large variation, with differences between isotopomers exceeding 10‰Ṫhus, individual 13C isotopomers of cellulose constitute distinct 13C inputs into major global C pools such as wood and soil organic matter. When glucose units with the observed intramolecular 13C pattern are broken down along alternative catabolic pathways, it must be expected that respired CO2 with strongly differing δ13C will be released; indicating that intramolecular 13C variation affects isotope signals of atmosphere-biosphere C exchange fluxes. taking this variation into account will improve modelling of the global C cycle. Furthermore, cluster analysis shows that tree-ring glucose exhibits several independent intramolecular 13C signals, which constitute distinct ecophysiological information channels. Thus, whole-molecule 13C analysis likely misses a large part of the isotope information stored in tree rings. As we have shown for deuterium (Ehlers et al., 2015, PNAS, 112, 15585), intramolecular isotope signals allow tracing plant acclimation over centuries, and intramolecular 13C distributions will also improve our understanding of 13C signatures of global C fluxes.

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

PubMed

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.

Penialidins A-C with strong antibacterial activities from Penicillium sp., an endophytic fungus harboring leaves of Garcinia nobilis.

PubMed

Jouda, Jean-Bosco; Kusari, Souvik; Lamshöft, Marc; Mouafo Talontsi, Ferdinand; Douala Meli, Clovis; Wandji, Jean; Spiteller, Michael

2014-10-01

Three new polyketides named penialidins A-C (1-3), along with one known compound, citromycetin (4), were isolated from an endophytic fungus, Penicillium sp., harbored in the leaves of the Cameroonian medicinal plant Garcinia nobilis. Their structures were elucidated by means of spectroscopic and spectrometric methods (NMR and HRMS(n)). The antibacterial efficacies of the new compounds (1-3) were tested against the clinically-important risk group 2 (RG2) bacterial strains of Staphylococcus aureus and Escherichia coli. The ecologically imposing strains of E. coli (RG1), Bacillus subtilis and Acinetobacter sp. BD4 were also included in the assay. Compound 3 exhibited pronounced activity against the clinically-relevant S. aureus as well as against B. subtilis comparable to that of the reference standard (streptomycin). Compound 2 was also highly-active against S. aureus. By comparing the structures of the three new compounds (1-3), it was revealed that altering the substitutions at C-10 and C-2 can significantly increase the antibacterial activity of 1. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer.

PubMed

Spence, Michael J; Bottrell, Simon H; Thornton, Steven F; Richnow, Hans H; Spence, Keith H

2005-09-01

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.

A comparison of freeze-drying and oven-drying preparation methods for bulk and compound-specific carbon stable isotope analyses: examples using the benthic macroinvertebrates Stenopsyche marmorata and Epeorus latifolium.

PubMed

Akamatsu, Fumikazu; Suzuki, Yaeko; Kato, Yoshikazu; Yoshimizu, Chikage; Tayasu, Ichiro

2016-01-15

Carbon stable isotope analysis of bulk samples and fatty acids is an established method for tracing carbon flow pathways and reconstructing trophic interactions, but there is no consensus on which sample drying method should be used for sample preparation. The aim of this study was to determine if freeze-drying and oven-drying treatments used to prepare samples of the benthic macroinvertebrates Stenopsyche marmorata and Epeorus latifolium for bulk and fatty-acid-specific carbon stable isotope analysis yield different isotopic ratio values. Five individuals each from two species were split in half; one half was freeze-dried and the other half was oven-dried. The samples were ground and the δ(13)C values of the bulk samples and eight fatty acids were measured following combustion using an isotope ratio mass spectrometer coupled to an elemental analyzer or gas chromatography system. The mean difference in the bulk and fatty acid δ(13)C values between freeze-dried and oven-dried samples was small (≤0.1‰ in both cases), although relatively large variations were observed in individual fatty-acid-specific δ(13)C values (maximum of ≤0.9 ‰). There were no significant differences in either bulk sample or fatty-acid-specific δ(13)C values between freeze-dried or oven-dried samples of the same species. Freeze-drying and oven-drying are equally acceptable methods for preparing freshly caught S. marmorata and E. latifolium samples for bulk and fatty-acid-specific carbon stable isotope analyses. Copyright © 2015 John Wiley & Sons, Ltd.

The crystal structures of six (2E)-3-aryl-1-(5-halogeno-thio-phen-2-yl)prop-2-en-1-ones.

PubMed

Naik, Vasant S; Yathirajan, Hemmige S; Jasinski, Jerry P; Smolenski, Victoria A; Glidewell, Christopher

2015-09-01

The structures of six chalcones containing 5-halogeno-thio-phen-2-yl substituents are reported: (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13ClOS, (I), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-ethyl-phen-yl)prop-2-en-1-one, C15H13BrOS, (II), are isostructural in space group P-1, while (2E)-1-(5-chloro-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one, C15H13ClO2S, (III), and (2E)-1-(5-bromo-thio-phen-2-yl)-3-(4-eth-oxy-phen-yl)prop-2-en-1-one C15H13BrO2S, (IV), are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I) and (II), but in the structures of compounds (III) and (IV), the mol-ecules are linked into C(7) chains by means of C-H⋯O hydrogen bonds. In the structure of (2E)-3-(4-bromo-phen-yl)-1-(5-chloro-thio-phen-2-yl)prop-2-en-1-one, C13H8BrClOS, (V), there are again no hydrogen bonds nor π-π stacking inter-actions but in that of (2E)-1-(5-bromo-thio-phen-2-yl)-3-(3-meth-oxy-phen-yl)prop-2-en-1-one, C14H11BrO2S, (VI), the mol-ecules are linked into C(5) chains by C-H⋯O hydrogen bonds. In each of compounds (I)-(VI), the mol-ecular skeletons are close to planarity, and there are short halogen⋯halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). Comparisons are made with the structures of some similar compounds.

Potential of ion chromatography coupled to isotope ratio mass spectrometry via a liquid interface for beverages authentication.

PubMed

Guyon, Francois; Gaillard, Laetitia; Brault, Audrey; Gaultier, Nicolas; Salagoïty, Marie-Hélène; Médina, Bernard

2013-12-27

New tools for the determination of characteristic parameters for food authentication are requested to prevent food adulteration from which health concerns, unfair competition could follow. A new coupling in the area of compound-specific carbon 13 isotope ratio (δ(13)C) analysis was developed to simultaneously quantify δ(13)C values of sugars and organic acids. The coupling of ion chromatography (IC) together with isotope ratio mass spectrometry (IRMS) can be achieved using a liquid interface allowing a chemical oxidation (co) of organic matter. Synthetic solutions containing 1 polyol (glycerol), 3 carbohydrates (sucrose, glucose and fructose) and 12 organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric) were used to optimize chromatographic conditions (concentration gradient and 3 types of column) and the studied isotopic range (-32.28 to -10.65‰) corresponds to the values found in food products. Optimum chromatographic conditions are found using an IonPac AS15, an elution flow rate of 0.3mLmin(-1) and a linear concentration gradient from 2 to 76mM (rate 21mMmin(-1)). Comparison between δ(13)C value individually obtained for each compound with the coupling IRMS and elemental analyzer, EA-IRMS, and the ones measured on the mixture of compounds by IC-co-IRMS does not reveal any isotope fractionation. Thus, under these experimental conditions, IC-co-IRMS results are accurate and reproducible. This new coupling was tested on two food matrices, an orange juice and a sweet wine. Some optimization is necessary as the concentration range between sugars and organic acids is too large: an increase in the filament intensity of the IRMS is necessary to simultaneously detect the two compound families. These first attempts confirm the good results obtained on synthetic solutions and the strong potential of the coupling IC-co-IRMS in food authentication area. Copyright © 2013 Elsevier B.V. All rights reserved.

C-13 nuclear magnetic resonance in organic geochemistry.

NASA Technical Reports Server (NTRS)

Balogh, B.; Wilson, D. M.; Burlingame, A. L.

1972-01-01

Study of C-13 nuclear magnetic resonance (NMR) spectra of polycyclic fused systems. The fingerprint qualities of the natural abundance in C-13 NMR spectra permitting unequivocal identification of these compounds is discussed. The principle of structural additivity of C-13 NMR information is exemplified on alpha and beta androstanes, alpha and beta cholestanes, ergostanes, sitostanes, and isodecanes.

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

PubMed

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.

Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2004-03-30

The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

Contribution of microorganisms to non-extractable residue formation during biodegradation of ibuprofen in soil.

PubMed

Nowak, Karolina M; Girardi, Cristobal; Miltner, Anja; Gehre, Matthias; Schäffer, Andreas; Kästner, Matthias

2013-02-15

Non-extractable residues (NER) formed during biodegradation of organic contaminants in soil are considered to be mainly composed of parent compounds or their primary metabolites with hazardous potential. However, in the case of biodegradable organic compounds, the soil NER may also contain microbial biomass components, for example fatty acids (FA) and amino acids (AA). After cell death, these biomolecules are subsequently incorporated into non-living soil organic matter (SOM) and are stabilised ultimately forming hardly extractable residues of biogenic origin. We investigated biodegradation of (13)C(6)-ibuprofen, in particular the metabolic incorporation of the (13)C-label into FA and AA and their fate in soil over 90 days. (13)C-FA and (13)C-AA amounts in the living microbial biomass fraction initially increased, then decreased over time and were continuously incorporated into the non-living SOM pool. The (13)C-FA in the non-living SOM remained stable from day 59 whereas the contents of (13)C-AA slightly increased until the end. After 90 days, nearly all NER were biogenic as they were made up almost completely by natural biomass compounds. The presented data demonstrated that the potential environmental risks related to the ibuprofen-derived NER are overestimated. Copyright © 2012 Elsevier B.V. All rights reserved.

Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems

USGS Publications Warehouse

Kellerman, Anne M.; Guillemette, François; Podgorski, David C.; Aiken, George R.; Butler, Kenna D.; Spencer, Robert G. M.

2018-01-01

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ13C-dissolved organic carbon (DOC) and Δ14C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ14C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA254), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ13C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.

Paleoreconstruction of organic carbon inputs to an oxbow lake in the Mississippi River watershed: Effects of dam construction and land use change on regional inputs

NASA Astrophysics Data System (ADS)

Bianchi, Thomas S.; Galy, Valier; Rosenheim, Brad E.; Shields, Michael; Cui, Xingqian; Van Metre, Peter

2015-10-01

We use a dated sediment core from Lake Whittington (USA) in the lower Mississippi River to reconstruct linkages in the carbon cycling and fluvial sediment dynamics over the past 80 years. Organic carbon (OC) sources were characterized using bulk (δ13C, ramped pyrolysis-oxidation (PyrOx) 14C, δ15N, and TN:OC ratios) and compound-specific (lignin phenols and fatty acids, including δ13C and 14C of the fatty acids) analyses. Damming of the Missouri River in the 1950s, other hydrological modifications to the river, and soil conservation measures resulted in reduced net OC export, in spite of increasing OC concentrations. Decreasing δ13C values coincided with increases in δ15N, TN:OC ratios, long-chain fatty acids, and lignin-phenol concentrations, suggesting increased inputs of soil-derived OC dominated by C3 vegetation, mainly resulting from changes in farming practices and crop distribution. However, ramped PyrOx 14C showed no discernible differences downcore in thermochemical stability, indicating a limited impact on soil OC turnover.

Synthesis, Antiinflammatory and Antimicrobial Activity of Some New 1-(3-Phenyl-3,4-Dihydro-2H-1,3-Benzoxazin-6-yl)-Ethanone Derivatives.

PubMed

Akhter, Mymoona; Husain, A; Akhter, N; Khan, M S Y

2011-01-01

Synthesis of title compounds (4a-j) was carried out by following aminomethylation Mannich reaction. Test compounds were effective in inhibiting edema induced by carrageenan. The percent inhibition obseved was in the range of 25-83.3%. Compound (4c, e, h and j) were also tested for analgesic effect and showed percent protection ranging between 57-65%. All the synthesized compounds were active against E. coli and S. aureus but only compounds (4 b, c, e, i and j) were active against B. subtilis. All these compound were also found active against A. niger. Compound 4j was the most active compound with 83.3% inhibition of edema, 65.35% percent protection and inhibited all the three bacterial strains.

Isotope fractionation associated with the direct photolysis of 4-chloroaniline.

PubMed

Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Erickson, Paul R; Bolotin, Jakov; Hofstetter, Thomas B

2015-04-07

Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs(+) as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵC and ϵN, between -1.2 ± 0.2‰ to -2.7 ± 0.2‰ for C and -0.6 ± 0.2‰ to -9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs(+), we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of (13)C-AKIE vs (15)N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

Synthesis of labeled oxalic acid derivatives

DOEpatents

Martinez, Rodolfo A.; Unkefer, Clifford J.; Alvarez, Marc A.

2004-06-22

The present invention is directed to labeled compounds, specifically ##STR1## where each C* is selected from the group consisting of a carbon-12, i.e., .sup.12 C, or a carbon-13, i.e., .sup.13 C and at least one C* is .sup.13 C, R.sup.1 is selected from the group of C.sub.1 -C.sub.4 lower alkyl and aryl, and X is selected from the group of --NR.sup.2 R.sup.3 where R.sup.2 and R.sup.3 are each independently selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl, --SR.sup.4 where R.sup.4 is selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl, and --OR.sup.5 where R.sup.5 is selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl with the proviso that when R.sup.1 is methyl then R.sup.5 is other than methyl, when R.sup.1 is ethyl then R.sup.5 is other than ethyl, and when R.sup.1 is benzyl then R.sup.5 is other than benzyl.

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.

PubMed

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.

Malate as a key carbon source of leaf dark-respired CO2 across different environmental conditions in potato plants.

PubMed

Lehmann, Marco M; Rinne, Katja T; Blessing, Carola; Siegwolf, Rolf T W; Buchmann, Nina; Werner, Roland A

2015-09-01

Dissimilation of carbon sources during plant respiration in support of metabolic processes results in the continuous release of CO2. The carbon isotopic composition of leaf dark-respired CO2 (i.e. δ (13) C R ) shows daily enrichments up to 14.8‰ under different environmental conditions. However, the reasons for this (13)C enrichment in leaf dark-respired CO2 are not fully understood, since daily changes in δ(13)C of putative leaf respiratory carbon sources (δ (13) C RS ) are not yet clear. Thus, we exposed potato plants (Solanum tuberosum) to different temperature and soil moisture treatments. We determined δ (13) C R with an in-tube incubation technique and δ (13) C RS with compound-specific isotope analysis during a daily cycle. The highest δ (13) C RS values were found in the organic acid malate under different environmental conditions, showing less negative values compared to δ (13) C R (up to 5.2‰) and compared to δ (13) C RS of soluble carbohydrates, citrate and starch (up to 8.8‰). Moreover, linear relationships between δ (13) C R and δ (13) C RS among different putative carbon sources were strongest for malate during daytime (r(2)=0.69, P≤0.001) and nighttime (r(2)=0.36, P≤0.001) under all environmental conditions. A multiple linear regression analysis revealed δ (13) C RS of malate as the most important carbon source influencing δ (13) C R . Thus, our results strongly indicate malate as a key carbon source of (13)C enriched dark-respired CO2 in potato plants, probably driven by an anapleurotic flux replenishing intermediates of the Krebs cycle. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Pyrolysis compound specific isotopic analysis (δ13C and δD Py-CSIA) of soil organic matter size fractions under four vegetation covers.

NASA Astrophysics Data System (ADS)

Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.; Almendros, Gonzalo; De la Rosa, José M.; González-Pérez, José A.

2015-04-01

A chemical characterization of soil organic matter (SOM) under different ground cover from a Mediterranean climate (Doñana National Park, Andalusia, Spain) is approached using bulk δ15N, δ13C, δ18O and δD isotopic analysis (C/TC-IRMS) and δ13C and δD pyrolysis compound specific isotopic analysis (Py-CSIA: Py-GC-C/TC-IRMS). Soil samples were collected in sandy soils, Arenosols (WRB 2006) from the Doñana National Park (SW Spain) under different vegetation cover: cork oak (Quercus suber, QS), eagle fern (Pteridium aquilinum, PA), pine (Pinus pinea, PP) and rockrose (Halimium halimifolium, HH). Two size fractions; coarse (C: 1-2 mm) and fine (F: <0.05 mm) were studied from each soil. A complete conventional analytical pyrolysis (Py-GC/MS) of these samples have been studied in detail (Jiménez-Morillo et al., 2015). Bulk isotopic analysis of stable light elements (δ15N, δ13C, δ18O and δD) revealed particular isotopic signatures showing differences related with the main vegetation cover and the different soil size fraction. All samples had a carbon isotopic signature between -26 and -29 ‰, which indicated that the organic matter in the two fractions of each soil sample derived from C3-type plants. The bulk δD isotopic signature in whole soil sample indicate a lower deuterium fractionation occurs in SOM under arboreal than under no-arboreal vegetation, this can be caused by the occurrence of a higher water evaporation rate under bush vegetation and/or to differences due to leaf morphology as previously described (Leaney et al., 1985). A δ15N vs. δ18O chart may provide some clues about N origin in the soil and particularly about the original source of nitrates (Kendall et al., 1996). In in all sample and size fractions our values are in the chart area corresponding to NO3 in precipitation, with lighter δ18O (c. 20 ‰) values compatible with fertilizers may be from adjacent crops. In addition we were able to assign δ13C and δD values for a number of specific SOM compounds released directly from pyrolysis (Py-CSIA); lipids (Alkenes), aromatic unspecific (alkylphenols), lignin (methoxyphenols) and polysaccharides (anhydrosugars) derived molecules. For all coarse fractions the δ13C and δD values had the same general behavior with sugar derived molecules being enriched in the heavy isotope. Regarding alkenes δ13C isotopic signature, this was variable and dependent upon the main cover vegetation that may reflect different fractionations at different synthesis stages (Chikaraishi & Naraoka, 2001), The δD values for specific compounds had a similar behavior to that for δ13C, being the sugar derived compounds the most deuterium enriched in comparison with lipid and lignin derived pyrolysis products. A conspicuous δD fractionation was observed for the sugar derived compounds in the fine fractions as compared with the coarse ones, with a depletion in deuterium, mainly for the PA sample where the depletion was the highest (c. -140 ‰). This may points to the occurrence of biological reworking with a higher microbiological activity fixing the lighter isotope in the soil fine organic fractions. It is known that lipid hydrogen is deuterium depleted relative to bulk organic hydrogen (Smith and Epstein, 1970). In line with this, in our study the lipid derived compounds had the largest deuterium depleted signature with a difference between bulk and lipid δD values was c. -35‰. This fractionation was highest in Pine (PP) and Rockrose (HH). The combination of traditional techniques for the study of SOM i.e. Py-GC/MS and IRMS, with new hyphenated analytical pyrolysis techniques i.e. Py-CSIA opens new possibilities and windows of information in SOM research. Our findings points to the occurrence of more or less complex processes that affects SOM chemical characteristics; whereas the coarse fraction resembles the chemical structure of the above vegetation, this SOM "memory" is less defined in the fine fractions, probably due to biologically mediated chemical conversions, additions and selective preservation of refractory chemical structures. SOM bulk IRMS and Py-CSIA are also informative about relevant plant physiological processes, OM sources and OM evolution status. Acknowledgments: N.T Jiménez-Morillo is funded by a FPI research grant (BES-2013-062573). Dr. J.M. de la Rosa is the recipient of a fellowship from the JAE-Doc subprogram financed by the CSIC and the European Social Fund. The GEOFIRE Project (CGL2012-38655-C04-01), funded by the Spanish Ministry for Economy and Competitiveness is also acknowledged. Chikaraishi Y, Naraoka H. 2001. Organic hydrogen-carbon isotope signatures of terrestrial higher plants during biosynthesis for distinctive photosynthesis pathways. Geochemical Journal 35: 451-458. Jiménez-Morillo NT, González-Vila FJ, Jordán A, Zavala LM, De la Rosa JM, González-Pérez JA. 2015. Speciation of organic matter in sandy soil size fractions as revealed by analytical pyrolysis (Py-GC/MS) and FT-IR spectroscopy. Geophysical Research Abstracts 17, EGU2015-435. Kendall C, Silva SR, Chang CCY, Burns DA, Campbell DH, Shanley JB. 1996. Use of the Delta 18-O and Delta 15-N of nitrate to determine sources of nitrate in early spring runoff in forested catchments, Isotopes in Water Resources Management. International Atomic Energy Agency symposium, v. 1, pp. 167-176. Leaney FW, Osmond CB, Allison GB, Ziegler H. 1985. Hydrogen-isotope composition of leaf water in C3 and C4 plants: its relationship to the hydrogen-isotope composition of dry matter. Planta Vol164, 2: 215-220. Smith, BN, Epstein S. 1970. Biogeochemistry of the stable isotopes of hydrogen and carbon in salt marsh biota. Plant Physiol. 46: 738-742.

Theoretical estimation of 13C-D clumped isotope effects in methyl of several organic compound

NASA Astrophysics Data System (ADS)

LIU, Q.; Yin, X.; Liu, Y.

2015-12-01

Recent developments in mass spectrometry and tunable infrared laser direct absorption spectroscopy make it possible to measure 13C-D clumped isotope effects of methane. These techniques can be further applied to determine 13C-D clumped isotope effects of methyl fragments, therefore need accurate equilirbium Δi values to calibrate experimental measurements. In this study, we calculate temperature depandences of 13C-D clumped isotope signatures in methyl of several organic compounds including ethane, propane, acetic acid, etc. Our calculation are performed at CCSD/6-311+G(3df,3pd) by using Gaussian 03 program with no scale treament. Our results show that the Δi values of 13C-D clumping in methyl fragments of different organic compounds yield similar signals (~5.5‰ at 25˚C, slightly lower than Δi value of 13C-D clumping in methane). For testing the calculated accuracy, theoretical treaments beyond the harmonic level by including several higher-order corrections to the Bigeleisen-Mayer equation are used. Contributions from higher-order corrections (e.g., AnZPE, AnEXC, VrZPE, VrEXC, QmCorr and CenDist) are estimated to repire the ignorings of the Bigeleisen-Mayer equation (the anharmonic effects of vibration, vibration-rotation coupling, quantum mechanics and centrifugal distortion for rotation, etc.) for the calculation of partition function ratios. The results show that the higher-order corrections contribute ~0.05‰ at 25˚C, which is similar to the contribution for calculating 13C-D clumped isotope signature of methane. By comparing our calculated frequencies to the measured ones, the uncertainty of our calculation of Δi values 13C-D clumping in methyl fragments is considered to be within ~0.05‰ at room temperature.

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

PubMed

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.

Cytotoxic triterpenoid saponins from the fruits of Aesculus pavia L.

PubMed

Zhang, Zhizhen; Li, Shiyou

2007-08-01

Continued chemical investigation on the fruits of North American Aesculus pavia L. resulted in the isolation and identification of 13 polyhydroxyoleanene pentacyclic triterpenoid saponins, named aesculiosides IIe-IIk (1-7), and IIIa-IIIf (8-13), together with 18 known compounds: aesculiosides Ia-Ie (14-18), IIa-IId (19-22), IVa-IVc (23-25), 3-O-[beta-D-galactopyranosyl(1-->2)]-alpha-L-arabinofuranosyl(1-->3)-beta-D-glucuronopyranosyl-21,22-O-diangeloyl-3beta,15 alpha,16 alpha,21 beta,22 alpha,28-hexahydroxyolean-12-ene (26), 3-O-[beta-D-glucopyranosyl(1-->2)]-alpha-L-arabinofuranosyl(1-->3)-beta-D-glucuronopyranosyl-21,22-O-diangeloyl-3beta,16 alpha,21 beta,22 alpha,24 beta,28-hexahydroxyolean-12-ene (27), 3-O-[beta-D-galactopyranosyl(1-->2)]-alpha-L-arabinofuranosyl(1-->3)-beta-D-glucuronopyranosyl-21,22-O-diangeloyl-3beta,16 alpha,21 beta,22 alpha,28-pentahydroxyolean-12-ene (28), R(1)-barrigenol (29), scopolin (30), and 5-methoxyscopolin (31). The structures of these compounds were elucidated by spectroscopic and chemical analyses. Compounds 14-22 and 26-28 were tested in vitro for their activity against 59 cell lines from nine different human cancers including leukemia, non-small cell lung, colon, CNS, melanoma, ovarian, renal, prostate, and breast. It was found that compounds with two-acyl groups at C-21 and C-22 had cytotoxic activity for all cell lines tested with GI(50) 0.175-8.71 microM, while compounds without acyl groups at C-21 and C-22 had weak or no cytotoxic activity. These results suggest that the acyl groups at C-21 and C-22 are essential for their activity.

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

DOEpatents

Martinez, Rodolfo A. , Unkefer; Clifford J. , 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##

Ganoboninketals A-C, Antiplasmodial 3,4-seco-27-Norlanostane Triterpenes from Ganoderma boninense Pat.

PubMed

Ma, Ke; Ren, Jinwei; Han, Junjie; Bao, Li; Li, Li; Yao, Yijian; Sun, Chen; Zhou, Bing; Liu, Hongwei

2014-08-22

Three new nortriterpenes, ganoboninketals A-C (1-3), featuring rearranged 3,4-seco-27-norlanostane skeletons and highly complex polycyclic systems were isolated from the medicinal mushroom Ganoderma boninense. The structures of the new metabolites were established by spectroscopic methods. The absolute configurations in 1-3 were assigned by electronic circular dichroism (ECD) calculations. Compounds 1-3 showed antiplasmodial activity against Plasmodium falciparum with IC50 values of 4.0, 7.9, and 1.7 μM, respectively. Compounds 1 and 3 also displayed weak cytotoxicity against A549 cell line with IC50 values of 47.6 and 35.8 μM, respectively. Compound 2 showed weak cytotoxicity toward HeLa cell line with an IC50 value of 65.5 μM. Compounds 1-3 also presented NO inhibitory activity in the LPS-induced macrophages with IC50 values of 98.3, 24.3, and 60.9 μM, respectively.

Substrate and Enzyme Specificity of the Kinetic Isotope Effects Associated with the Dioxygenation of Nitroaromatic Contaminants.

PubMed

Pati, Sarah G; Kohler, Hans-Peter E; Pabis, Anna; Paneth, Piotr; Parales, Rebecca E; Hofstetter, Thomas B

2016-07-05

Compound-specific isotope analysis (CSIA) is a promising approach for tracking biotransformation of organic pollutants, but isotope fractionation associated with aromatic oxygenations is only poorly understood. We investigated the dioxygenation of a series of nitroaromatic compounds to the corresponding catechols by two enzymes, namely, nitrobenzene and 2-nitrotoluene dioxygenase (NBDO and 2NTDO) to elucidate the enzyme- and substrate-specificity of C and H isotope fractionation. While the apparent (13)C- and (2)H-kinetic isotope effects of nitrobenzene, nitrotoluene isomers, 2,6-dinitrotoluene, and naphthalene dioxygenation by NBDO varied considerably, the correlation of C and H isotope fractionation revealed a common mechanism for nitrobenzene and nitrotoluenes. Similar observations were made for the dioxygenation of these substrates by 2NTDO. Evaluation of reaction kinetics, isotope effects, and commitment-to-catalysis based on experiment and theory showed that rates of dioxygenation are determined by the enzymatic O2 activation and aromatic C oxygenation. The contribution of enzymatic O2 activation to the reaction rate varies for different nitroaromatic substrates of NBDO and 2NTDO. Because aromatic dioxygenation by nonheme iron dioxygenases is frequently the initial step of biodegradation, O2 activation kinetics may also have been responsible for the minor isotope fractionation reported for the oxygenation of other aromatic contaminants.

Holocene cyclic climatic variations and the role of the Pacific Ocean as recorded in varved sediments from northeastern China

NASA Astrophysics Data System (ADS)

Chu, Guoqiang; Sun, Qing; Xie, Manman; Lin, Yuan; Shang, Wenyu; Zhu, Qingzen; Shan, Yabing; Xu, Deke; Rioual, Patrick; Wang, Luo; Liu, Jiaqi

2014-10-01

We present an n-alkane and compound-specific carbon isotope record of the past 9 ka from the annually laminated sedimentary sequence of Lake Xiaolongwan, northeastern China. The n-alkane distribution suggests that Lake Xiaolongwan has undergone a shift from an oligotrophic state with low algal production and little emergent/submerged macrophytes in the early Holocene, to a eutrophic state with high algal production and abundant emergent/submerged macrophytes since the middle Holocene. The pattern of variation observed in the biomarker proxies ACL (the n-alkane average chain length), Paq (aquatic macrophyte versus aquatic macrophyte and terrestrial plant ratio), and LPTP (lake productivity/terrigenous organic production) is throughout the record similar to that of the total organic carbon. The variation of compound-specific carbon isotopic values in the middle- and short-chain alkanes was mainly regulated by lake productivity and the accumulating organic pool through time. In this forested region, where the vegetation is dominated by C3 plants, the long-chain n-alkanes (C27-C31) are predominantly derived from leaf wax lipids. The compound-specific δ13C27-31 value is sensitive to effective precipitation, and therefore represents a useful indicator of regional monsoonal precipitation. Spectral analysis on the δ13C27-31 time series reveals significant periodicities of 87-89, 205-212, 1020-1050 and 1750-2041 years. On the centennial timescale, the quasi-periodicities around 88 and 210 years suggest a strong link between solar activity and monsoon rainfall. The millennial monsoon cycle in northeastern China is associated with sea surface temperature (SST) variations in two active centers of the summer monsoon, the western Pacific Subtropical High (WPSH) and the Okhotsk High. Increasing SST in the subtropical sea may cause a northwards shift of the WPSH, which extends the monsoon rain band (Meiyu) to northeastern China, and thus increasing rainfall in that region. Meanwhile, decreasing SST in the Okhotsk Sea may strengthen the Okhotsk high, bringing more moisture into northeastern China. We suggest that the Pacific Ocean is a main regulator for summer monsoon rainfall in northeastern China at present and at different time scales during the Holocene.

Synthesis, Antiinflammatory and Antimicrobial Activity of Some New 1-(3-Phenyl-3,4-Dihydro-2H-1,3-Benzoxazin-6-yl)-Ethanone Derivatives

PubMed Central

Akhter, Mymoona; Husain, A.; Akhter, N.; Khan, M. S. Y

2011-01-01

Synthesis of title compounds (4a-j) was carried out by following aminomethylation Mannich reaction. Test compounds were effective in inhibiting edema induced by carrageenan. The percent inhibition obseved was in the range of 25-83.3%. Compound (4c, e, h and j) were also tested for analgesic effect and showed percent protection ranging between 57-65%. All the synthesized compounds were active against E. coli and S. aureus but only compounds (4 b, c, e, i and j) were active against B. subtilis. All these compound were also found active against A. niger. Compound 4j was the most active compound with 83.3% inhibition of edema, 65.35% percent protection and inhibited all the three bacterial strains. PMID:22131632

Synthesis of oxazolines and oxazines

DOEpatents

Benicewicz, Brian C.; Mitchell, Michael A.

1995-01-01

A process of preparing an oxazoline or oxazine compound of the formula ##STR1## wherein X is an atom selected from the group of oxygen and sulfur, R is selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-10 fluoroalkyl, aryl and substituted-aryl, and n is 2 or 3 comprising ring-closing a compound of the formula ##STR2## wherein X is an atom selected from the group of oxygen and sulfur, R is selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-10 fluoroalkyl, aryl, and substituted aryl, n is 2 or 3, and Y is a bromine or chlorine atom in the presence of a basic reagent consisting essentially of a fluoride salt supported on an inorganic solid substrate is disclosed together with the compounds, 5-bromomethyl-2-phenyl-1,3-oxazoline, 5-methylene-2-phenyl-1,3-oxazine and 4,4-dimethyl-2-vinyl-1,3-oxazoline.

A serendipitous discovery of antifreeze protein-specific activity in C-linked antifreeze glycoprotein analogs.

PubMed

Eniade, Adewale; Purushotham, Madhusudhan; Ben, Robert N; Wang, J B; Horwath, Kathleen

2003-01-01

Structurally diverse carbon-linked (C-linked) analogs of antifreeze glycoprotein (AFGP) have been prepared via linear or convergent solid phase synthesis. These analogs range in molecular weight from approx 1.5-4.1 KDa and do not possess the beta-D-galactose-1,3-alpha-D-N-acetylgalactosamine carbohydrate moiety or the L-threonine-L-alanine-L-alanine polypeptide backbone native to the AFGP wild-type. Despite these dramatic structural modifications, the 2.7-KDa and 4.1-KDa analogs possess antifreeze protein-specific activity as determined by recrystallization-inhibition (RI) and thermal hysteresis (TH) assays. These analogs are weaker than the wild-type in their activity, but nanoliter osmometry indicates that these compounds are binding to ice and affecting a localized freezing point depression. This is the first example of a C-linked AFGP analog that possesses TH and RI activity and suggests that the rational design and synthesis of chemically and biologically stable AFGP analogs is a feasible and worthwhile endeavor. Given the low degree of TH activity, these compounds may prove useful for the protection of cells during freezing and thawing cycles.

Synthesis, anti-inflammatory, bactericidal activities and docking studies of novel 1,2,3-triazoles derived from ibuprofen using click chemistry.

PubMed

Angajala, Kishore Kumar; Vianala, Sunitha; Macha, Ramesh; Raghavender, M; Thupurani, Murali Krishna; Pathi, P J

2016-01-01

Nonsteroidal anti-inflammatory drugs are of vast therapeutic benefit in the treatment of different types of inflammatory conditions. 1,2,3-Triazoles and their derivatives have a wide range of applications as anti-bacterial, anti-fungal, anti-tubercular, cytostatic, anti-HIV, anti-allergic, anti-neoplastic and anti-inflammatory (AI) agents. Considering the individual biological and medicinal importance of ibuprofen and 1,2,3-triazoles, we wanted to explore novel chemical entities based on ibuprofen and triazole moieties towards their biological significance. Click chemistry has utilized as an ideal strategy to prepare novel ibuprofen-based 1,4-disubstituted 1,2,3-triazole containing molecules. These compounds were screened for their in vivo AI activity, among all the synthesized analogues 13o was shown potent effect than the reference AI drug ibuprofen at the same concentration (10 mg/kg body weight). Compounds 13l, 13g, 13c, 13k, 13i, 13n, 13m and 13j were shown significant AI activity. These triazole analogues were also screened for their bactericidal profile. Compounds 13c, 13i, 13l and 13o exhibited considerable bactericidal activity against gram positive and gram negative strains. In addition to this, molecular docking studies were also carried out into cyclooxygenase-2 active site to predict the affinity and orientation of these novel compounds (13a-q). In summary, we have designed and synthesized 1,2,3-triazole analogues of ibuprofen in good yields using Click chemistry approach. AI and bactericidal activities of these compounds were evaluated and shown remarkable results.

Evidencing 98 secondary metabolites of Penicillium verrucosum using substrate isotopic labeling and high-resolution mass spectrometry.

PubMed

Hautbergue, Thaïs; Puel, Olivier; Tadrist, Souria; Meneghetti, Lauriane; Péan, Michel; Delaforge, Marcel; Debrauwer, Laurent; Oswald, Isabelle P; Jamin, Emilien L

2017-12-15

Industrial applications of fungal compounds, coupled with the emergence of fungal threats to natural ecosystems and public health, have increased interest in filamentous fungi. Among all pathogenic fungi, Penicillium verrucosum is one of the most common mold-infecting stored cereals in temperate regions. However, it is estimated that 80% of fungal secondary metabolites remain unknown. To detect new P. verrucosum compounds, an untargeted metabolomic approach was applied to fungus grown on wheat grains labeled with stable isotopes: (i) natural grains (99% 12 C); (ii) grains enriched with 97% of 13 C; and (iii) grains enriched with 53% of 13 C and 97% of 15 N. Analyses performed by high-performance liquid chromatography coupled with high-resolution mass spectrometry (HPLC-HRMS) enabled the specific detection of fungal metabolites, and the unambiguous characterization of their chemical formulas. In this way, 98 secondary metabolites were detected and their chemical formulas were determined. Of these, only 18 identifications could be made based on databases, the literature and mass spectrometry fragmentation experiments, with the result that 80 were totally unknown. Molecular networks were generated to analyze these results, leading to the characterization by MS n experiments of a new fungisporin produced by P. verrucosum. More generally, this article provides precise mass spectrometric data about all these compounds for further studies of the Penicillium metabolome. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel extracellular glycosidase activity from Rhodotorula mucilaginosa: its application potential in wine aroma enhancement.

PubMed

Hu, K; Zhu, X L; Mu, H; Ma, Y; Ullah, N; Tao, Y S

2016-02-01

The aim of the work was to evaluate the application potential of a glycosidase extract of one indigenous non-Saccharomyces strain in wine aroma enhancement. The isolate was selected from a local winemaking region in China for its high β-glucosidase level and was identified as Rhodotorula mucilaginosa. The tolerance of the glycosidase extract to the typical winemaking conditions was assessed using the activity of its β-glucosidase. After that, the hydrolysis capacity of R. mucilaginosa glycosidase for liberation of grape aroma glycosides was characterized in comparison to commercial enzyme preparations. Results of this work revealed that glycosidase extract from R. mucilaginosa proved to be active in the presence of 0-20% (w/v) glucose, 0-20% (v/v) ethanol and at pH 3·0-5·0. In the hydrolysis of aroma precursors, enzymes obtained from different origins possessed various levels of specificity and activity, showing high origin dependence (α = 0·05). Compared to commercial enzymes, the indigenous R. mucilaginosa glycosidase extract presented better catalytic preference for the 'fruity and floral' glycosides of benzenic compounds and C13 -norisoprenoids, but less sensitivity to the glycosides of C6 compounds and volatile phenols. This work presents a novel extracellular glycosidase preparation from an indigenous Rhodotorula mucilaginosa strain selected from a local winemaking region in China. This enzyme extract exhibits strong tolerance towards winemaking conditions. It shows hydrolysis specificity for glycosides of benzenic compounds and C13 -norisoprenoids, proving a potential candidate for improving floral and fruity aroma characteristics of wine. © 2015 The Society for Applied Microbiology.

Characterization of diesel fuel by chemical separation combined with capillary gas chromatography (GC) isotope ratio mass spectrometry (IRMS).

PubMed

Harvey, Scott D; Jarman, Kristin H; Moran, James J; Sorensen, Christina M; Wright, Bob W

2012-09-15

The purpose of this study was to perform a preliminary investigation of compound-specific isotope analysis (CSIA) of diesel fuels to evaluate whether the technique could distinguish diesel samples from different sources/locations. The ability to differentiate or correlate diesel samples could be valuable for discovering fuel tax evasion schemes or for environmental forensic studies. Two urea adduction-based techniques were used to isolate the n-alkanes from the fuel. Both carbon isotope ratio (δ(13)C) and hydrogen isotope ratio (δD) values for the n-alkanes were then determined by CSIA in each sample. The samples investigated had δ(13)C values that ranged from -30.1‰ to -26.8‰, whereas δD values ranged from -83‰ to -156‰. Plots of δD versus δ(13)C with sample n-alkane points connected in order of increasing carbon number gave well-separated clusters with characteristic shapes for each sample. Principal components analysis (PCA) with δ(13)C, δD, or combined δ(13)C and δD data was applied to extract the maximum information content. PCA scores plots could clearly differentiate the samples, thereby demonstrating the potential of this approach for distinguishing (e.g., fingerprinting) fuel samples using δ(13)C and δD values. Copyright © 2012 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.

PubMed

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.

Stereoselective synthesis, spectral and antimicrobial studies of some cyanoacetyl hydrazones of 3-alkyl-2,6-diarylpiperidin-4-ones

NASA Astrophysics Data System (ADS)

Velayutham Pillai, M.; Rajeswari, K.; Vidhyasagar, T.

2014-11-01

A series of novel cyanoacetyl hydrazones of 3-alkyl-2,6-diarylpiperidin-4-ones were synthesized stereoselectively and characterized by IR, Mass, 1H NMR, 13C NMR, 1H-1H COSY and 1H-13C COSY spectra. The stereochemistry of the synthesized compounds was established using NMR spectra. Antimicrobial screening of the synthesized compounds revealed their antibacterial and antifungal potencies. Growth inhibition of Enterobacter Aerogenes by compound 15 was found to be superior to the standard drug.

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

NASA Astrophysics Data System (ADS)

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

Twilight zone sponges from Guam yield theonellin isocyanate and psammaplysins I and J.

PubMed

Wright, Anthony D; Schupp, Peter J; Schrör, Jan-Philipp; Engemann, Anna; Rohde, Sven; Kelman, Dovi; de Voogd, Nicole; Carroll, Anthony; Motti, Cherie A

2012-03-23

From the organic extracts of two Guam sponges, Rhaphoxya sp. and Suberea sp., determined to have cytotoxic and chemopreventive activities, three new compounds, theonellin isocyanate (1) and psammaplysins I and J (5, 6), and six previously reported compounds (2-4, 7-9) were isolated and characterized spectroscopically ((1)H and (13)C NMR, MS, IR, UV, [α](D)). The two new metabolites (5 and 6) isolated from the Suberea sp. sponge are rare examples of compounds containing a bromotyramine moiety rather than the more usual dibromo analogue. For the compounds isolated from the Rhaphoxya sp., this is the first report of the known compounds 2-4 being found in a single sponge. For previously reported compounds 2-4 complete unambiguous (1)H and (13)C NMR data are provided.

Synthesis of new artemisinin analogues from artemisinic acid modified at C-3 and C-13 and their antimalarial activity.

PubMed

Han, J; Lee, J G; Min, S S; Park, S H; Angerhofer, C K; Cordell, G A; Kim, S U

2001-09-01

Artemisinic acid (2) was modified through allylic oxidation at C-3 or conjugate addition at C-13 to afford 12 methyl artemisinate derivatives (4-15). Photooxidation of the derivatives yielded eight new artemisinin analogues, including 13-cyanoartemisinin (16), 13-methoxycarbonyl artemisinin (17), 13-methoxyartemisinin (18), 13-ethylsulfonylartemisinin (19), 13-nitromethylartemisinin (20), 13-(1-nitroethyl)artemisinin (21), (3R)-3-hydroxyartemisinin (22), and (3R)-3-acetoxyartemisinin (23). Among the analogues, only compound 20 had antimalarial activity comparable to artemisinin (1).

Contributions of root and shoot derived-C to soil organic matter throughout an agricultural soil profile assessed by compound-specific 13C analysis

NASA Astrophysics Data System (ADS)

Mendez-Millan, Mercedes; Dignac, Marie-France; Rumpel, Cornelia; Rasse, Daniel P.; Derenne, Sylvie

2010-05-01

The turnover of soil organic matter (SOM) is generally studied in the topsoil horizons, where the highest concentrations of organic carbon (OC) are found. Subsoils, although containing lower amounts of organic carbon compared to topsoils, greatly contribute to the total carbon stocks within a soil profile. An increase in SOM aliphaticity was observed during SOM degradation, and also down the soil profile, suggesting that the stable pool of SOM is enriched in aliphatic structures. These alkyl-C structures might mainly derive from cutins and suberins, two biomacromolecules, which contain biomarkers specific for shoot and root plant biomass. The aim of this study was to use cutin and suberin structural units to follow the incorporation of plant biomass originating from roots and shoots throughout an agricultural soil profile. We measured the 13C natural abundance of root and shoot biomarkers in samples taken from 15 to 105 cm depth in a C3/C4 chronosequence. After 9 years of maize (C4) cropping, the distribution of root biomarkers (diacids) significantly changed and their concentration increased compared to the wheat (CC3) soil. The largest increase was observed at 60-75 cm where diacids reached up to 134 ?g/gOC compared to 23 ?g/gOC in the wheat soil. Higher inputs from maize root biomass are also suggested by an average 13C enrichment of the root markers in the maize compared to the wheat soil.

Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

DOEpatents

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

2008-01-22

The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S--, --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [.sup.13C]methacrylic acid by reacting a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13CH.sub.2)-- aryl sulfone precursor with .sup.13CHI to form a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate, and, reacting the (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate with sodium hydroxide, followed by acid to form [.sup.13C]methacrylic acid. The present invention is further directed to a process of preparing [.sup.2H.sub.8]methyl methacrylate by reacting a (HOOC--C(C.sup.2H.sub.3).sub.2-- aryl sulfinyl intermediate with CD.sub.3I to form a (.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate, and heating the(.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate at temperatures and for time sufficient to form [.sup.2H.sub.8]methyl methacrylate.

Is Lutein a Physiologically Important Ligand for Transthyretin in Humans?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Liwei

Lutein and zeaxanthin are the only carotenoids accumulated in the macula of the human retina and are known as the macular pigments (MP). These pigments account for the yellow color of the macula and appear to play an important role in protecting against age-related macular degeneration (AMD). The uptake of lutein and zeaxanthin in human eyes is remarkably specific. It is likely that specific transport or binding proteins are involved. The objective is to determine whether transthyretin (TTR) is a transport protein in human plasma and could thus deliver lutein from the blood to the retina. In this study, theymore » used a biosynthetic 13C-lutein tracer and gas chromatography-combustion interfaced-isotope ratio mass spectrometry (GCC-IRMS) to gain the requisite sensitivity to detect the minute amounts of lutein expected as a physiological ligand for human transthyretin. The biosynthetic 13C-labeled lutein tracer was purified from algae. Healthy women (n = 4) each ingested 1 mg of 13C-labeled lutein daily for 3 days and a blood sample was collected 24 hours after the final dose. Plasma TTR was isolated by retinol-binding protein (RBP)-sepharose affinity chromatography and extracted with chloroform. The 13C/ 12C ratio in the TTR extract was measured by GCC-IRMS. There was no 13C-lutein enrichment in the pure TTR extract. This result indicated that lutein is not associated with TTR in human plasma after ingestion in physiological amounts. Some hydrophobic compounds with yellow color may bind to human TTR in the plasma. However, this association needs to be further proved by showing specificity. The study provides a new approach for carotenoid-binding protein studies using a stable isotope tracer method combined with the high precision of GCC-IRMS. The mechanism of selective transport, uptake, and accumulation of lutein in human macula remain to be determined.« less

Superconductivity in the presence of disorder in skutterudite-related La 3Co 4Sn 13 and La 3Ru 4Sn 13 compounds: Electrical transport and magnetic studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slebarski, A.; Maska, M. M.; Fijalkowski, M.

2015-06-25

La 3Co 4Sn 13 and La 3Ru 4Sn 13 were categorized as BCS superconductors. In a plot of the critical field H c2 vs T, La 3Ru 4Sn 13 displays a second superconducting phase at the higher critical temperature T c*, characteristic of inhomogeneous superconductors, while La 3Co 4Sn 13 shows bulk superconductivity below T c. We observe a decrease in critical temperatures with external pressure and magnetic field for both compounds. Additionally, for La 3Ru 4Sn 13 we find that T c*/dP>dT c/dP. The pressure dependences of T c are interpreted according to the McMillan theory and understood tomore » be a consequence of lattice stiffening. The investigation of the superconducting state of La 3Co xRu 4–xSn 13 shows a T c* that is larger then T c for x < 4. Furthermore, this unique and unexpected observation is discussed as a result of the local disorder and/or the effect of chemical pressure when Ru atoms are partially replaced by smaller Co atoms.« less

Pyrolysis-gas chromatography-isotope ratio mass spectrometry for monitoring natural additives in polylactic acid active food packages.

PubMed

Llana-Ruíz-Cabello, M; Pichardo, S; Jiménez-Morillo, N T; González-Vila, F J; Guillamón, E; Bermúdez, J M; Aucejo, S; Camean, A M; González-Pérez, J A

2017-11-24

Compound-specific isotope analysis (CSIA) usually requires preparative steps (pretreatments, extraction, derivatization) to get amenable chromatographic analytes from bulk geological, biological or synthetic materials. Analytical pyrolysis (Py-GC/MS) can help to overcome such sample manipulation. This communication describe the results obtained by hyphenating analytical pyrolysis (Py-GC) with carbon isotope-ratio mass spectrometry (IRMS) for the analysis of a polylactic acid (PLA) a based bio-plastic extruded with variable quantities of a natural plant extract or oregano essential oil. The chemical structural information of pyrolysates was first determined by conventional analytical pyrolysis and the measure of δ 13 C in specific compounds was done by coupling a pyrolysis unit to a gas chromatograph connected to a continuous flow IRMS unit (Py-GC-C-IRMS). Using this Py-CSIA device it was possible to trace natural additives with depleted δ 13 C values produced by C3 photosystem vegetation (cymene: -26.7‰±2.52; terpinene: -27.1‰±0.13 and carvacrol: -27.5‰±1.80 from oregano and two unknown structures: -23.3‰±3.32 and -24.4‰±1.70 and butyl valerate: -24.1‰±3.55 from Allium spp.), within the naturally isotopically enriched bio-plastic backbone derived from corn (C4 vegetation) starch (cyclopentanones: -14.2‰±2.11; lactide enantiomers: -9.2‰±1.56 and larger polymeric units: -17.2‰±1.71). This is the first application of Py-CSIA to characterize a bio-plastic and is shown as a promising tool to study such materials, providing not only a fingerprinting, but also valuable information about the origin of the materials, allowing the traceability of additives and minimizing sample preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

Photodegradation of crude oil: liquid injection and headspace solid-phase microextraction for crude oil analysis by gas chromatography with mass spectrometer detector.

PubMed

D'Auria, Maurizio; Racioppi, Rocco; Velluzzi, Vincenzina

2008-04-01

The fate of crude oil under irradiation is studied. After UV irradiation, the fraction present in the highest percentage shifts from the C8-C9 fractions to C13, using gas chromatography-mass spectrometry (GC-MS) analysis in solution. An increase of the relative amount of the C13-C25 fraction is observed, while a decrease in the relative amount of the C7-C12 fractions is present. In headspace solid-phase microextraction (HS-SPME) analysis, the C8-C10 fractions represent 53% of all the compounds detected. A decrease in the relative amount of the C8-C10 fractions is observed, while C11-C15 fractions increase. The irradiation of crude oil with a solar simulator gives a mixture the analysis of which using GC-MS in solution furnishes the same type of results: the relative amounts of linear alkanes and aromatic compounds increase, while a sharp decrease in the relative amounts of branched and cyclic alkanes is observed. In the SPME analysis, a decreased relative amount of branched alkanes and alkenes, and an increase in the relative amounts of cyclic alkanes and aromatic compounds are observed. Analysis of the distribution of the compounds in all the types of compound shows that a dynamic equilibrium between different compounds and different types of compounds is present. To confirm the presence of a dynamic equilibrium, the irradiation of methylcyclohexane in the presence of 2-methylnaphthalene shows the presence in the reaction mixture of a small amount of tetradecane.

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.

PubMed

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.

A New Method for Carbon Isotopic Analysis of Nanogram Quantities of Carbon from Dissolved Chitin Using A Spooling-wire Microcombustion Interface

NASA Astrophysics Data System (ADS)

Zhao, Y.; Nelson, D. M.; Clegg, B. F.; Berry, J.; Hu, F.

2016-12-01

δ13C analysis of specific taxa or compounds is commonly used for investigating past environmental change, including methane dynamics in lakes. However, most analytical methods require large sample sizes, prohibiting routine analysis of fossils of individual taxa found in sediment deposits. For example, 10-100 individual head capsules of fossil midges are required for δ13C analysis using an elemental analyzer (EA) interfaced with an isotope-ratio mass spectrometer (IRMS). Here we present a new method that uses a spooling-wire microcombustion (SWiM) device interfaced with an IRMS for measuring δ13C values of carbon dissolved from individual head capsules of chitinous aquatic zooplankton. We extracted chitin (a major biochemical component of insect exoskeleton) from modern midge material obtained from four commercial suppliers. We first assessed the effects of sample treatments on carbon yields and δ13C values of dissolved chitin by varying the concentration of HCl used for dissolution, the duration of reaction in HCl, and the temperature of dissolution. We then investigated potential fractionation of carbon isotopes associated with chitin dissolution, by comparing δ13C values of dissolved chitin obtained via SWiM-IRMS with those from untreated head capsules obtained via a EA-IRMS. The average δ13C values of untreated head capsules varied between -25.1 and -30.1‰. Higher acid concentrations and temperatures, as well as longer reaction times, increased dissolution of carbon from the head capsules and the precision of δ13C values. For example, carbon yields from reaction of head capsules with 6N HCl at 25°C increased from 1 to 3 Vs as reaction times increased from 1 to 24 hours. Acid concentration and reaction time had the greatest influence on carbon yields and isotopic precision. The δ13C values of dissolved chitin mirrored the δ13C values of untreated head capsules with minimal offset of absolute values, which suggests no systematic fractionation associated with dissolution. Overall, these results indicate that carbon isotopic analysis of dissolved chitin using the SWiM-IRMS system offers a reliable new method to determine taxa-specific δ13C values for chitinous aquatic zooplankton. In ongoing work, we are applying this tool to reconstruct past methane dynamics in Arctic lakes during the Holocene.

Wild rabbit host and some parasites show trophic-level relationships for delta 13C and delta 15N: a first report.

PubMed

Boag, B; Neilson, R; Robinson, D; Scrimgeour, C M; Handley, L L

1998-01-01

We report the first isotopic study of an animal host-parasite system. Parasitic, intestinal nematodes, Graphidium strigosum and Passalurus ambiguus, were 15N-enriched relative to their host, the European rabbit Oryctolagus cuniculus, while parasitic cestodes, Cittataenia denticulata and Mosgovoyia pectinata, were 15N-depleted, suggesting different trophic relationships. Host embryos were more similar in their delta 13C and delta 15N values to maternal muscle than were any of the parasites. Coprophagy, the direct recycling of food by the rabbit eating its own faeces, did not lead to isotopic differences between stomach contents and faeces, suggesting that the major point for isotopic discrimination in lagomorph nitrogen metabolism is in the animal rather than in the gut. We conclude that bulk delta 13C and delta 15N can reveal valuable new information about host-parasite relationships, and these could be explored further at the biochemical level using compound-specific isotopic analyses.

Tracing the flow of plant carbohydrates into the rhizosphere

NASA Astrophysics Data System (ADS)

Gleixner, Gerd

2016-04-01

We investigated the flow of 13C labeled CO2 from plant sugars in leaves, stems and roots into rhizospheric organisms, respired CO2 and soil organic matter in order to better understand the role of the plant-microorganism-soil-continuum for ecosystem carbon cycling. We compared trees and grassland species that had different sugar transport strategies, storage compartments, community compositions and environmental stresses. We used short but highly enriched 13C pulses at controlled CO2 concentrations and temperatures that avoided non-physiological plant responses. We used compound specific 13C measurements of sugars and phospholipids (PLFA) to calculate the carbon turnover of plant sugars and rhizospheric microorganisms. Our results unexpectedly identified transport limitations in the root-shoot carbohydrate transfer, diurnal variations in label respiration and community effects in the carbon transfer to microbial groups. Our results highlight that sophisticated experimental setups and analytical techniques are necessary to gain new knowledge on ecosystem carbon cycling under climate change.

Paleoreconstruction of organic carbon inputs to an oxbow lake in the Mississippi River watershed: Effects of dam construction and land use change on regional inputs

USGS Publications Warehouse

Bianchi, Thomas S.; Galy, Valier; Rosenheim, Brad E.; Shields, Michael; Cui, Xingquan; Van Metre, Peter C.

2015-01-01

We use a dated sediment core from Lake Whittington (USA) in the lower Mississippi River to reconstruct linkages in the carbon cycling and fluvial sediment dynamics over the past 80 years. Organic carbon (OC) sources were characterized using bulk (δ13C, ramped pyrolysis-oxidation (PyrOx) 14C, δ15N, and TN:OC ratios) and compound-specific (lignin phenols and fatty acids, including δ13C and 14C of the fatty acids) analyses. Damming of the Missouri River in the 1950s, other hydrological modifications to the river, and soil conservation measures resulted in reduced net OC export, in spite of increasing OC concentrations. Decreasing δ13C values coincided with increases in δ15N, TN:OC ratios, long-chain fatty acids, and lignin-phenol concentrations, suggesting increased inputs of soil-derived OC dominated by C3 vegetation, mainly resulting from changes in farming practices and crop distribution. However, ramped PyrOx 14C showed no discernible differences downcore in thermochemical stability, indicating a limited impact on soil OC turnover.

Heart-cutting two-dimensional gas chromatography in combination with isotope ratio mass spectrometry for the characterization of the wax fraction in plant material.

PubMed

Dumont, Emmie; Tienpont, Bart; Higashi, Nobukazu; Mitsui, Kazuhisa; Ochiai, Nobuo; Kanda, Hirooki; David, Frank; Sandra, Pat

2013-11-22

Gas chromatography coupled to isotope ratio mass spectrometry after on-line combustion (GC-C-IRMS) and high temperature conversion (GC-HTC-IRMS) is used for compound specific isotope ratio determination. This determination can only be performed successfully if the target solutes are fully resolved from other compounds. A new instrumental set-up consisting of heart-cutting two-dimensional GC based on capillary flow technology and a low thermal mass GC oven in combination with an isotope ratio mass spectrometer is presented. Capillary flow technology was also used in all column and interface connections for robust and leak-free operation. The new configuration was applied to the characterization of wax compounds in tobacco leaf and corresponding smoke samples. It is demonstrated that high accuracy is obtained, both in the determination of δ(13)C and δ(2)H values, allowing the study of biosynthesis and delivery mechanisms of naturally occurring compounds in tobacco. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis, Characterization, and Anti-Cancer Activity of Some New N'-(2-Oxoindolin-3-ylidene)-2-propylpentane hydrazide-hydrazones Derivatives.

PubMed

El-Faham, Ayman; Farooq, Muhammad; Khattab, Sherine N; Abutaha, Nael; Wadaan, Mohammad A; Ghabbour, Hazem A; Fun, Hoong-Kun

2015-08-13

Eight novel N'-(2-oxoindolin-3-ylidene)-2-propylpentane hydrazide-hydrazone derivatives 4a-h were synthesized and fully characterized by IR, NMR ((1)H-NMR and (13)C-NMR), elemental analysis, and X-ray crystallography. The cyto-toxicity and in vitro anti-cancer evaluation of the prepared compounds have been assessed against two different human tumour cell lines including human liver (HepG2) and leukaemia (Jurkat), as well as in normal cell lines derived from human embryonic kidney (HEK293) using MTT assay. The compounds 3e, 3f, 4a, 4c, and 4e revealed promising anti-cancer activities in tested human tumour cells lines (IC50 values between 3 and 7 μM) as compared to the known anti-cancer drug 5-Fluorouracil (IC50 32-50 μM). Among the tested compounds, 4a showed specificity against leukaemia (Jurkat) cells, with an IC50 value of 3.14 μM, but this compound was inactive in liver cancer and normal cell lines.

Synthesis, fluorescence, TGA and crystal structure of thiazolyl-pyrazolines derived from chalcones

NASA Astrophysics Data System (ADS)

Suwunwong, T.; Chantrapromma, S.; Fun, H.-K.

2015-04-01

Thiazolyl-pyrazolines 3a-3d were synthesized in a three step procedure using chalcones as starting materials and characterized by FT-IR, UV-Vis, and 1H NMR techniques. The crystal structure of compound 3a was also determined by X-ray diffraction analysis. Compound 3a crystallized out in the orthorhombic P212121 space group with the unit cell dimensions: a = 5.2106(2) Å, b = 12.4341(5) Å, c = 33.3254(13) Å, α = β = γ = 90°, V = 2159.12(15) Å3, Z = 4, D cald = 1.372 M gm-3 and F(000) = 928. Fluorescence of 3a-3d were studied in solid state and acetonitrile solution. It was found that, these compounds exhibit the green fluorescence light (506-508 nm) in both solid and solution states. The pH stability on fluorescence property and the thermal gravimetric analysis of compound 3a were specifically carried out. It was revealed that 3a shows high thermal stability up to around 250°C and presenting high stability in various pH ranges in the acetonitrilewater matrix.

The Importance of Zostera marina to a Local Food Web Based on the Analysis of Compound Specific Isotopes in Maquoit Bay, Gulf of Maine

NASA Astrophysics Data System (ADS)

Doolittle, H. A.; Johnson, B. J.; Ambrose, W. G.; Locke, W.; Harris, C. M.

2010-12-01

Zostera marina (also known as eelgrass) is an important primary producer in near shore ecosystems in the Gulf of Maine, providing both habitat and nutrients for a variety of organisms (e.g., crustaceans, polychaetes, gastropods, and fish). The purpose of this study is to use compound specific δ13C analyses of essential amino acids to determine the degree to which organic matter derived from isotopically distinct primary producers (e.g., eelgrass, phytoplankton, and epiphytic algae) contribute to the diets of snails, shrimp, and fish in an eelgrass system in Casco Bay. Maquoit Bay, located in northwestern Casco Bay, in the Gulf of Maine, is a shallow estuarine system that is characterized by silt and clay sized sediments and the presence of extensive eelgrass beds. Amino acid concentrations and δ13C compositions were determined for a variety of sample-types collected in July-August, 2010, from three sites in the study area, including muscle tissue from Tautogolabrus adspersus (cunner), Gasterosteus aculeatus (3-spined stickleback), Nassarius obsoletus (snail), and Mysis spp. (shrimp), seston (i.e., phytoplankton), Z. marina, and epiphytic algae. TFAA amino acid derivatives of the total hydrolyzate were analyzed by GC-FID for amino acid concentration, and by GC-c-IRMS- for carbon isotope composition. Muscle tissue was dominated by glutamic and aspartic acids, and leucine, whereas Zostera marina was dominated by aspartic and glutamic acids, and proline. Phenylalanine and leucine in Z. marina are approximately 10 ‰ enriched in 13C relative to these same amino acids in the seston. The carbon isotope values of these essential amino acids are significantly more enriched in 13C for N. obsoletus than for T. adspersus, G. aculeatus, and Mysis spp. These data suggest that organic matter derived from Z. marina and/or epiphytic algae is more important in the diets of N. obsoletus, and organic matter derived from seston is more important for the diets of T. adspersus, G. aculeatus, and Mysis spp. These isotopic relationships provide a means to interpret essential amino acids extracted from well-preserved archaeological remains.

Multiple Cosmic Sources for Meteorite Macromolecules?

PubMed Central

Watson, Jonathan S.; Meredith, William; Love, Gordon D.; Gilmour, Iain; Snape, Colin E.

2015-01-01

Abstract The major organic component in carbonaceous meteorites is an organic macromolecular material. The Murchison macromolecular material comprises aromatic units connected by aliphatic and heteroatom-containing linkages or occluded within the wider structure. The macromolecular material source environment remains elusive. Traditionally, attempts to determine source have strived to identify a single environment. Here, we apply a highly efficient hydrogenolysis method to liberate units from the macromolecular material and use mass spectrometric techniques to determine their chemical structures and individual stable carbon isotope ratios. We confirm that the macromolecular material comprises a labile fraction with small aromatic units enriched in 13C and a refractory fraction made up of large aromatic units depleted in 13C. Our findings suggest that the macromolecular material may be derived from at least two separate environments. Compound-specific carbon isotope trends for aromatic compounds with carbon number may reflect mixing of the two sources. The story of the quantitatively dominant macromolecular material in meteorites appears to be made up of more than one chapter. Key Words: Abiotic organic synthesis—Carbonaceous chondrite—Cosmochemistry—Meteorites. Astrobiology 15, 779–786. PMID:26418568

Relative contribution of C3 and C4 type terrestrial organic matter in the Mahanadi offshore (Bay of Bengal) sediments and climatic implication.

NASA Astrophysics Data System (ADS)

da Silva, Rheane; Mazumdar, Aninda; Naik, Bg

2017-04-01

C3 and C4 are dominant vegetation in terrestrial environment. The primary product of photosynthesis of C3 plants is a 3 carbon bearing compound called phosphoglycerate (PGA). In contrast, CO2 is transferred to bundle sheath cells via 4 carbon bearing compound oxaloacetate/mallate and fixed by RuBiSCO in C4 plants. This marked variation in CO2 diffusion across stomata and enzymatic pathways lead to differences in stable carbon isotope ratios. Factors that control relative abundance of these vegetation types are concentration of p-CO2, temperature and humidity. Low p-CO2, air temperature below cross over temperature and aridity are the climatic parameters favoring expansion of C4 type vegetation, whereas higher extreme conditions promote greater C3 type production (Ehleringer, J. R, 2005). In marine sediment n-alkane (lipid fraction) distribution and compound specific isotope ratios are ideal markers to characterize nature of terrestrial organic flux owing to high diagenetic stability and near 100% extraction efficiency. We report here the relative abundance of C3-C4 vegetation over 8 marine isotope stages covering 300kyr. A 39.08 m long core (MD 161-19) was collected onboard ORV Marion Dufresne, at a water depth of 1480 m (Lat: 18 59.1092N Long: 85 41.1669E) (Mazumdar., et. al. 2014) for the study of sediment physico chemical properties and their link to paleoclimatic variation. The carbon isotope ratios of C-27 n-alkane range from -35.3‰ to -23.6‰ VPDB. 13C enrichment trends indicate a greater contribution from C4 vegetation type and 13C depletion trends are attributed to greater flux of C3 type vegetation. Mass balance calculation to reconstruct the temporal variation in C3/ C4 ratios is carried out using the end member values of -34.5‰ and -19.8‰ respectively (Collister.,et. al. 1994). The calculated C3/C4 ratio is 27:73 at LGM and shifts to 71:29 around 6 kyr BP. Based on results, we observe that colder isotope substages characterized by lower pCO2 saw relative expansion of C4 vegetation while warmer, high pCO2 periods supported C3 expansion. A high resolution work is being carried out to get better understanding on actual limiting factors across the last 300 ky responsible for changes in C3 vs C4 expansion. Our data may help in understanding how vegetation may respond to future global warming and climate change including pCO2 build up, change in air temperature and monsoonal rainfall. References: • Collister, James W., et al. "Compound-specific δ 13C analyses of leaf lipids from plants with differing carbon dioxide metabolisms." Organic Geochemistry 21.6-7 (1994): 619-627. • Ehleringer, J. R. The influence of atmospheric CO2, temperature, and water on the abundance of C3/C4 taxa. In A history of atmospheric CO2 and its effects on plants, animals, and ecosystems Springer New York 214-231 (2005). • Mazumdar, A., et al. "Pore-water chemistry of sediment cores off Mahanadi Basin, Bay of Bengal: Possible link to deep seated methane hydrate deposit." Marine and Petroleum Geology 49 (2014): 162-175.

Basic-functionalized recyclable ionic liquid catalyst: A solvent-free approach for Michael addition of 1,3-dicarbonyl compounds to nitroalkenes under ultrasound irradiation.

PubMed

Narayanaperumal, Senthil; da Silva, Rodrigo César; Feu, Karla Santos; de la Torre, Alexander Fernández; Corrêa, Arlene G; Paixão, Márcio Weber

2013-05-01

A task-specific ionic liquid (TSIL) has been introduced as a recyclable catalyst in Michael addition. A series of nitroalkenes and various C-based nucleophiles were reacted in the presence of 30mol% of recyclable basic-functionalized ionic liquid. Good to excellent yields were obtained in 30min under ultrasound irradiation. Copyright © 2012 Elsevier B.V. All rights reserved.

The crystal structures of six (2E)-3-aryl-1-(5-halogeno­thio­phen-2-yl)prop-2-en-1-ones

PubMed Central

Naik, Vasant S.; Yathirajan, Hemmige S.; Jasinski, Jerry P.; Smolenski, Victoria A.; Glidewell, Christopher

2015-01-01

The structures of six chalcones containing 5-halogeno­thio­phen-2-yl substituents are reported: (2E)-1-(5-chloro­thio­phen-2-yl)-3-(4-ethyl­phen­yl)prop-2-en-1-one, C15H13ClOS, (I), and (2E)-1-(5-bromo­thio­phen-2-yl)-3-(4-ethyl­phen­yl)prop-2-en-1-one, C15H13BrOS, (II), are isostructural in space group P-1, while (2E)-1-(5-chloro­thio­phen-2-yl)-3-(4-eth­oxy­phen­yl)prop-2-en-1-one, C15H13ClO2S, (III), and (2E)-1-(5-bromo­thio­phen-2-yl)-3-(4-eth­oxy­phen­yl)prop-2-en-1-one C15H13BrO2S, (IV), are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I) and (II), but in the structures of compounds (III) and (IV), the mol­ecules are linked into C(7) chains by means of C—H⋯O hydrogen bonds. In the structure of (2E)-3-(4-bromo­phen­yl)-1-(5-chloro­thio­phen-2-yl)prop-2-en-1-one, C13H8BrClOS, (V), there are again no hydrogen bonds nor π–π stacking inter­actions but in that of (2E)-1-(5-bromo­thio­phen-2-yl)-3-(3-meth­oxy­phen­yl)prop-2-en-1-one, C14H11BrO2S, (VI), the mol­ecules are linked into C(5) chains by C—H⋯O hydrogen bonds. In each of compounds (I)–(VI), the mol­ecular skeletons are close to planarity, and there are short halogen⋯halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). Comparisons are made with the structures of some similar compounds. PMID:26396857

Bioactive spirans and other constituents from the leaves of Cannabis sativa f. sativa.

PubMed

Guo, Tian-Tian; Zhang, Jian-Chun; Zhang, Hai; Liu, Qing-Chao; Zhao, Yong; Hou, Yu-Fei; Bai, Lu; Zhang, Li; Liu, Xue-Qiang; Liu, Xue-Ying; Zhang, Sheng-Yong; Bai, Nai-Sheng

2017-08-01

In this paper, 17 compounds (1-17) were isolated from the leaves of Hemp (Cannabis sativa f. sativa). Among the isolates, two were determined to be new spirans: cannabispirketal (1), and α-cannabispiranol 4'-O-β-D-glucopyranose (2) by 1D and 2D NMR spectroscopy, LC-MS, and HRESIMS. The known compounds 7, 8, 10, 13, 15, and 16 were isolated from Hemp (C. sativa f. sativa) for the first time. Furthermore, compounds 8 and 13 were isolated from the nature for the first time. All isolated compounds were evaluated for cytotoxicity on different tissue-derived passage cancer cell lines through cell viability and apoptosis assay. Among these compounds, compounds 5, 9 and 16 exhibited a broad-spectrum antitumor effect via inhibiting cell proliferation and promoting apoptosis. These results obtained have provided valuable clues to the understanding of the cytotoxic profile for these isolated compounds from Hemp (C. sativa f. sativa).

Determination of polar organic solutes in oil-shale retort water

USGS Publications Warehouse

Leenheer, J.A.; Noyes, T.I.; Stuber, H.A.

1982-01-01

A variety of analytical methods were used to quantitatively determine polar organic solutes in process retort water and a gas-condensate retort water produced in a modified in situ oil-shale retort. Specific compounds accounting for 50% of the dissolved organic carbon were identified in both retort waters. In the process water, 42% of the dissolved organic carbon consisted of a homologous series of fatty acids from C2 to C10. Dissolved organic carbon percentages for other identified compound classes were as follows: aliphatic dicarboxylic acids, 1.4%; phenols, 2.2%; hydroxypyridines, 1.1%; aliphatic amides, 1.2%. In the gas-condensate retort water, aromatic amines were most abundant at 19.3% of the dissolved organic carbon, followed by phenols (17.8%), nitriles (4.3%), aliphatic alcohols (3.5%), aliphatic ketones (2.4%), and lactones (1.3%). Steam-volatile organic solutes were enriched in the gas-condensate retort water, whereas nonvolatile acids and polyfunctional neutral compounds were predominant organic constituents of the process retort water.

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

PubMed

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 biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation. © 2012, The Author(s). Ground Water © 2012, National Ground Water Association.

Effect of atomic disorder and Ce doping on superconductivity of Ca 3 Rh 4 Sn 13 : Electric transport properties under high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ślebarski, Andrzej; Goraus, Jerzy; Maśka, Maciej M.

2016-06-13

Here, we report the observation of a superconducting state below ~8 K coexistent with a spin-glass state caused by atomic disorder in Ce substituted Ca 3Rh 4Sn 13. Measurements of specific heat, resistivity, and magnetism reveal the existence of inhomogeneous superconductivity in samples doped with Ce with superconducting critical temperatures T c higher than those observed in the parent compound. For Ca 3Rh 4Sn 13, the negative value of the change in resistivity ρ with pressure P, dρ/dP correlates well with the calculated decrease in the density of states (DOS) at the Fermi energy with P. In conclusion, based onmore » band-structure calculations performed under pressure, we demonstrate how the change in DOS would affect T c of Ca 3Rh 4Sn 13 under negative lattice pressure in samples that are strongly defected by quenching.« less

NMR analysis and chemical shift calculations of poly(lactic acid) dimer model compounds with different tacticities

USDA-ARS?s Scientific Manuscript database

In this work, PLA dimer model compounds with different tacticities were synthesized and studied in detail by 1H and 13C NMR in three solvents, CDCl3/CCl4 (20/80 v/v), CDCl3 and DMSO-d6. All the peaks in the 1H and 13C NMR spectra were assigned with the help of two-dimensional NMR. Although the solve...

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

NASA Astrophysics Data System (ADS)

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, but as deciduous versus evergreen plants, then a re-examination of the PETM terrestrial carbon isotope excursion and its causes may be necessary.

Evidence for Methyl-Compound-Activated Life in Coal Bed System 2 km Below Sea Floor

NASA Astrophysics Data System (ADS)

Trembath-reichert, E.; Morono, Y.; Dawson, K.; Wanger, G.; Bowles, M.; Heuer, V.; Hinrichs, K. U.; Inagaki, F.; Orphan, V. J.

2014-12-01

IODP Expedition 337 set the record for deepest marine scientific drilling down to 2.4 kmbsf. This cruise also had the unique opportunity to retrieve deep cores from the Shimokita coal bed system in Japan with the aseptic and anaerobic conditions necessary to look for deep life. Onboard scientists prepared nearly 1,700 microbiology samples shared among five different countries to study life in the deep biosphere. Samples spanned over 1 km in sampling depths and include representatives of shale, sandstone, and coal lithologies. Findings from previous IODP and deep mine expeditions suggest the genetic potential for methylotrophy in the deep subsurface, but it has yet to be observed in incubations. A subset of Expedition 337 anoxic incubations were prepared with a range of 13C-methyl substrates (methane, methylamine, and methanol) and maintained near in situ temperatures. To observe 13C methyl compound metabolism over time, we monitored the δ13C of the dissolved inorganic carbon (by-product of methyl compound metabolism) over a period of 1.5 years. Elemental analysis (EA), ion chromatograph (IC), 13C volatile fatty acid (VFA), and mineral-associated microscopy data were also collected to constrain initial and endpoint conditions in these incubations. Our geochemical evidence suggests that the coal horizon incubated with 13C-methane showed the highest activity of all methyl incubations. This provides the first known observation of methane-activated metabolism in the deep biosphere, and suggests there are not only active cells in the deeply buried terrigenous coal bed at Shimokita, but the presence of a microbial community activated by methylotrophic compounds.

Tracing the link between plant volatile organic compound emissions and CO2 fluxes and by stable isotopes

NASA Astrophysics Data System (ADS)

Werner, Christiane; Wegener, Frederik; Jardine, Kolby

2015-04-01

The vegetation exerts a large influence on the atmosphere through the emission of volatile organic compounds (VOCs) and the emission and uptake of the greenhouse gas CO2. Despite the enormous importance, processes controlling plant carbon allocation into primary and secondary metabolism, such as photosynthetic carbon uptake, respiratory CO2 emission and VOC synthesis, remains unclear. Moreover, vegetation-atmosphere CO2 exchange is associated with a large isotopic imprint due to photosynthetic carbon isotope discrimination and 13C-fractionation during respiratory CO2 release1. The latter has been proposed to be related to carbon partitioning in the metabolic branching points of the respiratory pathways and secondary metabolism, which are linked via a number of interfaces including the central metabolite pyruvate. Notably, it is a known substrate in a large array of secondary pathways leading to the biosynthesis of many volatile organic compounds (VOCs), such as volatile isoprenoids, oxygenated VOCs, aromatics, fatty acid oxidation products, which can be emitted by plants. Here we investigate the linkage between VOC emissions, CO2 fluxes and associated isotope effects based on simultaneous real-time measurements of stable carbon isotope composition of branch respired CO2 (CRDS) and VOC fluxes (PTR-MS). We utilized positionally specific 13C-labeled pyruvate branch feeding experiments in the mediterranean shrub (Halimium halimifolium) to trace the partitioning of C1, C2, and C3 carbon atoms of pyruvate into VOCs versus CO2 emissions in the light and in the dark. In the light, we found high emission rates of a large array of VOC including volatile isoprenoids, oxygenated VOCs, green leaf volatiles, aromatics, sulfides, and nitrogen containing VOCs. These observations suggest that in the light, H. halimifolium dedicates a high carbon flux through secondary biosynthetic pathways including the pyruvate dehydrogenase bypass, mevalonic acid, MEP/DOXP, shikimic acid, and fatty acid pathways. Moreover, we found that high VOC emissions were closely related to 13CO2 decarboxylation from pyruvate-1-13C in the light, while mitochondrial respiration mas markedly down-regulated. Moreover, we found that in the dark, VOC emissions dramatically declined while respiration was stimulated with 13CO2 emissions under pyruvate-1-13C exceeding those under pyruvate-2-13C and pyruvate-2,3-13C during light-dark transitions. Our observations suggest VOC emissions are associated with significant pyruvate C1 decarboxylation. Moreover, the data suggests that light fundamentally controls the partitioning of assimilated carbon in leaves by regulating the competition for pyruvate between secondary biosynthetic reactions (e.g. VOC production) and mitochondrial respiration. Our investigation provides novel tool to better understand the mechanistic links between primary and secondary carbon metabolism in plants with important implications for a better understanding biosphere-atmosphere exchange of CO2 and VOCs. References 1. Werner C. & Gessler A. (2011) Diel variations in the carbon isotope composition of respired CO2 and associated carbon sources: a review of dynamics and mechanisms. Biogeosciences 8, 2437-2459 2. Jardine K, Wegener F, Abrell L, vonHaren J, Werner C (2014) Phytogenic biosynthesis and emission of methyl acetate. PCE 37, 414-424.

Design, Synthesis and Evaluation of Novel Phthalimide Derivatives as in Vitro Anti-Microbial, Anti-Oxidant and Anti-Inflammatory Agents.

PubMed

Lamie, Phoebe F; Phillopes, John N; El-Gendy, Ahmed O; Rarova, Lucie; Gruz, Jiri

2015-09-14

Sixteen new phthalimide derivatives were synthesized and evaluated for their in vitro anti-microbial, anti-oxidant and anti-inflammatory activities. The cytotoxicity for all synthesized compounds was also determined in cancer cell lines and in normal human cells. None of the target derivatives had any cytotoxic activity. (ZE)-2-[4-(1-Hydrazono-ethyl) phenyl]isoindoline-1,3-dione (12) showed remarkable anti-microbial activity. Its activity against Bacillus subtilis was 133%, 106% and 88.8% when compared with the standard antibiotics ampicillin, cefotaxime and gentamicin, respectively. Compound 12 also showed its highest activities in Gram negative bacteria against Pseudomonas aeruginosa where the percentage activities were 75% and 57.6% when compared sequentially with the standard antibiotics cefotaxime and gentamicin. It was also found that the compounds 2-[4-(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolidin-3-yl)phenyl]isoindoline-1,3-dione (13b) and 2-[4-(3-methyl-5-thioxo-4-phenyl-1,2,4-triazolidin-3-yl)phenyl]isoindoline-1,3-dione (13c) had anti-oxidant activity. 4-(N'-{1-[4-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-phenyl]-ethylidene}-hydrazino)-benzenesulfonamide (17c) showed the highest in vitro anti-inflammatory activity of the tested compounds (a decrease of 32%). To determine the mechanism of the anti-inflammatory activity of 17c, a docking study was carried out on the COX-2 enzyme. The results confirmed that 17c had a higher binding energy score (-17.89 kcal/mol) than that of the ligand celecoxib (-17.27 kcal/mol).

Bulk and compound-specific isotope analysis of long-chain n-alkanes from a 85,000 year sediment core from Lake Peten Petén Itzá, Guatemala

NASA Astrophysics Data System (ADS)

Mays, J.; Brenner, M.; Curtis, J. H.; Curtis, K.; Hodell, D. A.; Correa-Metrio, A.; Escobar, J.; Dutton, A. L.; Zimmerman, A. R.; Guilderson, T. P.

2013-12-01

Sediment core PI-6 from Lake Petén Itzá, Guatemala possesses an 85-ka record of climate from lowland Central America. Variations in sediment lithology suggest large, abrupt changes in precipitation during the last glacial and deglacial periods, and into the early Holocene. Study of cores from nearby Lake Quexil demonstrated the utility of using the carbon isotopic composition of leaf wax n-alkanes to infer changes in terrestrial vegetation (Huang et al. 2001). Forty-nine samples were taken from composite Petén Itzá core PI-6 to measure carbon isotopes of bulk organic carbon and long-chain n alkanes. Changes in δ13C values indicate shifts in the relative proportion of C3 to C4 biomass. The record shows largest δ13C variations are associated with Heinrich Events. Carbon isotope values in sediments deposited during the Last Glacial Maximum (LGM) indicate moderate precipitation and little rainfall fluctuation. The deglacial was a period of pronounced climate variability, e.g. the Bölling-Allerod and Younger Dryas. Arid times of the deglacial were inferred from samples with the greatest δ13C values in organic matter, reflecting the largest proportion of C4 plants. Such inferences are supported by stable isotope measurements on ostracod shells and analysis of pollen from the same sample depths in core PI-6. Carbon stable isotope measures on bulk organic carbon and n alkane compounds show similar trends throughout the record and the C:N ratio of Petén Itzá sediments indicates a predominantly allochthonous source for bulk organic matter. Hence, isotope measures on bulk organic carbon (δ13CTOC) in sediments from this lake are sufficient to infer climate-driven shifts in vegetation, making n-alkane extraction and isotope analysis superfluous.

Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

NASA Astrophysics Data System (ADS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.

2015-04-01

Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic compounds is critical for understanding deep subsurface ecosystems and the origin of organic compounds on Mars and other planets.

Bioactivity-Guided Metabolite Profiling of Feijoa ( Acca sellowiana) Cultivars Identifies 4-Cyclopentene-1,3-dione as a Potent Antifungal Inhibitor of Chitin Synthesis.

PubMed

Mokhtari, Mona; Jackson, Michael D; Brown, Alistair S; Ackerley, David F; Ritson, Nigel J; Keyzers, Robert A; Munkacsi, Andrew B

2018-06-06

Pathogenic fungi continue to develop resistance against current antifungal drugs. To explore the potential of agricultural waste products as a source of novel antifungal compounds, we obtained an unbiased GC-MS profile of 151 compounds from 16 commercial and experimental cultivars of feijoa peels. Multivariate analysis correlated 93% of the compound profiles with antifungal bioactivities. Of the 18 compounds that significantly correlated with antifungal activity, 5 had not previously been described from feijoa. Two novel cultivars were the most bioactive, and the compound 4-cyclopentene-1,3-dione, detected in these cultivars, was potently antifungal (IC 50 = 1-2 μM) against human-pathogenic Candida species. Haploinsufficiency and fluorescence microscopy analyses determined that the synthesis of chitin, a fungal-cell-wall polysaccharide, was the target of 4-cyclopentene-1,3-dione. This fungal-specific mechanism was consistent with a 22-70-fold reduction in antibacterial activity. Overall, we identified the agricultural waste product of specific cultivars of feijoa peels as a source of potential high-value antifungal compounds.

Stabilization of glucose-C in microbial cell membranes (PLFA) and cell walls (amino sugars) evaluated by 13C-labelling in a field experiment

NASA Astrophysics Data System (ADS)

Gunina, Anna; Kuzyakov, Yakov; Glaser, Bruno

2015-04-01

Microorganisms control carbon (C) cycle and strongly contribute to formation of soil organic matter. Strong differences in the turnover of microbial groups and cellular compounds complicate the assessment of their contribution to microbial food webs and C sequestration in soil in situ. The uptake and incorporation of 13C labeled glucose by microbial groups were traced during 50 days after the labeling under field conditions. 13C was analysed: i) in the cytosolic pool by chloroform fumigation extraction, ii) in cell membranes by phospholipid fatty acids (PLFA), iii) in cell walls by amino sugars, and iv) remaining in bulk soil. This allowed tracing C in microbial groups as well as cellular compounds. Mean residence times (MRT) of C in PLFA and the cytosol were 47 and 150 days, respectively. Such long cytosol MRT depends on its heterogeneous composition, which includes high and low molecular weight organics. Amino sugars were mainly originated from microbial residues and thus, observation periods higher than 1 year are required for estimation of their MRT. Relative 13C incorporation (13C portion in total pool C) was the highest for PLFAs (~1.5% at day 3), whereas 13C content of the cytosol and amino sugars was one and two orders of magnitude less, respectively. Relative 13C incorporation into amino sugars of living microorganisms showed only 0.57% on day 3. Therefore, the turnover of cell membrane components is two times faster than that of cell walls, even in living microorganisms. Both PLFAs and amino sugars showed that glucose C was preferentially used by bacteria. 13C incorporation into bacterial cell walls and membranes decreased with time, but increased or remained constant for fungi, reflecting faster turnover of bacteria than fungi. Consequently, bacteria contribute more to the decomposition of low molecular weight organics, whereas fungi consume bacterial products or necromass and contribute more to long-term C stabilisation. Thus, tracing of 13C in cellular compounds with contrasting turnover provides key information to C fluxes through the soil microbial food-web and elucidates the role of distinct groups as well as individual cellular compartments in SOM formation and C sequestration.

Cellulose and Lignin Carbon Isotope Signatures in Sphagnum Moss Reveal Complementary Environmental Properties

NASA Astrophysics Data System (ADS)

Loisel, J.; Nichols, J. E.; Kaiser, K.; Beilman, D. W.; Yu, Z.

2016-12-01

The carbon isotope signature (δ13C) of Sphagnum moss is increasingly used as a proxy for past surface wetness in peatlands. However, conflicting interpretations of these carbon isotope records have recently been published. While the water film hypothesis suggests that the presence of a thick (thin) water film around hollow (hummock) mosses leads to less (more) negative δ13C values, the carbon source hypothesis poses that a significant (insignificant) amount of CH4 assimilation by hollow (hummock) mosses leads to more (less) negative δ13C values. To evaluate these competing mechanisms and their impact on moss δ13C, we gathered 30 moss samples from 6 peatlands in southern Patagonia. Samples were collected along a strong hydrological gradient, from very dry hummocks (80 cm above water table depth) to submerged hollows (5 cm below water surface). These peat bogs have the advantage of being colonized by a single cosmopolitan moss species, Sphagnum magellanicum, limiting potential biases introduced by species-specific carbon discrimination. We measured δ13C from stem cellulose and leaf waxes on the same samples to quantify compound-specific carbon signatures. We found that stem cellulose and leaf-wax lipids were both strongly negatively correlated with moss water content, suggesting a primary role of water film thickness on carbon assimilation. In addition, isotopic fractionation during wax synthesis was greater than for cellulose. This offset decreases as conditions get drier, due to (i) a more effective carbon assimilation, or (ii) CH4 uptake through symbiosis with methanotrophic bacteria within the leaves of wet mosses. Biochemical analysis (carbohydrates, amino acids, hydrophenols, cutin acids) of surface moss are currently being conducted to characterize moss carbon allocation under different hydrological conditions. Overall, this modern calibration work should be of use for interpreting carbon isotope records from peatlands.

Carbon and nitrogen isotope effects associated with the dioxygenation of aniline and diphenylamine.

PubMed

Pati, Sarah G; Shin, Kwanghee; Skarpeli-Liati, Marita; Bolotin, Jakov; Eustis, Soren N; Spain, Jim C; Hofstetter, Thomas B

2012-11-06

Dioxygenation of aromatic rings is frequently the initial step of biodegradation of organic subsurface pollutants. This process can be tracked by compound-specific isotope analysis to assess the extent of contaminant transformation, but the corresponding isotope effects, especially for dioxygenation of N-substituted, aromatic contaminants, are not well understood. We investigated the C and N isotope fractionation associated with the biodegradation of aniline and diphenylamine using pure cultures of Burkholderia sp. strain JS667, which can biodegrade both compounds, each by a distinct dioxygenase enzyme. For diphenylamine, the C and N isotope enrichment was normal with ε(C)- and ε(N)-values of -0.6 ± 0.1‰ and -1.0 ± 0.1‰, respectively. In contrast, N isotopes of aniline were subject to substantial inverse fractionation (ε(N) of +13 ± 0.5‰), whereas the ε(C)-value was identical to that of diphenylamine. A comparison of the apparent kinetic isotope effects for aniline and diphenylamine dioxygenation with those from abiotic oxidation by manganese oxide (MnO(2)) suggest that the oxidation of a diarylamine system leads to distinct C-N bonding changes compared to aniline regardless of reaction mechanism and oxidant involved. Combined evaluation of the C and N isotope signatures of the contaminants reveals characteristic Δδ(15)N/Δδ(13)C-trends for the identification of diphenylamine and aniline oxidation in contaminated subsurfaces and for the distinction of aniline oxidation from its formation by microbial and/or abiotic reduction of nitrobenzene.

Arylglycerol-γ-Formyl Ester as an Aromatic Ring Cleavage Product of Nonphenolic β-O-4 Lignin Substructure Model Compounds Degraded by Coriolus versicolor†

PubMed Central

Kawai, Shingo; Umezawa, Toshiaki; Higuchi, Takayoshi

1985-01-01

4-Ethoxy-3-methoxyphenylglycerol-γ-formyl ester (compound IV) was identified as a degradation product of both 4-ethoxy-3-methoxyphenylglycerol-β-syringaldehyde ether (compound I) and 4-ethoxy-3-methoxyphenylglycerol-β-2,6-dimethoxyphenyl ether (compound II) by a ligninolytic culture of Coriolus versicolor. An isotopic experiment with a 13C-labeled compound (compound II′) indicated that the formyl group of compound IV was derived from the β-phenoxyl group of β-O-4 dimer as an aromatic ring cleavage fragment. However, compound IV was not formed from 4-ethoxy-3-methoxyphenylglycerol-β-guaiacyl ether (compound III). γ-Formyl arylglycerol (compound IV) could be a precursor of 4-ethoxy-3-methoxyphenylglycerol (compound VI), because 3-(4-ethoxy-3-methoxyphenyl)-1-formyloxy propane (compound VII) was cleaved to give 3-(4-ethoxy-3-methoxyphenyl)-1-propanol (compound VIII) by C. versicolor. 4-Ethoxy-3-methoxyphenylglycerol-β,γ-cyclic carbonate (compound V), previously found as a degradation product of compound III by Phanerochaete chrysosporium (T. Umezawa, and T. Higuchi, FEBS Lett., 25:123-126, 1985), was also identified from the cultures with compound I, II, and III and degraded to give the arylglycerol (compound VI). An isotopic experiment with 13C-labeled compounds II′ and III′ indicated that the carbonate carbon of compound V was derived from the β-phenoxyl groups of β-O-4 substructure. PMID:16346950

77 FR 5207 - Approval and Promulgation of Air Quality Implementation Plans; Delaware; Amendments to the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-02

... compound (VOC) emissions from industrial cleaning solvents facilities, automobile and light-duty truck... Organic Compounds,'' section 13.0, ``Automobile and Light-Duty Truck Coating Operations,'' section 16.0... requirements based on EPA CTGs. Amendments to section 13.0 establish (1) applicability for specific automobile...

A dual positional specific lipoxygenase functions in the generation of flavor compounds during climacteric ripening of apple

PubMed Central

Schiller, Doreen; Contreras, Carolina; Vogt, Jörg; Dunemann, Frank; Defilippi, Bruno G; Beaudry, Randolph; Schwab, Wilfried

2015-01-01

Lipoxygenase (LOX) is an important contributor to the formation of aroma-active C6 aldehydes in apple (Malus × domestica) fruit upon tissue disruption but little is known about its role in autonomously produced aroma volatiles from intact tissue. We explored the expression of 22 putative LOX genes in apple throughout ripening, but only six LOXs were expressed in a ripening-dependent manner. Recombinant LOX1:Md:1a, LOX1:Md:1c, LOX2:Md:2a and LOX2:Md:2b proteins showed 13/9-LOX, 9-LOX, 13/9-LOX and 13-LOX activity with linoleic acid, respectively. While products of LOX1:Md:1c and LOX2:Md:2b were S-configured, LOX1:Md:1a and LOX2:Md:2a formed 13(R)-hydroperoxides as major products. Site-directed mutagenesis of Gly567 to an alanine converted the dual positional specific LOX1:Md:1a to an enzyme with a high specificity for 9(S)-hydroperoxide formation. The high expression level of the corresponding MdLOX1a gene in stored apple fruit, the genetic association with a quantitative trait locus for fruit ester and the remarkable agreement in regio- and stereoselectivity of the LOX1:Md:1a reaction with the overall LOX activity found in mature apple fruits, suggest a major physiological function of LOX1:Md:1a during climacteric ripening of apples. While LOX1:Md:1c, LOX2:Md:2a and LOX2:Md:2b may contribute to aldehyde production in immature fruit upon cell disruption our results furnish additional evidence that LOX1:Md:1a probably regulates the availability of precursors for ester production in intact fruit tissue. PMID:26504564

Direct dating of archaeological pottery by compound-specific 14C analysis of preserved lipids.

PubMed

Stott, Andrew W; Berstan, Robert; Evershed, Richard P; Bronk-Ramsey, Christopher; Hedges, Robert E M; Humm, Martin J

2003-10-01

A methodology is described demonstrating the utility of the compound-specific 14C technique as a direct means of dating archaeological pottery. The method uses automated preparative capillary gas chromatography employing wide-bore capillary columns to isolate individual compounds from lipid extracts of archaeological potsherds in high purity (>95%) and amounts (>200 microg) sufficient for radiocarbon dating using accelerator mass spectrometry (AMS). A protocol was developed and tested on n-alkanes and n-carboxylic acids possessing a broad range of 14C ages. Analytical blanks and controls allowed background 14C measurements to be assessed and potential sources of errors to be detected, i.e., contamination with modern or dead 14C, isotopic fraction effects, etc. A "Russian doll" method was developed to transfer isolated target compounds onto tin powder/capsules prior to combustion and AMS analyses. The major advantage of the compound-specific technique is that 14C dates obtained for individual compounds can be directly linked to the commodities processed in the vessels during their use, e.g., animal fats. The compound-specific 14C dating protocol was validated on a suite of ancient pottery whose predicted ages spanned a 5000-year date range. Initial results indicate that meaningful correlations can be obtained between the predicted date of pottery and that of the preserved lipids. These findings constitute an important step forward to the direct dating of archaeological pottery.

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

NASA Astrophysics Data System (ADS)

McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

2004-10-01

Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (

Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

NASA Astrophysics Data System (ADS)

McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

2004-10-01

Long-chain, odd-carbon-numbered C25 to C35n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (

Relationships between carbon isotope evolution and variation of microbes during the Permian-Triassic transition at Meishan Section, South China

NASA Astrophysics Data System (ADS)

Luo, Genming; Huang, Junhuang; Xie, Shucheng; Wignall, Paul B.; Tang, Xinyan; Huang, Xianyu; Yin, Hongfu

2010-06-01

This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ13Ccarb-kero = δ 13Ccarb - δ 13Ckero) and the difference between carbonate and n-C19 alkane compound-specific carbon isotopes (Δ13Ccarb- n-C19 = δ 13Ccarb - δ 13C n-C19) during the Permian-Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23-25 and 26-29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ13Ccarb-kero and Δ13Ccarb- n-C19, which are mainly affected by CO2-fixing enzyme and pCO2, oscillated frequently during the Permian-Triassic transition. Both the variations of Δ13Ccarb- n-C19 and Δ13Ccarb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ13Ccarb- n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ13Ccarb- n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian-Triassic crisis.

Hypersaline Microbial Mat Lipid Biomarkers

NASA Technical Reports Server (NTRS)

Jahnke, Linda L.; Embaye, Tsegereda; Turk, Kendra A.; Summons, Roger E.

2002-01-01

Lipid biomarkers and compound specific isotopic abundances are powerful tools for studies of contemporary microbial ecosystems. Knowledge of the relationship of biomarkers to microbial physiology and community structure creates important links for understanding the nature of early organisms and paleoenvironments. Our recent work has focused on the hypersaline microbial mats in evaporation ponds at Guerrero Negro, Baja California Sur, Mexico. Specific biomarkers for diatoms, cyanobacteria, archaea, green nonsulfur (GNS), sulfate reducing, sulfur oxidizing and methanotrophic bacteria have been identified. Analyses of the ester-bound fatty acids indicate a highly diverse microbial community, dominated by photosynthetic organisms at the surface. The delta C-13 of cyanobacterial biomarkers such as the monomethylalkanes and hopanoids are consistent with the delta C-13 measured for bulk mat (-10%o), while a GNS biomarker, wax esters (WXE), suggests a more depleted delta C-13 for GNS biomass (-16%o). This isotopic relationship is different than that observed in mats at Octopus Spring, Yellowstone National Park (YSNP) where GNS appear to grow photoheterotrophic ally. WXE abundance, while relatively low, is most pronounced in an anaerobic zone just below the cyanobacterial layer. The WXE isotope composition at GN suggests that these bacteria utilize photoautotrophy incorporating dissolved inorganic carbon (DIC) via the 3-hydroxypropionate pathway using H2S or H2.

Synthesis, spectroscopic characterization, and antibacterial evaluation of new Schiff bases bearing benzimidazole moiety

NASA Astrophysics Data System (ADS)

Redayan, Muayed Ahmed; Salih Hussein, Maha; Tark lafta, Ashraf

2018-05-01

The present work comprise synthesis of new derivatives for Schiff bases bearing benzimidazole ring. Compounds 1(a-d) were prepared by reaction of o-pheneylenediamine with a various of amino acids (glycine, alanine, phenyl alanine and tyrosine) in the presence 6N HCl to yielded derivatives of benzimidazole compounds containing free –NH2 group. Then these compounds used to prepare different Schiff bases through reaction with various of aromatic aldehydes. The chemical structure of synthesized compounds were confirmed by FTIR,1H,13C-NMR, and 13C-NMR dept135 spectroscopy. Some selected compounds were evaluated in vitro for their antibacterial activity against two types of Gram-positive bacteria namely (Staphylococcous aureus, Bacillus subtilis) and Gram-negative bacteria namely (Pseudomonas aeruginosa, Escherichia coli). Most of the results of the antibacterial activity of these compounds were good when compared with the standard antibiotic ampicillin and ciprofloxacin.

Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

NASA Technical Reports Server (NTRS)

Cooper, George

2004-01-01

Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

A review of dicarboxylic acids and related compounds in atmospheric aerosols: Molecular distributions, sources and transformation

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; Bikkina, Srinivas

2016-03-01

This review aims to update our understanding on molecular distributions of water-soluble dicarboxylic acids and related compounds in atmospheric aerosols with a focus on their geographical variability, size distribution, sources and formation pathways. In general, molecular distributions of diacids in aerosols from the continental sites and over the open ocean waters are often characterized by the predominance of oxalic acid (C2) followed by malonic acid (C3) and/or succinic acid (C4), while those sampled over the polar regions often follow the order of C4 ≥ C2 and C3. The most abundant and ubiquitous diacid is oxalic acid, which is principally formed via atmospheric oxidation of its higher homologues of long chain diacids and other pollution-derived organic precursors (e.g., olefins and aromatic hydrocarbons). However, its occurrence in marine aerosols is mainly due to the transport from continental outflows (e.g., East Asian outflow during winter/spring to the North Pacific) and/or governed by photochemical/aqueous phase oxidation of biogenic unsaturated fatty acids (e.g., oleic acid) and isoprene emitted from the productive open ocean waters. The long-range atmospheric transport of pollutants from mid latitudes to the Arctic in dark winter facilitates to accumulate the reactants prior to their intense photochemical oxidation during springtime polar sunrise. Furthermore, the relative abundances of C2 in total diacid mass showed similar temporal trends with downward solar irradiation and ambient temperatures, suggesting the significance of atmospheric photochemical oxidation processing. Compound-specific isotopic analyses of oxalic acid showed the highest δ13C among diacids whereas azelaic acid showed the lowest value, corroborating the significance of atmospheric aging of oxalic acid. On the other hand, other diacids gave intermediate values between these two diacids, suggesting that aging of oxalic acid is associated with 13C enrichment.

Synthesis, crystal structure and antioxidant evaluation of C-4-acetamidophenylcalix[4]pyrogallolarene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abosadiya, Hamza M.; Hasbullah, Siti Aishah; Yamin, Bohari M.

2015-09-25

C-4-acetamidophenylcalix[4]pyrogallolarene was synthesized by an acid catalyzed condensation reaction of pyrogallol with 4-acetamidobenzaldehyde. The compound was characterized by IR, {sup 1}H and {sup 13}C NMR spectroscopy. Single crystal X-ray analysis revealed that the molecule crystallized in a triclinic system with space group Pī and the unit cell dimensions a= 12.2948(16) Å, b= 13.4423(17) Å, c= 13.5906(18) Å, α =107.549(4)°, β =102.034(4)°, γ =90.535(4)°, Z= 1 and V= 2088.2(5) Å{sup 3}. The macrocyclic calix adopts a chair (C{sub 2h}) conformation and the molecule is associated with eight DMSO molecules of crystallization. Antioxidant test by DPPH method showed that the compound exhibitsmore » good antioxidant activity of about 72%.« less

A novel tridentate Schiff base dioxo-molybdenum(VI) complex: synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, ¹H NMR and ¹³C NMR spectra.

PubMed

Saheb, Vahid; Sheikhshoaie, Iran; Stoeckli-Evans, Helen

2012-09-01

A new dioxo-molybdenum(VI) complex [MoO(2)(L)(H(2)O)] has been synthesized, using 5-methoxy 2-[(2-hydroxypropylimino)methyl]phenol as tridentate ONO donor Schiff base ligand (H(2)L) and MoO(2)(acac)(2). The yellow crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the UV-visible, FTIR, (1)H NMR and (13)C NMR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TDDFT) method is used to calculate the electronic transitions of the complex. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR shielding tensors computed at the B3LYP/DGDZVP level of theory is in agreement with experimental (1)H NMR spectra. However, the (13)C NMR shielding tensors computed at the B3LYP level, employing a combined basis set of DGDZVP for Mo and 6-31+G(2df,p) for other atoms, are in better agreement with experimental (13)C NMR spectra. The electronic transitions calculated at the B3LYP/DGDZVP level by using TD-DFT method is in accordance with the observed UV-visible spectrum of the compound. Copyright © 2012 Elsevier B.V. All rights reserved.

Discrete taxa of saprotrophic fungi respire different ages of carbon from Antarctic soils.

PubMed

Newsham, Kevin K; Garnett, Mark H; Robinson, Clare H; Cox, Filipa

2018-05-18

Different organic compounds have distinct residence times in soil and are degraded by specific taxa of saprotrophic fungi. It hence follows that specific fungal taxa should respire carbon of different ages from these compounds to the atmosphere. Here, we test whether this is the case by radiocarbon ( 14 C) dating CO 2 evolved from two gamma radiation-sterilised maritime Antarctic soils inoculated with pure single cultures of four fungi. We show that a member of the Helotiales, which accounted for 41-56% of all fungal sequences in the two soils, respired soil carbon that was aged up to 1,200 years BP and which was 350-400 years older than that respired by the other three taxa. Analyses of the enzyme profile of the Helotialean fungus and the fluxes and δ 13 C values of CO 2 that it evolved suggested that its release of old carbon from soil was associated with efficient cellulose decomposition. Our findings support suggestions that increases in the ages of carbon respired from warmed soils may be caused by changes to the abundances or activities of discrete taxa of microbes, and indicate that the loss of old carbon from soils is driven by specific fungal taxa.

Evaluation of ethyl tert-butyl ether biodegradation in a contaminated aquifer by compound-specific isotope analysis and in situ microcosms.

PubMed

Bombach, Petra; Nägele, Norbert; Rosell, Mònica; Richnow, Hans H; Fischer, Anko

2015-04-09

Ethyl tert-butyl ether (ETBE) is an upcoming groundwater pollutant in Europe whose environmental fate has been less investigated, thus far. In the present study, we investigated the in situ biodegradation of ETBE in a fuel-contaminated aquifer using compound-specific stable isotope analysis (CSIA), and in situ microcosms in combination with total lipid fatty acid (TLFA)-stable isotope probing (SIP). In a first field investigation, CSIA revealed insignificant carbon isotope fractionation, but low hydrogen isotope fractionation of up to +14‰ along the prevailing anoxic ETBE plume suggesting biodegradation of ETBE. Ten months later, oxygen injection was conducted to enhance the biodegradation of petroleum hydrocarbons (PH) at the field site. Within the framework of this remediation measure, in situ microcosms loaded with [(13)C6]-ETBE (BACTRAP(®)s) were exposed for 119 days in selected groundwater wells to assess the biodegradation of ETBE by TLFA-SIP under the following conditions: (i) ETBE as main contaminant; (ii) ETBE as main contaminant subjected to oxygen injection; (iii) ETBE plus other PH; (iv) ETBE plus other PH subjected to oxygen injection. Under all conditions investigated, significant (13)C-incorporation into microbial total lipid fatty acids extracted from the in situ microcosms was found, providing clear evidence of ETBE biodegradation. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of saponins and flavonoids in ivy leaf extracts using HPLC-DAD.

PubMed

Yu, Miao; Shin, Young June; Kim, Nanyoung; Yoo, Guijae; Park, SeonJu; Kim, Seung Hyun

2015-04-01

A new method for the determination of six compounds, chlorogenic acid, rutin, nicotiflorin, hederacoside C, hederasaponin B and α-hederin, in ivy leaf extracts using high-performance liquid chromatography with diode array detector was developed. The chromatographic separation was performed on a YMC Hydrosphere C18 analytical column using a gradient elution of 0.1% phosphoric acid and acetonitrile. The method was validated in terms of specificity, linearity (r(2) > 0.9999), precision [relative standard deviation (RSD) < 0.36%] and accuracy (97.4-103.8%). The limit of detection and limit of quantification were <20.32 and 61.56 ng for all analytes, respectively. The tested compounds were found to be stable in the ivy leaf extract from 0 to 48 h, and the RSD value for each compound was <0.90%. The validated method was successfully applied to quantify all six compounds in a 30% ethanol ivy leaf extract and 13 ivy leaf extract products. The results showed that all the tested products satisfied the minimum requirement for the content of hederacoside C. However, there were some differences between the contents of other constituents. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

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

NASA Astrophysics Data System (ADS)

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.

Trivanillic polyphenols with anticancer cytostatic effects through the targeting of multiple kinases and intracellular Ca2+ release

PubMed Central

Lamoral-Theys, Delphine; Wauthoz, Nathalie; Heffeter, Petra; Mathieu, Véronique; Jungwirth, Utte; Lefranc, Florence; Nève, Jean; Dubois, Jacques; Dufrasne, François; Amighi, Karim; Berger, Walter; Gailly, Philippe; Kiss, Robert

2012-01-01

Abstract Cancer cells exhibit de-regulation of multiple cellular signalling pathways and treatments of various types of cancers with polyphenols are promising. We recently reported the synthesis of a series of 33 novel divanillic and trivanillic polyphenols that displayed anticancer activity, at least in vitro, through inhibiting various kinases. This study revealed that minor chemical modifications of a trivanillate scaffold could convert cytotoxic compounds into cytostatic ones. Compound 13c, a tri-chloro derivative of trivanillic ester, displayed marked inhibitory activities against FGF-, VEGF-, EGF- and Src-related kinases, all of which are implicated not only in angiogenesis but also in the biological aggressiveness of various cancer types. The pan-anti-kinase activity of 13c occurs at less than one-tenth of its mean IC50in vitro growth inhibitory concentrations towards a panel of 12 cancer cell lines. Of the 26 kinases for which 13c inhibited their activity by >75%, eight (Yes, Fyn, FGF-R1, EGFR, Btk, Mink, Ret and Itk) are implicated in control of the actin cytoskeleton organization to varying degrees. Compound 13c accordingly impaired the typical organization of the actin cytoskeleton in human U373 glioblastoma cells. The pan-anti-kinase activity and actin cytoskeleton organization impairment provoked by 13c concomitantly occurs with calcium homeostasis impairment but without provoking MDR phenotype activation. All of these anticancer properties enabled 13c to confer therapeutic benefits in vivo in a mouse melanoma pseudometastatic lung model. These data argue in favour of further chemically modifying trivanillates to produce novel and potent anticancer drugs. PMID:21810170

Novel aldehyde and thiosemicarbazone derivatives: Synthesis, spectroscopic characterization, structural studies and molecular docking studies

NASA Astrophysics Data System (ADS)

Karakurt, Tuncay; Tahtaci, Hakan; Subasi, Nuriye Tuna; Er, Mustafa; Ağar, Erbil

2016-12-01

In this study our purpose is that, synthesis and characterization of compounds containing the aldehyde and thiosemicarbazone groups and comparison of the theoretical results with the experimental results. The structures of all synthesized compounds were elucidated by IR, 1H NMR, 13C NMR, elemental analyses techniques. The structure of compound (4) (C9H8N4O2S) was also elucidated by X-ray diffraction analysis. In addition, the theoretical IR spectrum, 1H NMR and 13C NMR chemical shift values, frontier molecular orbital values (FMO) of these molecules were analyzed by using Becke-3- Lee-Yang-Parr (B3LYP) method with LanL2DZ basis set. Finally, molecular docking studies were performed on synthesized compounds using the 4DKI beta-lactam protein structure to determine the potential binding mode of inhibitors.

A new approach to understand methylmercury (CH3Hg) sources and transformation pathways: Compound-specific carbon stable isotope analysis by GC-C-IRMS

NASA Astrophysics Data System (ADS)

Baya, P. A.; Point, D.; Amouroux, D. P.; Lebreton, B.; Guillou, G.

2015-12-01

Methylmercury (CH3Hg) is a potent neurotoxin which is readily assimilated by organisms and bio-accumulates in aquatic food webs. In humans, consumption of CH3Hg contaminated marine fish is the major route of mercury exposure. However, our understanding of CH3Hg transformation pathways is still incomplete. To close this knowledge gap, we propose to explore the stable carbon isotopic composition (δ13C) of the methyl group of CH3Hg for a better understanding of its sources and transformation mechanisms. The method developed for the determination of the δ13C value of CH3Hg in biological samples involves (i) CH3Hg selective extraction, (ii) derivatization, and (iii) separation by gas chromatography (GC) prior to analysis by combustion isotope ratio mass spectrometry (C-IRMS). We present the figures of merit of this novel method and the first δ13C signatures for certified materials (ERM-CE464, BCR414) and biological samples at different marine trophic levels (i.e., tuna fish, zooplankton). The implications of this new approach to trace the pathways associated with Hg methylation and the mechanisms involved will be discussed.

Variability in the carbon isotope composition of individual amino acids in plant proteins from different sources: 1 Leaves.

PubMed

Lynch, Anthony H; Kruger, Nicholas J; Hedges, Robert E M; McCullagh, James S O

2016-05-01

The natural carbon isotope composition of individual amino acids from plant leaf proteins has been measured to establish potential sources of variability. The plant leaves studied, taken from a range of plant groups (forbs, trees, grasses, and freshwater aquatic plants), showed no significant influence of either season or environment (water and light availability) on their Δδ(13)C values. Plant groups did, however, differ in carbon isotope composition, although no consistent differences were identified at the species level. A discriminant analysis model was constructed which allowed leaves from (1) nettles, (2) Pooideae, (3) other Poales, (4) trees and (5) freshwater higher plants to be distinguished from each other on the basis of their natural abundance (13)C/(12)C ratios of individual amino acids. Differences in carbon isotope composition are known to be retained, to some extent, in the tissues of their consumers, and hence an understanding of compound-specific variation in (13)C/(12)C fractional abundance in plants has the potential to provide dietary insights of value in archaeological and ecological studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Novel endohedral derivatives of Sc3N C2n (n = 34, 40) and unique tether controlled bis-functionalization of fullerenes

NASA Astrophysics Data System (ADS)

Ceron Hernandez, Maira Raquel

Since the discovery of fullerenes in 1985, their exohedral functionalization has been necessary to increase their solubility and explore their properties and potential applications in materials science and medicinal chemistry. This thesis provides a short overview of the importance of electronic, size and shape complementarity in determining the structures of specific endohedral fullerene compounds. This is followed by a description of a new method for the separation of scandium nitride endohedral fullerenes Sc3N C2n (n = 34, 39 and 40), and their monofunctionalization. We also present the regioselective synthesis of easily isolable bis-derivatives of C60, C70, and M3N Ih-C80 (M = Sc, Lu) using 1,3-dipolar, addition/elimination (Bingel reaction) and diazo cycloadditions. The following sections are composed of a brief introduction and a pre-peer reviewed version of the published article, each section follows its own nomenclature and numerical order. The experimental section in each section includes methods, synthesis and characterization of the most relevant compounds.

Effects of acidification, lipid removal and mathematical normalization on carbon and nitrogen stable isotope compositions in beaked whale (Ziphiidae) bone.

PubMed

Tatsch, Ana Carolina C; Secchi, Eduardo R; Botta, Silvina

2016-02-15

The analysis of stable isotopes in tissues such as teeth and bones has been used to study long-term trophic ecology and habitat use in marine mammals. However, carbon isotope ratios (δ(13) C values) can be altered by the presence of (12) C-rich lipids and carbonates. Lipid extraction and acidification are common treatments used to remove these compounds. The impact of lipids and carbonates on carbon and nitrogen isotope ratios (δ(15) N values), however, varies among tissues and/or species, requiring taxon-specific protocols to be developed. The effects of lipid extraction and acidification and their interaction on carbon and nitrogen isotope values were studied for beaked whale (Ziphiidae) bone samples. δ(13) C and δ(15) N values were determined in quadruplicate samples: control, lipid-extracted, acidified and lipid-extracted followed by acidification. Samples were analyzed by means of elemental analysis isotope ratio mass spectrometry. Furthermore, the efficiency of five mathematical models developed for estimating lipid-normalized δ(13) C values from untreated δ(13) C values was tested. Significant increases in δ(13) C values were observed after lipid extraction. No significant changes in δ(13) C values were found in acidified samples. An interaction between both treatments was demonstrated for δ(13) C but not for δ(15) N values. No change was observed in δ(15) N values for lipid-extracted and/or acidified samples. Although all tested models presented good predictive power to estimate lipid-free δ(13) C values, linear models performed best. Given the observed changes in δ(13) C values after lipid extraction, we recommend a priori lipid extraction or a posteriori lipid normalization, through simple linear models, for beaked whale bones. Furthermore, acidification seems to be an unnecessary step before stable isotope analysis, at least for bone samples of ziphiids. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Quorum sensing inhibitors from marine bacteria Oceanobacillus sp. XC22919.

PubMed

Chen, Xiaochun; Chen, Jianwei; Yan, Yinchun; Chen, Su; Xu, Xuewei; Zhang, Huawei; Wang, Hong

2018-02-12

In this study, three active compounds isolated from Oceanobacillus sp. XC22919 were identified as 2-methyl-N-(2'-phenylethyl) butyramide (1), 3-methyl-N-(2'-phenylethyl)-butyramide (2) and benzyl benzoate (3), and were first reported to exhibit the apparent quorum sensing inhibitory activities against C. violaceum 026 and P. aeruginosa. Compounds 1-3 inhibited violacein production of C. violaceum 026 by 10.5-55.7, 11.2-55.7, and 27.2%-95.7%, respectively, and inhibited pyocyanin production of P. aeruginosa by 1.7-50.8, 39.1-90.7, and 57.2%-98.7%, respectively. The azocasein-degrading proteolytic rates of P. aeruginosa were observed by 13.4-31.5, 13.4-28.8, and 11.3%-21.1%, respectively. With respect to elastase, the range of inhibition of activity of compounds 1-3 was 2.1-30.3, 4.2-18.2, and 8.9%-15.7%, respectively. Compounds 1 and 3 also showed a concentration-dependent attenuation in biofilm formation, with the maximum of 50.6% inhibition, and 37.7% inhibition at 100 μg/mL, respectively.

Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

1989-01-01

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

Zwitterionic and free forms of arylmethyl Meldrum's acids.

PubMed

Mierina, Inese; Mishnev, Anatoly; Jure, Mara

2015-09-01

C-Alkyl (including C-arylmethyl) derivatives of Meldrum's acids are attractive building blocks in organic synthesis, mainly due to the unusually high acidity of the resulting compounds. Three examples, namely 5-[4-(diethylamino)benzyl]-2,2-dimethyl-1,3-dioxane-4,6-dione, C17H23NO4, (I), 2,2-dimethyl-5-(2,4,6-trimethoxybenzyl)-1,3-dioxane-4,6-dione, C16H20O7, (II), and 5-(4-hydroxy-3,5-dimethoxybenzyl)-2,2-dimethyl-1,3-dioxane-4,6-dione, C15H18O7, (III), have been synthesized, characterized by NMR and IR spectroscopy, and studied by single-crystal X-ray structure analysis. The nature of the different substituents resulted in remarkable differences in both the molecular conformations and the crystal packing arrangements. The presence of a substituent with a basic centre in compound (I) leads to the formation of an inner salt accompanied by drastic changes in the conformation of the 1,3-dioxane-4,6-dione fragment. By virtue of strong N-H···O hydrogen bonds, the residues are assembled into infinite chains with the graph-set descriptor C(10). Compound (II) contains methoxy groups in both the ortho- and para-positions of the arylmethyl fragment. Because of the absence of classical hydrogen-bond donors in this structure, the crystal packing is controlled by van der Waals forces and weak C-H···O interactions. Compound (III) contains methoxy groups in both meta-positions and a hydroxy group in the para-position. Supramolecular tetrameric synthons which comprise hydrogen-bonded dimers associated into tetramers through π-π interactions of overlapping benzene rings were observed.

Root carbon decomposition and microbial biomass response at different soil depths

NASA Astrophysics Data System (ADS)

Rumpel, C.

2012-12-01

The relationship between root litter addition and soil organic matter (SOM) formation in top- versus subsoils is unknown. The aim of this study was to investigate root litter decomposition and stabilisation in relation to microbial parameters in different soil depths. Our conceptual approach included incubation of 13C-labelled wheat roots at 30, 60 and 90 cm soil depth for 36 months under field conditions. Quantitative root carbon contribution to SOM was assessed, changes of bulk root chemistry studied by solid-state 13C NMR spectroscopy and lignin content and composition was assessed after CuO oxidation. Compound-specific isotope analysis allowed to assess the role of root lignin for soil C storage in the different soil depths. Microbial biomass and community structure was determined after DNA extraction. After three years of incubation, O-alkyl C most likely assigned to polysaccharides decreased in all soil depth compared to the initial root material. The degree of root litter decomposition assessed by the alkyl/O-alkyl ratio decreased with increasing soil depth, while aryl/O-alkyl ratio was highest at 60 cm depth. Root-derived lignin showed depth specific concentrations (30 < 90 < 60 cm). Its composition was soil depth independent suggesting that microbial communities in all three soil depths had similar degradation abilities. Microbial biomass C and fungi contribution increased after root litter addition. Their community structure changed after root litter addition and showed horizon specific dynamics. Our study shows that root litter addition can contribute to C storage in subsoils but did not influence C storage in topsoil. We conclude that specific conditions of single soil horizons have to be taken into account if root C dynamics are to be fully understood.

N-(5-chloro-1,3-benzodioxol-4-yl)-7-[2-(4-methylpiperazin-1-yl)ethoxy]-5- (tetrahydro-2H-pyran-4-yloxy)quinazolin-4-amine, a novel, highly selective, orally available, dual-specific c-Src/Abl kinase inhibitor.

PubMed

Hennequin, Laurent F; Allen, Jack; Breed, Jason; Curwen, Jon; Fennell, Michael; Green, Tim P; Lambert-van der Brempt, Christine; Morgentin, Rémy; Norman, Richard A; Olivier, Annie; Otterbein, Ludovic; Plé, Patrick A; Warin, Nicolas; Costello, Gerard

2006-11-02

Src family kinases (SFKs) are nonreceptor tyrosine kinases that are reported to be critical for cancer progression. We report here a novel subseries of C-5-substituted anilinoquinazolines that display high affinity and specificity for the tyrosine kinase domain of the c-Src and Abl enzymes. These compounds exhibit high selectivity for SFKs over a panel of recombinant protein kinases, excellent pharmacokinetics, and in vivo activity following oral dosing. N-(5-Chloro-1,3-benzodioxol-4-yl)-7-[2-(4-methylpiperazin-1-yl)ethoxy]-5-(tetrahydro-2H-pyran-4-yloxy)quinazolin-4-amine (AZD0530) inhibits c-Src and Abl enzymes at low nanomolar concentrations and is highly selective over a range of kinases. AZD0530 displays excellent pharmacokinetic parameters in animal preclinically and in man (t(1/2) = 40 h). AZD0530 is a potent inhibitor of tumor growth in a c-Src-transfected 3T3-fibroblast xenograft model in vivo and led to a significant increase in survival in a highly aggressive, orthotopic model of human pancreatic cancer when dosed orally once daily. AZD0530 is currently undergoing clinical evaluation in man.

Contribution of microbial carbon to soil fractions: significance of diverse microbial group biochemistry

NASA Astrophysics Data System (ADS)

Throckmorton, H.; Bird, J. A.; Dane, L.; Firestone, M. K.; Horwath, W. R.

2011-12-01

The importance of diverse microbial groups to soil C maintenance is still a matter of debate. This study follows the turnover of 13C labeled nonliving residues from diverse microbial groups into soil physical fractions in situ in a temperate forest in California (CA) and a tropical forest in Puerto Rico (PR), during 5 sampling points per site- over a 3 and 2 year period, respectively. Microbial groups include fungi, actinomycetes, Gm(+) bacteria, and Gm(-) bacteria, isolated from CA and PR soils to obtain temperate and tropical isolates composited of 3-4 species per group. The selected density fractionation approach isolated: a "light fraction" (LF), non-mineral aggregate "occluded fraction" (OF), and a "mineral bound fraction" (MF). Pyrolysis gas chromatography mass spectrometry (Py-GC-MS) was employed to characterize microbial group isolates, whole soils, and fractions. Microbial isolates contained unique biochemical fingerprints: temperate and tropical fungi and tropical Gm(-) were characterized by a low abundance of phenol, benzene, and N-compounds compared with other microbial group isolates. Py-GC-MS revealed compositional differences among soil fractions at both sites, likely attributed to differences in the decomposition stage and C source material (ie. plant vs. microbial). For both sites, benzene and N-compounds were greatest in the MF; lignin and phenol compounds were greatest in the LF; and lipids were greatest in the OF. The trend for polysaccharides differed between sites, with the greatest concentration in the CA OF; and for PR with the lowest concentration in the OF, and similar concentrations in the LF and MF. SOM chemistry was most similar between sites in the LF, compared with the OF and MF, suggesting that differences in SOM chemistry between sites may be more attributed to differential decomposition processes than unique litter quality inputs. A substantial portion of microbial C moved from the LF into the OF, and the MF by the first sampling point for both sites. Microbial C inputs were more stable in the OF and MF than the LF throughout the course of the study at both sites. There were no differences in 13C recovery among microbial isolates in any fractions in PR, despite minor differences in overall turnover rates. In CA, there were some differences among microbial isolates in 13C recovery in the LF and OF, which related to 13C recoveries in whole soils. In the CA MF, microbial 13C recoveries did not significantly differ, and in generally low variability among treatments was observed. Results support increased protection of microbial C via association with the MF; however, differential sorption of various microbial group isolates over others was not observed. Overall results suggest that inherent properties of microbial residues may be more important to determining its stability in CA soils when it is 1) unassociated with the mineral matrix (LF); or 2) physically occluded within aggregates; compared with that intimately associated with mineral surfaces (MF). Compound-specific recovery of microbial isolates with Py-GC-MS-IRMS will be discussed.

Charge-associated effects of fullerene derivatives on microbialstructural integrity and central metabolism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Yinjie J.; Ashcroft, Jared M.; Chen, Ding

2007-01-23

The effects of four types of fullerene compounds (C60,C60-OH, C60-COOH, C60-NH2) were examined on two model microorganisms(Escherichia coli W3110 and Shewanella oneidensis MR-1). Positivelycharged C60-NH2 at concentrations as low as 10 mg/L inhibited growth andreduced substrate uptake for both microorganisms. Scanning ElectronMicroscopy (SEM) revealed damage to cellular structures.Neutrally-charged C60 and C60-OH had mild negative effects on S.oneidensis MR-1, whereas the negatively-charged C60-COOH did not affecteither microorganism s growth. The effect of fullerene compounds onglobal metabolism was further investigated using [3-13C]L-lactateisotopic labeling, which tracks perturbations to metabolic reaction ratesin bacteria by examining the change in the isotopic labeling pattern inthe resultingmore » metabolites (often amino acids).1-3 The 13C isotopomeranalysis from all fullerene-exposed cultures revealed no significantdifferences in isotopomer distributions from unstressed cells. Thisresult indicates that microbial central metabolism is robust toenvironmental stress inflicted by fullerene nanoparticles. In addition,although C60-NH2 compounds caused mechanical stress on the cell wall ormembrane, both S. oneidensis MR-1 and E. coli W3110 can efficientlyalleviate such stress by cell aggregation and precipitation of the toxicnanoparticles. The results presented here favor the hypothesis thatfullerenes cause more membrane stress4, 5, 6 than perturbation to energymetabolism7« less

Identifying root exudates in field contaminated soil systems

NASA Astrophysics Data System (ADS)

Rosenfeld, C.; Martinez, C. E.

2012-12-01

Carbon (C) compounds exuded from plant roots comprise a significant and reactive fraction of belowground C pools. These exudates substantially alter the soil directly surrounding plant roots and play a vital role in the global C cycle, soil ecology, and ecosystem mobility of both nutrients and contaminants. In soils, the solubility and bioavailability of metals such as iron, zinc, and cadmium are intricately linked to the quantity and chemical characteristics of the C compounds allocated to the soil by plants. Cadmium (Cd), a toxic heavy metal, forms stronger bonds with reduced S- and N-containing compounds than with carboxylic acids, which may influence exudate composition in hyperaccumulator and tolerant plants grown in Cd contaminated soils. We hypothesize that hyperaccumulator plants will exude a larger quantity of aromatic N and chelating di- and tri-carboxylic acid molecules, while plants that exclude heavy metals from uptake will exude a larger proportion of reduced S containing molecules. This study examines how a variety of techniques can measure the low concentrations of complex organic mixtures exuded by hyperaccumulator and non-hyperaccumulator plants grown in Cd-contaminated soils. Two congeneric plants, Thlaspi caerulescens (Ganges ecotype), and T. caerulescens (Prayon ecotype) were grown in 0.5 kg pots filled with Cd-contaminated field soils from Chicago, IL. Field soils were contaminated as a result of the application of contaminated biosolids in the 1960's and 1970's. Pots were fitted for rhizon soil moisture samplers, micro-lysimeters developed for in situ collection of small volumes in unsaturated soils, prior to planting. Plants were grown for 8 weeks before exudate collection. After the 8 weeks of growth, a pulse-chase isotope tracer method using the C stable isotope, 13C, was employed to differentiate plant-derived compounds from background soil and microbial-derived compounds. Plants were placed in a CO2 impermeable chamber, and the soil surface was covered by CO2 impermeable sheets to ensure that all 13C in the soil results from photoassimilated C released by roots and not soil-atmosphere gas exchange. Ambient CO2 was drawn down in the system until the CO2 concentration within the tent was less than 50 ppm, after which the labeled 13CO2 was introduced, returning the CO2 concentration to the ambient level (~375 ppm). The CO2 pulse lasted for 60 minutes to allow enough time for 13C assimilation within the plants. In order to determine the ideal sampling time, soil pore water samples were extracted every 1-2 hours following the 13C pulse application, over the course of 24 hours. Samples were analyzed for delta 13C as well as %C, and results indicate that the greatest plant-derived dissolved organic C is present at about 6 hours following the 13C pulse. A second experiment will also be conducted using a combination of NMR and mass spectrometry methods to obtain detailed information regarding chemical structures within exudate samples.

Physico-chemical protection, rather than biochemical composition, governs the responses of soil organic carbon decomposition to nitrogen addition in a temperate agroecosystem.

PubMed

Tan, Wenbing; Wang, Guoan; Huang, Caihong; Gao, Rutai; Xi, Beidou; Zhu, Biao

2017-11-15

The heterogeneous responses of soil organic carbon (SOC) decomposition in different soil fractions to nitrogen (N) addition remain elusive. In this study, turnover rates of SOC in different aggregate fractions were quantified based on changes in δ 13 C following the conversion of C 3 to C 4 vegetation in a temperate agroecosystem. The turnover of both total organic matter and specific organic compound classes within each aggregate fraction was inhibited by N addition. Moreover, the intensity of inhibition increases with decreasing aggregate size and increasing N addition level, but does not vary among chemical compound classes within each aggregate fraction. Overall, the response of SOC decomposition to N addition is dependent on the physico-chemical protection of SOC by aggregates and minerals, rather than the biochemical composition of organic substrates. The results of this study could help to understand the fate of SOC in the context of increasing N deposition. Copyright © 2017 Elsevier B.V. All rights reserved.

A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site

NASA Astrophysics Data System (ADS)

Nijenhuis, Ivonne; Schmidt, Marie; Pellegatti, Eleonora; Paramatti, Enrico; Richnow, Hans Hermann; Gargini, Alessandro

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50 years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in 13C (<-60‰) suggesting production lines which have used depleted methane for synthesis. The other source had typical carbon isotope compositions of >-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, 13C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas.

Chemical Constituents of Murraya tetramera Huang and Their Repellent Activity against Tribolium castaneum.

PubMed

You, Chun-Xue; Guo, Shan-Shan; Zhang, Wen-Juan; Geng, Zhu-Feng; Liang, Jun-Yu; Lei, Ning; Du, Shu-Shan; Deng, Zhi-Wei

2017-08-20

Sixteen compounds were isolated from the leaves and stems of Murraya tetramera Huang. Based on the NMR and MS spectral results, the structures were determined. It was confirmed that the isolated compounds included three new compounds ( 9 , 10 and 13 ) and one new natural product ( 8 ), which were identified asmurratetra A ( 9 ), murratetra B ( 10 ), murratetra C ( 13 ) and [2-(7-methoxy-2-oxochromen-8-yl)-3-methylbut-2-enyl]3-methylbut-2-enoate ( 8 ), respectively. Meanwhile, the repellent activity against Tribolium castaneum was investigated for 13 of these isolated compounds. The results showed that the tested compounds had various levels of repellent activity against T. castaneum . Among them, compounds 1 (4(15)-eudesmene-1β,6α-diol), 11 (isoferulic acid) and 16 (2,3-dihydroxypropyl hexadecanoate) showed fair repellent activity against T. castaneum . They might be considered as potential leading compounds for the development of natural repellents.

Organic compound composition in soil and sediments collected in Jackson, Mississippi.

PubMed

Gołębiowski, Marek; Stepnowski, Piotr; Hemmingway, Tometrick; Leszczyńska, Danuta

2016-01-01

The aim of our study was to identify organic pollutants found in soil and sediment samples collected within the Jackson, MS metropolitan area. The chemical characterization of the organic compound fractions in soil and sediment samples was carried out by separating the organic fraction using column chromatography (CC) and quantitatively analyzing the polycyclic aromatic hydrocarbons (PAHs), n-alkanes and other organic compounds using gas chromatography-electron impact mass spectrometry (GC-MS). Fifty-six compounds were identified and quantified in the soil samples and 33 compounds were identified and quantified in the sediment samples. The PAHs, n-alkanes and other organic compound profiles in the soil and sediment samples were compared. The percentage contents of the organic compounds in the soil samples were very diverse (from traces to 12.44 ± 1.47%). The compounds present in the highest concentrations were n-alkanes: n-C31 (12.44 ± 1.47%), n-C29 (11.64 ± 1.21%), and n-C33 (8.95 ± 1.08%). The components occurring in smaller quantities (from 1% to 5%) were 2 PAHs (fluoranthene 1.28 ± 0.25%, pyrene 1.16 ± 0.20%), 10 n-alkanes from n-C21 (1.25 ± 0.29%) to n-C32 (2.67 ± 0.52%) and 11 other compounds (e.g., 2-pentanol, 4-methyl (3.33 ± 0.44%), benzyl butyl phthalate (4.25 ± 0.59%), benzenedicarboxylic acid (1.14 ± 0.08%), ethane, 1,1-diethoxy (3.15 ± 0.41) and hexadecanoic acid (2.52 ± 0.34). The soil samples also contained 30 compounds present in concentrations <1% (e.g., anthracene (0.13 ± 0.04%), n-C20 (0.84 ± 0.21%) and acetic acid (0.12 ± 0.04%). The compounds present in the highest concentrations in the sediment samples were PAHs: pyrene (7.73 ± 1.15%) and fluoranthene (6.23 ± 1.07%) and n-alkanes: n-C31 (6.74 ± 1.21%), n-C29 (6.65 ± 0.98%) and n-C27 (6.13 ± 1.09%). The remaining organic compounds were present in smaller quantities (< 5%).

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

PubMed

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.

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

PubMed

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.

Carbon and hydrogen isotope fractionation during aerobic biodegradation of quinoline and 3-methylquinoline.

PubMed

Cui, Mingchao; Zhang, Wenbing; Fang, Jun; Liang, Qianqiong; Liu, Dongxuan

2017-08-01

Compound-specific isotope analysis has been used extensively to investigate the biodegradation of various organic pollutants. To date, little isotope fractionation information is available for the biodegradation of quinolinic compounds. In this study, we report on the carbon and hydrogen isotope fractionation during quinoline and 3-methylquinoline aerobic microbial degradation by a Comamonas sp. strain Q10. Degradation of quinoline and 3-methylquinoline was accompanied by isotope fractionation. Large hydrogen and small carbon isotope fractionation was observed for quinoline while minor carbon and hydrogen isotope fractionation effects occurred for 3-methylquinoline. Bulk carbon and hydrogen enrichment factors (ε bulk ) for quinoline biodegradation were -1.2 ± 0.1 and -38 ± 1‰, respectively, while -0.7 ± 0.1 and -5 ± 1‰ for 3-methylquinoline, respectively. This reveals a potential advantage for employing quinoline as the model compound and hydrogen isotope analysis for assessing aerobic biodegradation of quinolinic compounds. The apparent kinetic isotope effects (AKIE C ) values of carbon were 1.008 ± 0.0005 for quinoline and 1.0048 ± 0.0005 for 3-methylquinoline while AKIE H values of hydrogen of 1.264 ± 0.011 for quinoline and 1.0356 ± 0.0103 for 3-methylquinoline were obtained. The combined evaluation of carbon and hydrogen isotope fractionation yields Λ values (Λ = Δδ 2 H/Δδ 13 C ≈ εH bulk /εC bulk ) of 29 ± 2 for quinoline and 8 ± 2 for 3-methylquinoline. The results indicate that the substrate specificity may have a significant influence on the isotope fractionation for the biodegradation of quinolinic compounds. The substrate-specific isotope enrichment factors would be important for assessing the behavior and fate of quinolinic compounds in the environment.

A comparative molecular and isotopic investigation of seep carbonates from mussel and tubeworm environments of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Feng, D.; Guan, H.; Wu, N.; Chen, D.

2017-12-01

At deep-sea hydrocarbon seeps, macrofauna such as mussels and tubeworms and authigenic carbonate outcrops are common. It has been suggested that the distinct metabolic process of the macrofauna could modify the sedimentary geochemistry of their ambient environments. To better understand if the differences in the geochemical environments of mussels and tubeworms can be archived in the associated carbonates, lipid biomarker inventory and compound-specific isotopes of the carbonates from mussel and tubeworm environments from two seep sites were analyzed. The large δ13C offset (-32‰) of SRB-derived fatty acids (FAs) between tubeworm and mussel carbonates were partially attributed to the distinct effects on isotope fraction by specific metabolic process of the macrofauna. In such processes, the isotope fraction of chemosynthetic symbionts and physical action of mussel activities could result in local 13C enrichment, whereas the sufficient sulfate released through the tubeworm roots resulting in a persistent production of methane-derived bicarbonate and the enrichment of lighter carbon at subsurface sediments. Compared to mussel carbonates, the significantly higher concentrations of DAGEs and FAs as well as the smaller δ13C offset (Δδ13CDAGEs-FAs) than that of the mussel carbonates, suggest that the DAGEs and at least part of FAs found in tubeworm carbonates biosynthesized by SRB species other than DSS cluster. This DAGE-producing SRB is most likely involved in the hydrogen-driven SR instead of methane-fueled SR because a variety of SRB other than members of DSS cluster on hydrogen was isolated in presence of ANME-1 assemblage. The substantial amounts of DAGEs with strong 13C-depletions in tubeworm ecosystem may provide an important clue for their sources and role in the AOM process.

Nitroalkenes and sesquiterpene hydrocarbons from the frontal gland of three prorhinotermes termite species.

PubMed

Piskorski, Rafal; Hanus, Robert; Vasícková, Sona; Cvacka, Josef; Sobotník, Jan; Svatos, Ales; Valterová, Irena

2007-09-01

Frontal gland contents of soldiers of three Prorhinotermes species, Prorhinotermes canalifrons, Prorhinotermes inopinatus, and Prorhinotermes simplex, consisted of two groups of compounds: nitroalkenes and sesquiterpene hydrocarbons. Analysis by gas chromatography-mass spectrometry revealed (E)-1-nitropentadec-1-ene as the major component of the glands with mean values of 152, 207, and 293 microg/individual for P. canalifrons, P. inopinatus, and P. simplex, respectively. Four other 1-nitroalkenes (C13, C14, C16, and C17), and two nitrodienes (C15 and C17) were also detected in the three species. The C17:1 nitroalkene was identified as (E)-1-nitroheptadec-1-ene. The sesquiterpene composition of the gland was species-specific: P. simplex contained (3Z,6E)-alpha-farnesene (mean of 39 microg/individual), while P. canalifrons and P. inopinatus contained the same compound (means of 0.5 and 1.5 microg/individual, respectively) as well as the (3E,6E) isomer (means of 1.8 and 0.7 microg/individual, respectively). Two other sesquiterpenes, trans-beta-bergamotene and (Z)-gamma-bisabolene, were also found in low quantities in the frontal gland of P. canalifrons.

An improved 13C-tracer method for the study of lignin structure and reactions : differential 13C-NMR

Treesearch

Noritsugu Terashima; Dmitry Evtuguin; Carlos Pascoal Neto; Jim Parkas; Magnus Paulsson; Ulla Westermark; Sally Ralph; John Ralph

2003-01-01

The technique of selective 13C-enrichment of specific carbons in lignin combined with 13C-NMR differential spectrometry between spectra of 13C-enriched and unenriched lignins (Ä13C-NMR) provides definitive information on the structure of the lignin macromolecule. Improvements were made on, (1) specific 13C-enrichment of almost all carbons involved in inter-unit bonds...

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

PubMed

Preston, Tom

2014-01-01

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

Development and evaluation of a high-performance liquid chromatography/isotope ratio mass spectrometry methodology for delta13C analyses of amino sugars in soil.

PubMed

Bodé, Samuel; Denef, Karolien; Boeckx, Pascal

2009-08-30

Amino sugars have been used as biomarkers to assess the relative contribution of dead microbial biomass of different functional groups of microorganisms to soil carbon pools. However, little is known about the dynamics of these compounds in soil. The isotopic composition of individual amino sugars can be used as a tool to determine the turnover of these compounds. Methods to determine the delta(13)C of amino sugars using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) have been proposed in literature. However, due to derivatization, the uncertainty on the obtained delta(13)C is too high to be used for natural abundance studies. Therefore, a new high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS) methodology, with increased accuracy and precision, has been developed. The repeatability on the obtained delta(13)C values when pure amino sugars were analyzed were not significantly concentration-dependent as long as the injected amount was higher than 1.5 nmol. The delta(13)C value of the same amino sugar spiked to a soil deviated by only 0.3 per thousand from the theoretical value. 2009 John Wiley & Sons, Ltd.

HPLC-Guided Isolation, Purification and Characterization of Phenylpropanoid and Phenolic Constituents of Nutmeg Kernel (Myristica fragrans).

PubMed

Chiu, Sharon; Wang, Thomas; Belski, Martin; Abourashed, Ehab A

2016-04-01

Many studies on the biological activities of nutmeg continue to appear in the literature. The most common targets include GIT, CNS, oxidative stress and inflammation. However, results obtained from most studies are often inconsistent due to the variability of utilized samples, lack of standardized nutmeg products or insufficient amounts of pure compounds for comprehensive follow-up investigation. To address the consistency and supply issue we utilized available technology to develop a reproducible procedure for preparation of specific extracts and isolation of the major phenolic constituents present in nutmeg kemel. A well-defined and reproducible sequence of extraction, fractionation and chromatographic purification was adopted and was guided by HPLC fingerprinting. Spectroscopic methods, mainly NMR, and mass spectrometry were utilized to identify each compound. Thirteen compounds were isolated in a pure form and identified as: elemicin (1), isoelemicin (2), myristicin (4), surinamensin (5), malabaricone C (6), 2-(3'-allyl-2',6'-dimethoxy-phenyloxy)-l- acetoxy-(3,4-dimethoxyphenyl)-propyl ester (7), methoxylicarin A (8), licarin A (9), malabaricone B (10), licarin C (11), 5'-methoxylicarin B (12), licarin B (13), and 2-(3'-allyl-2',6'-dimethoxy-phenyloxy)-l-methyl-5-methoxy-1,2-dihydrobenzofuran (3, a new compound). With repeated isolation runs, these pure compounds can be prepared in quantities sufficient for biological evaluation as needed. The availability of purified compounds will also allow the development of specific, accurate, and sensitive analytical procedures for pharmacokinetic studies and for quality control of nutmeg products. Both aspects are essential for nutmeg-focused drug discovery. The same approach can also be adapted to other medicinal plants of potential interest.

Authenticity testing of environment-friendly Korean rice (Oryza sativa L.) using carbon and nitrogen stable isotope ratio analysis.

PubMed

Chung, Ill-Min; Park, Sung-Kyu; Lee, Kyoung-Jin; An, Min-Jeong; Lee, Ji-Hee; Oh, Yong-Taek; Kim, Seung-Hyun

2017-11-01

The increasing demand for organic foods creates, in turn, a pressing need for the development of more accurate tools for the authentication of organic food in order to ensure both fair trade and food safety. This study examines the feasibility of δ 13 C and δ 15 N analyses as potential tools for authentication of environment-friendly rice sold in Korea. δ 13 C and δ 15 N examination in different rice grains showed that environment-friendly rice can be successfully distinguished from conventional rice. No multi-residue pesticides were detected in the examined rice samples, including conventional rice. This study demonstrates the complementary feasibility of δ 13 C and δ 15 N analyses for the authentication of environment-friendly rice sold in Korea in cases where pesticide residue analysis alone is insufficient for discrimination of organic and conventional rice. In future, complementary analyses including compound-specific isotope ratio analysis might be employed for improving the reliability of organic authentication. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Chemical Constituents from Leaves of "Chuju" Chrysanthemum morifolium and Their Antioxidant Activities in vitro].

PubMed

Wei, Qiang; Ji, Xiao-ying; Long, Xian-shun; Li, Qian-rong; Yin, Hao

2015-02-01

To study the chemical constituents from the leaves of "Chuju" Chrysanthemum morifolium. All compounds were separated and purified by column chromatography over silica gel, Sephadex LH-20 and preparative HPLC. Their structures were identified by spectral methods including 1H-NMR and 13C-NMR. 21 compounds were isolated and identified as octa-cosyl alcohol (1), β-sitosterol (2), lupeol (3), α-amyrin (4), daucosterol (5), ineupatorolide B (6), syringin (7), chlorogenic acid (8), petasiphenol (9), physcion (10), acacetin (11), eupatilin (12), quercetin (13), diosmetin (14), luteolin (15), apigenin (16), apigenin- 7-O-β-D-glucopyranoside (17), quercetin-3-O-β-D-glucopyranoside (18), luteolin-7-O-β-D-gluco pyranoside (19), apigenin-7-O-β-D- neospheroside (20), and acacetin-7-O-β-D-glucoside (21). Compounds 1-12, 18 and 20 are isolated from this plant for the first time. Compounds 10, 13, 14, 15 and 16 have shown strong antioxidant activities by DPPH · scavenging activity better than Vit C.

Very-long-chain 1,2- and 1,3-bifunctional compounds from the cuticular wax of Cosmos bipinnatus petals.

PubMed

Buschhaus, Christopher; Peng, Chen; Jetter, Reinhard

2013-07-01

Four uncommon classes of very-long-chain compounds were identified and quantified in the petal wax of Cosmos bipinnatus (Asteraceae). The first two were homologous series of alkane 1,2-diols and 1,3-diols, both ranging from C20 to C26. The upper and lower petal surfaces contained 0.11 and 0.09 μg/cm(2) of 1,2-diols, respectively. 1,3-Diols were present at quantities one order of magnitude less than the 1,2-diols. Both series had similar chain length distributions, with 6-20%, 59-73% and 20-31% of the C20, C22 and C24 diols, respectively. The other two compound classes were primary and secondary monoacetates of C20-C24 1,2-diols. The monoacetates had chain length profiles similar to the free 1,2-diols, and amounted to 0.04 and 0.09 μg/cm(2) on the adaxial and abaxial sides, respectively. Methods were developed to minimize acyl migration during monoacetate isomer analyses. The ratios of diol 1-acetates to diol 2-acetates averaged close to 3:5, and thus opposite to the chemical equilibrium ratio of 7:3. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of low molecular weight fungal compounds on inflammatory gene transcription and expression in mouse alveolar macrophages.

PubMed

Rand, Thomas G; Dipenta, J; Robbins, C; Miller, J D

2011-04-25

The inflammatory potential and molecular mechanisms underscoring inflammatory responses of lung cells to compounds from fungi that grow on damp building materials is poorly understood in vitro. In this study we evaluated the effect of pure fungal compounds on potentiating acute inflammatory response in primary mouse alveolar macrophages (AMs) and tested the hypothesis that AM responses to low molecular weight fungal compounds exhibit temporal and compound specificity that mimic that observed in the whole lung. Transcriptional responses of 13 inflammation/respiratory burst-associated genes (KC=Cxcl1, Cxcl2, Cxcl5, Cxcl10, Ccl3, Ccl112, Ccl20, IL-1β, Il-6, ifi27 Tnfα, iNOS and Blvrb) were evaluated in mouse AMs exposed to a 1ml (10(-8)mol) dose of either pure atranone C, brevianimide, cladosporin, curdlan, LPS, neoechinulin A & B, sterigmatocystin or TMC-120A for 2h, 4h and 12h PE using customized reverse transcription (RT)-PCR based arrays. Multianalyte ELISA was used to measure expression of 6 pro-inflammatory cytokines common to the transcriptional assays (Cxcl1, Cxcl10, Ccl3, IL1β, Ifn-λ and Tnf-α) to determine whether gene expression corresponded to the transcription data. Compared to controls, all of these compounds induced significant (≥2.5-fold or ≤-2.5-fold change at p≤0.05) time- and compound-specific transcriptional gene alterations in treatment AMs. The highest number of transcribed genes were in LPS treatment AMs at 12h PE (12/13) followed by neoechinulin B at 4h PE (11/13). Highest fold change values (>30) were associated with KC, Cxcl2, Cxcl5 and IL1β genes in cells exposed to LPS. Compound exposures also induced significant (p≤0.05) time- and compound-specific pro-inflammatory responses manifest as differentially elevated Cxcl1, Cxcl10, Ccl3, Ifn-λ and Tnf-α concentrations in culture supernatant of treatment AMs. Dissimilarity in transcriptional responses in AMs and our in vivo model of lung disease is likely attributable to whole lung vs. isolated cell responsive and dose differences between the two studies. The results not only indicate that low molecular weight compounds from fungi that grow in damp built environments are potently pro-inflammatory in vitro, it further highlights the important role AMs play in innate lung defence, and against exposure to low molecular weight fungal compounds. These observations further support our position that exposure to low molecular weight compounds from indoor-associated fungi may provoke some of the inflammatory health effects reported from humans in damp building environments. They also open up a hypothesis building process that could explain the rise of non-atopic asthma associated with fungi. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Oxidation of Half-Lantern Pt2(II,II) Compounds by Halocarbons. Evidence of Dioxygen Insertion into a Pt(III)-CH3 Bond.

PubMed

Sicilia, V; Baya, M; Borja, P; Martín, A

2015-08-03

The half-lantern compound [{Pt(bzq)(μ-N^S)}2] (1) [bzq = benzo[h]quinoline, HN^S = 2-mercaptopyrimidine (C4H3N2HS)] reacts with CH3I and haloforms CHX3 (X = Cl, Br, I) to give the corresponding oxidized diplatinum(III) derivatives [{Pt(bzq)(μ-N^S)X}2] (X = Cl 2a, Br 2b, I 2c). These compounds exhibit half-lantern structures with short intermetallic distances (∼2.6 Å) due to Pt-Pt bond formation. The halogen abstraction mechanisms from the halocarbon molecules by the Pt2(II,II) compound 1 were investigated. NMR spectroscopic evidence using labeled reagents support that in the case of (13)CH3I the reaction initiates with an oxidative addition through an SN2 mechanism giving rise to the intermediate species [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}]. However, with haloforms the reactions proceed through a radical-like mechanism, thermally (CHBr3, CHI3) or photochemically (CHCl3) activated, giving rise to mixtures of species [X(bzq)Pt(μ-N^S)2Pt(bzq)R] (3a-c) and [X(bzq)Pt(μ-N^S)2Pt(bzq)X] (2a-c). In these cases the presence of O2 favors the formation of species 2 over 3. Transformation of 3 into 2 was possible upon irradiation with UV light. In the case of [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}] (3d), in the presence of O2 the formation of the unusual methylperoxo derivative [I(bzq)Pt(μ-N^S)2Pt(bzq)(O-O(13)CH3)}] (4d) was detected, which in the presence of (13)CH3I rendered the final product [{Pt(bzq)(μ-N^S)I}2] (2c) and (13)CH3OH.

Isotope ratio mass spectrometry in nutrition research

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luke, A.H.

Many of the biochemical pathways and processes that form the foundation of modern nutrition research was elucidated using stable isotopes as physiological tracers. Since the discovery of stable isotopes, improvements and innovations in mass spectrometry and chromatography have led to greatly expanded applications. This research project was designed to evaluate gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) as a tool for isotopic tracer studies and to delineate the operational parameters for the analysis of {sup 13}C-labeled cholesterol, leucine and {alpha}-ketoisocaproate. The same isotope ratio mass spectrometer was then used as the base instrument for the ratio mass spectrometer was then usedmore » as the base instrument for the development of two additional inlet systems: a continuous-flow inlet for the analyses of {sup 13}C and {sup 18}O as CO{sub 2} and a filament inlet for on-line combustion and isotopic analysis of non-volatile organic compounds. Each of these three inlets was evaluated and their utility in nutrition research illustrated. GC/C/IRMS was used to analyze cholesterol, leucine and {alpha}-ketoisocaproate with good accuracy, precision and little isotopic memory. For all three compounds the detection limits achieved well surpassed currently used technologies. For compounds that can be well separated by GC, GC/C/IRMS is a valuable analytical tool. The continuous-flow inlet provided good accuracy and precision for measurements of {sup 13}CO{sub 2} from breath tests and {sup 18}O as CO{sub 2} from total energy expenditure tests. Most importantly, the continuous-flow inlet increased sample throughput by at least a factor of three over conventional analytical techniques. The filament inlet provided accurate and precise {sup 13}C ratio measurements of both natural abundance and enriched standards of non-volatile organic compounds of physiological interest.« less

δ 13C of free and macromolecular aromatic structures in the murchison meteorite

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

1998-05-01

Analyses of the organic compounds in the Murchison meteorite have led to a greater understanding of the nature of extraterrestrial organic materials. However, the relationship between low and high molecular weight material remains poorly understood. To investigate this relationship, untreated Murchison was subjected to supercritical fluid extraction (SFE) to obtain the free organic components in the meteorite. Toluene and other volatile aromatic hydrocarbons dominated the extract, and the carbon isotopic composition of these molecules was determined by gas chromatography-isotope ratio-mass spectrometry (GCIRMS). δ 13C values of the aromatic hydrocarbons ranged from -28.8 to -5.8‰. These compounds displayed a 13C-enrichment with increasing carbon number suggesting an origin by cracking. The high molecular weight organic material in the meteorite was isolated and subjected to hydrous pyrolysis. This procedure produced a number of aromatic products, the majority of which were volatile aromatic hydrocarbons, particularly toluene. SFE was used to extract and successfully retain them. This enabled the first carbon isotopic analysis of this poorly understood material to be performed at the molecular level by GCIRMS. δ 13C values for aromatic pyrolysis products occupied a range from -24.6 to -5.6‰. The trend of 13C-enrichment with increasing carbon number, observed in the free compounds, was also evident in the macromolecular fragments. Furthermore, the organic fragments of the macromolecular material were consistently 13C-enriched when compared to structurally identical free molecules. This suggested that the free aromatic hydrocarbons in Murchison were produced by the preterrestrial degradation of the organic macromolecular material. This natural degradation event was extended by the hydrous pyrolysis experiment.

A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

NASA Astrophysics Data System (ADS)

Tang, Yongchun; Huang, Yongsong; Ellis, Geoffrey S.; Wang, Yi; Kralert, Paul G.; Gillaizeau, Bruno; Ma, Qisheng; Hwang, Rong

2005-09-01

A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C 13-C 21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ 13C values increase by ˜4‰ and δD values increase by ˜50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH ‡) and entropy (ΔΔS ‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C 20 ( n-icosane), the changes in enthalpy are calculated to be ˜1340 J mol -1 (320 cal mol -1) and 230 J mol -1 (55 cal mol -1) for D-H and 13C- 12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite reflectance values corresponding to the onset of thermal cracking of normal alkanes. The experimental and theoretical results of this study have significant implications for the use of compound-specific hydrogen isotope data in petroleum geochemical and paleoclimatological studies. However, there are many other geochemical processes that will significantly affect observed hydrogen isotopic compositions (e.g., biodegradation, water washing, isotopic exchange with water and minerals) that must also be taken into consideration.

Microbial alteration of normal alkane δ13C and δD in sedimentary archives

NASA Astrophysics Data System (ADS)

Brittingham, A.; Hren, M. T.; Hartman, G.

2016-12-01

Long-carbon chain normal alkanes (e.g. C25-C33) are produced by a wide range of terrestrial plants and commonly preserved in ancient sediments. These serve as a potential paleoclimate proxy because their hydrogen (δD) and carbon (δ13C) isotope values reflect the combined effect of plant-specific species effects and responses to environmental conditions. While these are commonly believed to remain unaltered at low burial temperatures (e.g. <150°C), there is still uncertainty around the role microbes play during the breakdown of these compounds in stored sediment and the potential risk for isotopic alteration. We analyzed two sets of identical samples to assess the role of microbial and other degradation process on the hydrogen and carbon isotope composition of these compounds. The first set of sediment samples were collected in the summer of 2011 from central Armenia, a region with continental climate, and allowed to sit in sealed bags at room temperature for three years. A second and identical set was collected in 2014 and frozen immediately. Stored samples showed high amounts of medium chain length n-alkanes (C19-C26), produced by microorganisms, which were absent from the samples that were collected in 2014 and frozen immediately after sampling. Along with the presence of medium chain length n-alkanes, the average chain length of n-alkanes from C25-C33 decreased significantly in all 2011 samples. Storage of the samples over three years resulted in altered δD and δ13C values of C29 and C31 n-alkanes. While δD values were heavier relative to the control by 4-25‰, δ13C values were mostly lighter (maximum change of -4.2‰ in C29 and -2.9‰ in C31). DNA analysis of the soil showed Rhodococcus and Aeromicrobium, genera that contain multiple coding regions for alkane degrading enzymes CYP153 and AlkB, increased by an order of magnitude during sample storage (from 0.7% to 7.5% of bacteria present). The proliferation of alkane degrading bacteria, combined with the large changes of long-chain n-alkane isotope values, suggest that bacteria may play a larger role than previously expected in altering the measured δD and δ13C values of long-chain n-alkanes during storage. This poses a potentially significant issue for all manner of samples that are not stored frozen, including a variety of sedimentary cores.

Molecular Dynamics Simulation Study on the Binding and Stabilization Mechanism of Antiprion Compounds to the "Hot Spot" Region of PrPC.

PubMed

Zhou, Shuangyan; Liu, Xuewei; An, Xiaoli; Yao, Xiaojun; Liu, Huanxiang

2017-11-15

Structural transitions in the prion protein from the cellular form, PrP C , into the pathological isoform, PrP Sc , are regarded as the main cause of the transmissible spongiform encephalopathies, also known as prion diseases. Hence, discovering and designing effective antiprion drugs that can inhibit PrP C to PrP Sc conversion is regarded as a promising way to cure prion disease. Among several strategies to inhibit PrP C to PrP Sc conversion, stabilizing the native PrP C via specific binding is believed to be one of the valuable approaches and many antiprion compounds have been reported based on this strategy. However, the detailed mechanism to stabilize the native PrP C is still unknown. As such, to unravel the stabilizing mechanism of these compounds to PrP C is valuable for the further design and discovery of antiprion compounds. In this study, by molecular dynamics simulation method, we investigated the stabilizing mechanism of several antiprion compounds on PrP C that were previously reported to have specific binding to the "hot spot" region of PrP C . Our simulation results reveal that the stabilization mechanism of specific binding compounds can be summarized as (I) to stabilize both the flexible C-terminal of α2 and the hydrophobic core, such as BMD42-29 and GN8; (II) to stabilize the hydrophobic core, such as J1 and GJP49; (III) to stabilize the overall structure of PrP C by high binding affinity, as NPR-056. In addition, as indicated by the H-bond analysis and decomposition analysis of binding free energy, the residues N159 and Q160 play an important role in the specific binding of the studied compounds and all these compounds interact with PrP C in a similar way with the key interacting residues L130 in the β1 strand, P158, N159, Q160, etc. in the α1-β2 loop, and H187, T190, T191, etc. in the α2 C-terminus although the compounds have large structural difference. As a whole, our obtained results can provide some insights into the specific binding mechanism of main antiprion compounds to the "hot spot" region of PrP C at the molecular level and also provide guidance for effective antiprion drug design in the future.

Unusual open chain quinolinyl peroxol and its alcohol counterpart obtained through a modified Skraup-Doebner-Von Miller quinoline synthesis: theoretical studies and complete (1) H- and (13) C-NMR assignments.

PubMed

Fotie, Jean; Kemami Wangun, Hilaire V; Dreux, Katelyn; Sommerfeld, Thomas; Pittman, Jacob

2012-01-01

Because of their extreme instability, it is generally difficult to synthesize and fully characterize open chain peroxides, also known as peroxols. In our attempt to investigate the mechanism of the Skraup-Doebner-Von Miller quinoline synthesis, we were able to obtain an unusual open chain peroxy-quinoline, namely, 4-(8-ethoxy-2,3-dihydro-1H-cyclopenta[c]quinolin-4-yl)butane-1-peroxol (1), and its alcohol counterpart, namely 4-(8-ethoxy-2,3-dihydro-1H-cyclopenta[c]quinolin-4-yl)butan-1-ol (2) obtained as a side product during the same reaction. Although structurally similar, these two compounds appeared to display some very distinct physical and spectroscopic characteristics. This work reports detailed NMR studies and full (1) H and (13)  C NMR assignments for these two compounds. These assignments are based upon the analysis of the NMR spectra of these compounds including (1) H, (13)  C, COSY, gHSQC and gHMBC. The effect of the peroxide functional group on the chemical shift of neighboring carbons and protons was also investigated by comparing the NMR data of these two compounds. Furthermore, the effects of potential hydrogen bondings in 1, 2, and possible 1-1 dimer, 2-2 dimer and in prototypical model systems, as well as the stability of these compounds, were investigated computationally. The computed dissociation energies and NMR data support the interpretation of the experimental data. Copyright © 2012 John Wiley & Sons, Ltd.

Synthesis and Characterization of Polyether Adducts of Barium and Strontium Carboxylates and Their Use in the Formation of MTiO(3) Films.

PubMed

Wojtczak, William A.; Atanassova, Paolina; Hampden-Smith, Mark J.; Duesler, Eileen

1996-11-20

The synthesis, characterization, and reactivity of new polyether adducts of strontium and barium carboxylates of general composition M(O(2)CCF(3))(n)()(L) (M = Ba, L = 15-crown-5, (1); M = Ba (2), Sr (3), respectively, with L = tetraglyme are reported. The compounds were synthesized by reaction of BaCO(3) or MH(2) (M = Sr or Ba) with organic acids in the presence of the polyether ligands. These compounds have been characterized by IR and (13)C and (1)H NMR spectroscopies, elemental analyses, and thermogravimetric analysis. The species Ba(2)(O(2)CCF(3))(4)(15-crown-5)(2) (1) and [Ba(2)(O(2)CCF(3))(4)(tetraglyme)](infinity) (2), were also characterized by single-crystal X-ray diffraction. Ba(2)(O(2)CCF(3))(4)(15-crown-5)(2) (1) crystallizes in the orthorhombic space group Cccm with cell dimensions of a = 13.949(1) Å, b = 19.376(2) Å, c = 16.029(1) Å, and Z = 8. [Ba(2)(O(2)CCF(3))(4)(tetraglyme)](infinity) (2) crystallizes in the monoclinic space group C2/c with cell dimensions of a = 12.8673(12) Å, b = 16.6981(13) Å, c = 15.1191(12) Å, beta = 99.049(8) degrees, and Z = 4. Compounds 1-3 thermally decompose at high temperatures in the solid state to give MF(2). However, solutions of compounds 1-3 dissolved in ethanol with Ti(O-i-Pr)(4) give crystalline perovskite phase MTiO(3) films, or in the case of mixtures of 2 and 3, Ba(1)(-)(x)()Sr(x)()TiO(3) films below 600 degrees C when spin coated onto silicon substrates and thermally treated. The crystallinity, purity, and elemental composition of the films was determined by glancing angle X-ray diffraction and Auger electron spectroscopy.

[The compounds from n-butanol fraction of Alpinia oxyphylla].

PubMed

Xie, Bin-Bin; Hou, Lei; Guo, Bao-Lin; Huang, Wen-Hua; Yu, Jing-Guang

2014-11-01

Nine compounds were isolated from the n-butanol fraction of 95% ethanol extract of the fruit of Alpinia oxyphylla Miq. with a combination of various chromatographic approaches, including MDS resin, silica gel, reverse phase C18 and preparative HPLC. On the basis of spectroscopic data analysis, they were elucidated as (1R, 4R, 10R)-1β, 4α-dihydroxy-11, 12, 13-trinor-5, 6-eudesmen-7-one (1), 1β, 4β-dihydroxy-11, 12, 13-trinor-8, 9-eudesmen-7-one (2), oxyphyllenone A (3), oxyphyllenone B (4), rhamnocitrin (5), staphylionoside D (6), benzyl-1-O-β-D-glucopyranoside (7), 2-O-β-D-glucopyranosyl-(1S)-phenylethylene glycol (8), and (S)-1-phenylethyl-β-D-glucopyranoside (9). Among them, compound 1 is a new sesquiterpene, named as oxyphyllenone C; compounds 8 and 9 are new natural products; compounds 2 and 6 were isolated from the genus Alpinia for the first time, and compound 7 was isolated from A. oxyphylla for the first time.

Synthetic, Infrared, 1Hand 13CNMR Spectral Studies on N-(p-Substituted Phenyl)-p-Substituted Benzenesulphonamides, p-X'C6H4SO2NH- (p-XC6H4), where X' or X = H, CH3, C2H5, F, Cl or Br

NASA Astrophysics Data System (ADS)

Gowda, B. Thimme; Jayalakshmi, K. L.; Shetty, Mahesha

2004-05-01

Thirty N-(p-substituted phenyl)-p-substituted benzenesulphonamides of the general formula, p-X'C6H4SO2NH(p-XC6H4), where X' or X = H, CH3, C2H5, F, Cl or Br, are synthesised and their infrared spectra in the solid state and 1H and 13C NMR spectra in solution are measured. The N-H stretching vibrational frequencies, νN-H vary in the range 3334 - 3219 cm-1, while the asymmetric and symmetric SO2 vibrations appear in the ranges 1377 - 1311 cm-1 and 1182 - 1151 cm-1, respectively. The compounds exhibit S-N and C-N stretching vibrational absorptions in the ranges 937 - 898 cm-1 and 1310 - 1180 cm-1, respectively. There are no particular trends in the variation of these frequencies on substitution with either electron withdrawing or electron donating groups. The 1H and 13C chemical shifts of N-(p-substituted phenyl)-p-substituted benzenesulphonamides, are assigned to various protons and carbons of the two benzene rings. Further, incremental shifts of the ring protons and carbons due to -SO2NH(p-XC6H4) groups in the compounds of the formula, C6H5SO2NH(p-XC6H4), and p-X'C6H4SO2- and p-X'C6H4SO2NH- groups in the compounds of the formula, p-X'C6H4SO2NH(C6H5) are computed and used to calculate the 1H and 13C chemical shifts of the parallely substituted compounds of the general formula p-X'C6H4SO2NH(p-XC6H4). The computed values agree well with the observed chemical shifts. The above incremental shifts are found to correlate with the Hammett substituent parameters.

Seasonal changes in particulate and dissolved organic matter composition and quality in the Lena River Delta

NASA Astrophysics Data System (ADS)

Mollenhauer, G.; Winterfeld, M.; Hefter, J.; Bodenstab, L.; Morgenstern, A.; Eulenburg, A.; Heim, B.; Koch, B.; Schefuss, E.; Moerth, C. M.; Rethemeyer, J.

2016-12-01

Arctic rivers are known to export large quantities of carbon by discharge of dissolved and particulate organic carbon (DOC, POC), and in a warming and progressively moister Arctic, these exports may increase resulting in a reduction of arctic continental carbon stocks. These rivers have highly variable discharge rates with a pronounced maximum during the spring freshet associated with highest concentrations of DOC and POC. Most studies investigating the isotopic composition and quality of carbon exported by Arctic rivers rely on samples taken in summer during base flow, which is due to the logistical challenges associated with sampling in the remote Arctic permafrost regions. Here we present a record of δ13C and Δ14C of DOC and POC collected between late May during the freshet and late August 2014 in the Lena River Delta. POC Δ14C shows an initial trend towards older values in the spring samples, which is reversed in summer, associated with a shift towards more depleted δ13C values. We interpret this aging trend as reflecting progressive thawing throughout the ice-free season, resulting in mobilization of progressively older carbon from deeper thawed layers. The summer reversal indicates admixture of aquatic organic matter. DOC Δ14C, in contrast, remains at relatively modern levels with rather constant δ13C values throughout the sampling period. We furthermore analysed the biomarker composition of Lena Delta particulate OM collected in spring and summer. From spring to summer, we observe trends in abundance of individual leaf-wax derived biomarkers indicating higher abundance of algal biomass in the summer particles. Trends in soil microbial biomarkers and compound-specific δD of leaf-wax lipids suggest a shift in sources towards higher contributions from the southern catchment in summer. DOC composition investigated with FT-ICR-MS changes from spring with higher abundances of compounds with high H/C and low O/C ratios to late summer, when fewer compounds were found. Our results illustrate the seasonal variability in composition and sources of organic matter discharged by the Lena River. Paired with the strong seassonality of the hydrograph, this implies that total annual discharge of organic matter contains a disproportionally high contribution from the northern part of the catchment.

Specific recognition of polyphenols by molecularly imprinted polymers based on a ternary deep eutectic solvent.

PubMed

Fu, Najing; Li, Liteng; Liu, Xiao; Fu, Nian; Zhang, Chenchen; Hu, Liandong; Li, Donghao; Tang, Baokun; Zhu, Tao

2017-12-29

Typically, a target compound is selected as a template for a molecularly imprinted polymer (MIP); however, some target compounds are not suitable as templates because of their poor solubility. Using the tailoring properties of a deep eutectic solvent (DES), the insoluble target compound caffeic acid was transformed into a ternary choline chloride-caffeic acid-ethylene glycol (ChCl-CA-EG) DES, which was then employed as a template to prepare MIPs. The ternary DES-based MIPs were characterized by Fourier transform infrared spectroscopy, elemental analysis, scanning electron microscopy, and atomic force microscopy. The effects of time, temperature, ionic strength, and pH on the recognition processes for four polyphenols (caffeic acid, protocatechuic acid, catechin, and epicatechin) by 13 ChCl-CA-EG ternary DES-based MIPs was investigated using high-performance liquid chromatography. The recognition specificity of the MIPs for CA was significantly better than that for the other polyphenols, and the MIPs exhibited obvious characteristics of chromatographic packing materials. In addition, the recognition processes mainly followed a second-order kinetics model and the Freundlich isotherm model, which together indicated that the MIPs mainly recognized the polyphenols by chemical interactions including ion exchange, electron exchange, and new bond formation. Furthermore, the specific recognition ability of the MIPs for polyphenols, which was better than those of C 18 , C 8 , or non-molecularly imprinted polymer adsorbents, was successfully applied to the recognition of polyphenols in a Radix asteris sample. The transformation of an insoluble target compound in a polymeric DES for MIP preparation and recognition is a novel and feasible strategy suitable for use in further MIP research developments. Copyright © 2017 Elsevier B.V. All rights reserved.

Classification of nine malathion emulsion samples by using carbon isotope ratios and the ratio of organic solvents.

PubMed

Suto, Nana; Kawashima, Hiroto

2017-01-01

The compound specific isotope analysis is nowadays an important and powerful tool in geochemical, environmental and forensics field. On November 2013, Aqli Foods Corporation in Japan dealt with complaints about stench from frozen foods produced. Subsequently, very high concentrations of organophosphorus pesticide as malathion, ethylbenzene and xylene were detected in recovered frozen foods. In particular case, we present the method to measure the stable carbon isotope ratio (δ 13 C) of nine malathion emulsion pesticides using gas chromatography/isotope ratio mass spectrometry (GC/IRMS) to identify the source. The δ 13 C values of malathion ranged from -30.6‰ to -29.5‰. Because malathion used in all malathion emulsions sold in Japan is imported from the same overseas company, Cheminova, Denmark. The δ 13 C values of ethylbenzene ranged from -28.2‰ to -20.8‰ and those of m,p-xylene from -28.7‰ to -25.2‰. The differences in the δ 13 C values may be because of the material itself and chemical processing. We also determined the ratio of ethylbenzene to m,p-xylene and finally categorized the nine malathion samples into five groups on the basis of this ratio and the δ 13 C values of ethylbenzene and m,p-xylene. The results of isotopic fractionation during volatilization (refrigerate, room temperature and incubator) was negligible small. Copyright © 2016 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

Soil Fertilization Leads to a Decline in Between-Samples Variability of Microbial Community δ13C Profiles in a Grassland Fertilization Experiment

PubMed Central

Veresoglou, Stavros D.; Thornton, Barry; Menexes, George; Mamolos, Andreas P.; Veresoglou, Demetrios S.

2012-01-01

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 δ13C 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 δ13C 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. PMID:22962602

Volatile non-terpenoid hydrocarbons from Ligusticum grayi roots

USDA-ARS?s Scientific Manuscript database

The root essential oil of Ligusticum grayi Coult. & Rose (Apiaceae) contains three volatile non-terpenoid hydrocarbons: the known C11 compound viridene, whose structure is hereby corrected to 1-[(2Z)-pent-2-en-1-yl]cyclohexa-1,3-diene; and the heretofore unreported C10 compounds 1-[(2Z)-but-2-en-1-y...

Thiazolidinediones as a novel class of algicides against red tide harmful algal species.

PubMed

Kim, Yeon-Mi; Wu, Ying; Duong, Thi Uyen; Ghodake, Gajanan S; Kim, Si Wouk; Jin, Eonseon; Cho, Hoon

2010-12-01

This paper reports the synthesis of 28 thiazolidinedione derivatives along with their algicidal activity against microalgae causing harmful algal blooming. Among the 28 compounds tested, most showed effective algicidal activity against Heterosigma akashiwo, Chattonella marina, and Cochlodinium polykrikoides, while non-harmful algae were relatively tolerant to these thiazolidinedione derivatives. Compounds 6, 13, and 22 were the most potent against C. polykrikoides with IC₅₀ values <0.5 µM. Among the thiazolidinedione derivatives tested, compounds 7, 13, 27, and 28 were extremely competent and selective to C. polykrikoides with IC₅₀ values ranging from 0.1 to 2 µM, while C. marina and H. akashiwo showed an IC₅₀ value ranging from 30 to 130 µM. These results show that some thiazolidinedione derivatives can act as potent algicides against harmful algal blooms.

Synthesis and in vitro evaluation of new derivatives of 2-substituted-6-fluorobenzo[d]thiazoles as cholinesterase inhibitors.

PubMed

Imramovský, Aleš; Pejchal, Vladimír; Štěpánková, Šárka; Vorčáková, Katarína; Jampílek, Josef; Vančo, Ján; Šimůnek, Petr; Královec, Karel; Brůčková, Lenka; Mandíková, Jana; Trejtnar, František

2013-04-01

A series of novel cholinesterase inhibitors based on 2-substituted 6-fluorobenzo[d]thiazole were synthesised and characterised by IR, (1)H, (13)C and (19)F NMR spectroscopy and HRMS. Purity was checked by elemental analyses. The novel carbamates were tested for their ability to inhibit acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). The toxicity of the most active compounds was investigated using a standard in vitro test with HepG2 cells, and the ratio between biological activity and toxicity was determined. In addition, the toxicity of the most active compounds was evaluated against MCF7 cells using the xCELLigence system. Structure-activity relationships reflecting the dependence of cholinesterase inhibitors on the lipophilicity of the compounds as well as on the Taft polar and steric substituent constants are discussed. The specific orientation of the inhibitors in the binding site of acetylcholinesterase was determined using molecular docking of the most active compound. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis, single crystal X-ray, spectroscopic (FT-IR, UV-vis, fluorescence, 1H &13C NMR), computational (DFT/B3LYP) studies of some imidazole based picrates

NASA Astrophysics Data System (ADS)

Arockia doss, M.; Rajarajan, G.; Thanikachalam, V.; Selvanayagam, S.; Sridhar, B.

2018-04-01

2,4,5-triphenyl-1H-imidazol-3-ium picrate (1), 2-(4-fluorophenyl)-4,5-diphenyl-1H-imidazol-3-ium picrate (2), 2-(4-methylphenyl)-4,5-diphenyl-1H-imidazol-3-ium picrate (3) were synthesised. These compounds 1-3 were characterized by elemental, FT-IR, 1H NMR and 13C NMR analyses. The structure of compound 3 was further confirmed by single crystal X-ray diffraction. The studies reveal that the molecule is associated with weak Nsbnd H⋯O and Csbnd H⋯N and van der Waals interactions which are responsible for the formation and strengthening of supramolecular assembly. The nature of the interactions and their importance are explored using the Hirshfeld surface method. The physicochemical properties of the compounds 1-3 were evaluated by UV-vis spectroscopy, fluorescence spectroscopy, and thermogravimetric analysis. According to thermal data the salts possess excellent thermal stabilities with decomposition temperatures ranging from 220 to 280 °C. Second-harmonic generation (SHG) results exposed that the picrates 1-3 were about 1.13-1.50 times greater than potassium dihydrogen phosphate (KDP). Here we also used Density functional theory (DFT) calculations in order to investigate the opto-electronic properties. The obtained theoretical results validate with available experimental data.

Who's on first? Part I: Influence of plant growth on C association with fresh soil minerals

NASA Astrophysics Data System (ADS)

Neurath, R.; Whitman, T.; Nico, P. S.; Pett-Ridge, J.; Firestone, M. K.

2015-12-01

Mineral surfaces provide sites for carbon stabilization in soils, protecting soil organic matter (SOM) from microbial degradation. SOM distributed across mineral surfaces is expected to be patchy and certain minerals undergo re-mineralization under dynamic soil conditions, such that soil minerals surfaces can range from fresh to thickly-coated with SOM. Our research investigates the intersection of microbiology and geochemistry, and aims to build a mechanistic understanding of plant-derived carbon (C) association with mineral surfaces and the factors that determine SOM fate in soil. Plants are the primary source of C in soil, with roots exuding low-molecular weight compounds during growth and contributing more complex litter compounds at senescence. We grew the annual grass, Avena barbata, (wild oat) in a 99 atom% 13CO2 atmosphere in soil microcosms incubated with three mineral types representing a spectrum of reactivity and surface area: quartz, kaolinite, and ferrihydrite. These minerals, isolated in mesh bags to exclude roots but not microorganisms, were extracted and analyzed for total C and 13C at multiple plant growth stages. At plant senescence, the quartz had the least mineral-bound C (0.40 mg-g-1) and ferrihydrite the most (0.78 mg-g-1). Ferrihydrite and kaolinite also accumulated more plant-derived C (3.0 and 3.1% 13C, respectively). The experiment was repeated with partially digested 13C-labled root litter to simulate litter decomposition during plant senescence. Thus, we are able evaluate contributions derived from living and dead root materials on soil minerals using FTIR and 13C-NMR. We find that mineral-associated C bears a distinct microbial signature, with soil microbes not only transforming SOM prior to mineral association, but also populating mineral surfaces over time. Our research shows that both soil mineralogy and the chemical character of plant-derived compounds are important controls of mineral protection of SOM.

A dimeric ArC2 compound from Peperomia pellucida.

PubMed

Bayma, J D; Arruda, M S; Müller, A H; Arruda, A C; Canto, W C

2000-12-01

Pellucidin A, a novel dimeric ArC2 compound, together with dill-apiol have been isolated from the aerial parts of Peperomia pellucida. The structure of pellucidin A was established by 1D and 2D NMR spectroscopy (1H-1H COSY; 1H-13C COSY; DEPT; NOESY and double irradiation) and other spectroscopic techniques. The biogenesis of pellucidin A is also briefly discussed.

Ecological Evaluation of Proposed Discharge of Dredged Material into Ocean Waters.

DTIC Science & Technology

1977-07-01

Methyl mercury Ref. 6 Oil and grease p. 229 - 5 5 Step 7.3 Petroleum hydrocarbons p. 226 Step 6.3 Phenol p. 241 Method SlO Method )I 78 p. 514 p. 4...and its compounds c. Cadmium and its compounds d. Petroleum hydrocarbons e. Known or suspected carcinogens, mutagens, or teratogens. 6 (This is a...its compounds 12 Cadmium and its compounds 12 6 0 Petroleum hydrocarbons : Aliphat ic 13 Aromatic 13 G8 0 0 * 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Table

Isolation and characterization of two hydroperoxide lyase genes from grape berries : HPL isogenes in Vitis vinifera grapes.

PubMed

Zhu, Bao-Qing; Xu, Xiao-Qing; Wu, Yu-Wen; Duan, Chang-Qing; Pan, Qiu-Hong

2012-07-01

C6 compounds are the major fraction of the volatile profiles of grape berries, contributing the typical 'green' aroma to the grape and wine. Hydroperoxide lyase (HPL) catalyzes the cleavage of fatty acid hydroperoxides to produce C6 compounds. Two hypothetical genes, VvHPL1 and VvHPL2 were cloned from grape berries (Vitis vinifera L. Cabernet Sauvignon). Bioinformatics analysis revealed that the proteins encoded by these two genes both belong to subfamily of cytochrome P450 and contain typical conserved domains of HPLs, and have high identity with HPLs from other plants. Prokaryotically-expressed VvHPL1 and VvHPL2 with thioredoxin-6xHis-fusion partner were confirmed to have enzymatic activity. VvHPL1 is specific for 13-HPOD (T) producing C6 aldehydes with relatively higher activity and VvHPL2 catalyzes the cleavage of both 9- and 13-hydroperoxides producing C6 aldehydes and C9 aldehydes respectively. Analysis of real time-PCR showed that VvHPL2 was highly expressed in the leaves and the flowers of the grapes, while relatively low transcript abundance was detected in the berries, tendril and stems; VvHPL1 had high expression in all detected tissues. During grape berry development, the expression of these two isogenes presented similar trends with a rapid increase after veraison and a decrease at full-ripen stage, which roughly corresponded to the accumulation of their volatile products. These data lay an essential foundation for further study on the accumulation and control of C6 volatiles in grape berries.

Nitrification and growth of autotrophic nitrifying bacteria and Thaumarchaeota in the coastal North Sea

NASA Astrophysics Data System (ADS)

Veuger, B.; Pitcher, A.; Schouten, S.; Sinninghe Damsté, J. S.; Middelburg, J. J.

2012-11-01

Nitrification and the associated growth of autotrophic nitrifiers, as well as the contributions of bacteria and Thaumarchaeota to total autotrophic C-fixation by nitrifiers were investigated in the Dutch coastal North Sea from October 2007 to March 2008. Rates of nitrification were determined by incubation of water samples with 15N-ammonium and growth of autotrophic nitrifiers was measured by incubation with 13C-DIC in the presence and absence of nitrification inhibitors (nitrapyrin and chlorate) in combination with compound-specific stable isotope (13C) analysis of bacterial- and Thaumarchaeotal lipid biomarkers. Net nitrification during the sampling period was evident from the concentration dynamics of ammonium, nitrite and nitrate. Measured nitrification rates were high (41-221 nmol N l-1h-1). Ammonium assimilation was always substantially lower than nitrification with nitrification on average contributing 89% (range 73-97%) to total ammonium consumption. 13C-DIC fixation into bacterial and Thaumarchaeotal lipids was strongly reduced by the nitrification inhibitors (27-95%). The inhibitor-sensitive 13C-PLFA pool was dominated by the common PLFAs 16:0, 16:1ω7c and 18:1ω7c throughout the whole sampling period and occasionally also included the polyunsaturated fatty acids 18:2ω6c and 18:3ω3. Cell-specific 13C-DIC fixation activity of the nitrifying bacteria was much higher than that of the nitrifying Thaumarchaeota throughout the whole sampling period, even during the peak in Thaumarchaeotal abundance and activity. This suggests that the contribution of autotrophic Thaumarchaeota to nitrification during winter in the coastal North Sea may have been smaller than expected from their gene abundance. These results emphasize the importance of direct measurements of the actual activity of bacteria and Thaumarchaeota, rather than abundance measurements only, in order to elucidate their biogeochemical importance. The ratio between rates of nitrification versus DIC fixation by nitrifiers was higher or even much higher than typical values for autotrophic nitrifiers, indicating that little DIC was fixed relative to the amount of energy that was generated by nitrification.

Severe acute respiratory syndrome coronavirus replication inhibitor that interferes with the nucleic acid unwinding of the viral helicase.

PubMed

Adedeji, Adeyemi O; Singh, Kamalendra; Calcaterra, Nicholas E; DeDiego, Marta L; Enjuanes, Luis; Weiss, Susan; Sarafianos, Stefan G

2012-09-01

Severe acute respiratory syndrome (SARS) is a highly contagious disease, caused by SARS coronavirus (SARS-CoV), for which there are no approved treatments. We report the discovery of a potent inhibitor of SARS-CoV that blocks replication by inhibiting the unwinding activity of the SARS-CoV helicase (nsp13). We used a Förster resonance energy transfer (FRET)-based helicase assay to screen the Maybridge Hitfinder chemical library. We identified and validated a compound (SSYA10-001) that specifically blocks the double-stranded RNA (dsRNA) and dsDNA unwinding activities of nsp13, with 50% inhibitory concentrations (IC(50)s) of 5.70 and 5.30 μM, respectively. This compound also has inhibitory activity (50% effective concentration [EC(50)] = 8.95 μM) in a SARS-CoV replicon assay, with low cytotoxicity (50% cytotoxic concentration [CC(50)] = >250 μM), suggesting that the helicase plays a still unidentified critical role in the SARS-CoV life cycle. Enzyme kinetic studies on the mechanism of nsp13 inhibition revealed that SSYA10-001 acts as a noncompetitive inhibitor of nsp13 with respect to nucleic acid and ATP substrates. Moreover, SSYA10-001 does not affect ATP hydrolysis or nsp13 binding to the nucleic acid substrate. SSYA10-001 did not inhibit hepatitis C virus (HCV) helicase, other bacterial and viral RNA-dependent RNA polymerases, or reverse transcriptase. These results suggest that SSYA10-001 specifically blocks nsp13 through a novel mechanism and is less likely to interfere with the functions of cellular enzymes that process nucleic acids or ATP. Hence, it is possible that SSYA10-001 inhibits unwinding by nsp13 by affecting conformational changes during the course of the reaction or translocation on the nucleic acid. SSYA10-001 will be a valuable tool for studying the specific role of nsp13 in the SARS-CoV life cycle, which could be a model for other nidoviruses and also a candidate for further development as a SARS antiviral target.

Importance of seagrass as a carbon source for heterotrophic bacteria in a subtropical estuary (Florida Bay)

NASA Astrophysics Data System (ADS)

Williams, Clayton J.; Jaffé, Rudolf; Anderson, William T.; Jochem, Frank J.

2009-11-01

A stable carbon isotope approach was taken to identify potential organic matter sources incorporated into biomass by the heterotrophic bacterial community of Florida Bay, a subtropical estuary with a recent history of seagrass loss and phytoplankton blooms. To gain a more complete understanding of bacterial carbon cycling in seagrass estuaries, this study focused on the importance of seagrass-derived organic matter to pelagic, seagrass epiphytic, and sediment surface bacteria. Particulate organic matter (POM), seagrass epiphytic, seagrass ( Thalassia testudinum) leaf, and sediment surface samples were collected from four Florida Bay locations with historically different organic matter inputs, macrophyte densities, and primary productivities. Bulk (observed and those reported previously) and compound-specific bacterial fatty acid δ 13C values were used to determine important carbon sources to the estuary and benthic and pelagic heterotrophic bacteria. The δ 13C values of T. testudinum green leaves with epiphytes removed ranged from -9.9 to -6.9‰. Thalassia testudinum δ 13C values were significant more enriched in 13C than POM, epiphytic, and sediment samples, which ranged from -16.4 to -13.5, -16.2 to -9.6, and -16.7 to -11.0‰, respectively. Bacterial fatty acid δ 13C values (measured for br14:0, 15:0, i15:0, a15:0, br17:0, and 17:0) ranged from -25.5 to -8.2‰. Assuming a -3‰ carbon source fractionation from fatty acid to whole bacteria, pelagic, epiphytic, and sediment bacterial δ 13C values were generally more depleted in 13C than T. testudinum δ 13C values, more enriched in 13C than reported δ 13C values for mangroves, and similar to reported δ 13C values for algae. IsoSource mixing model results indicated that organic matter derived from T. testudinum was incorporated by both benthic and pelagic bacterial communities, where 13-67% of bacterial δ 13C values could arise from consumption of seagrass-derived organic matter. The IsoSource model, however, failed to discriminate clearly the fraction of algal (0-86%) and mangrove (0-42%) organic matter incorporated by bacterial communities. These results indicate that pelagic, epiphytic, and sediment surface bacteria consumed organic matter from a variety of sources. Bacterial communities incorporated consistently seagrass-derived organic matter, the dominant macrophyte in Florida Bay, but seagrass δ 13C values alone could not account fully for bacterial δ 13C values.

Synthesis of empagliflozin, a novel and selective sodium-glucose co-transporter-2 inhibitor, labeled with carbon-14 and carbon-13.

PubMed

Hrapchak, Matt; Latli, Bachir; Wang, Xiao-Jun; Lee, Heewon; Campbell, Scot; Song, Jinhua J; Senanayake, Chris H

2014-10-01

Empagliflozin, (2S,3R,4R,5S,6R)-2-[4-chloro-3-[[4-[(3S)-oxolan-3-yl]oxyphenyl]methyl]phenyl]-6-(hydroxymethyl)oxane-3,4,5-triol was recently approved by the FDA for the treatment of chronic type 2 diabetes mellitus. Herein, we report the synthesis of carbon-13 and carbon-14 labeled empagliflozin. Carbon-13 labeled empagliflozin was prepared in five steps and in 34% overall chemical yield starting from the commercially available α-D-glucose-[(13)C6]. For the radiosynthesis, the carbon-14 atom was introduced in three different positions of the molecule. In the first synthesis, Carbon-14 D-(+)-gluconic acid δ-lactone was used to prepare specifically labeled empagliflozin in carbon-1 of the sugar moiety in four steps and in 19% overall radiochemical yield. Carbon-14 labeled empagliflozin with the radioactive atom in the benzylic position was obtained in eight steps and in 7% overall radiochemical yield. In the last synthesis carbon-14 uniformly labeled phenol was used to give [(14)C]empagliflozin in eight steps and in 18% overall radiochemical yield. In all these radiosyntheses, the specific activities of the final compounds were higher than 53 mCi/mmol, and the radiochemical purities were above 98.5%. Copyright © 2014 John Wiley & Sons, Ltd.

[Non-alkaloid components from Sophora flavescens].

PubMed

Zhang, Chi; Ma, Yue; Gao, Hui-Min; Liu, Xiao-Qian; Chen, Liang-Mian; Zhang, Qi-Wei; Wang, Zhi-Min; Li, An-Ping

2013-10-01

Five compounds were obtained from the stems and leaves of Sophora flavescens Ait. and ten compounds were obtained from the roots of S. flavescens by various chromatography methods including silica gel column chromatography and preparative HPLC. Their structures were identified on the basis of spectroscopic methods including 1H-NMR, 13C-NMR and ESI-MS, as corchionoside C (1), syringing (2), 2'-deoxythymidin (3), coniferin (4), benzyl O-beta-D-glucopyranoside (5), piscidic acid (6), trifolirhizin (7), kurarinone (8), trifolirhizin-6'-monoacetate (9), sophoraflavanone G (10), isoxanthohumol (11), noranhydroicaritin (12), 4'-methoxyisoflavone-7-O-beta-D-apiofuranosyl-(1 --> 6)-beta-D-glucopyranoside (13), kushenol O (14) and 6"-beta-D-xylopyranosylgenistin (15). Compounds 1-6 were isolated from the Sophora genus for the first time.

Homonuclear long-range correlation spectra from HMBC experiments by covariance processing.

PubMed

Schoefberger, Wolfgang; Smrecki, Vilko; Vikić-Topić, Drazen; Müller, Norbert

2007-07-01

We present a new application of covariance nuclear magnetic resonance processing based on 1H--13C-HMBC experiments which provides an effective way for establishing indirect 1H--1H and 13C--13C nuclear spin connectivity at natural isotope abundance. The method, which identifies correlated spin networks in terms of covariance between one-dimensional traces from a single decoupled HMBC experiment, derives 13C--13C as well as 1H--1H spin connectivity maps from the two-dimensional frequency domain heteronuclear long-range correlation data matrix. The potential and limitations of this novel covariance NMR application are demonstrated on two compounds: eugenyl-beta-D-glucopyranoside and an emodin-derivative. Copyright (c) 2007 John Wiley & Sons, Ltd.

Probing metabolic processes of intact soil microbial communities using position-specific 13C-labeled glucose

NASA Astrophysics Data System (ADS)

Fairbanks, D. E.; Hungate, B. A.; KOCH, G. W.; Schwartz, E.; Dijkstra, P.

2012-12-01

Soils represent one of the largest carbon pools in the terrestrial biosphere and fluxes into or out of this pool may feedback to current climate change. Understanding the mechanisms behind microbial processes regulating C cycling, microbial turnover, and soil organic matter stabilization is hindered by our lack of understanding of the details of microbial physiology in soils. Position-specific 13C labeled metabolic tracers are proposed as a new way to probe microbial community energy production, biosynthesis, C use efficiency (the proportion of substrate incorporated into microbial biomass), and enables the determination of C fluxes through the various C metabolic pathways. We determined the 13CO2 production from microbial communities within a one hour time frame by adding six isotopomers (1-13C, 2-13C, 3-13C, 4-13C, 5-13C, 6-13C) of glucose in parallel incubations using a young volcanic soil (Pinyon-juniper wood, near Sunset Crater, Flagstaff, Arizona). We compared the measured rates of position-specific 13CO2 production with modeled results based on glucose (1-13C and U-13C) and pyruvate (1-13C and 2,3-13C) incubations. These labeling and modeling techniques may improve our ability to analyze the biochemistry and ecophysiology of intact soil microbial communities.

Determination of perfluorinated compounds in fish fillet homogenates: method validation and application to fillet homogenates from the Mississippi River.

PubMed

Malinsky, Michelle Duval; Jacoby, Cliffton B; Reagen, William K

2011-01-10

We report herein a simple protein precipitation extraction-liquid chromatography tandem mass spectrometry (LC/MS/MS) method, validation, and application for the analysis of perfluorinated carboxylic acids (C7-C12), perfluorinated sulfonic acids (C4, C6, and C8), and perfluorooctane sulfonamide (FOSA) in fish fillet tissue. The method combines a rapid homogenization and protein precipitation tissue extraction procedure using stable-isotope internal standard (IS) calibration. Method validation in bluegill (Lepomis macrochirus) fillet tissue evaluated the following: (1) method accuracy and precision in both extracted matrix-matched calibration and solvent (unextracted) calibration, (2) quantitation of mixed branched and linear isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) with linear isomer calibration, (3) quantitation of low level (ppb) perfluorinated compounds (PFCs) in the presence of high level (ppm) PFOS, and (4) specificity from matrix interferences. Both calibration techniques produced method accuracy of at least 100±13% with a precision (%RSD) ≤18% for all target analytes. Method accuracy and precision results for fillet samples from nine different fish species taken from the Mississippi River in 2008 and 2009 are also presented. Copyright © 2010 Elsevier B.V. All rights reserved.

Opportunistic feeding on various organic food sources by the cold-water coral Lophelia pertusa

NASA Astrophysics Data System (ADS)

Mueller, C. E.; Larsson, A. I.; Veuger, B.; Middelburg, J. J.; van Oevelen, D.

2014-01-01

The ability of the cold-water coral Lophelia pertusa to exploit different food sources was investigated under standardized conditions in a flume. The tested food sources, dissolved organic matter (DOM, added as dissolved free amino acids), bacteria, algae, and zooplankton (Artemia) were deliberately enriched in 13C and 15N. The incorporation of 13C and 15N was traced into bulk tissue, fatty acids, hydrolysable amino acids, and the skeleton (13C only) of L. pertusa. Incorporation rates of carbon (ranging from 0.8-2.4 μg C g-1 DW d-1) and nitrogen (0.2-0.8 μg N g-1 DW d-1) into coral tissue did not differ significantly among food sources indicating an opportunistic feeding strategy. Although total food assimilation was comparable among sources, subsequent food processing was dependent on the type of food source ingested and recovery of assimilated C in tissue compounds ranged from 17% (algae) to 35% (Artemia). De novo synthesis of individual fatty acids by L. pertusa occurred in all treatments as indicated by the 13C enrichment of individual phospholipid-derived fatty acids (PLFAs) in the coral that were absent in the added food sources. This indicates that the coral might be less dependent on its diet as a source of specific fatty acids than expected, with direct consequences for the interpretation of in situ observations on coral nutrition based on lipid profiles.

Opportunistic feeding on various organic food sources by the cold-water coral Lophelia pertusa

NASA Astrophysics Data System (ADS)

Mueller, C. E.; Larsson, A. I.; Veuger, B.; Middelburg, J. J.; van Oevelen, D.

2013-07-01

The ability of the cold-water coral Lophelia pertusa to exploit different food sources was investigated under standardized conditions in a flume. All tested food sources, dissolved organic matter (DOM, added as dissolved free amino acids), bacteria, algae, and zooplankton (Artemia) were deliberately enriched in 13C and 15N. The incorporation of 13C and 15N was traced into bulk tissue, fatty acids, hydrolysable amino acids, and the skeleton (13C only) of L. pertusa. Incorporation rates of carbon (ranging from 0.8-2.4 µg C g-1 DW d-1) and nitrogen (0.2-0.8 µg N g-1 DW d-1) into coral tissue did not differ significantly among food sources indicating an opportunistic feeding strategy. Although total food assimilation was comparable among sources, subsequent food processing was dependent on the type of food source ingested and recovery of assimilated C in tissue compounds ranged from 17% (algae) to 35% (Artemia). De novo synthesis of individual fatty acids by L. pertusa occurred in all treatments as indicated by the 13C enrichment of individual phospholipid-derived fatty acids (PLFAs) in the coral that were absent in the added food sources. This indicates that the coral might be less dependent on its diet as a source of specific fatty acids than expected, with direct consequences for the interpretation of in situ observations on coral nutrition based on lipid profiles.

Simultaneous quantification and identification of individual chemicals in metabolite mixtures by two-dimensional extrapolated time-zero (1)H-(13)C HSQC (HSQC(0)).

PubMed

Hu, Kaifeng; Westler, William M; Markley, John L

2011-02-16

Quantitative one-dimensional (1D) (1)H NMR spectroscopy is a useful tool for determining metabolite concentrations because of the direct proportionality of signal intensity to the quantity of analyte. However, severe signal overlap in 1D (1)H NMR spectra of complex metabolite mixtures hinders accurate quantification. Extension of 1D (1)H to 2D (1)H-(13)C HSQC leads to the dispersion of peaks along the (13)C dimension and greatly alleviates peak overlapping. Although peaks are better resolved in 2D (1)H-(13)C HSQC than in 1D (1)H NMR spectra, the simple proportionality of cross peaks to the quantity of individual metabolites is lost by resonance-specific signal attenuation during the coherence transfer periods. As a result, peaks for individual metabolites usually are quantified by reference to calibration data collected from samples of known concentration. We show here that data from a series of HSQC spectra acquired with incremented repetition times (the time between the end of the first (1)H excitation pulse to the beginning of data acquisition) can be extrapolated back to zero time to yield a time-zero 2D (1)H-(13)C HSQC spectrum (HSQC(0)) in which signal intensities are proportional to concentrations of individual metabolites. Relative concentrations determined from cross peak intensities can be converted to absolute concentrations by reference to an internal standard of known concentration. Clustering of the HSQC(0) cross peaks by their normalized intensities identifies those corresponding to metabolites present at a given concentration, and this information can assist in assigning these peaks to specific compounds. The concentration measurement for an individual metabolite can be improved by averaging the intensities of multiple, nonoverlapping cross peaks assigned to that metabolite.

Measurement of 13C chemical shift tensor principal values with a magic-angle turning experiment.

PubMed

Hu, J Z; Orendt, A M; Alderman, D W; Pugmire, R J; Ye, C; Grant, D M

1994-08-01

The magic-angle turning (MAT) experiment introduced by Gan is developed into a powerful and routine method for measuring the principal values of 13C chemical shift tensors in powdered solids. A large-volume MAT probe with stable rotation frequencies down to 22 Hz is described. A triple-echo MAT pulse sequence is introduced to improve the quality of the two-dimensional baseplane. It is shown that measurements of the principal values of chemical shift tensors in complex compounds can be enhanced by using either short contact times or dipolar dephasing pulse sequences to isolate the powder patterns from protonated or non-protonated carbons, respectively. A model compound, 1,2,3-trimethoxybenzene, is used to demonstrate these techniques, and the 13C principal values in 2,3-dimethylnaphthalene and Pocahontas coal are reported as typical examples.

Chemical vs. biotechnological synthesis of C13-apocarotenoids: current methods, applications and perspectives.

PubMed

Cataldo, Vicente F; López, Javiera; Cárcamo, Martín; Agosin, Eduardo

2016-07-01

Apocarotenoids are natural compounds derived from the oxidative cleavage of carotenoids. Particularly, C13-apocarotenoids are volatile compounds that contribute to the aromas of different flowers and fruits and are highly valued by the Flavor and Fragrance industry. So far, the chemical synthesis of these terpenoids has dominated the industry. Nonetheless, the increasing consumer demand for more natural and sustainable processes raises an interesting opportunity for bio-production alternatives. In this regard, enzymatic biocatalysis and metabolically engineered microorganisms emerge as attractive biotechnological options. The present review summarizes promising bioengineering approaches with regard to chemical production methods for the synthesis of two families of C13-apocarotenoids: ionones/dihydroionones and damascones/damascenone. We discuss each method and its applicability, with a thorough comparative analysis for ionones, focusing on the production process, regulatory aspects, and sustainability.

MIR hollow waveguide (HWG) isotope ratio analyzer for environmental applications

NASA Astrophysics Data System (ADS)

Wang, Zhenyou; Zhuang, Yan; Deev, Andrei; Wu, Sheng

2017-05-01

An advanced commercial Mid-InfraRed Isotope Ratio (IR2) analyzer was developed in Arrow Grand Technologies based on hollow waveguide (HWG) as the sample tube. The stable carbon isotope ratio, i.e. δ13C, was obtained by measuring the selected CO2 absorption peaks in the MIR. Combined with a GC and a combustor, it has been successfully employed to measure compound specific δ13C isotope ratios in the field. By using both the 1- pass HWG and 5-path HWG, we are able to measure δ13C isotope ratio at a broad CO2 concentration of 300 ppm-37,500 ppm. Here, we demonstrate its applications in environmental studies. The δ13C isotope ratio and concentration of CO2 exhaled by soil samples was measured in real time with the isotope analyzer. The concentration was found to change with the time. We also convert the Dissolved Inorganic Carbon (DIC) into CO2, and then measure the δ13C isotope ratio with an accuracy of better than 0.3 ‰ (1 σ) with a 6 min test time and 1 ml sample usage. Tap water, NaHCO3 solvent, coca, and even beer were tested. Lastly, the 13C isotope ratio of CO2 exhaled by human beings was obtained <10 seconds after simply blowing the exhaled CO2 into a tube with an accuracy of 0.5‰ (1 σ) without sample preconditioning. In summary, a commercial HWG isotope analyzer was demonstrated to be able to perform environmental and health studies with a high accuracy ( 0.3 ‰/Hz1/2 1 σ), fast sampling rate (up to 10 Hz), low sample consumption ( 1 ml), and broad CO2 concentration range (300 ppm-37,500 ppm).

4'-alpha-C-Branched N,O-nucleosides: synthesis and biological properties.

PubMed

Chiacchio, Ugo; Genovese, Filippo; Iannazzo, Daniela; Piperno, Anna; Quadrelli, Paolo; Antonino, Corsaro; Romeo, Roberto; Valveri, Vincenza; Mastino, Antonio

2004-07-15

The synthesis of 4'-alpha-C-branched N,O-nucleosides has been described, based on the 1,3-dipolar cycloaddition of nitrones with vinyl acetate followed by coupling with silylated nucleobases, The obtained compounds have been evaluated for their activity against HSV-1, HSV-2, HTLV-1. Cytotoxicity and apoptotic activity have been also investigated: compound 10c shows moderate apoptotic activity in Molt-3 cells.

Sorption Behavior of Dye Compounds onto Natural Sediment of Qinghe River.

PubMed

Liu, Ruixia; Liu, Xingmin; Tang, Hongxiao; Su, Yongbo

2001-07-15

The objective of this study is to assess the adsorption behavior of C.I. Basic Yellow X-5GL, C.I. Basic Red 13, C.I. Direct Blue 86, C.I. Vat Yellow 2, and C.I. Mordant Black 11 on natural sediment and to identify sediment characteristics that play a predominant role in the adsorption of the dyes. The potentiometric titration experiment is used to investigate acid-base properties of the sediment surface with a constant capacitance surface complexation model. The parameters controlling the sorption such as solution pH and ion strength, as well as the influence of organic carbon and Ca(2+) ion on the adsorption, are evaluated. It is shown that the titration data can be successfully described by the surface protonation and deprotonation model with the least-squares FITEQL program 2.0. The sorption isotherm data are fitted to the Freundlich equation in a nonlinear form (1/n=0.3-0.9) for all tested dyes. With increasing pH value, the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86 on the sediment decreases, while for C.I. Basic Yellow X-5GL and C.I. Basic Red 13, the extent of sorption slightly increases. In addition, ion strength also exhibits a considerably different effect on the sorption behavior of these dye compounds. The addition of Ca(2+) can greatly reduce the sorption of C.I. Basic Red 13 on the sediment surface, while it enhances the sorption of C.I. Direct Blue 6. The removal of organic carbon decreases the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86. In contrast, the sorption of C.I. Basic Red 13 and C.I. Basic Yellow X-5GL is obviously enhanced after the removal of organic carbon. The differences in adsorption behavior are mainly attributed to the physicochemical properties of these dye compounds. Copyright 2001 Academic Press.

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR

PubMed Central

Yau, Wai-Ming; Thurber, Kent R.; Tycko, Robert

2014-01-01

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25–30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2–6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92–128 for cross-polarized 13C NMR signals from 15N,13C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6–3.8 s for 1H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute 13C NMR signal amplitudes and build-up times, are approximately 2–4 times lower than with the best triradicals. PMID:24887201

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR

NASA Astrophysics Data System (ADS)

Yau, Wai-Ming; Thurber, Kent R.; Tycko, Robert

2014-07-01

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25-30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2-6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92-128 for cross-polarized 13C NMR signals from 15N,13C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6-3.8 s for 1H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute 13C NMR signal amplitudes and build-up times, are approximately 2-4 times lower than with the best triradicals.

Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR.

PubMed

Yau, Wai-Ming; Thurber, Kent R; Tycko, Robert

2014-07-01

We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25-30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2-6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92-128 for cross-polarized (13)C NMR signals from (15)N,(13)C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6-3.8s for (1)H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute (13)C NMR signal amplitudes and build-up times, are approximately 2-4 times lower than with the best triradicals. Published by Elsevier Inc.

Efficient Synthesis of Molecular Precursors for Para-Hydrogen-Induced Polarization of Ethyl Acetate-1-(13) C and Beyond.

PubMed

Shchepin, Roman V; Barskiy, Danila A; Coffey, Aaron M; Manzanera Esteve, Isaac V; Chekmenev, Eduard Y

2016-05-10

A scalable and versatile methodology for production of vinylated carboxylic compounds with (13) C isotopic label in C1 position is described. It allowed synthesis of vinyl acetate-1-(13) C, which is a precursor for preparation of (13) C hyperpolarized ethyl acetate-1-(13) C, which provides a convenient vehicle for potential in vivo delivery of hyperpolarized acetate to probe metabolism in living organisms. Kinetics of vinyl acetate molecular hydrogenation and polarization transfer from para-hydrogen to (13) C via magnetic field cycling were investigated. Nascent proton nuclear spin polarization (%PH ) of ca. 3.3 % and carbon-13 polarization (%P13C ) of ca. 1.8 % were achieved in ethyl acetate utilizing 50 % para-hydrogen corresponding to ca. 50 % polarization transfer efficiency. The use of nearly 100% para-hydrogen and the improvements of %PH of para-hydrogen-nascent protons may enable production of (13) C hyperpolarized contrast agents with %P13C of 20-50 % in seconds using this chemistry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SST and terrestrial n-alkanes records in sediment of the Korean Plateau, East Sea (Japan Sea) during the last 400 kyr: Paleoceanographic and paleoclimatic implications

NASA Astrophysics Data System (ADS)

Hyun, Sangmin; Suh, Yean Jee; Kim, Jin Kyung

2014-05-01

SST variation was reconstructed using alkenones and their variation was compared with terrestrial n-alkanes signature from the sediment of the Korean Plateau, East Sea (Japan Sea) during the last 400 ka. SST variation showed glacial-interglacial time scale variation with a maximum temperature of 26 oC in MIS 7, and a minimum of 12 oC at MIS 2 and 6. The distribution of terrestrial n-alkanes signatures is characterized by the occurrence of high odd number predominance in most samples, however minor dominance of a specific compound (nC27 only) was the additional characteristic.bAverage Chain Length (ACL) and Carbon Preferences Index (ICP), derived from n-alkane distributions, showed a similar shifting between glacial-interglacial time-scale. This suggests that paleovegetation communities changed in response to paleoclimatological variations, and the input of terrestrial compound is strongly linked with paleoclimatology. In the previous work, isotopic composition of δ13C and δ15N of organic matter showed extreme temporal variation since MIS 11 suggesting influx of a large amount of terrestrial organic matters from the neighboring continent during MIS 2, 8 and 10. In particular, depleted values of δ13C during MIS 2, 8 and 10 were coincident with lower nitrogen isotope values indicating local paleoceanographic effects such as paleoproductivity changes. Decoupling of δ13C and δ15N during MIS 1, 3, 5, and 7, and coupling of the two during MIS 8 and 11 is observed, which can be interpreted as local productivity changes. The alkenones SST and n-alkanes signature coincided with carbon and nitrogen isotope variation in terms of glacial-interglacial time scale suggesting that the paleoenvironments in the East Sea is sensitive to the global climate changes associated with not only orbital-scale glacial-interglacial variations but also local paleceanographic variations.

C-Methylated Flavonoid Glycosides from Pentarhizidium orientale Rhizomes and Their Inhibitory Effects on the H1N1 Influenza Virus.

PubMed

Huh, Jungmoo; Ha, Thi Kim Quy; Kang, Kyo Bin; Kim, Ki Hyun; Oh, Won Keun; Kim, Jinwoong; Sung, Sang Hyun

2017-10-27

Thirteen C-methylated flavonoid glycosides (1-13), along with 15 previously known flavonoids (14-28), were isolated from rhizomes of Pentarhizidium orientale. Among these compounds, matteuorienates D-K (1-8) were obtained as analogues of matteuorienates A-C (14-16), which contain a characteristic 3-hydroxy-3-methylglutaryl (HMG) moiety. The structures of 1-13 were characterized by spectroscopic analysis and chemical derivatization. The isolates were evaluated for their antiviral activities against influenza virus (H1N1), with compounds 21, 22, 23, 25, and 26 showing inhibitory effects (IC 50 of 23.9-30.3 μM) against neuraminidases.

Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC.

PubMed

Negahdar, Leila; Gonzalez-Quiroga, Arturo; Otyuskaya, Daria; Toraman, Hilal E; Liu, Li; Jastrzebski, Johann T B H; Van Geem, Kevin M; Marin, Guy B; Thybaut, Joris W; Weckhuysen, Bert M

2016-09-06

Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13 C nuclear magnetic resonance ( 13 C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13 C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.

Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

NASA Astrophysics Data System (ADS)

Billmark, K. A.; Macko, S. A.; Swap, R. J.

2003-12-01

This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

Synthesis, biological evaluation and molecular modeling of novel series of pyridine derivatives as anticancer, anti-inflammatory and analgesic agents

NASA Astrophysics Data System (ADS)

Helal, M. H.; El-Awdan, S. A.; Salem, M. A.; Abd-elaziz, T. A.; Moahamed, Y. A.; El-Sherif, A. A.; Mohamed, G. A. M.

2015-01-01

This paper presents a combined synthesis; characterization, computational and biological activity studies of novel series of pyridines heterocyclic compounds. The compounds have been characterized by elemental analyses and spectral like IR, 1H NMR, 13C NMR and MS studies. Michael addition of substituted-2-methoxycarbonylacetanilide 2a,b on the α-substituted cinnamonitriles 3a-d gave the corresponding 2-pyridone derivatives 5-10. Structures of the titled compounds cited in this article were elucidated by spectrometric data (IR, 1H NMR, 13C NMR and MS). The molecular modeling of the synthesized compounds has been drawn and their molecular parameters were calculated. Also, valuable information is obtained from the calculation of molecular parameters including electronegativity, net dipole moment of the compounds, total energy, electronic energy, binding energy, HOMO and LUMO energy. Various in vitro antitumor as well as in vivo anti-inflammatory and analgesic activities of the synthesized compounds were investigated. Evaluation of anti-inflammatory activity of test compounds was performed using carrageenan induced paw edema in rats. All the tested compounds showed moderate to good activity. The SAR results indicate that all compounds showed moderate to good activity, among these 7 and 10 compounds having -N(CH3)2 group are most effective.

Distinguishing between old and modern permafrost sources in the northeast Siberian land-shelf system with compound-specific δ2H analysis

NASA Astrophysics Data System (ADS)

Vonk, Jorien E.; Tesi, Tommaso; Bröder, Lisa; Holmstrand, Henry; Hugelius, Gustaf; Andersson, August; Dudarev, Oleg; Semiletov, Igor; Gustafsson, Örjan

2017-08-01

Pleistocene ice complex permafrost deposits contain roughly a quarter of the organic carbon (OC) stored in permafrost (PF) terrain. When permafrost thaws, its OC is remobilized into the (aquatic) environment where it is available for degradation, transport or burial. Aquatic or coastal environments contain sedimentary reservoirs that can serve as archives of past climatic change. As permafrost thaw is increasing throughout the Arctic, these reservoirs are important locations to assess the fate of remobilized permafrost OC.

We here present compound-specific deuterium (δ2H) analysis on leaf waxes as a tool to distinguish between OC released from thawing Pleistocene permafrost (ice complex deposits; ICD) and from thawing Holocene permafrost (from near-surface soils). Bulk geochemistry (%OC; δ13C; %total nitrogen, TN) was analyzed as well as the concentrations and δ2H signatures of long-chain n-alkanes (C21 to C33) and mid- to long-chain n-alkanoic acids (C16 to C30) extracted from both ICD-PF samples (n = 9) and modern vegetation and O-horizon (topsoil-PF) samples (n = 9) from across the northeast Siberian Arctic. Results show that these topsoil-PF samples have higher %OC, higher OC / TN values and more depleted δ13C-OC values than ICD-PF samples, suggesting that these former samples trace a fresher soil and/or vegetation source. Whereas the two investigated sources differ on the bulk geochemical level, they are, however, virtually indistinguishable when using leaf wax concentrations and ratios. However, on the molecular isotope level, leaf wax biomarker δ2H values are statistically different between topsoil PF and ICD PF. For example, the mean δ2H value of C29 n-alkane was -246 ± 13 ‰ (mean ± SD) for topsoil PF and -280 ± 12 ‰ for ICD PF. With a dynamic isotopic range (difference between two sources) of 34 to 50 ‰; the isotopic fingerprints of individual, abundant, biomarker molecules from leaf waxes can thus serve as endmembers to distinguish between these two sources. We tested this molecular δ2H tracer along with another source-distinguishing approach, dual-carbon (δ13C-Δ14C) isotope composition of bulk OC, for a surface sediment transect in the Laptev Sea. Results show that general offshore patterns along the shelf-slope transect are similar, but the source apportionment between the approaches vary, which may highlight the advantages of either. This study indicates that the application of δ2H leaf wax values has potential to serve as a complementary quantitative measure of the source and differential fate of OC thawed out from different permafrost compartments.

Early diagenesis of bacteriohopanepolyol derivatives: Formation of fossil homohopanoids

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Van Duin, Adri C. T.; Hollander, David; Kohnen, Math E. L.; De Leeuw, Jan W.

1995-12-01

Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95%) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C 35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80%) of the total extended hopane skeletons (C 31-C 35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52%) towards the thermodynamic equilibrium (52-53%) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols "en passant" isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C 35 hopane skeletons and free C 31 hopanes 13C contents are in some cases even larger. These data show that the diagenetic pathways of bacteriohopanepolyol derivatives are more complex than previously recognized and reveal that multiple precursor bacteriohopanepolyol derivatives prone to different diagenetic pathways have to be envisaged to account for the differences observed.

Puupehenol, a potent antioxidant antimicrobial meroterpenoid from a Hawaiian deep-water Dactylospongia sp. sponge.

PubMed

Hagiwara, Kehau; Garcia Hernandez, Jaaziel E; Harper, Mary Kay; Carroll, Anthony; Motti, Cherie A; Awaya, Jonathan; Nguyen, Hoang-Yen; Wright, Anthony D

2015-02-27

From the organic extract of a deep-water Hawaiian sponge Dactylospongia sp., a new potent antioxidant and antimicrobial meroterpenoid, puupehenol (1), was isolated. The structure of 1 was determined using spectroscopic techniques ((1)H and (13)C NMR, MS, IR, UV, [α]D). The known compound puupehenone (2) was also isolated and suggested as a probable artifact of the isolation procedures. Complete unambiguous (1)H and (13)C NMR data are provided for compounds 1 and 2. Bioassays performed with 1 and 2 showed them both to be very effective antioxidants and to have antimicrobial properties.

Use of headspace SPME-GC-MS for the analysis of the volatiles produced by indoor molds grown on different substrates.

PubMed

Van Lancker, Fien; Adams, An; Delmulle, Barbara; De Saeger, Sarah; Moretti, Antonio; Van Peteghem, Carlos; De Kimpe, Norbert

2008-10-01

An automated headspace solid phase microextraction method followed by GC-MS analysis was used to evaluate and compare the in vitro production of microbial volatile organic compounds (MVOCs) on malt extract agar, plasterboard and wallpaper. Five fungal strains were isolated from the walls of water-damaged houses and identified. In addition, four other common molds were studied. In general, MVOC production was the highest on malt extract agar. On this synthetic medium, molds typically produced 2-methylpropanol, 2-methylbutanol and 3-methylbutanol. On wallpaper, mainly 2-ethylhexanol, methyl 2-ethylhexanoate and compounds of the C8-complex such as 1-octene-3-ol, 3-octanone, 3-octanol and 1,3-octadiene were detected. The detection of 2-ethylhexanol and methyl 2-ethylhexanoate indicates an enhanced degradation of the substrate by most fungi. For growth on plasterboard, no typical metabolites were detected. Despite these metabolite differences on malt extract agar, wallpaper and plasterboard, some molds also produced specific compounds independently of the used substrate, such as trichodiene from Fusarium sporotrichioides and aristolochene from Penicillium roqueforti. Therefore, these metabolites can be used as markers for the identification and maybe also mycotoxin production of these molds. All five investigated Penicillium spp. in this study were able to produce two specific diterpenes, which were not produced by the other species studied. These two compounds, which remain unidentified until now, therefore seem specific for Penicillium spp. and are potentially interesting for the monitoring of this fungal genus. Further experiments will be performed with other Penicillium spp. to study the possibility that these two compounds are specific for this group of molds.

Structural characterization and identification of biflavones in Selaginella tamariscina by liquid chromatography-diode-array detection/electrospray ionization tandem mass spectrometry.

PubMed

Zhang, Yi-Xuan; Li, Qiu-Yue; Yan, Li-Li; Shi, Yue

2011-08-15

Biflavonoids, a special class of flavonoids, are widely distributed in gymnosperm plants and have various biological activities. They are also major bioactive ingredients in Selaginella tamariscina. In this work, we report the use of high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and electrospray ionization multi-stage tandem mass spectrometry (ESI-MS(n)) to study the fragmentation behavior of three main types of biflavonoids using seven biflavonoid reference compounds and analyze the biflavonoids in Selaginella tamariscina. The most useful fragmentations in terms of structural identification are those involving the C-ring cleavage of biflavonoids. For amentoflavone-type biflavonoids (containing flavonoid parts I and II), fragmentation on the flavonoid part II at positions 1/3 and 0/4 are the primary pathways, whereas the chances are greater for C-ring cleavage fragmentation occurring on flavonoid part I at positions 1/3 and 1/4 for robustaflavone-type biflavonoids. However, the predominant diagnostic ions of the specific C-O-C-connected hinokiflavone-type biflavonoids are a series of ions resulting from the rupture of the connective C-O bond. Based on the fragmentation patterns of these reference compounds, 17 biflavonoids were identified in an extract of Selaginella tamariscina, three of which have not been previously reported as constituents of this plant. This study provides a powerful approach for the online structural elucidation and identification of different types of biflavonoids and positional isomers from Selaginella tamariscina and other biflavonoids distributed in related plants and prescriptions. Copyright © 2011 John Wiley & Sons, Ltd.

Microbes mediate carbon and nitrogen retention in shallow photic sediments

NASA Astrophysics Data System (ADS)

Hardison, A.; Anderson, I.; Canuel, E. A.; Tobias, C.; Veuger, B.

2009-12-01

Sediments in shallow coastal bays are sites of intense biogeochemical cycling facilitated by a complex microbial consortium. Unlike deeper coastal environments, much of the benthos is illuminated by sunlight in these bays. As a result, benthic autotrophs such as benthic microalgae (BMA) and macroalgae play an integral role in nutrient cycling. Investigating pathways of carbon (C) and nitrogen (N) flow through individual compartments within the sediment microbial community has previously proved challenging due to methodological difficulties. However, it is now possible using stable isotopes and microbial biomarkers such as fatty acids and amino acids to track C and N flow through individual microbial pools. We investigated the uptake and retention of C and N by bacteria and BMA in a shallow subtidal system. Using bulk and compound specific isotopic analysis, we traced the pathways of dissolved inorganic 13C and 15N under various treatments: 1) in ambient light or dark, 2) from porewater or water column sources, and 3) in the presence or absence of bloom forming nuisance macroalgae. Excess 13C and 15N in THAAs and excess 13C in total PLFAs showed a strong dependence on light. Enrichment of these pools represents uptake by the microbial community, which can include both autotrophic and heterotrophic components. Higher excess 13C in benthic microalgal fatty acids (C20, C22 PUFAs) provides evidence that benthic microalgae were fixing 13C. Aditionally, the ratio of excess 13C in branched fatty acids to microbial fatty acids (BAR) and excess 13C and 15N in D-Ala to L-Ala (D/L-Ala) were low, suggesting dominance by benthic microalgae over bacteria to total label incorporation. Our results support uptake and retention of C and N by the sediment microbial community and indicate a tight coupling between BMA and bacteria in shallow illuminated systems. This uptake is diminished in the presence of macroalgae, likely due to shading and/or nutrient competition. Therefore, macroalgae reduce the retention of C and N within surface sediments, diminishing the role of the microbial community in nutrient cycling processes.

Reductive amination derivatization for the quantification of garlic components by isotope dilution analysis.

PubMed

Lin, Yi-Reng; Huang, Mei-Fang; Wu, You-Ying; Liu, Meng-Chieh; Huang, Jing-Heng; Chen, Ziyu; Shiue, Yow-Ling; Wu, Chia-En; Liang, Shih-Shin

2017-09-01

In this work, we synthesized internal standards for four garlic organosulfur compounds (OSCs) by reductive amination with 13 C, D 2 -formaldehyde, and developed an isotope dilution analysis method to quantitate these organosulfur components in garlic samples. Internal standards were synthesized for internal absolute quantification of S-allylcysteine (SAC), S-allylcysteine sulfoxide (alliin), S-methylcysteine (SMC), and S-ethylcysteine (SEC). We used a multiple reaction monitoring (MRM) to detect 13 C, D 2 -formaldehyde-modified OSCs by ultrahigh-performance liquid phase chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and obtained MS spectra showing different ratios of 13 C, D 2 -formaldehyde-modified and H 2 -formaldehyde-modified compounds. The resulting labeled and unlabeled OSCs were exhibited correlation coefficient (R 2 ) ranged from 0.9989 to 0.9994, respectively. The average recoveries for four OSCs at three concentration levels ranged from 89% to 105%. By 13 C, D 2 -formaldehyde and sodium cyanoborohydride, the reductive amination-based method can be utilized to generate novel internal standard for isotope dilution and to extend the quantitative application. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxidation of C18 Hydroxy-Polyunsaturated Fatty Acids to Epoxide or Ketone by Catalase-Related Hemoproteins Activated with Iodosylbenzene.

PubMed

Teder, Tarvi; Boeglin, William E; Brash, Alan R

2017-07-01

Small catalase-related hemoproteins with a facility to react with fatty acid hydroperoxides were examined for their potential mono-oxygenase activity when activated using iodosylbenzene. The proteins tested were a Fusarium graminearum 41 kD catalase hemoprotein (Fg-cat, gene FGSG_02217), a Pseudomonas fluorescens Pfl01 catalase (37.5 kD, accession number WP_011333788.1), and a Mycobacterium avium ssp. paratuberculosis 33 kD catalase (gene MAP-2744c). 13-Hydroxy-octadecenoic acids (which are normally unreactive) were selected as substrates because these enzymes react specifically with the corresponding 13S-hydroperoxides (Pakhomova et al. 18:2559-2568, 5; Teder et al. 1862:706-715, 14). In the presence of iodosylbenzene Fg-cat converted 13S-hydroxy-fatty acids to two products: the 15,16-double bond of 13S-hydroxy α-linolenic acid was oxidized stereospecifically to the 15S,16R-cis-epoxide or the 13-hydroxyl was oxidized to the 13-ketone. Products were identified by UV, HPLC, LC-MS, NMR and by comparison with authentic standards prepared for this study. The Pfl01-cat displayed similar activity. MAP-2744c oxidized 13S-hydroxy-linoleic acid to the 13-ketone, and epoxidized the double bonds to form the 9,10-epoxy-13-hydroxy, 11,12-epoxy-13-hydroxy, and 9,10-epoxy-13-keto derivatives; equivalent transformations occurred with 9S-hydroxy-linoleic acid as substrate. In parallel incubations in the presence of iodosylbenzene, human catalase displayed no activity towards 13S-hydroxy-linoleic acid, as expected from the highly restricted access to its active site. The results indicated that with suitable transformation to Compound I, monooxygenase activity can be demonstrated by these catalase-related hemoproteins with tyrosine as the proximal heme ligand.

An alternative and robust synthesis of [(13) C4 ]Baraclude® (entecavir).

PubMed

Easter, John A; Burrell, Richard C; Bonacorsi, Samuel J

2013-10-01

Stable isotope-labeled [(13) C4 ]entecavir (1) was prepared in 11 steps. Commercially available [(13) C]guanidine hydrochloride and diethyl[1,2,3-(13) C3 ]malonate were condensed to yield 2-amino[2,4,5,6-(13) C4 ]pyrimidine-4,6-diol (8). This was converted to the desired purine (7) in five steps. Introduction of the chiral epoxide was followed by subsequent deprotection to give [(13) C4 ]entecavir (1), in an overall yield of 5.7% from labeled precursors. The chemical purity of the title compound was determined to be >99% by HPLC. The isotopic distribution was determined by mass spectrometry to be 282[M + 4], 98.4%; 281[M + 3], 1.6%; and 278[M + 0], <0.1%. Copyright © 2013 John Wiley & Sons, Ltd.

Comparison of Vegetation Change Inferred From Palynology and Compound-Specific Carbon Isotopes of Lipid Biomarkers in the Maya Lowlands of Peten, Guatemala

NASA Astrophysics Data System (ADS)

Newell, S. D.; Hodell, D. A.; Curtis, J. H.; Brenner, M.; Venz-Curtis, K.

2005-12-01

The Petén region of northern Guatemala has been occupied by humans for more than 3000 years. Expansion of the Maya civilization during the Preclassic (~1000 BC to AD 250) and Classic (AD 250 to AD 900) Periods was accompanied by increasing deforestation of Petén watersheds and accelerated rates of soil erosion. Palynological data from Petén lake cores illustrate the near elimination of high forest taxa and prevalence of disturbance taxa (grasses, weeds) during the height of Classic Maya occupation (~AD 500 to AD 800). After flourishing during the Classic Period between AD 250 and 800, Maya population densities declined significantly in the Petén, thereby curtailing human pressures on the landscape. This cycle of population expansion and decline in the Petén provides a natural historical experiment that has been used to study the response of tropical vegetation to long-term changes in land-use by humans. We measured the carbon isotopic composition of long-chain n-alkanes of leaf waxes in two cores from Lakes Sacnab and Salpetén in the Petén Lake District of the southern Maya Lowlands. The carbon isotopic composition of leaf waxes has been shown to be a reliable indicator of the relative proportion of C3 to C4 biomass in a watershed. Biomarker results were compared directly to a pollen profile from Lake Salpetén. Although the general pattern of increased C4 abundance inferred from δ13C of long-chain n-alkanes and increased disturbance taxa from pollen studies agree during the period of Maya occupation, the two proxies differ in detail suggesting they are recording different characteristics of watershed vegetation. For example, the highest long-chain δ13C values (representing greatest C4 biomass) occurred during early settlement of the basins in the early to middle Preclassic Period (1300 to 500 BC) when Maya population densities were relatively low. This period also corresponded to the time of greatest erosion rates in the Salpetén basin (Anselmetti et al., in prep.). In contrast, pollen profiles indicate the highest percentages of disturbance taxa and lowest high forest taxa from 250 BC to AD 700 in the late Preclassic and Classic Periods, when both the δ13C of long-chain n-alkanes and erosion rates declined. The high compound-specific δ13C values in the early to middle Preclassic Period may be greatly influenced by the early cultivation of maize (a C4 plant) along the shoreline. In contrast, maize is generally under-represented in pollen profiles because of its large size and difficulty of transport. Pollen may be more representative of vegetation over a larger area than the lipid biomarkers, but is biased towards tropical vegetation that is pollinated by wind and does not reflect those plants that depend on pollination by insects or self-fertilization. The δ13C of long-chain n-alkanes, on the other hand, may provide a reliable proxy for estimating the relative changes in C3 to C4 biomass, but it cannot be used to interpret changes in forest structure and composition. We conclude that the δ13C of long-chain n-alkanes and pollen are recording different aspects of watershed vegetation in Petén, and should be used in tandem to infer the response of tropical vegetation to past changes in Maya land-use.

New furanones from the plant endophytic fungus Pestalotiopsis besseyi.

PubMed

Liu, Haitao; Liu, Shuchun; Guo, Liangdong; Zhang, Yonggang; Cui, Langjun; Ding, Gang

2012-11-27

Pestalafuranones A-E (compounds 1-5), five new 2(5H)-furanones, have been isolated from cultures of an isolate of Pestalotiopsis besseyi. The structures of these compounds were elucidated mainly by analysis of their NMR spectroscopic data and HRESIMS experiments. Pestalafuranones A-C (compounds 1-3) displayed weak inhibitory effects against HIV-1 replication in C8166 cells, whereas pestalafuranones D (4) and E (5) showed moderate antifungal activity against the plant pathogens Verticillium dahiae and Alternaria longipes.

Synthesis and evaluation of new benzodioxole-based dithiocarbamate derivatives as potential anticancer agents and hCA-I and hCA-II inhibitors.

PubMed

Altıntop, Mehlika Dilek; Sever, Belgin; Akalın Çiftçi, Gülşen; Kucukoglu, Kaan; Özdemir, Ahmet; Soleimani, Seyedeh Sara; Nadaroglu, Hayrunnisa; Kaplancıklı, Zafer Asım

2017-01-05

In the current work, new benzodioxole-based dithiocarbamate derivatives were synthesized via the reaction of N-(1,3-benzodioxol-5-ylmethyl)-2-chloroacetamide with appropriate sodium salts of N,N-disubstituted dithiocarbamic acids. These derivatives were evaluated for their cytotoxic effects on A549 human lung adenocarcinoma and C6 rat glioma cell lines. N-(1,3-Benzodioxol-5-ylmethyl)-2-[4-(4-nitrophenyl)-1-piperazinylthiocarbamoylthio]acetamide (10) can be identified as the most promising anticancer agent against C6 cell line due to its notable inhibitory effect on C6 cells with an IC 50 value of 23.33 ± 7.63 μg/mL when compared with cisplatin (IC 50  = 19.00 ± 5.29 μg/mL). On the other hand, compound 10 did not show any significant cytotoxic activity against A549 cell line. The compounds were also tested for their in vitro inhibitory effects on hCA-I and hCA-II. Generally, the tested compounds were more effective on CAs than acetazolamide, the reference agent. Among these compounds, N-(1,3-benzodioxol-5-ylmethyl)-2-[(morpholinyl)thiocarbamoylthio]acetamide (3) and N-(1,3-benzodioxol-5-ylmethyl)-2-[(thiomorpholinyl)thiocarbamoylthio]acetamide (4) were found to be the most effective compounds on hCA-I with IC 50 values of 0.346 nM and 0.288 nM, and hCA-II with IC 50 values of 0.287 nM and 0.338 nM, respectively. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Unexplored antifungal activity of linear battacin lipopeptides against planktonic and mature biofilms of C. albicans.

PubMed

De Zoysa, Gayan Heruka; Glossop, Hugh Douglas; Sarojini, Vijayalekshmi

2018-02-25

Novel antifungal agents are required against pathogenic fungi such as Candida albicans. We report the anticandidal activity of battacin lipopeptide antibiotics with previously unexplored antifungal activity. From amongst sixteen battacin lipopeptides tested against C. alibicans (SC5314) the 4-methyl hexanoyl conjugated trimeric lipopeptide 13 emerged as the lead candidate with a MIC of 6.25 μM and negligible haemolysis of mouse red blood cells. The potency of this lipopeptide was maintained under acidic conditions. Additionally, antifungal activity was further enhanced with amphotericin B at its non-haemolytic concentrations. Herein we have demonstrated for the first time that battacin lipopeptides prevent C. albicans biofilm colonisation as well as inhibit pre-formed biofilms of this fungal pathogen. XTT biofilm assays revealed that 13 prevented colonisation of C. albicans biofilms at its MIC (6.25 μM) and, at a higher concentration, eradicated 24 h (25 μM) and 48 h (62.5 μM) old preformed biofilms. In comparison, we found that amphotericin at much lower concentrations prevented biofilm colonisation (0.78 μM) and inhibited 24 h old preformed biofilms (6.25 μM), however was completely inactive against 48 h old preformed biofilms. Thus, lipopeptide 13 is more effective than amphotericin at eradicating more mature C. albicans biofilms. The membrane lytic mechanism of action of compound 13 was validated by a colorimetric assay using lipid vesicles mimicking fungal membranes in which compound 13 effected an immediate dark purple to red colour transition of suspended vesicles upon peptide interaction. In addition, TEM images of C. albicans cells exposed to 13 showed clearly disrupted cellular membranes. Interestingly, compound 13 increased the endogenous generation of reactive oxygen species (ROS) in a concentration dependent manner. In the presence of an antioxidant, ascorbic acid, ROS production was diminished yet antifungal activity persisted, possibly indicating that ROS production is a secondary effect from membrane lysis caused by lipopeptide 13. The lipopeptide was non-haemolytic against mouse red blood cells at the highest tested concentration (1 mM). Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Crystal structures, in-silico study and anti-microbial potential of synthetic monocarbonyl curcuminoids

NASA Astrophysics Data System (ADS)

Ud Din, Zia; Serrano, N. F. G.; Ademi, Kastriot; Sousa, C. P.; Deflon, Victor Marcelo; Maia, Pedro Ivo da Silva; Rodrigues-Filho, Edson

2017-09-01

In this work the screening of 20 unsymmetrical chalcone and curcuminoids analogues in regard of their antimicrobial properties was conducted. Electron donating groups in the aromatic rings in the chalcone and curcuminoid derivatives produced higher antimicrobial effect. Compounds 1, 9 and 15 exhibited good activity against Escherichia coli and Staphylococcus aureus. These compounds were further evaluated against nine micro-organisms of pathological interest. Pharmmaper was used for target fishing of compounds against important bacterial targets. Molecular Docking helped to verify the results of these compounds against the selected bacterial target D-alanyl-D-alanine carboxypeptidase (PDB ID: 1PW1). The crystal structure of ligand and docked conformers in the active site of 1PW1 were analyzed. As a result structure-activity relationships are proposed. Structures of compounds 14 and 16 were obtained through single crystals X-ray diffraction studies. Compound 14 crystallizes in monoclinic space group P21/c with unit cell dimensions a = 13.1293(3) Å, b = 17.5364(4) Å, c = 15.1433(3) Å, β = 95.6440(10), V = 3469.70(13) Å3 and Z = 8. Compound 16 crystallizes in triclinic space group Pī with unit cell dimensions a = 6.8226(4) Å, b = 7.2256(4) Å, c = 18.1235(12) Å, β = 87.322(4), V = 850.57(9) Å3 and Z = 2.

Elucidating MTBE degradation in a mixed consortium using a multidisciplinary approach.

PubMed

Bastida, Felipe; Rosell, Mònica; Franchini, Alessandro G; Seifert, Jana; Finsterbusch, Stefanie; Jehmlich, Nico; Jechalke, Sven; von Bergen, Martin; Richnow, Hans H

2010-08-01

The structure and function of a microbial community capable of biodegrading methyl-tert-butyl ether (MTBE) was characterized using compound-specific stable isotope analysis (CSIA), clone libraries and stable isotope probing of proteins (Protein-SIP). The enrichment culture (US3-M), which originated from a gasoline-impacted site in the United States, has been enriched on MTBE as the sole carbon source. The slope of isotopic enrichment factors (epsilon(C) of -2.29+/-0.03 per thousand; epsilon(H) of -58+/-6 per thousand) for carbon and hydrogen discrimination (Deltadelta(2)H/Deltadelta(13)C) was on average equal to Lambda=24+/-2, a value closely related to the reaction mechanism of MTBE degradation in Methylibium petroleiphilum PM1. 16S rRNA gene libraries revealed sequences belonging to M. petroleiphilum PM1, Hydrogenophaga sp., Thiothrix unzii, Rhodobacter sp., Nocardiodes sp. and different Sphingomonadaceae bacteria. Protein-SIP analysis of the culture grown on (13)C-MTBE as the only carbon source revealed that proteins related to members of the Comamonadaceae family, such as Delftia acidovorans, Acidovorax sp. or Comamonas sp., were not (13)C-enriched, whereas proteins related to M. petroleiphilum PM1 showed an average incorporation of 94.5 atom%(13)C. These results indicate a key role for this species in the degradation of MTBE within the US3-M consortia. The combination of CSIA, molecular biology and Protein-SIP facilitated the analysis of an MTBE-degrading mixed culture from a functional and phylogenetic point of view.

Hyperpolarized nanodiamond with long spin-relaxation times

NASA Astrophysics Data System (ADS)

Rej, Ewa; Gaebel, Torsten; Boele, Thomas; Waddington, David E. J.; Reilly, David J.

2015-10-01

The use of hyperpolarized agents in magnetic resonance, such as 13C-labelled compounds, enables powerful new imaging and detection modalities that stem from a 10,000-fold boost in signal. A major challenge for the future of the hyperpolarization technique is the inherently short spin-relaxation times, typically <60 s for 13C liquid-state compounds, which limit the time that the signal remains boosted. Here we demonstrate that 1.1% natural abundance 13C spins in synthetic nanodiamond can be hyperpolarized at cryogenic and room temperature without the use of free radicals, and, owing to their solid-state environment, exhibit relaxation times exceeding 1 h. Combined with the already established applications of nanodiamonds in the life sciences as inexpensive fluorescent markers and non-cytotoxic substrates for gene and drug delivery, these results extend the theranostic capabilities of nanoscale diamonds into the domain of hyperpolarized magnetic resonance.

[Spectral characteristics of decomposition of incorporated straw in compound polluted arid loess].

PubMed

Fan, Chun-Hui; Zhang, Ying-Chao; Xu, Ji-Ting; Wang, Jia-Hong

2014-04-01

The original loess from western China was used as soil sample, the spectral methods of scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS), elemental analysis, Fourier transform infrared spectroscopy (FT-IR) and 13C nuclear magnetic resonance (13C NMR) were used to investigate the characteristics of decomposed straw and formed humic acids in compound polluted arid loess. The SEM micrographs show the variation from dense to decomposed surface, and finally to damaged structure, and the EDS data reveal the phenomenon of element transfer. The newly-formed humic acids are of low aromaticity, helpful for increasing the activity of organic matters in loess. The FTIR spectra in the whole process are similar, indicating the complexity of transformation dynamics of humic acids. The molecular structure of humic acids becomes simpler, shown from 13C NMR spectra. The spectral methods are useful for humic acids identification in loess region in straw incorporation process.

Synthesis, molecular structure and vibrational spectra of 1,3-bis(1-adamantyl)-2-phenylpropan-1,3-diones

NASA Astrophysics Data System (ADS)

Babjaková, Eva; Dastychová, Lenka; Hanulíková, Barbora; Kuřitka, Ivo; Nečas, Marek; Vašková, Hana; Vícha, Robert

2015-04-01

The interest in the oxo-enol tautomerism of 1,3-dioxo compounds is justified by their usefulness in many synthetic fields. A series of new 1,3-bis(1-adamantyl)propan-1,3-diones with a variably substituted phenyl ring at the C2 position was prepared either by the reaction of an appropriate Grignard reagent with adamatane-1-carbonyl chloride or by SEAr on the unsubstituted 1,3-bis(1-adamantyl)-2-phenylpropan-1,3-dione. In addition to the single crystal X-ray diffraction analysis of three of the prepared compounds, the experimental 1H and 13C NMR, IR and Raman spectroscopic data were assigned and compared to those obtained by DFT computations. In the solid state, the syn-dioxo forms were exclusively observed, which are shown to also predominate in CHCl3 solutions. The analysis of the Hirshfeld surface revealed that H⋯H and O⋯H contacts dominate the intermolecular interactions in the solid state, whereas π⋯π stacking plays a marginal role.

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

PubMed

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.

High-resolution detection of adulteration of maize oil using multi-component compound-specific delta13C values of major and minor components and discriminant analysis.

PubMed

Mottram, Hazel R; Woodbury, Simon E; Rossell, J Barry; Evershed, Richard P

2003-01-01

Maize oil commands a premium price and is thus a target for adulteration with cheaper vegetable oils. Detection of this activity presents a particular challenge to the analyst because of the natural variability in the fatty acid composition of maize oils and because of their high sterol and tocopherol contents. This paper describes a method that allows detection of adulteration at concentrations of just 5% (m/m), based on the Mahalanobis distances of the principal component scores of the delta(13)C values of major and minor vegetable oil components. The method makes use of a database consisting of delta(13)C values and relative abundances of the major fatty acyl components of over 150 vegetable oils. The sterols and tocopherols of 16 maize oils and 6 potential adulterant oils were found to be depleted in (13)C by a constant amount relative to the bulk oil. Moreover, since maize oil contains particularly high levels of sterols and tocopherols, their delta(13)C values were not significantly altered when groundnut oil was added up to 20% (m/m) and it is possible to use the values for the minor components to predict the values that would be expected in a pure oil; therefore, comparison of the predicted values with those obtained experimentally allows adulteration to be detected. A refinement involved performing a discriminant analysis on the delta(13)C values of the bulk oil and the major fatty acids (16:0, 18:1 and 18:2) and using the Mahalanobis distances to determine the percentage of adulterant oil present. This approach may be refined further by including the delta(13)C values of the minor components in the discriminant analysis thereby increasing the sensitivity of the approach to concentrations at which adulteration would not be attractive economically. Copyright 2003 John Wiley & Sons, Ltd.

Identification of Hepatitis C Virus Inhibitors Targeting Different Aspects of Infection Using a Cell-Based Assay

PubMed Central

Yu, Xuemei; Sainz, Bruno; Petukhov, Pavel A.

2012-01-01

With 2 to 3% of the worldwide population chronically infected, hepatitis C virus (HCV) infection continues to be a major health care burden. Unfortunately, current interferon-based treatment options are not effective in all patients and are associated with significant side effects. Consequently, there is an ongoing need to identify and develop new anti-HCV therapies. Toward this goal, we previously developed a cell-based HCV infection assay for antiviral compound screening based on a low-multiplicity-of-infection approach that uniquely allows for the identification of antiviral compounds that target cell culture-derived HCV (HCVcc) at any step of the viral infection cycle. Using this assay, here we report the screening of the NCI Diversity Set II library, containing 1,974 synthesized chemical compounds, and the identification of compounds with specific anti-HCV activity. In combination with toxicity counterscreening, we identified 30 hits from the compound library, 13 of which showed reproducible and dose-dependent inhibition of HCV with mean therapeutic indices (50% cytotoxic concentration [CC50]/50% effective concentration [EC50]) of greater than 6. Using HCV pseudotype and replicon systems of multiple HCV genotypes, as well as infectious HCVcc-based assembly and secretion analysis, we determined that different compounds within this group of candidate inhibitors target different steps of viral infection. The compounds identified not only will serve as biological probes to study and further dissect the biology of viral infection but also should facilitate the development of new anti-HCV therapeutic treatments. PMID:22948883

Synthesis, in-vitro antibacterial, antifungal, and molecular modeling of potent anti-microbial agents with a combined pyrazole and thiophene pharmacophore.

PubMed

Mabkhot, Yahia Nasser; Kaal, Nahed Ahmed; Alterary, Seham; Al-Showiman, Salim S; Barakat, Assem; Ghabbour, Hazem A; Frey, Wolfgang

2015-05-14

Ethyl 5-acetyl-4-methyl-2-(phenylamino)thiophene-3-carboxylate (2) and there derivatives 3a-c, 4, 6a-c and 9a-f were synthesized. The structure of compound 2 was deduced by 1H-NMR, 13C-NMR, FT-IR, MS, microanalysis, and single-crystal X-ray crystallography. The compound crystallized in the monoclinic system, with space group P21/c and cell coordinates a = 8.5752(16) Å, b = 21.046(4) Å, c = 8.2941(12) Å, β = 101.131(6)°, V = 1468.7(4) Å3, and Z = 4. Compounds 2, 3a-c, 4, 5a-c and 9a-f were subjected into in vitro antimicrobial activity tests. Compounds 3a and 3c were more potent than standard drug amphotericin B, showing MIC values of 23.8 ± 0.42 and 24.3 ± 0.68, respectively, against Aspergillus fumigatus while the standard drug MIC was 23.7 ± 0.1. Compound 3c was also more potent (MIC 24.8 ± 0.64) than the standard drug amphotericin B (MIC 19.7 ± 0.2) against Syncephalastrum racemosum. Compounds 4 and 9f also showed promising anti-microbial activity. Molecular modeling was performed for the most active compounds.

Tissue and size-related changes in the fatty acid and stable isotope signatures of the deep sea grenadier fish Coryphaenoides armatus from the Charlie-Gibbs Fracture Zone region of the Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Mayor, Daniel J.; Sharples, Caroline J.; Webster, Lynda; Walsham, Pamela; Lacaze, Jean-Pierre; Cousins, Nicola J.

2013-12-01

Coryphaenoides armatus is a cosmopolitan deep-sea fish that plays a major role in the ecology of abyssal ecosystems. We investigated the trophic ecology and physiology of this species by determining the δ13C, δ15N and fatty acid signatures of muscle, liver and ovary tissues of individuals collected from ∼2700 m to the north and south of the Charlie-Gibbs Fracture Zone (CGFZ) of the Mid-Atlantic Ridge, NE Atlantic. Fatty acid and δ13C data both suggested that C. armatus shows an ontogenetic dietary shift, with the relative contributions of benthic and pelagic prey decreasing and increasing respectively as the animals grow. They also indicated that dietary overlap between animals living to the north and south of the CGFZ increases as they grow, suggesting that larger animals forage over greater distances and are not hindered by the presence of the CGFZ. Comparison of tissue-specific fatty acid signatures with previously published data suggests compositional homeostasis of the fatty acids 20:5(n-3) and 22:6(n-3) in the muscle, and 18:1(n-9) in the liver tissues. We ascribe this primarily to strict physiological requirements for these compounds, rather than simply to their abundance in the diet. We pose several speculative mechanisms to explain the observed trends in tissue-specific δ13C and δ15N values, illustrating some of the numerous processes that can influence the isotopic signatures of bulk tissues.

Preparation and comparative evaluation of 99m Tc-HYNIC-cNGR and 99m Tc-HYNIC-PEG2 -cNGR as tumor-targeting molecular imaging probes.

PubMed

Vats, Kusum; Satpati, Drishty; Sharma, Rohit; Kumar, Chandan; Sarma, Haladhar Dev; Banerjee, Sharmila

2018-02-01

The tripeptide sequence asparagine-glycine-arginine (NGR) specifically recognizes aminopeptidase N (APN or CD13) receptors highly expressed on tumor cells and vasculature. Thus, NGR peptides can precisely deliver therapeutic and diagnostic compounds to CD13 expressing cancer sites. In this regard, 2 NGR peptide ligands, HYNIC-c(NGR) and HYNIC-PEG 2 -c(NGR), were synthesized, radiolabeled with 99m Tc, and evaluated in CD13-positive human fibrosarcoma HT-1080 tumor xenografts. The radiotracers, 99m Tc-HYNIC-c(NGR) and 99m Tc-HYNIC-PEG 2 -c(NGR), could be prepared in approximately 95% radiochemical purity and exhibited excellent in vitro and in vivo stability. The radiotracers were hydrophilic in nature with log P values being -2.33 ± 0.05 and -2.61 ± 0.08. The uptake of 2 radiotracers 99m Tc-HYNIC-c(NGR) and 99m Tc-HYNIC-PEG 2 -c(NGR) was similar in nude mice bearing human fibrosarcoma HT-1080 tumor xenografts, which was significantly reduced (P < .05) during blocking studies. The 2 radiotracers being hydrophilic cleared rapidly from blood, liver, and intestine and were excreted through renal pathway. The pharmacokinetics of 99m Tc-labeled HYNIC peptide could not be modulated through introduction of PEG 2 unit, thus posing a challenge for studies with other linkers towards enhanced tumor uptake and retention. Copyright © 2017 John Wiley & Sons, Ltd.

Cyclic 2,3-diphosphoglycerate as a component of a new branch in gluconeogenesis in Methanobacterium thermoautotrophicum delta H.

PubMed

Gorkovenko, A; Roberts, M F

1993-07-01

A unique compound, cyclic 2,3-diphosphoglycerate (cDPG), is the major soluble carbon and phosphorus solute in Methanobacterium thermoautotrophicum delta H under optimal conditions of cell growth. It is a component of an unusual branch in gluconeogenesis in these bacteria. [U-13C]acetate pulse-[12C]acetate chase methodology was used to observe the relationship between cDPG and other metabolites (2-phosphoglycerate and 2,3-diphosphoglycerate [2-PG and 2,3-DPG, respectively]) of this branch. It was demonstrated that cells could grow exponentially under conditions in which 2-PG and 2,3-DPG, rather than cDPG, were the major solutes. While the total concentration of these three phosphorylated molecules was maintained, rapid interconversion of 13C label among them was observed. Label flow from 2-PG to 2,3-DPG to cDPG to polymer is the usual direction in this pathway in exponentially growing cells, while the reverse reactions sometimes predominate in the stationary phase. Evidence of the presence of a polymeric compound in this pathway was provided by 13C nuclear magnetic resonance (one-dimensional and two-dimensional INADEQUATE) studies of solubilized cell debris.

Cyclic 2,3-diphosphoglycerate as a component of a new branch in gluconeogenesis in Methanobacterium thermoautotrophicum delta H.

PubMed Central

Gorkovenko, A; Roberts, M F

1993-01-01

A unique compound, cyclic 2,3-diphosphoglycerate (cDPG), is the major soluble carbon and phosphorus solute in Methanobacterium thermoautotrophicum delta H under optimal conditions of cell growth. It is a component of an unusual branch in gluconeogenesis in these bacteria. [U-13C]acetate pulse-[12C]acetate chase methodology was used to observe the relationship between cDPG and other metabolites (2-phosphoglycerate and 2,3-diphosphoglycerate [2-PG and 2,3-DPG, respectively]) of this branch. It was demonstrated that cells could grow exponentially under conditions in which 2-PG and 2,3-DPG, rather than cDPG, were the major solutes. While the total concentration of these three phosphorylated molecules was maintained, rapid interconversion of 13C label among them was observed. Label flow from 2-PG to 2,3-DPG to cDPG to polymer is the usual direction in this pathway in exponentially growing cells, while the reverse reactions sometimes predominate in the stationary phase. Evidence of the presence of a polymeric compound in this pathway was provided by 13C nuclear magnetic resonance (one-dimensional and two-dimensional INADEQUATE) studies of solubilized cell debris. Images PMID:8320225

Trifluoromethylphenyl Carboxamides as Mosquito Adulticides

USDA-ARS?s Scientific Manuscript database

Twenty trifluoromethylphenyl carboxamides were synthesized and evaluated as mosquito adulticides. These compounds are safe, inexpensive to synthesize and are alternatives to current active ingredients found in commercial products. Compound structures were confirmed by TOF-MS, and 1H and 13C NMR spe...

Microwave assisted synthesis and anti-lipase activity of some new fluorine-containing benzimidazoles.

PubMed

Menteşe, E; Yilmaz, F; Ülker, S; Kahveci, B

2015-01-01

In this study, a new series of fluorine containing benzimidazoles (4a-l) and bisbenzimidazoles (6a-c, 8) were synthesized by the reaction of o-phenylenediamines with iminoester hydrochlorides (3a-l, 7) in methanol under microwave irradiation. The structures of these newly synthesized compounds were identified by IR, (1)H-NMR, (13)C-NMR, mass spectroscopy and elemental analysis data. The synthesized compounds were screened for their pancreatic lipase activities. Our results indicate that the compounds 6a, 6b and 6c can serve as an anti-lipase agent. The compounds 6b and 6c inhibited pancreatic lipase activity by 84.03% and 97.49% at a concentration of 3 µg/mL, respectively. © Georg Thieme Verlag KG Stuttgart · New York.

Characterisation and antimicrobial activity of biosurfactant extracts produced by Bacillus amyloliquefaciens and Pseudomonas aeruginosa isolated from a wastewater treatment plant.

PubMed

Ndlovu, Thando; Rautenbach, Marina; Vosloo, Johann Arnold; Khan, Sehaam; Khan, Wesaal

2017-12-01

Biosurfactants are unique secondary metabolites, synthesised non-ribosomally by certain bacteria, fungi and yeast, with their most promising applications as antimicrobial agents and surfactants in the medical and food industries. Naturally produced glycolipids and lipopeptides are found as a mixture of congeners, which increases their antimicrobial potency. Sensitive analysis techniques, such as liquid chromatography coupled to mass spectrometry, enable the fingerprinting of different biosurfactant congeners within a naturally produced crude extract. Bacillus amyloliquefaciens ST34 and Pseudomonas aeruginosa ST5, isolated from wastewater, were screened for biosurfactant production. Biosurfactant compounds were solvent extracted and characterised using ultra-performance liquid chromatography (UPLC) coupled to electrospray ionisation mass spectrometry (ESI-MS). Results indicated that B. amyloliquefaciens ST34 produced C 13-16 surfactin analogues and their identity were confirmed by high resolution ESI-MS and UPLC-MS. In the crude extract obtained from P. aeruginosa ST5, high resolution ESI-MS linked to UPLC-MS confirmed the presence of di- and monorhamnolipid congeners, specifically Rha-Rha-C 10 -C 10 and Rha-C 10 -C 10 , Rha-Rha-C 8 -C 10 /Rha-Rha-C 10 -C 8 and Rha-C 8 -C 10 /Rha-C 10 -C 8 , as well as Rha-Rha-C 12 -C 10 /Rha-Rha-C 10 -C 12 and Rha-C 12 -C 10 /Rha-C 10 -C 12 . The crude surfactin and rhamnolipid extracts also retained pronounced antimicrobial activity against a broad spectrum of opportunistic and pathogenic microorganisms, including antibiotic resistant Staphylococcus aureus and Escherichia coli strains and the pathogenic yeast Candida albicans. In addition, the rapid solvent extraction combined with UPLC-MS of the crude samples is a simple and powerful technique to provide fast, sensitive and highly specific data on the characterisation of biosurfactant compounds.

Promotion effect of constituents from the root of Polygonum multiflorum on hair growth.

PubMed

Sun, Ya Nan; Cui, Long; Li, Wei; Yan, Xi Tao; Yang, Seo Young; Kang, Jung Il; Kang, Hee Kyoung; Kim, Young Ho

2013-09-01

Two new compounds, gallic acid ester of torachrysone-8-O-β-D-glucoside (1) and (E)-2,3,5,4'-tetrahydroxystilbene-2-O-β-D-xyloside (4), along with eight known compounds (2, 3, 5-10) were isolated from a 70% ethanol extract of Polygonum multiflorum roots. The structures were determined by (1)H and (13)C NMR, HMQC, and HMBC spectrometry. Extracts of P. multiflorum have been reported to promote hair growth in vivo. This study was carried out to evaluate the effects of isolated compounds from P. multiflorum on promoting hair growth using dermal papilla cells (DPCs), which play an important role in hair growth. When DPCs were treated with compounds (1-10) from P. multiflorum, compounds 1, 2, 3, 6, and 10 increased the proliferation of DPCs compared with the control. Specifically, compound 2 (10 and 20 μM) induced a greater increase in the proliferation of DPCs than minoxidil (10 μM). Additionally, treatment of vibrissa follicles with compound 2 for 21 days increased hair-fiber length significantly. On the basis of this result, further investigation and optimization of these derivatives might help in the development of therapeutic agents for the treatment of alopecia. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Structures, bonding, and reaction chemistry of the neutral organogallium(I) compounds (GaAr)n(n = 1 or 2) (Ar = terphenyl or related ligand): an experimental investigation of Ga-Ga multiple bonding.

PubMed

Hardman, Ned J; Wright, Robert J; Phillips, Andrew D; Power, Philip P

2003-03-05

The synthesis, structure, and properties of several new organogallium(I) compounds are reported. The monovalent compounds GaAr* (Ar* = C(6)H(3)-2,6-Trip(2), Trip = C(6)H(2)-2,4,6-Pr(i)()(3), 1), GaAr# (Ar# = C(6)H(3)-2,6(Bu(t)Dipp)(2), Bu(t)Dipp = C(6)H(2)-2,6-Pr(i)(2)-4-Bu(t)(), 4), and the dimeric (GaAr')(2) (Ar' = C(6)H(3)-2,6-Dipp(2), Dipp = C(6)H(3)-2,6-Pr(i)(2), 6) were synthesized by the reaction of "GaI" with (Et(2)O)LiAr*, (Et(2)O)LiAr# (3), or (LiAr')(2). Compounds 1 and 4 were isolated as green crystals, whereas 6 was obtained as a brown-red crystalline solid. All three compounds dissolved in hydrocarbon solvents to give green solutions and almost identical UV/visible spectra. Cryoscopy of 1 and 6 showed that they were monomeric in cyclohexane. Crystals of 1 and 4 were unsuitable for X-ray crystal structure determinations, but an X-ray data set for 6 showed that it was weakly dimerized in the solid with a long Ga-Ga bond of 2.6268(7) A and a trans-bent CGaGaC core array. The 1,2-diiodo-1,2-diaryldigallane compounds [Ga(Ar*)I](2) (2), [Ga(Ar#)I](2) (5), and [Ga(Ar')I](2) (7) were isolated as byproducts of the synthesis of 1, 4, and 6. The crystal structures of 2 and 7 showed that they had planar ICGaGaCI core arrays with Ga-Ga distances near 2.49 A, consistent with Ga-Ga single bonding. Treatment of 1, 4, and 6 with B(C(6)F(5))(3) immediately afforded the 1:1 donor-acceptor complexes ArGa[B(C(6)F(5))(3)] (Ar = Ar*, 8; Ar#, 9; Ar', 10) that featured almost linear gallium coordination, Ga-B distances near the sum of the covalent radii of gallium and boron, as well as some close Ga...F contacts. Compound 1 also reacted with Fe(CO)(5) under ambient conditions to give Ar*GaFe(CO)(4) (11), which had been previously synthesized by the reaction of GaAr*Cl(2) with Na(2)Fe(CO)(4). Reaction of 1 with 2,3-dimethyl-1,3-butadiene afforded the compound [Ar*GaCH(2)C(Me)C(Me)CH(2)]2 (12) that had a 10-membered 1,5-Ga(2)C(8) ring with no Ga-Ga interaction. Stirring 1 or 6 with sodium readily gave Na(2)[Ar*GaGaAr*] (13) and Na(2)(Ar'GaGaAr') (14). The former species 13 had been synthesized previously by reduction of GaAr*Cl(2) with sodium and was described as having a Ga-Ga triple bond because of the short Ga-Ga distance and the electronic relationship between [Ar*GaGaAr*](2-) and the corresponding neutral group 14 alkyne analogues. Compound 14 has a similar structure featuring a trans-bent CGaGaC core, bridged by sodiums which were also coordinated to the flanking aryl rings of the Ar' ligands. The Ga-Ga bond length was found to be 2.347(1) A, which is slightly (ca. 0.02 A) longer than that reported for 13. Reaction of Ga[N(Dipp)C(Me)](2)CH, 15 (i.e., GaN(wedge)NDipp(2)), which is sterically related to 1, 4, and 6, with Fe(CO)(5) yielded Dipp(2)N(wedge)NGaFe(CO)(4) (16), whose Ga-Fe bond is slightly longer than that observed in 11. Reaction of the less bulky LiAr"(Ar"= C(6)H(3)-2,6-Mes(2)) with "GaI" afforded the new paramagnetic cluster Ga(11)Ar(4)" (17). The ready dissociation of 1, 4, and 6 in solution, the long Ga-Ga distance in 6, and the chemistry of these compounds showed that the Ga-Ga bonds are significantly weaker than single bonds. The reduction of 1 and 6 with sodium to give 13 and 14 supplies two electrons to the di-gallium unit to generate a single bond (in addition to the weak interaction in the neutral precursor) with retention of the trans-bent geometry. It was concluded that the stability of 13 and 14 depends on the matching size of the sodium ion, and the presence of Na-Ga and Na-Ar interactions that stabilize their Na(2)Ga(2) core structures.

Stereoregularity of poly (lactic acid) and their model compounds as studied by NMR and quantum chemical calculations

USDA-ARS?s Scientific Manuscript database

In order to understand the origin of the tacticity splitting in the NMR spectrum of poly(lactic acid), monomer model compound and dimer model compounds (both isotactic and syndiotactic) were synthesized and their 1H and 13C NMR chemical shifts observed. Two energetically stable conformations were o...

Syntheses, structures, and 1H, 13C{ 1H} and 119Sn{ 1H} NMR chemical shifts of a family of trimethyltin alkoxide, amide, halide and cyclopentadienyl compounds

DOE PAGES

Lichtscheidl, Alejandro G.; Janicke, Michael T.; Scott, Brian L.; ...

2015-08-21

The synthesis and full characterization, including Nuclear Magnetic Resonance (NMR) data ( 1H, 13C{ 1H} and 119Sn{ 1H}), for a series of Me 3SnX (X = O-2,6-tBu 2C 6H 3 (1), (Me 3Sn)N(2,6- iPr 2C 6H 3) (3), NH-2,4,6- tBu 3C 6H 2 (4), N(SiMe 3) 2 (5), NEt 2, C 5Me 5 (6), Cl, Br, I, and SnMe 3) compounds in benzene-d 6, toluene-d 8, dichloromethane-d 2, chloroform-d 1, acetonitrile-d 3, and tetrahydrofuran-d 8 are reported. The X-ray crystal structures of Me 3Sn(O-2,6- tBu 2C 6H 3) (1), Me 3Sn(O-2,6- iPr 2C 6H 3) (2), and (Me 3Sn)(NH-2,4,6- tBumore » 3C 6H 2) (4) are also presented. As a result, these compiled data complement existing literature data and ease the characterization of these compounds by routine NMR experiments.« less

Bismaleimide compounds

DOEpatents

Adams, Johnnie E.; Jamieson, Donald R.

1986-01-14

Bismaleimides of the formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C1 or Br, or R.sub.1 and R.sub.2 together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.1 and R.sub.2 are not t-butyl or t-butoxy; X is O, S or Se; n is 1-3; and the alkylene bridging group, optionally, is substituted by 1-3 methyl groups or by fluorine, form polybismaleimide resins which have valuable physical properties. Uniquely, these compounds permit extended cure times, i.e., they remain fluid for a time sufficient to permit the formation of a homogeneous melt prior to curing.

Fluorescence Excitation-Emission Matrix Regional Integration to Quantify Spectra for Dissolved Organic Matter

USGS Publications Warehouse

Chen, W.; Westerhoff, P.; Leenheer, J.A.; Booksh, K.

2003-01-01

Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the >10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (??i,n). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (??T,n = ????i,n) was observed for hydrophobic neutral DOM fractions, followed by lower ??T,n values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

3-Substituted 1,5-Diaryl-1 H-1,2,4-triazoles as Prospective PET Radioligands for Imaging Brain COX-1 in Monkey. Part 2: Selection and Evaluation of [11C]PS13 for Quantitative Imaging.

PubMed

Shrestha, Stal; Singh, Prachi; Cortes-Salva, Michelle Y; Jenko, Kimberly J; Ikawa, Masamichi; Kim, Min-Jeong; Kobayashi, Masato; Morse, Cheryl L; Gladding, Robert L; Liow, Jeih-San; Zoghbi, Sami S; Fujita, Masahiro; Innis, Robert B; Pike, Victor W

2018-06-13

In our preceding paper (Part 1), we identified three 1,5-bis-diaryl-1,2,4-triazole-based compounds that merited evaluation as potential positron emission tomography (PET) radioligands for selectively imaging cyclooxygenase-1 (COX-1) in monkey and human brain, namely, 1,5-bis(4-methoxyphenyl)-3-(alkoxy)-1 H-1,2,4-triazoles bearing a 3-methoxy (PS1), a 3-(2,2,2-trifluoroethoxy) (PS13), or a 3-fluoromethoxy substituent (PS2). PS1 and PS13 were labeled from phenol precursors by O- 11 C-methylation with [ 11 C]iodomethane and PS2 by O- 18 F-fluoroalkylation with [ 2 H 2 , 18 F]fluorobromomethane. Here, we evaluated these PET radioligands in monkey. All three radioligands gave moderately high uptake in brain, although [ 2 H 2 , 18 F]PS2 also showed undesirable radioactivity uptake in skull. [ 11 C]PS13 was selected for further evaluation, mainly based on more favorable brain kinetics than [ 11 C]PS1. Pharmacological preblock experiments showed that about 55% of the radioactivity uptake in brain was specifically bound to COX-1. An index of enzyme density, V T , was well identified from serial brain scans and from the concentrations of parent radioligand in arterial plasma. In addition, V T values were stable within 80 min, suggesting that brain uptake was not contaminated by radiometabolites. [ 11 C]PS13 successfully images and quantifies COX-1 in monkey brain, and merits further investigation for imaging COX-1 in monkey models of neuroinflammation and in healthy human subjects.

Antidiabetic compounds from Sarracenia purpurea used traditionally by the Eeyou Istchee Cree First Nation.

PubMed

Muhammad, Asim; Guerrero-Analco, Jose A; Martineau, Louis C; Musallam, Lina; Madiraju, Padma; Nachar, Abir; Saleem, Ammar; Haddad, Pierre S; Arnason, John T

2012-07-27

Through ethnobotanical surveys, the CIHR Team in Aboriginal Antidiabetic Medicines identified 17 boreal forest plants stemming from the pharmacopeia of the Cree First Nations of Eeyou Istchee (James Bay region of Northern Quebec) that were used traditionally against diabetes symptoms. The leaves of Sarracenia purpurea (pitcher plant), one of the identified Cree plants, exhibited marked antidiabetic activity in vitro by stimulating glucose uptake in C2C12 mouse muscle cells and by reducing glucose production in H4IIE rat liver cells. Fractionation guided by glucose uptake in C2C12 cells resulted in the isolation of 11 compounds from this plant extract, including a new phenolic glycoside, flavonoid glycosides, and iridoids. Compounds 6 (isorhamnetin-3-O-glucoside), 8 [kaempferol-3-O-(6″-caffeoylglucoside], and 11 (quercetin-3-O-galactoside) potentiated glucose uptake in vitro, which suggests they represent active principles of S. purpurea (EC(50) values of 18.5, 13.8, and 60.5 μM, respectively). This is the first report of potentiation of glucose uptake by compounds 6 and 8, while compound 11 (isolated from Vaccinium vitis) was previously shown to enhance glucose uptake. Treatment of H4IIE liver cells with the new compound 1, 6'-O-caffeoylgoodyeroside, decreased hepatic glucose production by reducing glucose-6-phosphatase enzymatic activity (IC(50) = 13.6 μM), which would contribute to lowering glycemia and to the antidiabetic potential of S. purpurea.

Indole Alkaloids from Chaetomium globosum.

PubMed

Xu, Guo-Bo; He, Gu; Bai, Huan-Huan; Yang, Tao; Zhang, Guo-Lin; Wu, Lin-Wei; Li, Guo-You

2015-07-24

Two new indole alkaloids chaetocochin J (1) and chaetoglobinol A (8), along with chetomin (2), chetoseminudin A (3), cochliodinol (9), and semicochliodinol (10), were isolated from the rice culture of the fungus Chaetomium globosum. Their structures were elucidated by spectral analysis. Three new epipolythiodioxopiperazines, chaetocochins G-I (5-7), were identified by the combination of UPLC and mass spectrometric analysis. Chaetocochin I contained two sulfur bridges, one formed by three sulfur atoms between C-3 and C-11a, and the other formed by four sulfur atoms between C-3' and C-6'. Chaetocochin I was readily transformed into chetomin (2), chetoseminudin A (3), chaetocochin D (4), chaetocochin G (5), and chaetocochin H (6) by losing sulfur atoms. Compounds 1-3, and 8 exhibited antibacterial activities against Bacillus subtilis with MICs of 25, 0.78, 0.78, and 50 μg/mL, respectively, but not against Gram-negative bacterium (Escherichia coli). Compounds 2 and 8 were inactive against Candida albicans, Fusarium graminearum, Fusarium vasinfectum, Saccharomyces cerevisiae, and Aspergillus niger even at the high concentrations of 200 and 100 μg/mL, respectively. Compound 8 showed free radical scavenging capacity against the 1,1-diphenyl-2-picryl-hydrazyl (DPPH) and 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid radical (ABTS(+•)), with IC50 values of 143.6 and 45.2 μM, respectively. The free radical scavenging capacity rates of compounds 1-3 on the DPPH and ABTS(+•) were less than 20% at the test concentrations (89.9-108.3 μM). The superoxide anion radical scavenging assay indicated that compounds 1-3, and 8 showed 14.8% (90.9 μM), 18.1% (90.9 μM), 51.5% (88.3 μM), and 30.4% (61.3 μM) superoxide anion radical scavenging capacity, respectively.

One-pot microwave assisted synthesis under green chemistry conditions, antioxidant screening, and cytotoxicity assessments of benzimidazole Schiff bases and pyrimido[1,2-a]benzimidazol-3(4H)-ones.

PubMed

Neochoritis, Constantinos G; Zarganes-Tzitzikas, Tryfon; Tsoleridis, Constantinos A; Stephanidou-Stephanatou, Julia; Kontogiorgis, Christos A; Hadjipavlou-Litina, Dimitra J; Choli-Papadopoulou, Theodora

2011-01-01

The synthesis of a number of benzimidazole Schiff bases 3 and 3-oxo-pyrimido[1,2-a]benzimidazoles 4 in excellent yields by a one-step sequence from the reaction of 2-aminobenzimidazole under green chemistry conditions is described. Structural assignments of the new compounds as well as complete assignment of (1)H and (13)C NMR signals have been unambiguously achieved based on the analysis of their (1)H and (13)C NMR (1D and 2D), IR, MS and elemental analysis data. To the synthesized Schiff bases the E-configuration was assigned on the basis of comparison of experimental and calculated (DFT) (13)C NMR chemical shifts. Compounds 3 and 4 were evaluated as inhibitors of lipoxygenase (LOX) and of lipid peroxidation (LPO). All the tested derivatives showed inhibition of lipid peroxidation, whereas most of them were found to have higher activation than the reference compound trolox; The Schiff bases 3e, 3h, and 3i, and the pyrimidobenzimidazoles 4a, 4e and 4f were found to be the most potent. The most potent LOX inhibitor within the subset of Schiff bases was found compound 3i, followed by 3f, whereas compounds 4a and 4g were found the most potent of the 3-oxo-pyrimido[1,2-a]benzimidazole group. Moreover, some cytotoxicity assessments were undertaken, whereupon it was found that Schiff base 3i and pyrimidobenzimidazoles 4e and 4f did not exhibit cytotoxicity at similar concentrations resembling thus the inhibitory activity of lipid peroxidation. The most cytotoxic Schiff base and pyrimidobenzimidazole were found to be 3d and 4c, respectively. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

Inhibition of PCAF histone acetyltransferase, cytotoxicity and cell permeability of 2-acylamino-1-(3- or 4-carboxy-phenyl)benzamides.

PubMed

Park, Woong Jae; Ma, Eunsook

2012-11-05

Small molecule HAT inhibitors are useful tools to unravel the role of histone acetyltransferases (HATs) in the cell and they also have relevance in oncology. We synthesized a series of 2-acylamino-1-(3- or 4-carboxyphenyl)benzamides 8–19 bearing C6, C8, C10, C12, C14, and C16 acyl chains at the 2-amino position of 2-aminobenzoic acid. Enzyme inhibition of these compounds was investigated using in vitro PCAF HAT assays. The inhibitory activities of compounds 8–10, 16, and 19 were similar to that of anacardic acid, and 17 was found to be more active than anacardic acid at 100 μM. Compounds 11–15 showed the low inhibitory activity on PCAF HAT. The cytotoxicity of the synthesized compounds was evaluated by SRB (sulforhodamine B) assay against seven human cancer cell lines: HT-29 (colon), HCT-116 (colon), MDA-231 (breast), A549 (lung), Hep3B (hepatoma), HeLa (cervical) and Caki (kidney) and one normal cell line (HSF). Compound 17 was more active than anacardic acid against human colon cancer (HCT 116, IC(50): 29.17 μM), human lung cancer (A549, IC₅₀: 32.09 μM) cell lines. 18 was more active than anacardic acid against human colon cancer (HT-29, IC₅₀: 35.49 μM and HCT 116, IC₅₀: 27.56 μM), human lung cancer (A549, IC₅₀: 30.69 μM), and human cervical cancer (HeLa, IC₅₀: 34.41 μM) cell lines. The apparent permeability coefficient (P(app), cm/s) values of two compounds (16 and 17) were evaluated as 68.21 and 71.48 × 10⁻⁶ cm/s by Caco-2 cell permeability assay.

Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters.

PubMed

Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su

2014-05-16

A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

Tautomerism in o-hydroxyanilino-1,4-naphthoquinone derivatives: Structure, NMR, HPLC and density functional theoretic investigations

NASA Astrophysics Data System (ADS)

Bhand, Sujit; Patil, Rishikesh; Shinde, Yogesh; Lande, Dipali N.; Rao, Soniya S.; Kathawate, Laxmi; Gejji, Shridhar P.; Weyhermüller, Thomas; Salunke-Gawali, Sunita

2016-11-01

Structure and spectral characteristics of 'Ortho' ((E)-4-hydroxy-2-(2‧-(4‧-R)-hydroxyphenyl)-imino)-naphthalen-1(2H)-one) and 'para' (2-(2‧-(4‧-R)-hydroxyphenyl)-amino)-1,4-naphthoquinone) tautomers of o-hydroxyanilino-1,4-naphthoquinone derivatives (Rdbnd H, 1A; sbnd CH3, 2A; and -Cl, 3A) are investigated using the 1H, 13C, DEPT, gDQCOSY, gHSQCAD NMR, HPLC, cyclic voltammetry techniques combined with the density functional theory. The compound 2A crystallizes in monoclinic space group P21/c. wherein the polymer chain is facilitated via Osbnd H⋯O and Csbnd H⋯O intermolecular hydrogen bonding. Marginal variations in bond distances in quinonoid and aminophenol moieties render structural flexibility to these compounds those in solution exist as exist in 'ortho - para' tautomers. 1H and 13C NMR spectra in DMSO-d6 showed two sets of peaks in all compounds; whereas only the para tautomer of for 1A and 2A, the para tautomer is predominant in CD3CN solution. Further the ortho-para interconversion is accompanied by a large up-field signals for C(3)sbnd H(3) in their 1H and 13C NMR spectra. These inferences are corroborated by the density functional theoretic calculations.

C isotope fractionation during heterotrophic activity driven carbonate precipitation

NASA Astrophysics Data System (ADS)

Balci, Nurgul; Demirel, Cansu

2016-04-01

Stable carbon isotopic fractionation during carbonate precipitation induced by environmentally enriched heterotrophic halophilic microorganims was experimentally investigated under various salinity (% 4.5, %8, %15) conditions at 30 °C. Halophilic heterotrophic microorganims were enriched from a hypersaline Lake Acigöl located in SW Turkey (Balci et al.,2015) and later used for the precipitation experiments (solid and liquid medium). The carbonate precipitates had relatively high δ13C values (-4.3 to -16.9 ‰) compared to the δ13C values of the organic compounds that ranged from -27.5 to -25.4 ‰. At salinity of 4.5 % δ13C values of carbonate ranged from -4.9 ‰ to -10.9 ‰ with a 13C-enrichment factor of +20 to +16 ‰ higher than the δ13C values of the associated DOC (-27.5) . At salinity 8 % δ13C values of carbonate ranged from -16.3 ‰ to -11.7 ‰ with a 13C-enrichment factor of+11.3 to+15.9 ‰ higher than the δ13C values of the associated DOC. The respected values for 15 % salinity ranged from -12.3 ‰ to -9.7 ‰ with a 13C-enrichment factor of +15.2 to+16.8 ‰ higher than the δ13C values of the associated DOC. The carbonate precipitates produced in the solid medium are more enriched in 13C relative to liquid culture experiments. These results suggest that the carbon in the solid was derived from both the bacterial oxidation of organic compounds in the medium and from the atmospheric CO2. A solid medium used in the experiments may have suppressed convective and advective mass transport favouring diffusion-controlled system. This determination suggests that the rate and equilibration of CO2 exchange with the atmosphere is the major control on C isotope composition of carbonate minerals precipitated in the experiments. Key words: Lake Acıgöl, halophilic bacteria, carbonate biomineralization, C isotopes References Nurgul Balci, Meryem Menekşe, Nevin Gül Karagüler, M. Şeref Sönmez,Patrick Meister 2015.Reproducing authigenic carbonate precipitation inthe hypersaline Lake Acıgöl (Turkey) with microbial cultures. Geomicrobiology Journal DOI: 10.1080/01490451.2015.1099763. TUBITAK (The Scientific and Technological Research Council of Turkey) Grant to N. BALCI (113Y464).

Grass material as process standard for compound-specific radiocarbon analysis

NASA Astrophysics Data System (ADS)

Cisneros-Dozal, Malu; Xu, Xiaomei; Bryant, Charlotte; Pearson, Emma; Dungait, Jennifer

2015-04-01

Compound-specific radiocarbon analysis (CSRA) is a powerful tool to study the carbon cycle and/or as a dating technique in paleoclimate reconstructions. The radiocarbon value of individual compounds can provide insight into turnover times, organic matter sources and in specific cases can be used to establish chronologies when traditional dating materials (e.g. macrofossils, pollen, charcoal) are not available. The isolation of compounds (or group of compounds) from parent material (e.g. soil, plant) for radiocarbon analysis can, however, introduce carbon contamination through chemical separation steps and preparative capillary gas chromatography (PCGC). In addition, the compounds of interest are often in low abundance which amplifies the contamination effect. The extraneous carbon can be of modern 14C age and/or 14C -free and its amount and 14C value must be determined for a given system/isolation procedure in order to report accurate 14C values. This can be achieved by using adequate standard materials but, by contrast with traditional radiocarbon dating, there are not established reference standards for CSRA work, in part because the type of standard material depends on the compounds of interest and the isolation procedure. Here we evaluate the use of n-alkanes extracted from single-year growth grass as modern process standard material for CSRA using PCGC isolation. The grass material has a known 14C value of 1.224 ± 0.006 fraction modern (FM) and the individual n-alkanes are expected to have a similar 14C value. In order to correct for the addition of extraneous carbon during PCGC isolation of the n-alkanes, we used commercially available compounds of modern 14C content and 14C -free (adipic acid, FM= 0.0015 ± 0.0001 and docosane, FM=1.059 ± 0.003) to evaluate our PCGC procedure. The corrected 14C values of the isolated n-alkanes extracted from the modern grass are within one sigma of the grass bulk 14C value for n-C29 and within two sigma for n-C23-C27, C31 and C33. Our results show that single-year growth grass can be a process standard suitable for quality control of extraction of n-alkanes (and potentially other compounds) from soil or plant material for CSRA.

Paleoproductivity vs. influx of terrestrial biomarker in sediment from the Korean Plateau, East Sea (Japan Sea) since the MIS 11

NASA Astrophysics Data System (ADS)

Hyun, Sangmin; Suh, Yean Jee; Ikehara, Miroru

2015-04-01

A piston core collected from the Korean Plateau, East Sea (Japan Sea) of Korea was conducted in terms of variations in paleoproductivity and influx of terrestrial biomarker. The distribution of terrestrial n-alkanes signatures is characterized by the occurrence of high odd number frequency with a minor contribution of specific compound (nC27 only). Average Chain Length (ACL) and Carbon Preferences Index (CPI), both of which are derived from n-alkane combination, show similar shifting between glacial and interglacial periods. Previous studies of SST variation have shown that glacial-interglacial scale changes were quite variable with the maximum range of 26oC in MIS 7, and the minimum range of 12oC during MIS 2 and 6. Therefore, paleovegetation communities had been changed in responding to paleoclimatological variations, and the input amount of terrestrial compound was strongly linked with paleoclimatologic changes. The isotopic composition of δ13C and δ15N of organic matter, which showed extreme temporal variation since MIS 11, indicates the influx of large amount of terrestrial organic matter from the neighboring terrestrial environments during MIS 2, 8 and 10. In particular, depleted values of δ13Corg during MIS 2, 8 and 10 were coincident with lower nitrogen isotope values indicating local paleoceanographic effects such as paleoproductivity changes. Decoupling between δ13Corg and δ15Norg during MIS 1, 3, 5, 7 and coupling of the two during MIS 8 and 11 can be observed, which appear to be interpreted as local productivity changes. In particular, high abundance of cholesterol and C21 n-alkanes, which were derived from diatom, increased during interglacial periods. Therefore, alkenones, SST and n-alkanes signatures coincide with δ13Corg and δ15Norg variations during glacial-interglacial cycles and further strongly associated with cholesterol abundance suggesting that the paleoenvironmental conditions in East Sea during glacial-interglacial periods were sensitive not only to global climate changes but also to local paleceanographic variations.

Differential spatio-temporal expression of carotenoid cleavage dioxygenases regulates apocarotenoid fluxes during AM symbiosis.

PubMed

López-Ráez, Juan A; Fernández, Iván; García, Juan M; Berrio, Estefanía; Bonfante, Paola; Walter, Michael H; Pozo, María J

2015-01-01

Apocarotenoids are a class of compounds that play important roles in nature. In recent years, a prominent role for these compounds in arbuscular mycorrhizal (AM) symbiosis has been shown. They are derived from carotenoids by the action of the carotenoid cleavage dioxygenase (CCD) enzyme family. In the present study, using tomato as a model, the spatio-temporal expression pattern of the CCD genes during AM symbiosis establishment and functioning was investigated. In addition, the levels of the apocarotenoids strigolactones (SLs), C13 α-ionol and C14 mycorradicin (C13/C14) derivatives were analyzed. The results suggest an increase in SLs promoted by the presence of the AM fungus at the early stages of the interaction, which correlated with an induction of the SL biosynthesis gene SlCCD7. At later stages, induction of SlCCD7 and SlCCD1 expression in arbusculated cells promoted the production of C13/C14 apocarotenoid derivatives. We show here that the biosynthesis of apocarotenoids during AM symbiosis is finely regulated throughout the entire process at the gene expression level, and that CCD7 constitutes a key player in this regulation. Once the symbiosis is established, apocarotenoid flux would be turned towards the production of C13/C14 derivatives, thus reducing SL biosynthesis and maintaining a functional symbiosis. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Efficient synthesis and physicochemical characterization of natural danshensu, its S isomer and intermediates thereof

NASA Astrophysics Data System (ADS)

Sidoryk, Katarzyna; Filip, Katarzyna; Cmoch, Piotr; Łaszcz, Marta; Cybulski, Marcin

2018-02-01

The synthesis and molecular structure details of R- 3,4-dihydroxyphenyl lactic acid (danshensu) and related compounds, i.e. S isomer and the key intermediates have been described. Danshensu is an important water soluble phenolic acid of Salvia miltiorrhiza herb (danshen or red sag) with numerous applications in traditional Chinese medicine (TCM). Our synthetic approach was based on the Knoevenagel condensation of the protected 3,4-dihydroxybenzaldehyd and Meldrum acid derivative, followed by asymmetric Sharples dihydroxylation, reductive mono dehydroxylation and final deprotection. All compounds were characterized by various spectroscopic techniques: 1H-, 13C- magnetic resonance (NMR); Fourier-transformed infrared (FTIR); Raman, HR mass spectroscopy. For the determination of compound optical purities original HPLC methods were developed which allowed for the efficient resolution of danshensu R and S enantiomers as well as its intermediate enantiomers, using commercially available chiral stationary phases. Furthermore, in order to better understand danshensu specificity as a potential API in drug formulation, the physicochemical properties of the compounds were studied by thermal analysis, including differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

Chemical constituents from Hericium erinaceus and their ability to stimulate NGF-mediated neurite outgrowth on PC12 cells.

PubMed

Zhang, Cheng-Chen; Yin, Xia; Cao, Chen-Yu; Wei, Jing; Zhang, Qiang; Gao, Jin-Ming

2015-11-15

One new meroterpenoid, named hericenone K (11), along with 10 known compounds (1-10), ergosterol peroxide (1), cerevisterol (2), 3β,5α,9α-trihydroxy-ergosta-7,22-dien-6-one (3), inoterpene A (4), astradoric acid C (5), betulin (6), oleanolic acid (7), ursolic acid (8), hemisceramide (9), and 3,4-dihydro-5-methoxy-2-methyl-2-(4'-methyl-2'-oxo-3'-pentenyl)-9(7H)-oxo-2H-furo[3,4-h]benzopyran (10), was isolated from the fruiting bodies of the mushroom Hericium erinaceus. Their structures were characterized on the basis of spectroscopic methods, as well as through comparison with previously reported data. Compounds 3-6, 8, and 9 were isolated from Hericium species for the first time. Compounds 10 and 11 was suggested to be racemic by the CD spectrum data and specific rotations, which ware resolved by chiral HPLC into respective enantiomers. Compounds 1-3, (±)-10, (-)-10 and (+)-10 in the presence of NGF (20 ng/mL) exerted a significant increase in neurite-bearing cells. Copyright © 2015 Elsevier Ltd. All rights reserved.

Examinations of the matrix isolation fourier transform infrared spectra of organic compounds: Part XII

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coleman, W. M., III; Gordon, B. M.; Lawrence, B. M.

1989-02-01

Matrix isolation Fourier transform infrared spectra (MI/FT-IR), massspectra (MS), carbon-13 Nuclear Magnetic Resonance (/sup 13/C-NMR) spectra,condensed-phase infrared spectra, and vapor-phase infrared (IR)spectra are presented for a series of terpene compounds. Subtle differencesin positional and configurational isomers commonly found withterpenes could be easily detected by the MI/FT-IR spectra. The resultsare comparable in some aspects to those obtainable from /sup 13/C-NMR andthin-film IR; however, most importantly, they are acquired at the lownanogram level for MI/FT-IR, as compared to the milligram level forthe other techniques. These results represent an advance in the technologyavailable for the analysis of complex mixtures such as essential oilscontainingmore » terpene-like molecules.« less

Geranylated 2-arylbenzofurans from Morus alba var. tatarica and their α-glucosidase and protein tyrosine phosphatase 1B inhibitory activities.

PubMed

Zhang, Ya-Long; Luo, Jian-Guang; Wan, Chuan-Xing; Zhou, Zhong-Bo; Kong, Ling-Yi

2014-01-01

Ten new geranylated 2-arylbenzofuran derivatives, including two monoterpenoid 2-arylbenzofurans (1 and 2), two geranylated 2-arylbenzofuran enantiomers (3a and 3b), and six geranylated 2-arylbenzofurans (4-9), along with four known 2-arylbenzofurans (10-13) were isolated from the root bark of Morus alba var. tatarica. Their structures and relative configurations were established on the basis of spectroscopic data analysis. Compounds 3-7 with one asymmetric carbon at C-7″ were supposed to be enantiomeric mixtures confirmed by chiral HPLC analysis, and the absolute configurations of each enantiomer in 3-7 were determined by Rh2(OCOCF3)4-induced CD and Snatzke's method. The enantiomers with the substituting group at C-2' exhibited better resolutions on a Chiralpak AD-H column than those with the substituting group at C-4'. Compounds 1-7, 10, 11 and 13, showed α-glucosidase inhibitory activities with IC50 values of 11.9-131.9 μM, and compounds 1 and 9-13 inhibited protein tyrosine phosphatase 1B (PTP1B) with IC50 values of 7.9-38.1 μM. Copyright © 2013 Elsevier B.V. All rights reserved.

The Influence of a Presence of a Heavy Atom on (13)C Shielding Constants in Organomercury Compounds and Halogen Derivatives.

PubMed

Wodyński, Artur; Gryff-Keller, Adam; Pecul, Magdalena

2013-04-09

(13)C nuclear magnetic resonance shielding constants have been calculated by means of density functional theory (DFT) for several organomercury compounds and halogen derivatives of aliphatic and aromatic compounds. Relativistic effects have been included through the four-component Dirac-Kohn-Sham (DKS) method, two-component Zeroth Order Regular Approximation (ZORA) DFT, and DFT with scalar effective core potentials (ECPs). The relative shieldings have been analyzed in terms of the position of carbon atoms with respect to the heavy atom and their hybridization. The results have been compared with the experimental values, some newly measured and some found in the literature. The main aim of the calculations has been to evaluate the magnitude of heavy atom effects on the (13)C shielding constants and to check what are the relative contributions of scalar relativistic effects and spin-orbit coupling. Another object has been to compare the DKS and ZORA results and to check how the approximate method of accounting for the heavy-atom-on-light-atom (HALA) relativistic effect by means of scalar effective core potentials on heavy atoms performs in comparison with the more rigorous two- and four-component treatment.

3D TOCSY-HSQC NMR for metabolic flux analysis using non-uniform sampling

DOE PAGES

Reardon, Patrick N.; Marean-Reardon, Carrie L.; Bukovec, Melanie A.; ...

2016-02-05

13C-Metabolic Flux Analysis ( 13C-MFA) is rapidly being recognized as the authoritative method for determining fluxes through metabolic networks. Site-specific 13C enrichment information obtained using NMR spectroscopy is a valuable input for 13C-MFA experiments. Chemical shift overlaps in the 1D or 2D NMR experiments typically used for 13C-MFA frequently hinder assignment and quantitation of site-specific 13C enrichment. Here we propose the use of a 3D TOCSY-HSQC experiment for 13C-MFA. We employ Non-Uniform Sampling (NUS) to reduce the acquisition time of the experiment to a few hours, making it practical for use in 13C-MFA experiments. Our data show that the NUSmore » experiment is linear and quantitative. Identification of metabolites in complex mixtures, such as a biomass hydrolysate, is simplified by virtue of the 13C chemical shift obtained in the experiment. In addition, the experiment reports 13C-labeling information that reveals the position specific labeling of subsets of isotopomers. As a result, the information provided by this technique will enable more accurate estimation of metabolic fluxes in larger metabolic networks.« less

Synthesis, structural, conformational and pharmacological study of some amides derived from 3 -methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-amine

NASA Astrophysics Data System (ADS)

Iriepa, I.; Bellanato, J.; Gálvez, E.; Gil-Alberdi, B.

2010-07-01

Some mono-substituted amides ( 2- 5) derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-amine were synthesized and studied by IR, 1H and 13C NMR spectroscopy. The crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dichlorobenzamido)-3-azabicyclo[3.3.1]nonane ( 3) was determined by X-ray diffraction. NMR data showed that all compounds adopt in CDCl 3 a preferred flattened chair-chair conformation with the N-CH 3 group in equatorial disposition. X-ray data agreed with this conformation in the case of compound 3. IR data revealed that compounds 2 and 3 present a C dbnd O⋯HN intermolecular bond in the solid state. This conclusion was also confirmed by X-ray data of compound 3. In the case of compound 5, IR results suggested intermolecular NH⋯N-heterocyclic bonding. On the contrary, in the pyrazine derivative ( 4), IR, 1H and 13C NMR data showed the presence of an intramolecular NH⋯N1″-heterocyclic hydrogen bond in the solid state and solution. Moreover, NMR and IR data showed a preferred trans disposition for the NH-C dbnd O group. NMR also revealed free rotation of the -NH-CO-R group around C9-NH bond. Pharmacological assays on mice were drawn to evaluate analgesic activity.

Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC

PubMed Central

2016-01-01

Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil. PMID:27668136

Improved end-member characterization of modern organic matter pools in the Ohrid Basin (Albania, Macedonia) and evaluation of new palaeoenvironmental proxies

NASA Astrophysics Data System (ADS)

Holtvoeth, J.; Rushworth, D.; Imeri, A.; Cara, M.; Vogel, H.; Wagner, T.; Wolff, G. A.

2015-08-01

We present elemental, lipid biomarker and compound-specific isotope (δ13C, δ2H) data for soils and leaf litter collected in the catchment of Lake Ohrid (Albania, Macedonia), as well as macrophytes, particulate organic matter and sediments from the lake itself. Lake Ohrid provides an outstanding archive of continental environmental change of at least 1.2 M years and the purpose of our study is to ground truth organic geochemical proxies that we developed in order to study past changes in the terrestrial biome. We show that soils dominate the lipid signal of the lake sediments rather than the vegetation or aquatic biomass, while compound-specific isotopes (δ13C, δ2H) determined for n-alkanoic acids confirm a dominant terrestrial source of organic matter to the lake. There is a strong imprint of suberin monomers on the composition of total lipid extracts and chain-length distributions of n-alkanoic acids, n-alcohols, ω-hydroxy acids and α,ω-dicarboxylic acids. Our end-member survey identifies that ratios of mid-chain length suberin-derived to long-chain length cuticular-derived alkyl compounds as well as their average chain length distributions can be used as new molecular proxies of organic matter sources to the lake. We tested these for the 8.2 ka event, a pronounced and widespread Holocene climate fluctuation. In SE Europe climate became drier and cooler in response to the event, as is clearly recognizable in the carbonate and organic carbon records of Lake Ohrid sediments. Our new proxies indicate biome modification in response to hydrological changes, identifying two phases of increased soil OM supply, first from topsoils and then from mineral soils. Our study demonstrates that geochemical fingerprinting of terrestrial OM should focus on the main lipid sources, rather than the living biomass. Both can exhibit climate-controlled variability, but are generally not identical.

Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

2004-07-20

The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

Linking 1D Transition-Metal Coordination Polymers and Different Inorganic Boron Oxides To Construct a Series of 3D Inorganic-Organic Hybrid Borates.

PubMed

Zhi, Shao-Chen; Wang, Yue-Lin; Sun, Li; Cheng, Jian-Wen; Yang, Guo-Yu

2018-02-05

Three inorganic-organic hybrid borates, M(1,4-dab)[B 5 O 7 (OH) 3 ] [M = Zn (1), Cd (2), 1,4-dab = 1,4-diaminobutane)] and Co(1,3-dap)[B 4 O 7 ] (3, 1,3-dap = 1,3-diaminopropane), which integrated characteristics of 1D coordination polymers and 1D/3D inorganic boron oxides have been obtained under solvothermal conditions. Compounds 1 and 2 are isostructural and crystallize in a centrosymmetric space group P2 1 /c; the 3D achiral structures of 1 and 2 consist of the nonhelical Zn/Cd-1,4-dap coordination polymers and 1D B-O chains. Compound 3 crystallizes in a chiral space group P4 3 2 1 2; the helical Co-1,3-dap coordination polymer chains are entrained within a 3D B-O network and finally form the chiral framework. Compounds 1-3 represent good examples of using coordination polymers to construct mixed-motif inorganic-organic hybrid borates. Compounds 1 and 2 display blue luminescence when excited with UV light.

Isolation and expression of three gibberellin 20-oxidase cDNA clones from Arabidopsis.

PubMed

Phillips, A L; Ward, D A; Uknes, S; Appleford, N E; Lange, T; Huttly, A K; Gaskin, P; Graebe, J E; Hedden, P

1995-07-01

Using degenerate oligonucleotide primers based on a pumpkin (Cucurbita maxima) gibberellin (GA) 20-oxidase sequence, six different fragments of dioxygenase genes were amplified by polymerase chain reaction from arabidopsis thaliana genomic DNA. One of these was used to isolate two different full-length cDNA clones, At2301 and At2353, from shoots of the GA-deficient Arabidopsis mutant ga1-2. A third, related clone, YAP169, was identified in the Database of Expressed Sequence Tags. The cDNA clones were expressed in Escherichia coli as fusion proteins, each of which oxidized GA12 at C-20 to GA15, GA24, and the C19 compound GA9, a precursor of bioactive GAs; the C20 tricarboxylic acid compound GA25 was formed as a minor product. The expression products also oxidized the 13-hydroxylated substrate GA53, but less effectively than GA12. The three cDNAs hybridized to mRNA species with tissue-specific patterns of accumulation, with At2301 being expressed in stems and inflorescences, At2353 in inflorescences and developing siliques, and YAP169 in siliques only. In the floral shoots of the ga1-2 mutant, transcript levels corresponding to each cDNA decreased dramatically after GA3 application, suggesting that GA biosynthesis may be controlled, at least in part, through down-regulation of the expression of the 20-oxidase genes.

Simultaneous determination of the quantity and isotopic signature of dissolved organic matter from soil water using high-performance liquid chromatography/isotope ratio mass spectrometry.

PubMed

Scheibe, Andrea; Krantz, Lars; Gleixner, Gerd

2012-01-30

We assessed the accuracy and utility of a modified high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS) system for measuring the amount and stable carbon isotope signature of dissolved organic matter (DOM) <1 µm. Using a range of standard compounds as well as soil solutions sampled in the field, we compared the results of the HPLC/IRMS analysis with those from other methods for determining carbon and (13)C content. The conversion efficiency of the in-line wet oxidation of the HPLC/IRMS averaged 99.3% for a range of standard compounds. The agreement between HPLC/IRMS and other methods in the amount and isotopic signature of both standard compounds and soil water samples was excellent. For DOM concentrations below 10 mg C L(-1) (250 ng C total) pre-concentration or large volume injections are recommended in order to prevent background interferences. We were able to detect large differences in the (13)C signatures of soil solution DOM sampled in 10 cm depth of plots with either C3 or C4 vegetation and in two different parent materials. These measurements also demonstrated changes in the (13)C signature that demonstrate rapid loss of plant-derived C with depth. Overall the modified HLPC/IRMS system has the advantages of rapid sample preparation, small required sample volume and high sample throughput, while showing comparable performance with other methods for measuring the amount and isotopic signature of DOM. Copyright © 2011 John Wiley & Sons, Ltd.

Triterpenoids from Acacia ataxacantha DC: antimicrobial and antioxidant activities.

PubMed

Amoussa, Abdou Madjid O; Lagnika, Latifou; Bourjot, Mélanie; Vonthron-Senecheau, Cathérine; Sanni, Ambaliou

2016-08-12

Acacia ataxacantha is a medicinal specie used extensively in traditional medicine of Benin republic to treat infectious diseases. Our previous study showed interesting antibacterial and antifungal activities against six strains of bacteria and six strains of fungi. The aim of this study was to investigate the antimicrobial and antioxidant activities of compounds isolated from A. ataxacantha. Chromatographic and spectroscopic methods were used to isolate and identify three compounds (1-3) from the bark of A. ataxacantha. Phytochemical investigation of A. ataxacantha (Fabaceae) led to the isolation of three triterpenoids (1-3). The structure of isolated compounds was established by differents spectroscopic methods such as UV, (1)H NMR, (13)C NMR, 2D NMR and Mass. All isolated compounds were tested for antimicrobial activity using agar disc-diffusion and microdilution methods. The radical scavenging activity of isolated compounds was assessed using 2,2-diphenyl-1-picrylhydrazyl (DPPH) method. Phytochemical investigation led to the isolation and identification of lupeol (1), betulinic acid (2) and betulinic acid-3-trans-caffeate (3). Moderate antimicrobial activity was obtained with compound 3 against methicillin-resitant Staphylococcus aureus, Enterococcus feacalis and Pseudomonas aeruginosa with MIC value of 25 μg/ml and Staphylococcus aureus (MIC of 50 μg/ml). Compounds 3 was more active against Staphylococcus epidermidis and Candida albicans with a MIC value of 12.5 μg/ml in boths cases. Compounds 3 had also interesting antioxidant activity with an IC50 of 3.57 μg/ml compared to quercetin (1.04 μg/ml). The overall results of this study provide evidence that the compound 3, isolated from A. ataxacantha, exhibit antimicrobial activity against Gram-positive and Gram-negative bacteria and yeast, especially against C. albicans.

Compound-specific carbon and hydrogen isotope analysis of sub-parts per billion level waterborne petroleum hydrocarbons

USGS Publications Warehouse

Wang, Y.; Huang, Y.; Huckins, J.N.; Petty, J.D.

2004-01-01

Compound-specific carbon and hydrogen isotope analysis (CSCIA and CSHIA) has been increasingly used to study the source, transport, and bioremediation of organic contaminants such as petroleum hydrocarbons. In natural aquatic systems, dissolved contaminants represent the bioavailable fraction that generally is of the greatest toxicological significance. However, determining the isotopic ratios of waterborne hydrophobic contaminants in natural waters is very challenging because of their extremely low concentrations (often at sub-parts ber billion, or even lower). To acquire sufficient quantities of polycyclic aromatic hydrocarbons with 10 ng/L concentration for CSHIA, more than 1000 L of water must be extracted. Conventional liquid/liquid or solid-phase extraction is not suitable for such large volume extractions. We have developed a new approach that is capable of efficiently sampling sub-parts per billion level waterborne petroleum hydrocarbons for CSIA. We use semipermeable membrane devices (SPMDs) to accumulate hydrophobic contaminants from polluted waters and then recover the compounds in the laboratory for CSIA. In this study, we demonstrate, under a variety of experimental conditions (different concentrations, temperatures, and turbulence levels), that SPMD-associated processes do not induce C and H isotopic fractionations. The applicability of SPMD-CSIA technology to natural systems is further demonstrated by determining the ??13C and ??D values of petroleum hydrocarbons present in the Pawtuxet River, RI. Our results show that the combined SPMD-CSIA is an effective tool to investigate the source and fate of hydrophobic contaminants in the aquatic environments.

Energy and Biocides Storage Compounds: Synthesis and Characterization of Energetic Bridged Bis(triiodoazoles).

PubMed

He, Chunlin; Zhao, Gang; Hooper, Joseph P; Shreeve, Jean'ne M

2017-11-06

Energetic bridged triiodopyrazoles and triiodoimidazoles were designed and synthsized by reacting potassium triiodopyrazolate or triiodoimidazolate with corresponding dichloro compounds. All compounds were fully characterized by 1 H and 13 C NMR spectroscopy, IR spectroscopy, and elemental analyses. The structure of compound 1 was further confirmed by single-crystal X-ray diffraction. All of the compounds exhibit good thermal stability with decomposition temperatures between 199 and 270 °C and high densities ranging from 2.804 to 3.358 g/cm 3 . The detonation performances and the detonation products were calculated by CHEETAH 7. Compound 3 (D v = 4765 m s -1 ; P = 17.9 GPa) and compound 7 (D v = 4841 m s -1 ; P = 18.5 GPa) show comparable detonation pressure to TNT, and high iodine content makes them promising as energy and biocides storage compounds.

Flexible method for conjugation of phenolic lignin model compounds to carrier proteins

DOE PAGES

Gao, Ruili; Lu, Fachuang; Zhu, Yimin; ...

2016-10-03

Linking lignin model compounds to carrier proteins is required either to raise antibodies to them or to structurally screen antibodies raised against lignins or models. This paper describes a flexible method to link phenolic compounds of interest to cationic bovine serum albumin (cBSA) without interfering with their important structural features. With the guaiacylglycerol- β-guaiacyl ether dimer, for example, the linking was accomplished in 89% yield with the number of dimers per carrier protein being as high as 50; NMR experiments on a 15N- and 13C-labeled conjugation product indicated that 13 dimers were added to the native lysine residues and themore » remainder (~37) to the amine moieties on the ethylenediamine linkers added to BSA; ~32% of the available primary amine groups on cBSA were therefore conjugated to the hapten. As a result, this loading is suitable for attempting to raise new antibodies to plant lignins and for screening.« less

A series of 2, 4, 5-trisubstituted oxazole: Synthesis, characterization and DFT modelling

NASA Astrophysics Data System (ADS)

Kadam, Vinay S.; Shaikh, Saminaparwin G.; Patel, Arun L.

2016-06-01

A new series of 2,4,5-trisubstituted oxazole were synthesized with good yields using simple methodology. All the compounds were thoroughly characterized by IR, NMR (1H and 13C) and mass spectrometry and structures of 2-(4-butyloxyphenyl)-4,5-dimethyloxazole (5b) and 4,5-dimethyl-2-(4-(octyloxy)phenyl)oxazole(5e) were unambiguously determined by X-ray crystallography. Evidently, the crystal structures of these compounds showed C-H⋯N and C-H⋯O intermolecular interactions. The electronic structures of these compounds were also studied by DFT at B3LYP/6-311G ++ level of theory.

Key intermediates in nitrogen transformation during microwave pyrolysis of sewage sludge: a protein model compound study.

PubMed

Zhang, Jun; Tian, Yu; Cui, Yanni; Zuo, Wei; Tan, Tao

2013-03-01

The nitrogen transformations with attention to NH3 and HCN were investigated at temperatures of 300-800°C during microwave pyrolysis of a protein model compound. The evolution of nitrogenated compounds in the char, tar and gas products were conducted. The amine-N, heterocyclic-N and nitrile-N compounds were identified as three important intermediates during the pyrolysis. NH3 and HCN were formed with comparable activation energies competed to consume the same reactive substances at temperatures of 300-800°C. The deamination and dehydrogenation of amine-N compounds from protein cracking contributed to the formation of NH3 (about 8.9% of Soy-N) and HCN (6.6%) from 300 to 500°C. The cracking of nitrile-N and heterocyclic-N compounds from the dehydrogenation and polymerization of amine-N generated HCN (13.4%) and NH3 (31.3%) between 500 and 800°C. It might be able to reduce the HCN and NH3 emissions through controlling the intermediates production at temperatures of 500-800°C. Copyright © 2013 Elsevier Ltd. All rights reserved.

Accelerator mass spectrometry analysis of aroma compound absorption in plastic packaging materials

NASA Astrophysics Data System (ADS)

Stenström, Kristina; Erlandsson, Bengt; Hellborg, Ragnar; Wiebert, Anders; Skog, Göran; Nielsen, Tim

1994-05-01

Absorption of aroma compounds in plastic packaging materials may affect the taste of the packaged food and it may also change the quality of the packaging material. A method to determine the aroma compound absorption in polymers by accelerator mass spectrometry (AMS) is being developed at the Lund Pelletron AMS facility. The high sensitivity of the AMS method makes it possible to study these phenomena under realistic conditions. As a first test low density polyethylene exposed to 14C-doped ethyl acetate is examined. After converting the polymer samples with the absorbed aroma compounds to graphite, the {14C }/{13C } ratio of the samples is measured by the AMS system and the degree of aroma compound absorption is established. The results are compared with those obtained by supercritical fluid extraction coupled to gas chromatography (SFE-GC).

Powder X-ray diffraction, infrared and 13C NMR spectroscopic studies of the homologous series of some solid-state zinc(II) and sodium(I) n-alkanoates

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Taylor, Richard A.

2015-03-01

A comparative study of the room temperature molecular packing and lattice structures for the homologous series of zinc(II) and sodium(I) n-alkanoates adduced from Fourier transform infrared and solid-state 13C NMR spectroscopic data in conjunction with X-ray powder diffraction measurements is carried out. For zinc carboxylates, metal-carboxyl bonding is via asymmetric bridging bidentate coordination whilst for the sodium adducts, coordination is via asymmetric chelating bidentate bonding. All compounds are packed in a monoclinic crystal system. Furthermore, the fully extended all-trans hydrocarbon chains are arranged as lamellar bilayers. For zinc compounds, there is bilayer overlap, for long chain adducts (nc > 8) but not for sodium compounds where methyl groups from opposing layers in the lamellar are only closely packed. Additionally, the hydrocarbon chains are extended along the a-axis of the unit cell for zinc compounds whilst for sodium carboxylates they are extended along the c-axis. These packing differences are responsible for different levels of Van der Waals effects in the lattices of these two series of compounds, hence, observed odd-even alternation is different. The significant difference in lattice packing observed for these two series of compounds is proposed to be due to the difference in metal-carboxyl coordination mode, arising from the different electronic structure of the central metal ions.

Process for producing phenolic compounds from lignins

DOEpatents

Agblevor, Foster A.

1998-01-01

A process for the production of low molecular weight phenolic compounds from lignins through the pyrolysis of the lignins in the presence of a strong base. In a preferred embodiment, potassium hydroxide is present in an amount of from about 0.1% to about 5% by weight, the pyrolysis temperature is from about 400.degree. C. to about 600.degree. C. at atmospheric pressure, and the time period for substantial completion of the reaction is from about 1-3 minutes. Examples of low molecular weight phenolic compounds produced include methoxyphenols, non-methoxylated phenols, and mixtures thereof.

Cajanusflavanols A-C, Three Pairs of Flavonostilbene Enantiomers from Cajanus cajan.

PubMed

He, Qi-Fang; Wu, Zhen-Long; Huang, Xiao-Jun; Zhong, Yuan-Lin; Li, Man-Mei; Jiang, Ren-Wang; Li, Yao-Lan; Ye, Wen-Cai; Wang, Ying

2018-02-02

Three pairs of new flavonostilbene enantiomers, cajanusflavanols A-C (1-3), along with their putative biogenetic precursors 4-6, were isolated from Cajanus cajan. Compound 1 possesses an unprecedented carbon skeleton featuring a unique highly functionalized cyclopenta[1,2,3-de]isobenzopyran-1-one tricyclic core. Compounds 2 and 3 are the first examples of methylene-unit-linked flavonostilbenes. Their structures with absolute configurations were elucidated by spectroscopic analyses, X-ray diffraction, and computational calculations. Compounds 1 and 2 exhibited significant in vitro anti-inflammatory activities.

The ability of white-rot fungi to degrade the endocrine-disrupting compound nonylphenol.

PubMed

Soares, Ana; Jonasson, Karin; Terrazas, Enrique; Guieysse, Benoit; Mattiasson, Bo

2005-03-01

Phanerochaete chrysosporium, Pleurotus ostreatus, Trametes versicolor and Bjerkandera sp. BOL13 were tested for their ability to degrade the endocrine-disrupting compound nonylphenol at an initial concentration of 100 mg l-1. The highest removals were achieved with T. versicolor and Bjerkandera sp. BOL13, which were able to degrade 97 mg l-1 and 99 mg l-1 of nonylphenol in 25 days of incubation, respectively. Nonylphenol removal was associated with the production of laccase by T. versicolor, but the levels of laccase, manganese peroxidase and lignin peroxidase produced by Bjerkandera sp. BOL13 were very low. At 14 degrees C, T. versicolor and Bjerkandera sp. BOL13 sustained the removal of 88 mg l-1 and 79 mg l-1 of nonylphenol, respectively. No pollutant removal was recorded at 4 degrees C, although both fungi could grow at this temperature in the absence of nonylphenol. A microtoxicity assay showed that the fungi produced compounds that were toxic to Vibrio fischerii; and thus a reduction in toxicity could not be correlated with nonylphenol metabolism. T. versicolor and Bjerkandera sp. BOL13 were capable of colonizing soil artificially contaminated with 430 mg kg-1 of nonylphenol. Only 1.3+/-0.1% of nonylphenol remained in the soil after 5 weeks of incubation.

Modeling Central Carbon Metabolic Processes in Soil Microbial Communities: Comparing Measured With Modeled

NASA Astrophysics Data System (ADS)

Dijkstra, P.; Fairbanks, D.; Miller, E.; Salpas, E.; Hagerty, S.

2013-12-01

Understanding the mechanisms regulating C cycling is hindered by our inability to directly observe and measure the biochemical processes of glycolysis, pentose phosphate pathway, and TCA cycle in intact and complex microbial communities. Position-specific 13C labeled metabolic tracer probing is proposed as a new way to study microbial community energy production, biosynthesis, C use efficiency (the proportion of substrate incorporated into microbial biomass), and enables the quantification of C fluxes through the central C metabolic network processes (Dijkstra et al 2011a,b). We determined the 13CO2 production from U-13C, 1-13C, 2-13C, 3-13C, 4-13C, 5-13C, and 6-13C labeled glucose and 1-13C and 2,3-13C pyruvate in parallel incubations in three soils along an elevation gradient. Qualitative and quantitative interpretation of the results indicate a high pentose phosphate pathway activity in soils. Agreement between modeled and measured CO2 production rates for the six C-atoms of 13C-labeled glucose indicate that the metabolic model used is appropriate for soil community processes, but that improvements can be made. These labeling and modeling techniques may improve our ability to analyze the biochemistry and (eco)physiology of intact microbial communities. Dijkstra, P., Blankinship, J.C., Selmants, P.C., Hart, S.C., Koch, G.W., Schwartz, E., Hungate, B.A., 2011a. Probing C flux patterns of soil microbial metabolic networks using parallel position-specific tracer labeling. Soil Biology & Biochemistry 43, 126-132. Dijkstra, P., Dalder, J.J., Selmants, P.C., Hart, S.C., Koch, G.W., Schwartz, E., Hungate, B.A., 2011b. Modeling soil metabolic processes using isotopologue pairs of position-specific 13C-labeled glucose and pyruvate. Soil Biology & Biochemistry 43, 1848-1857.

Cloning and characterization of a 9-lipoxygenase gene induced by pathogen attack from Nicotiana benthamiana for biotechnological application

PubMed Central

2011-01-01

Background Plant lipoxygenases (LOXs) have been proposed to form biologically active compounds both during normal developmental stages such as germination or growth as well as during responses to environmental stress such as wounding or pathogen attack. In our previous study, we found that enzyme activity of endogenous 9-LOX in Nicotiana benthamiana was highly induced by agroinfiltration using a tobacco mosaic virus (TMV) based vector system. Results A LOX gene which is expressed after treatment of the viral vectors was isolated from Nicotiana benthamiana. As the encoded LOX has a high amino acid identity to other 9-LOX proteins, the gene was named as Nb-9-LOX. It was heterologously expressed in yeast cells and its enzymatic activity was characterized. The yeast cells expressed large quantities of stable 9-LOX (0.9 U ml-1 cell cultures) which can oxygenate linoleic acid resulting in high yields (18 μmol ml-1 cell cultures) of hydroperoxy fatty acid. The product specificity of Nb-9-LOX was examined by incubation of linoleic acid and Nb-9-LOX in combination with a 13-hydroperoxide lyase from watermelon (Cl-13-HPL) or a 9/13-hydroperoxide lyase from melon (Cm-9/13-HPL) and by LC-MS analysis. The result showed that Nb-9-LOX possesses both 9- and 13-LOX specificity, with high predominance for the 9-LOX function. The combination of recombinant Nb-9-LOX and recombinant Cm-9/13-HPL produced large amounts of C9-aldehydes (3.3 μmol mg-1 crude protein). The yield of C9-aldehydes from linoleic acid was 64%. Conclusion The yeast expressed Nb-9-LOX can be used to produce C9-aldehydes on a large scale in combination with a HPL gene with 9-HPL function, or to effectively produce 9-hydroxy-10(E),12(Z)-octadecadienoic acid in a biocatalytic process in combination with cysteine as a mild reducing agent. PMID:21450085

4-Substituted thieno[2,3-d]pyrimidines as potent antibacterial agents: Rational design, microwave-assisted synthesis, biological evaluation and molecular docking studies.

PubMed

Gill, Rupinder K; Singh, Harpreet; Raj, Tilak; Sharma, Anuradha; Singh, Gagandeep; Bariwal, Jitender

2017-12-01

In an attempt to discover a new class of antibacterial agents with improved efficacy and to overcome the drug-resistant problems, some novel 4-substituted thieno[2,3-d]pyrimidines have been synthesized via microwave-assisted methodology and evaluated for their in vitro antibacterial activity against various pathogenic bacterial strains. Compounds 12b and 13c showed the promising inhibitory potencies against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli with MICs ranging from 2 to 10 μg/ml. Compound 13c was also found to be highly potent against methicillin-resistant S. aureus (MRSA) with MIC value of 4 μg/ml. Docking simulation studies have been performed to unravel the mode of action and association study indicate the binding of potent compounds with DHPS enzyme. In silico ADME studies suggest the drug-like characteristics of the potent compounds. © 2017 John Wiley & Sons A/S.

Effect of Vertical Shoot-Positioned, Scott-Henry, Geneva Double-Curtain, Arch-Cane, and Parral Training Systems on the Volatile Composition of Albariño Wines.

PubMed

Vilanova, Mar; Genisheva, Zlatina; Tubio, Miguel; Álvarez, Katia; Lissarrague, Jose Ramón; Oliveira, José Maria

2017-09-08

Viticultural practices influence both grape and wine quality. The influence of training systems on volatile composition was investigated for Albariño wine from Rías Baixas AOC in Northwest Spain. The odoriferous contribution of the compounds to the wine aroma was also studied. Volatile compounds belonging to ten groups (alcohols, C₆-compounds, ethyl esters, acetates, terpenols, C 13 -norisoprenoids, volatile phenols, volatile fatty acids, lactones and carbonyl compounds) were determined in Albariño wines from different training systems, Vertical Shoot-Positioned (VSP), Scott-Henry (SH), Geneva Double-Curtain (GDC), Arch-Cane (AC), and Parral (P) during 2010 and 2011 vintages. Wines from GDC showed the highest total volatile composition with the highest concentrations of alcohols, ethyl esters, fatty acids, and lactones families. However, the highest levels of terpenes and C 13 -norisoprenoids were quantified in the SH system. A fruitier aroma was observed in Albariño wines from GDC when odor activity values were calculated.

Fabrications of some kinds of 2-D frameworks consisting of nanosized polyoxomolybdate anion [Mo 36O 112(H 2O) 16] 8- via condensation processes

NASA Astrophysics Data System (ADS)

Eda, Kazuo; Iriki, Yuichi; Kawamura, Kenjiro; Ikuki, Takeshi; Hayashi, Masahiko

2007-12-01

We succeeded to prepare novel [Mo 36O 112(H 2O) 16] 8- ({Mo 36}) compounds by using 1,3-diamino-2-propanol ( βOHC 3-DA) and 1,3,5-tris(aminomethyl)benzene (MES-TA)+1,3-diaminopropane (C 3-DA) as linkers, and determined their crystal structures. We have confirmed they have unique two-dimensional (2-D) molybdenum oxide frameworks, which are formed by condensation of {Mo 36}s. Side-staggered arrays of {Mo 36}s, connected in lying position by eight bridges per a {Mo 36}, are formed in the compound with βOHC 3-DA, while herringbone arrays of {Mo 36}s, connected in standing position by four bridges per a {Mo 36}, are built in the compound with MES-TA+C 3-DA. The latter compound exhibited non-stoichiometric property, and its composition and cell parameters varied depending on the relative concentration of MES-TA in the mother solution.

Thiazole-based nitrogen mustards: Design, synthesis, spectroscopic studies, DFT calculation, molecular docking, and antiproliferative activity against selected human cancer cell lines

NASA Astrophysics Data System (ADS)

Łączkowski, Krzysztof Z.; Świtalska, Marta; Baranowska-Łączkowska, Angelika; Plech, Tomasz; Paneth, Agata; Misiura, Konrad; Wietrzyk, Joanna; Czaplińska, Barbara; Mrozek-Wilczkiewicz, Anna; Malarz, Katarzyna; Musioł, Robert; Grela, Izabela

2016-09-01

Synthesis, characterization and investigation of antiproliferative activity of ten thiazole-based nitrogen mustard against human cancer cells lines (MV4-11, A549, MCF-7 and HCT116) and normal mouse fibroblast (BALB/3T3) is presented. The structures of novel compounds were determined using 1H and 13C NMR, FAB(+)-MS, and elemental analyses. Among the derivatives, 5b, 5c, 5e, 5f and 5i were found to exhibit high activity against human leukaemia MV4-11 cells with IC50 values of 2.17-4.26 μg/ml. The cytotoxic activity of compound 5c and 5f against BALB/3T3 cells is up to 20 times lower than against cancer cell lines. Our results also show that compounds 5e and 5i have very strong activity against MCF-7 and HCT116 with IC50 values of 3.02-4.13 μg/ml. Moreover, spectroscopic characterization and cellular localization for selected compound were performed. In order to identify potential drug targets we perform computer simulations with DNA-binding site of hTopoI and hTopoII and quantum chemical calculation of interaction and binding energies in complexes of the five most active compounds with guanine.

Leishmanicidal Activities of Novel Synthetic Furoxan and Benzofuroxan Derivatives

PubMed Central

Dutra, Luiz Antônio; de Almeida, Letícia; Passalacqua, Thais G.; Reis, Juliana Santana; Torres, Fabio A. E.; Martinez, Isabel; Peccinini, Rosangela Gonçalves; Chin, Chung Man; Chegaev, Konstantin; Guglielmo, Stefano; Fruttero, Roberta

2014-01-01

A novel series of furoxan (1,2,5-oxadiazole 2-oxide) (compounds 3, 4a and -b, 13a and -b, and 14a to -f) and benzofuroxan (benzo[c][1,2,5]oxadiazole 1-oxide) (compounds 7 and 8a to -c) derivatives were synthesized, characterized, and evaluated for in vitro activity against promastigote and intracellular amastigote forms of Leishmania amazonensis. The furoxan derivatives exhibited the ability to generate nitric oxide at different levels (7.8% to 27.4%). The benzofuroxan derivative 8a was able to increase nitrite production in medium supernatant from murine macrophages infected with L. amazonensis at 0.75 mM after 48 h. Furoxan and benzofuroxan derivatives showed remarkable leishmanicidal activity against both promastigote and intracellular amastigote forms. Compounds 8a, 14a and -b, and 14d exerted selective leishmanicidal activities superior to those of amphotericin B and pentamidine. In vitro studies at pH 5.4 reveal that compound 8a is stable until 8 h and that compound 14a behaves as a prodrug, releasing the active aldehyde 13a. These compounds have emerged as promising novel drug candidates for the treatment of leishmaniasis. PMID:24913171

Antimutagenic activity of polymethoxyflavonoids from Citrus aurantium.

PubMed

Miyazawa, M; Okuno, Y; Fukuyama, M; Nakamura, S; Kosaka, H

1999-12-01

The methanol extract from Citrus aurantium showed a suppressive effect on umu gene expression of SOS response in Salmonella typhimurium TA1535/pSK1002 against the mutagen 2-(2-furyl)-3-(5-nitro-2-furyl)acrylamide (furylfuramide). The methanol extract from C. aurantium was successively re-extracted with hexane, dichloromethane, butanol, and water. A dichloromethane fraction showed a suppressive effect. The suppressive compounds in the dichloromethane fraction were isolated by SiO(2) column chromatography and identified as tetra-O-methylscutellarein (1), sinensetin (2), and nobiletin (3) by EI-MS and (1)H- and (13)C NMR spectroscopy. These compounds suppressed the furylfuramide-induced SOS response in the umu test. Gene expression was suppressed 67%, 45%, and 25% at a concentration of 0.6 micromol/mL, respectively. The ID(50) value (50% inhibition dose) of compound 1 was 0. 19 micromol/mL. These compounds were assayed with other mutagens, 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), which requires liver metabolizing enzymes, activated Trp-P-1, and UV irradiation. These compounds showed of all mutagen-induced SOS response in the umu test. In addition, compounds 1-3 exhibited antimutagenic activity in the S. typhimurium TA100 Ames test.

Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

NASA Technical Reports Server (NTRS)

Merritt, D. A.; Brand, W. A.; Hayes, J. M.

1994-01-01

In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

Spirotetronate antibiotics with anti-Clostridium activity from Actinomadura sp. 2EPS.

PubMed

Euanorasetr, Jirayut; Intra, Bungonsiri; Mongkol, Phayungsak; Chankhamhaengdecha, Surang; Tuchinda, Patoomratana; Mori, Mihoko; Shiomi, Kazuro; Nihira, Takuya; Panbangred, Watanalai

2015-02-01

The rare actinomycetes strain 2EPS was isolated from soil and analysis of cultural, morphological characteristics, diaminopimelic acid content of its cell wall, and 16S rRNA gene sequence indicates that 2EPS belongs to genus Actinomadura. In addition, neighbor-joining phylogenetic tree also confirmed the relationships of this strain to other members of Actinomadura. A butanol extract with antibacterial activity was purified by reversed-phase chromatography to obtain three bioactive compounds, designated as compounds 1, 2 and 3. The structures of these compounds were determined using spectroscopic analysis ((1)H-NMR and (13)C-NMR) and mass spectrometric analysis (HR-TOF-MS). Compounds 1-3 were identified and found to be the same as those included in the Japanese patent number JP 09227587 for spirotetronate antibiotics and are BE-45722A (1), BE-45722B (2) and BE-45722C (3), respectively. All compounds were active against Gram-positive bacteria (Staphylococcus aureus ATCC 25923, Bacillus cereus ATCC 14579, and B. subtilis ATCC 6633) with low MIC values between 0.08 and 5.0 µg/ml. Moreover, both 1 and 3 also exhibited strong activity, with similar MIC values, against Clostridium perfringens S107 at 0.63 µg/ml and C. difficile 630 at 0.08 µg/ml. These results suggest the identified spirotetronate compounds may have potential in the treatment of Clostridium infections. Overall, this analysis demonstrates that rare actinomycetes are a promising source for discovery of antimicrobial compounds.

Spectral characterization and antibacterial activity of an isolated compound from Memecylon edule leaves.

PubMed

Srinivasan, R; Natarajan, D; Shivakumar, M S

2017-03-01

Memecylon edule Roxb. (Melastamataceae family) is a small evergreen tree reported as having ethnobotanical and pharmacological properties. The present study was aimed to investigate the spectral characterization and antibacterial activity of isolated pure compound (3β-hydroxyurs-12-en-28-oic acid (ursolic acid)) from Memecylon edule leaves by performing bioassay guided isolation method. The structure derivation of isolated compound was done by different spectral studies like UV, FT-IR, LC-MS, CHNS analysis, 1D ( 1 H, 13 C and DEPT-135) and 2D-NMR (HSQC and HMBC), respectively. About 99.29% purity of the compound was found in LC analysis. 1 H NMR spectrum results of compound shown 48 protons appear at different shielded region and most of the protons were present in aliphatic region. Whereas, 13 C NMR spectral data resulted seven methyl carbons (CH3), nine methylene carbons (CH2), seven methine carbons (CH) and six non-hydrogenated carbons (C) which are characteristic of pentacyclic triterpene. The isolated pure compound was tested for its antibacterial properties against targeted human pathogens by performing agar well diffusion, MIC and MBC assays and the result exhibits better growth inhibitory effects against S. epidermidis and S. pneumoniae, with the MIC values of 1.56 and 3.15μg/ml. The outcome of this study suggests that the bioactive compound is used for development of plant based drugs in pharmaceutical industry for combating microbial mediated diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and TFT Properties of Fluorenyl Cored Conjugated Compound for Organic Thin Film Transistors.

PubMed

Kim, You Geun; Shaik, Baji; Jang, Yong Ju; Park, Song Yi; Kim, Jin Young; Lee, Sang-Gyeong

2016-03-01

The 5,5'-(4,4'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,1-phenylene))bis(2-hexylthieno[3,2-b]thiophene) FCBT (6) was synthesized by connecting the fluorenyl, thienothiophenyl and phenyl units. The compound was characterized by FT-IR, H1NMR, C13NMR and mass spectroscopy. The compound has shown good solubility and thermal stability over 417 degrees C. The compound has shown hole mobility of 4.76 x 10(-6) cm2Ns. The on-off ratio and threshold voltage were 7.5 x 10(2) and -8.26 V respectively.

Emerging New Strategies for Successful Metabolite Identification in Metabolomics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bingol, Ahmet K.; Bruschweiler-Li, Lei; Li, Dawei

2016-02-26

NMR is a very powerful tool for the identification of known and unknown (or unnamed) metabolites in complex mixtures as encountered in metabolomics. Known compounds can be reliably identified using 2D NMR methods, such as 13C-1H HSQC, for which powerful web servers with databases are available for semi-automated analysis. For the identification of unknown compounds, new combinations of NMR with MS have been developed recently that make synergistic use of the mutual strengths of the two techniques. The use of chemical additives to the NMR tube, such as reactive agents, paramagnetic ions, or charged silica nanoparticles, permit the identification ofmore » metabolites with specific physical chemical properties. In the following sections, we give an overview of some of the recent advances in metabolite identification and discuss remaining challenges.« less

Application of gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to detect the abuse of 17β-estradiol in cattle.

PubMed

Janssens, Geert; Mangelinckx, Sven; Courtheyn, Dirk; Prévost, Stéphanie; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

2013-07-31

Although the ability to differentiate between endogenous steroids and synthetic homologues on the basis of their (13)C/(12)C isotopic ratio has been known for over a decade, this technique has been scarcely implemented for food safety purposes. In this study, a method was developed using gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to demonstrate the abuse of 17β-estradiol in cattle, by comparison of the (13)C/(12)C ratios of the main metabolite 17α-estradiol and an endogenous reference compound (ERC), 5-androstene-3β,17α-diol, in bovine urine. The intermediate precisions were determined as 0.46 and 0.26‰ for 5-androstene-3β,17α-diol and 17α-estradiol, respectively. This is, to the authors' knowledge, the first reported use of GC-MS/C/IRMS for the analysis of steroid compounds for food safety issues.

Benzene-1,3-dicarboxylic acid 2,5-dimethylpyrrole derivatives as multiple inhibitors of bacterial Mur ligases (MurC-MurF).

PubMed

Perdih, Andrej; Hrast, Martina; Barreteau, Hélène; Gobec, Stanislav; Wolber, Gerhard; Solmajer, Tom

2014-08-01

Enzymes catalyzing the biosynthesis of bacterial peptidoglycan represent traditionally a collection of highly selective targets for novel antibacterial drug design. Four members of the bacterial Mur ligase family-MurC, MurD, MurE and MurF-are involved in the intracellular steps of peptidoglycan biosynthesis, catalyzing the synthesis of the peptide moiety of the Park's nucleotide. In our previous virtual screening campaign, a chemical class of benzene-1,3-dicarboxylic acid 2,5-dimethylpyrrole derivatives exhibiting dual MurD/MurE inhibition properties was discovered. In the present study we further investigated this class of compounds by performing inhibition assays on all four Mur ligases (MurC-MurF). Furthermore, molecular dynamics (MD) simulation studies of one of the initially discovered compound 1 were performed to explore its geometry as well as its energetic behavior based on the Linear Interaction Energy (LIE) method. Further in silico virtual screening (VS) experiments based on the parent active compound 1 were conducted to optimize the discovered series. Selected hits were assayed against all Escherichia coli MurC-MurF enzymes in biochemical inhibition assays and molecules 10-14 containing benzene-1,3-dicarboxylic acid 2,5-dimethylpyrrole coupled with five member-ring rhodanine moiety were found to be multiple inhibitors of the whole MurC-MurF cascade of bacterial enzymes in the micromolar range. Steady-state kinetics studies suggested this class to act as competitive inhibitors of the MurD enzyme towards d-Glu. These compounds represent novel valuable starting point in the development of novel antibacterial agents. Copyright © 2014 Elsevier Ltd. All rights reserved.

Online stable isotope analysis of dissolved organic carbon size classes using size exclusion chromatography coupled to an isotope ratio mass spectrometer.

PubMed

Malik, Ashish; Scheibe, Andrea; LokaBharathi, P A; Gleixner, Gerd

2012-09-18

Stable isotopic content of dissolved organic carbon (δ(13)C-DOC) provides valuable information on its origin and fate. In an attempt to get additional insights into DOC cycling, we developed a method for δ(13)C measurement of DOC size classes by coupling high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface was evaluated using various organic compounds, thoroughly tested with soil-water from a C3-C4 vegetation change experiment, and also applied to riverine and marine DOC. δ(13)C analysis of standard compounds resulted in excellent analytical precision (≤0.3‰). Chromatography resolved soil DOC into 3 fractions: high molecular weight (HMW; 0.4-10 kDa), low molecular weight (LMW; 50-400 Da), and retained (R) fraction. Sample reproducibility for measurement of δ(13)C-DOC size classes was ±0.25‰ for HMW fraction, ± 0.54‰ for LMW fraction, and ±1.3‰ for R fraction. The greater variance in δ(13)C values of the latter fractions was due to their lower concentrations. The limit of quantification (SD ≤0.6‰) for each size fraction measured as a peak is 200 ng C (2 mg C/L). δ(13)C-DOC values obtained in SEC mode correlated significantly with those obtained without column in the μEA mode (p < 0.001, intercept 0.17‰), which rules out SEC-associated isotopic effects or DOC loss. In the vegetation change experiment, fractions revealed a clear trend in plant contribution to DOC; those in deeper soils and smaller size fractions had less plant material. It was also demonstrated that the technique can be successfully applied to marine and riverine DOC without further sample pretreatment.

Cinnamoyl compounds as simple molecules that inhibit p300 histone acetyltransferase.

PubMed

Costi, Roberta; Di Santo, Roberto; Artico, Marino; Miele, Gaetano; Valentini, Paola; Novellino, Ettore; Cereseto, Anna

2007-04-19

Cinnamoly compounds 1a-c and 2a-d were designed, synthesized, and in vitro tested as p300 inhibitors. At different degrees, all tested compounds were proven to inactivate p300, particularly, derivative 2c was the most active inhibitor, also showing high specificity for p300 as compared to other histone acetyltransferases. Most notably, 2c showed anti-acetylase activity in mammalian cells. These compounds represent a new class of synthetic inhibitors of p300, characterized by simple chemical structures.

Biogenic Volatile Organic Compound and Respiratory CO2 Emissions after 13C-Labeling: Online Tracing of C Translocation Dynamics in Poplar Plants

PubMed Central

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

2011-01-01

Background Globally plants are the primary sink of atmospheric CO2, 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. Methodology 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 13CO2 to leaves or 13C-glucose to shoots via xylem uptake. The translocation of 13CO2 from the source to other plant parts could be traced by 13C-labeled isoprene and respiratory 13CO2 emission. Principal Finding In intact plants, assimilated 13CO2 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. 13C 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 CO2, to a minor extent from xylem-transported sugars (7–11%) and from photosynthetic intermediates with slower turnover rates (8–11%). Conclusion We quantified the plants' C loss as respiratory CO2 and BVOC emissions, allowing in tandem with metabolic analysis to deepen our understanding of ecosystem C flux. PMID:21387007

Insights into Mechanistic Models for Evaporation of Organic Liquids in the Environment Obtained by Position-Specific Carbon Isotope Analysis.

PubMed

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

2015-11-03

Position-specific isotope effects (PSIEs) have been measured by isotope ratio monitoring (13)C nuclear magnetic resonance spectrometry during the evaporation of 10 liquids of different polarities under 4 evaporation modes (passive evaporation, air-vented evaporation, low pressure evaporation, distillation). The observed effects are used to assess the validity of the Craig-Gordon isotope model for organic liquids. For seven liquids the overall isotope effect (IE) includes a vapor-liquid contribution that is strongly position-specific in polar compounds but less so in apolar compounds and a diffusive IE that is not position-specific, except in the alcohols, ethanol and propan-1-ol. The diffusive IE is diminished under forced evaporation. The position-specific isotope pattern created by liquid-vapor IEs is manifest in five liquids, which have an air-side limitation for volatilization. For the alcohols, undefined processes in the liquid phase create additional PSIEs. Three other liquids with limitations on the liquid side have a lower, highly position-specific, bulk diffusive IE. It is concluded that evaporation of organic pollutants creates unique position-specific isotope patterns that may be used to assess the progress of remediation or natural attenuation of pollution and that the Craig-Gordon isotope model is valid for the volatilization of nonpolar organic liquids with air-side limitation of the volatilization rate.

Multi-Spectroscopic Analysis of Seed Quality and 13C-Stable-Iotopologue Monitoring in Initial Growth Metabolism of Jatropha curcas L.

PubMed Central

Komatsu, Takanori; Ohishi, Risa; Shino, Amiu; Akashi, Kinya; Kikuchi, Jun

2014-01-01

In the present study, we applied nuclear magnetic resonance (NMR), as well as near-infrared (NIR) spectroscopy, to Jatropha curcas to fulfill two objectives: (1) to qualitatively examine the seeds stored at different conditions, and (2) to monitor the metabolism of J. curcas during its initial growth stage under stable-isotope-labeling condition (until 15 days after seeding). NIR spectra could non-invasively distinguish differences in storage conditions. NMR metabolic analysis of water-soluble metabolites identified sucrose and raffinose family oligosaccharides as positive markers and gluconic acid as a negative marker of seed germination. Isotopic labeling patteren of metabolites in germinated seedlings cultured in agar-plate containg 13C-glucose and 15N-nitrate was analyzed by zero-quantum-filtered-total correlation spectroscopy (ZQF-TOCSY) and 13C-detected 1H-13C heteronuclear correlation spectroscopy (HETCOR). 13C-detected HETOCR with 13C-optimized cryogenic probe provided high-resolution 13C-NMR spectra of each metabolite in molecular crowd. The 13C-13C/12C bondmer estimated from 1H-13C HETCOR spectra indicated that glutamine and arginine were the major organic compounds for nitrogen and carbon transfer from roots to leaves. PMID:25401292

Responses of Glossina morsitans morsitans to blends of electroantennographically active compounds in the odors of its preferred (buffalo and ox) and nonpreferred (waterbuck) hosts.

PubMed

Gikonyo, Nicholas K; Hassanali, Ahmed; Njagi, Peter G N; Saini, Rajinder K

2003-10-01

In a previous study, comparison of the behavior of teneral Glossina morsitans morsitans on waterbuck, Kobus defassa (a refractory host), and on two preferred hosts, buffalo, Syncerus caffer, and ox, Bos indicus, suggested the presence of allomones in the waterbuck odor. Examination of the volatile odors by coupled gas chromatography-electroantennographic detection showed that the antennal receptors of the flies detected constituents common to the three bovids (phenols and aldehydes), as well as a series of compounds specific to waterbuck, including C8-C13 methyl ketones, delta-octalactone, and phenols. In this study, behavioral respones of teneral G. m. morsitans to different blends of these compounds were evaluated in a choice wind tunnel. The flies' responses to known or putative attractant blends (the latter comprising EAG-active constituents common to all three animals and those common to buffalo and ox, excluding the known tseste attractants, 4-methylphenol and 3-n-propylphenol), and to putative repellent (the blend of EAG-active compounds specific to the waterbuck volatiles), were different. A major difference related to their initial and final behaviors. When a choice of attractant blends (known or putative) and clean air was presented, flies initially responded by flying upwind toward the odor source, but later moved downwind and rested on either side of the tunnel, with some preference for the side with the odor treatments. However, when presented with a choice of waterbuck-specific blend (putative repellent) and clean air, the flies' initial reaction appeared random; flies flew upwind on either side, but eventually settled down on the odorless side of the tunnel. Flies that flew up the odor plume showed an aversion behavior to the blend. The results lend further support to previous indications for the existence of a tsetse repellent blend in waterbuck body odor and additional attractive constituents in buffalo and ox body odors.

Synthesis of D-[U-{sup 13}C]Glucal, D-[U-{sup 13}C] Galactal, and L-[U-{sup 13}C]Fucose for NMR structure studies of oligosaccharides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, R.; Unkefer, C.J.; Silks, L.A. III

1996-12-31

The role of carbohydrates is well recognized in a variety of important biological phenomena such as cell surface recognition. Recent advances in carbohydrate chemistry, including the development of solid phase synthesis methods, have helped to provide significant quantities of material by offering general protocols for synthesis of well-defined, pure material. However, the study of the solution structure of oligosaccharides by nuclear magnetic resonance techniques have been hampered by the lack of enriched {sup 13}C material. In an effort to help alleviate this situation, we have been interested in the construction of the title compounds from a single economical carbon source,more » D-[U-{sup 13}C]glucose. Details of the syntheses will be provided.« less

Suppressive effects of caraway (Carum carvi) extracts on 2, 3, 7, 8-tetrachloro-dibenzo-p-dioxin-dependent gene expression of cytochrome P450 1A1 in the rat H4IIE cells.

PubMed

Naderi-Kalali, B; Allameh, A; Rasaee, M J; Bach, H-J; Behechti, A; Doods, K; Kettrup, A; Schramm, K-W

2005-04-01

Cytochrome P450 1A1 (CYP1A1) is among the cytochrome P450 classes known to convert xenobiotics and endogenous compounds to toxic and/or carcinogenic metabolites. Suppression of CYP1A1 over expression by certain compounds is implicated in prevention of cancer caused by chemical carcinogens. Chemopreventive agents containing high levels of flavonoids and steroids-like compounds are known to suppress CYP1A1. This study was carried out for assessment of the genomic and proteomic effects of caraway (Carum carvi) extracts containing high levels of both flavonoids and steroid-like substances on ethoxy resorufin dealkylation (EROD) activity and CYP1A1 at mRNA levels. Rat hepatoma cells co-treated with a CYP1A1 inducer i.e. TCDD (2, 3, 7, 8-tetrachlorodibenzo-p-dioxin) and different preparations of caraway extracts at concentrations of 0, 0.13, 1.3, and 13 microM in culture medium. After incubation (37 degrees C and 7% CO2 for 20 h), changes in EROD specific activity recorded and compared in cells under different treatments. The results show that caraway seed extract prepared in three different organic solvents suppressed the enzyme activity in hepatoma cells in a dose-dependent manner. The extracts added above 0.13 microM could significantly inhibit EROD activity and higher levels of each extract (1.3 and 13 microM) caused approximately 10-fold suppression in the enzyme activity. Accordingly, data obtained from the RT-PCR (TaqMan) clearly showed the suppressive effects of plant extract on CYP1A1-related mRNA expression. These data clearly show that substances in caraway seeds extractable in organic solvents can potentially reverse the TCDD-dependent induction in cytochrome P450 1A1.

Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

NASA Astrophysics Data System (ADS)

Carter, Korey P.; Kerr, Andrew T.; Taydakov, Ilya V.; Cahill, Christopher L.

2018-02-01

A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.

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

NASA Astrophysics Data System (ADS)

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.

The structure directing effect of organic cations onto the crystal structures of layered thioantimonates(III): Solvothermal synthesis and crystal structures of five new compounds containing the 2∞[Sb 8S 13] 2- anion

NASA Astrophysics Data System (ADS)

Puls, Angela; Näther, Christian; Kiebach, Ragnar; Bensch, Wolfgang

2006-09-01

The five new thioantimonates(III) ( iprH) 2[Sb 8S 13] ( I), (1,2-dapH) 2[Sb 8S 13] ( II), (1,3-dapH 2)[Sb 8S 13] ( III), (dienH 2)[Sb 8S 13]ṡ1.5H 2O ( IV), and (C 6H 9N 2)[Sb 8S 13]ṡ2.5H 2O ( V) were synthesised under solvothermal conditions ( ipr = iso-propylamine; 1,2-dap = 1,2-diaminopropane; 1,3-dap = 1,3-diaminopropane; dien = diethylentriamine; C 6H 9N 2 = 3-(aminoethyl)-pyridine). The structures of compounds I and II are topological very similar and a central motif is a Sb 10S 10 ring. On both sides of this ring Sb 5S 5 rings are condensed. These rings are connected via Sb 4S 4 rings leading to the sequence Sb 10S 10-Sb 5S 5-Sb 4S 4-Sb 5S 5-Sb 10Sb 10 in the [010] direction. Further interconnection into the two-dimensional [Sb 8S 13] 2- anion produces a large central Sb 18S 18 ring with dimensions of 11ṡ11 Å in both compounds. The two atoms thick layers are linear and stacked along the a axis generating large channels running along [010]. The layered anion of compound III is constructed by interconnection of the SbS 3 and SbS 4 units yielding Sb 19S 19, Sb 14S 14, Sb 13S 13, and Sb 8S 8 rings. The linear layers are two atoms thick and are stacked perpendicular to [001] to form channels running along the same direction. The last two compounds IV and V show a similar network topology. The layered anion is constructed by SbS 3 trigonal pyramids and SbS 4 units. The layer contains a Sb 12S 12 rings as the main structural motif. The corrugated layers extending in the (100) plane are two atoms thick and are stacked in a manner that large tunnels run along [100]. The total potential solvent areas are large and range from 20.7% for III to 35% for II.

Benzofuranyl Esters: Synthesis, Crystal Structure Determination, Antimicrobial and Antioxidant Activities.

PubMed

Kumar, C S Chidan; Then, Li Yee; Chia, Tze Shyang; Chandraju, Siddegowda; Win, Yip-Foo; Sulaiman, Shaida Fariza; Hashim, Nurul Shafiqah; Ooi, Kheng Leong; Quah, Ching Kheng; Fun, Hoong-Kun

2015-09-11

A series of five new 2-(1-benzofuran-2-yl)-2-oxoethyl 4-(un/substituted)benzoates 4(a-e), with the general formula of C₈H₅O(C=O)CH₂O(C=O)C₆H₄X, X = H, Cl, CH₃, OCH₃ or NO₂, was synthesized in high purity and good yield under mild conditions. The synthesized products 4(a-e) were characterized by FTIR, ¹H-, (13)C- and ¹H-(13)C HMQC NMR spectroscopic analysis and their 3D structures were confirmed by single-crystal X-ray diffraction studies. These compounds were screened for their antimicrobial and antioxidant activities. The tested compounds showed antimicrobial ability in the order of 4b < 4a < 4c < 4d < 4e and the highest potency with minimum inhibition concentration (MIC) value of 125 µg/mL was observed for 4e. The results of antioxidant activities revealed the highest activity for compound 4e (32.62% ± 1.34%) in diphenyl-2-picrylhydrazyl (DPPH) radical scavenging, 4d (31.01% ± 4.35%) in ferric reducing antioxidant power (FRAP) assay and 4a (27.11% ± 1.06%) in metal chelating (MC) activity.

Effects of oxygen and redox oscillation on degradation of cell-associated lipids in surficial marine sediments

NASA Astrophysics Data System (ADS)

Sun, Ming-Y. i.; Aller, Robert C.; Lee, Cindy; Wakeham, Stuart G.

2002-06-01

Degradation patterns of sedimentary algal lipids were tracked with time under variable redox treatments designed to mimic conditions in organic-rich, bioturbated deposits. Uniformly 13C-labeled algae were mixed with Long Island Sound surface muddy sediments and exposed to different redox regimes, including continuously oxic and anoxic, and oscillated oxic: anoxic conditions. Concentrations of several 13C-labeled algal fatty acids (16:1, 16:0 and 18:1), phytol and an alkene were measured serially. Results showed a large difference (∼10×) in first-order degradation rate constants of cell-associated lipids between continuously oxic and anoxic conditions. Exposure to oxic conditions increased the degradation of cell-associated lipids, and degradation rate constants were positive functions (linear or nonlinear) of the fraction of time sediments were oxic. Production of two new 13C-labeled compounds (iso-15:0 fatty acid and hexadecanol) further indicated that redox conditions and oxic: anoxic oscillations strongly affect microbial degradation of algal lipids and net synthesis of bacterial biomass. Production of 13C-labeled iso-15:0 fatty acid (a bacterial biomarker) was inversely proportional to the fraction of time sediments were oxic, rapidly decreasing after 10 days of incubation under oxic and frequently oscillated conditions. Turnover of bacterial biomass was faster under continuously or occasionally oxic conditions than under continuously anoxic conditions. 13C-labeled hexadecanol, an intermediate degradation product, accumulated under anoxic conditions but not under oxic or periodically oxic conditions. The frequency of oxic: anoxic oscillation clearly alters both the rate and pathways of lipid degradation in surficial sediments. Terminal degradation efficiency and lipid products from degradation of algal material depend on specific patterns of redox fluctuations.

Following isotopes in pulse-chase enriched aspen seedlings

NASA Astrophysics Data System (ADS)

Norris, C. E.; Wasylishen, R. E.; Landhäusser, S.; Quideau, S. A.

2011-12-01

One method to quantitatively trace biogeochemical fluxes through ecosystems, such as organic matter decomposition, is to use plant material enriched with stable isotopes. However, as plant macromolecules are known to vary in their rate of formation and decomposition, both the enrichment levels and the location of enrichment within the plant material should be characterized prior to decomposition and tracing studies. Aspen (Populus tremuloides Michx.) is a common tree species with a diverse organic matter chemical structure found in the western Canadian boreal forest. This study used a multi pulse and multi chase enrichment of stable isotopes (15N and 13C) on aspen seedlings to determine the seedling enrichment, isotope movement among plant tissues and translocation of isotopes within plant macromolecules e.g., carbohydrates and lignin. As expected, all tissues experienced increased enrichment with multiple pulses. An initial enrichment with 13C was observed in the leaves followed by translocation to the stems and roots while the 15N moved upward from the roots to leaves. The macromolecular chemistry of the organic carbon was further characterized using 13C solid state nuclear magnetic resonance spectroscopy. After the initial two hour chase period enrichment of the O-alkyl type (carbohydrate) carbon within the leaves was identified, followed by redistribution to more complex carbon compounds after the one week chase period. Root and stem tissues did not show the same pattern. Rather, changes in 13C enrichment were observed in shifting ethyl and methyl alkyl (lipid) carbon peak intensities for the stem samples while roots did not preferentially allocate 13C to a specific macromolecule. These results confirm that stable isotope enrichment of plants was non-uniform across macromolecules and tissue types. Enrichment of aspen seedlings was therefore dependant on the pulse-chase sequence used.

Hydrogen and carbon isotopes of petroleum and related organic matter

NASA Astrophysics Data System (ADS)

Yeh, Hsueh-Wen; Epstein, Samuel

1981-05-01

D/H and 13C /12C ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from -85 to -181‰, except for one distillate (-250‰) from the Kenai gas field; δ13C of crude oil ranges from -23.3 to -32.5‰, Variation in δD and δ13C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ13C between oil and coeval wax is slight. Gas fractions are 53-70 and 22.6-23.2‰ depleted in D and 13C, respectively, relative to the coexisting oil fractions. The δD and δ13C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.

Phytochemical investigation and hair growth studies on the rhizomes of Nardostachys jatamansi DC

PubMed Central

Gottumukkala, Venkateswara Rao; Annamalai, Tiruganasambandham; Mukhopadhyay, Triptikumar

2011-01-01

Nardostachys jatamansi DC rhizomes were subjected to extraction, fractionation, and isolation of terpenoid compounds. Three terpenoid compounds were isolated which are nardal, jatamansic acid, and nardin. These compounds were identified based on physical and spectral data (UV, IR,1H and13C NMR, 2D NMR, Mass) and comparison with authentic compounds. The crude extract, fractions, and two of the isolated compounds were tested for their hair growth activity. The hair growth studies showed good activities for the extract, fraction, and the isolated compounds. PMID:21716625

Synthesis, Anti-inflammatory and Antibacterial Activities of Novel Pyrazolo[4,3-g]pteridines.

PubMed

Abdel-Mohsen, Shawkat Ahmed; El-Emary, Talaat Ibrahim; El-Kashef, Hussein Salama

2016-01-01

A novel series of 6-substituted pyrazolo[3,4-g]pteridines 2-9 and pyrazolo[4,3-e][1,2,4]triazolo[1,5-c]pteridin-2(3H)-one (thione) 10 and 11 was synthesized using the starting compound 3,7-dimethyl-1-phenylpyrazolo[4',3':5,6]pyrazino[2,3-d][1,3]oxazin-5(1H)-one 2. The structure of the newly synthesized compounds was elucidated by IR, (1)H-NMR, (13)C-NMR, mass spectroscopy and elemental analyses. The anti-inflammatory activity of all the newly synthesized compounds was evaluated using the carrageenan-induced paw oedema test in rats using indomethacin as the reference drug. Compound 11 and the two derivatives 7f and 8b were the most active compounds, showing an activity comparable to indomethacin. Also, the synthesized compounds were evaluated for their antibacterial activity against Gram-positive bacteria (Staphylococcus aureus and Bacillus cereus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) using chloramphenicol as control. The pyrazolotriazolopteridin-2-thione 11, 6-hydroxyethyl- 6a, 6-(4-nitrophenyl)-7g, and 6-(phenylamino) 8b derivatives were found to be the most active compounds against the Gram-positive species. None of them showed any activity against Gram-negative species.

Turnover of microbial groups and cell components in soil: 13C analysis of cellular biomarkers

NASA Astrophysics Data System (ADS)

Gunina, Anna; Dippold, Michaela; Glaser, Bruno; Kuzyakov, Yakov

2017-01-01

Microorganisms regulate the carbon (C) cycle in soil, controlling the utilization and recycling of organic substances. To reveal the contribution of particular microbial groups to C utilization and turnover within the microbial cells, the fate of 13C-labelled glucose was studied under field conditions. Glucose-derived 13C was traced in cytosol, amino sugars and phospholipid fatty acid (PLFA) pools at intervals of 3, 10 and 50 days after glucose addition into the soil. 13C enrichment in PLFAs ( ˜ 1.5 % of PLFA C at day 3) was an order of magnitude greater than in cytosol, showing the importance of cell membranes for initial C utilization. The 13C enrichment in amino sugars of living microorganisms at day 3 accounted for 0.57 % of total C pool; as a result, we infer that the replacement of C in cell wall components is 3 times slower than that of cell membranes. The C turnover time in the cytosol (150 days) was 3 times longer than in PLFAs (47 days). Consequently, even though the cytosol pool has the fastest processing rates compared to other cellular compartments, intensive recycling of components here leads to a long C turnover time. Both PLFA and amino-sugar profiles indicated that bacteria dominated in glucose utilization. 13C enrichment decreased with time for bacterial cell membrane components, but it remained constant or even increased for filamentous microorganisms. 13C enrichment of muramic acid was the 3.5 times greater than for galactosamine, showing a more rapid turnover of bacterial cell wall components compared to fungal. Thus, bacteria utilize a greater proportion of low-molecular-weight organic substances, whereas filamentous microorganisms are responsible for further C transformations. Thus, tracing 13C in cellular compounds with contrasting turnover rates elucidated the role of microbial groups and their cellular compartments in C utilization and recycling in soil. The results also reflect that microbial C turnover is not restricted to the death or growth of new cells. Indeed, even within living cells, highly polymeric cell compounds are constantly replaced and renewed. This is especially important for assessing C fluxes in soil and the contribution of C from microbial residues to soil organic matter.

Biochemical constituents of a wild strain of Schizophyllum commune isolated from Achanakmar-Amarkantak Biosphere Reserve (ABR), India.

PubMed

Tripathi, Arpita Mani; Tiwary, Bhupendra N

2013-08-01

A wild strain of Schizophyllum commune (MTCC 9670) isolated from Achanakmar-Amarkantak Biosphere Reserve of Central India was evaluated for the production of bioactive compounds. The chemical constituents of wild and in vitro grown cultures were compared. Under optimized conditions, different organic and aqueous extracts from mycelia and fruiting bodies were used to extract chemical components from the cultures grown in vitro. The gas chromatography combined wih mass spectrometry analysis of extracts identified two phenolic compounds, namely Phenyl benzoate (C13H10O2) and 4-(phenyl methoxy) phenol (C13H12O2) in the ethanolic extract of in vitro grown fruiting bodies and one antibacterial compound Pyrrolo (1, 2-a) piperazine-3, 6-dione (C7H10O2N2) in the methanolic extract of mycelia. High-performance liquid chromatography analysis revealed that the gallic acid and L-ascorbic acid were identifiable antioxidant components in the extracts possessing high free radical scavenging activity. The findings suggest that the wild strain of S. commune may serve as the source of novel bioactive compounds with effective antimicrobial and antioxidant activities.

Rhodomollacetals A-C, PTP1B Inhibitory Diterpenoids with a 2,3:5,6-Di-seco-grayanane Skeleton from the Leaves of Rhododendron molle.

PubMed

Zhou, Junfei; Sun, Na; Zhang, Hanqi; Zheng, Guijuan; Liu, Junjun; Yao, Guangmin

2017-10-06

Three novel diterpenoids with an unprecedented 2,3:5,6-di-seco-grayanane carbon skeleton, rhodomollacetals A-C (1-3), are isolated from the leaves of Rhododendron molle. Their structures are elucidated by comprehensive spectroscopic techniques and single-crystal X-ray diffraction. Rhodomollacetal A (1) possesses a novel cis/cis/cis/cis-fused 6/6/6/6/5 pentacyclic ring system, featuring an unprecedented 11,13,18-trioxa-pentacyclo [8.7.1.1 5,8 .0 2,8 .0 12,17 ]nonadecane scaffold. Compounds 2 and 3 have a rare 4-oxatricyclo[7.2.1.0 1,6 ]dodecane moiety and a 2,3-dihydro-4H-pyran-4-one unit. Compounds 1-3 showed moderate PTP1B inhibitory activities, and their molecular dockings were investigated.

Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

DOEpatents

Alvarez, Marc A.; Martinez, Rodolfo A.; Unkefer, Clifford J.

2010-02-16

The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group.

Isolation and identification of curcumin and bisacurone from rhizome extract of temu glenyeh (Curcuma soloensis. Val)

NASA Astrophysics Data System (ADS)

Vitasari, Rista A.; Wibowo, Fajar R.; Marliyana, Soerya D.; Widyo Wartono, M.

2016-02-01

Temu glenyeh (Curcuma soloensis. Val) is one of the medicinal plants that grow in Surakarta. This plant is similar with C. longa and C. Xanthoriza. Chemical constituents from an extract of the plant have never been studied. In this paper, we report the isolation of a terpenoid and curcumin from the rhizome of C. soloensis. The isolation was employed by soxhlet apparatus using acetone as solvent. The fractionation and purification of the compound from the acetone extracts were undertaken by vacuum liquid chromatography and flash chromatography. Identification of compounds used spectroscopy methods, such as FTIR, NMR (1H NMR, 13C NMR, COSY, HSQC and HMBC) and GC-MS. Isolated compounds were identified as curcumin (1) and bisacurone (2).

A new ent-clerodane diterpenoid from Crassocephalum bauchiense Huch. (Asteraceae).

PubMed

Tchinda, Alembert T; Mouokeu, Simplice R; Ngono, Rosalie A N; Ebelle, Madeleine R E; Mokale, Aristide L K; Nono, Diane K; Frédérich, Michel

2015-01-01

A phytochemical investigation of the whole plant of Crassocephalum bauchiense Huch. resulted in the isolation of a new clerodane diterpenoid, ent-2β,18,19-trihydroxycleroda-3,13-dien-16,15-olide (1), together with two known flavonoids 3',5-dihydroxy-4',5',6,7,8-pentamethoxyflavone (2) and 4',5-dihydroxy-3',5',6,7,8-pentamethoxyflavone (3). The compounds were tested against the chloroquine-sensitive 3D7 strain of Plasmodium falciparum. Compound 2 showed weak activity (IC50 = 10.1 g/mL) whilst compounds 1 and 3 were inactive. The structures of the compounds were elucidated by using detailed spectral analyses, especially (1)H and (13)C NMR, (1)H-(1)H COSY, NOESY, HMBC and HR-ESI-MS.

Synthesis, characterization and cholinesterase enzymes inhibitory activity of 1-[3-methyl-5-(2,6,6-trimethyl-cyclohex-1-enyl)-4,5-dihydro-pyrazol-1-yl]-ethanone

NASA Astrophysics Data System (ADS)

Mehdi, Sayed Hasan; Ghalib, Raza Murad; Hashim, Rokiah; da Silva, M. Fátima C. Guedes; Sulaiman, Othman; Murugaiyah, Vikneswaran; Marimuthu, Mani Maran; Naqvi, Mehnaz

2013-10-01

The crystal structure of the title compound, 1-[3-methyl-5-(2,6,6-trimethyl-cyclohex-1-enyl)-4,5-dihydro-pyrazol-1-yl]-ethanone has been determined by single crystal X-ray diffraction. It crystallizes in the orthorhombic space group P212121. The FTIR as well as the 1H and 13C NMR spectra of the compound were also recorded and briefly discussed. Compound 1 demonstrated good inhibitory activity against butyrylcholinesterase (BChE; IC50 = 46.42 μM) comparable to physostigmine. However it showed moderate inhibitory activity against acetylcholinesterase (AChE; IC50 = 157.31 μM). It showed moderate inhibitory activity against acetylcholinesterase and selective inhibitory activity towards butyrylcholinesterase enzyme.

YTTRIUM BERYLLIDE AND COMPOUNDS OF THE TYPE ABe$sub 1$$sub 3$

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matyushenko, N.N.; Tikhinskii, G.F.

1963-11-01

Studies were made on the Be-Y system in order to establish the existence of intermetallides in it and to systematize the compounds of type ABe/sub 13/ according to their formula volumes. The existence of a cubic phase YBe/sub 13/, isomorphous with NaZn/sub 13/ and with a lattice period a = 10.238 plus or minus 0.002 A, was established. It was concluded that the known ABe/sub 13/ beryllides can be divided into three groups according to their volume relationships to the volume of the A component: Sc, Hf, Zr; Mg, Er, Y, Ca, Am; Np, U, Pu, Th, Ce, La. (P.C.H.)

Four new triterpenoids from the leaves of Psidium guajava.

PubMed

Shao, Meng; Wang, Ying; Huang, Xiao-Jun; Fan, Chun-Lin; Zhang, Qing-Wen; Zhang, Xiao-Qi; Ye, Wen-Cai

2012-01-01

Four new triterpenoids, psiguanins A-D (1-4), along with 13 known ones (5-17), were isolated from the leaves of Psidium guajava. The structures of new compounds were determined as 2α,3β-dihydroxy-taraxer-20-en-28-oic acid (1), 2α,3β,12α,13β-tetrahydroxy-urs-28-oic acid (2), 2α,3β,12β,13β-tetrahydroxy-urs-28-oic acid (3), and 2α,3β,12β,13α-tetrahydroxy-urs-28-oic acid (4), respectively, on the basis of comprehensive spectroscopic methods and molecular modeling calculation. Among them, compound 4 was characterized as an unusual ursane-type triterpenoid with cis-fused C/D ring system.

Biodegradation of coal-related model compounds. [C. versicolor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, J.A.; Stewart, D.L.; McCulloch, M.

1988-01-01

The details of the specific reactions of lignin biodegradation, and the biochemistry involved, have been primarily based on the use of low molecular weight compounds representing specific substructures rather than the complex, polymeric lignin material. The authors have studied the reactions of model compounds having coal-related functionalities (ester linkages, ether linkages, PAH) with the intact organisms, cell-free filtrate, and cell-free enzyme of C. versicolor to better understand the process of biosolubilization. Many of the degradation products have been identified by gas chromatography/mass spectrometry (GC/MS). Results are discussed.

Transformations of the chemical compositions of high molecular weight DOM along a salinity transect: Using two dimensional correlation spectroscopy and principal component analysis approaches

NASA Astrophysics Data System (ADS)

Abdulla, Hussain A. N.; Minor, Elizabeth C.; Dias, Robert F.; Hatcher, Patrick G.

2013-10-01

In a study of chemical transformations of estuarine high-molecular-weight (HMW, >1000 Da) dissolved organic matter (DOM) collected over a period of two years along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA, δ13C values, N/C ratios, and principal component analysis (PCA) of the solid-state 13C NMR (nuclear magnetic resonance) spectra of HMW-DOM show an abrupt change in both its sources and chemical structural composition occurring around salinity 20. HMW-DOM in the lower salinity region had lighter isotopic values, higher aromatic and lower carbohydrate contents relative to that in the higher salinity region. These changes around a salinity of 20 are possibly due to introduction of a significant amount of new carbon (autotrophic DOM) to the transect. PC-1 loadings plot shows that spatially differing DOM components are similar to previously reported 13C NMR spectra of heteropolysaccharides (HPS) and carboxyl-rich alicyclic molecules (CRAM). Applying two dimensional correlation spectroscopy techniques to 1H NMR spectra from the same samples reveals increases in the contribution of N-acetyl amino sugars, 6-deoxy sugars, and sulfated polysaccharides to HPS components along the salinity transect, which suggests a transition from plant derived carbohydrates to marine produced carbohydrates within the HMW-DOM pool. In contrast to what has been suggested previously, our combined results from 13C NMR, 1H NMR, and FTIR indicate that CRAM consists of at least two different classes of compounds (aliphatic polycarboxyl compounds and lignin-like compounds).

Synthesis, characterization and theoretical studies of 5-(benzylthio)-1-cylopentyl-1H-tetrazole

NASA Astrophysics Data System (ADS)

Saglam, S.; Disli, A.; Erdogdu, Y.; Marchewka, M. K.; Kanagathara, N.; Bay, B.; Güllüoğlu, M. T.

2015-01-01

In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, 1H NMR, 13C-APT and LC-MS spectroscopy techniques. The FT-IR, 1H NMR and 13C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G** basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities.

Synthesis, characterization and theoretical studies of 5-(benzylthio)-1-cylopentyl-1H-tetrazole.

PubMed

Saglam, S; Disli, A; Erdogdu, Y; Marchewka, M K; Kanagathara, N; Bay, B; Güllüoğlu, M T

2015-01-25

In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, (1)H NMR, (13)C-APT and LC-MS spectroscopy techniques. The FT-IR, (1)H NMR and (13)C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G(**), cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G(**) basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities. Copyright © 2014 Elsevier B.V. All rights reserved.

Biosynthesis of firefly luciferin in adult lantern: decarboxylation of L-cysteine is a key step for benzothiazole ring formation in firefly luciferin synthesis.

PubMed

Oba, Yuichi; Yoshida, Naoki; Kanie, Shusei; Ojika, Makoto; Inouye, Satoshi

2013-01-01

Bioluminescence in fireflies and click beetles is produced by a luciferase-luciferin reaction. The luminescence property and protein structure of firefly luciferase have been investigated, and its cDNA has been used for various assay systems. The chemical structure of firefly luciferin was identified as the D-form in 1963 and studies on the biosynthesis of firefly luciferin began early in the 1970's. Incorporation experiments using (14)C-labeled compounds were performed, and cysteine and benzoquinone/hydroquinone were proposed to be biosynthetic component for firefly luciferin. However, there have been no clear conclusions regarding the biosynthetic components of firefly luciferin over 30 years. Incorporation studies were performed by injecting stable isotope-labeled compounds, including L-[U-(13)C3]-cysteine, L-[1-(13)C]-cysteine, L-[3-(13)C]-cysteine, 1,4-[D6]-hydroquinone, and p-[2,3,5,6-D]-benzoquinone, into the adult lantern of the living Japanese firefly Luciola lateralis. After extracting firefly luciferin from the lantern, the incorporation of stable isotope-labeled compounds into firefly luciferin was identified by LC/ESI-TOF-MS. The positions of the stable isotope atoms in firefly luciferin were determined by the mass fragmentation of firefly luciferin. We demonstrated for the first time that D- and L-firefly luciferins are biosynthesized in the lantern of the adult firefly from two L-cysteine molecules with p-benzoquinone/1,4-hydroquinone, accompanied by the decarboxylation of L-cysteine.

1,2-Dibenzyltetradimethylamido-Dimolybdenum and -Ditungsten (M=M) Compounds and Their Reactions with Carbon Dioxide and 1,3-Diaryltriazines. A Radical Difference.

DTIC Science & Technology

1982-07-07

solution of a mixture of these Mo2- and MoW-containing compounds selectively precipitated the heterobimetallic single elec- tron oxidation product MoW...3.5 and reduction, using 0$ powdered zinc in acetonitrile at 25°C, yielded the heterobimetallic quadruply bonded compound MoW(O2CBu t )4. Katovic, V

Capsofulvesins A-C, cholinesterase inhibitors from Capsosiphon fulvescens.

PubMed

Fang, Zhe; Yang Jeong, Su; Ah Jung, Hyun; Sue Choi, Jae; Sun Min, Byung; Hee Woo, Mi

2012-01-01

Activity-directed isolation of the n-hexane and dichloromethane fractions of Capsosiphon fulvescens resulted in the identification of four new glycolipids (1-3): (2S)-1-O-(6Z,9Z,12Z,15Z-octadecatetraenoyl)-2-O-(4Z,7Z,10Z,13Z-hexadecatetraenoyl)-3-O-β-D-galactopyranosyl glycerol (1, capsofulvesin A), (2S)-l-O-(9Z,12Z,15Z-octadecatrienoyl)-2-O-(10Z,13Z-hexadecadienoyl)-3-O-β-D-galactopyranosyl glycerol (2, capsofulvesin B), (2S)-1-O-(6Z,9Z,12Z,15Z-octadecatetraenoyl)-3-O-β-D-galacatopyranosyl glycerol (3, capsofulvesin C). Compounds 1-6 exhibited acetylcholinesterase (AChE) inhibitory activities with IC(50) values ranging from 50.90 to 82.83 µM, whereas 2-6 showed butyrylcholinesterase (BChE) inhibitory activities with IC(50) values of 114.75-185.55 µM. Although most of the compounds isolated lacked scavenging activity for 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical and peroxynitrite (ONOO(-)), compound 8 showed ONOO(-) scavenging activity with an IC(50) value of 26.23 µg/mL.

Quantum mechanical and spectroscopic (FT-IR, 13C, 1H NMR and UV) investigations of 2-(5-(4-Chlorophenyl)-3-(pyridin-2-yl)-4,5-dihydropyrazol-1-yl)benzo[d]thiazole by DFT method

NASA Astrophysics Data System (ADS)

Diwaker

2014-07-01

The electronic, NMR, vibrational, structural properties of a new pyrazoline derivative: 2-(5-(4-Chlorophenyl)-3-(pyridine-2-yl)-4,5-dihydropyrazol-1-yl)benzo[d]thiazole has been studied using Gaussian 09 software package. Using VEDA 4 program we have reported the PED potential energy distribution of normal mode of vibrations of the title compound. We have also reported the 1H and 13C NMR chemical shifts of the title compound using B3LYP level of theory with 6-311++G(2d,2p) basis set. Using time dependent (TD-DFT) approach electronic properties such as HOMO and LUMO energies, electronic spectrum of the title compound has been studied and reported. NBO analysis and MEP surface mapping has also been calculated and reported using ab initio methods.

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

PubMed

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.

Synthesis of a water-soluble fullerene [C60] under ultrasonication.

PubMed

Ko, Weon-Bae; Heo, Jae-Young; Nam, Jae-Heon; Lee, Kyu-Bong

2004-03-01

A water-soluble fullerene [C60] is prepared with fullerene [C60] and a mixture of strong inorganic acids at the ratio (v/v) of 3:1 under ultrasonic condition at 25-43 degrees C. The MALDI-TOF MS and 13C-NMR spectra confirmed that the product of a water-soluble fullerene compound was C60.

N-Acetonitrile Functionalized Nitropyrazoles: Precursors to Insensitive Asymmetric N-Methylene-C Linked Azoles.

PubMed

Kumar, Dheeraj; Imler, Gregory H; Parrish, Damon A; Shreeve, Jean'ne M

2017-06-12

Properties of energetic compounds obtained by linking energetic pyrazoles to tetrazoles by means of N-methylene-C bridges can be fine-tuned. Reactions of pyrazole derivatives with chloroacetonitrile followed by conversion of the cyano group to tetrazole using click reactions in the presence of zinc chloride result in asymmetric N-methylene-C bridged azole-based energetic compounds. All the compounds were thoroughly characterized by IR and NMR [ 1 H, 13 C { 1 H}, 15 N] spectroscopy, elemental analysis, and differential scanning calorimetry (DSC), and for two compounds, further supported by single-crystal X-ray diffraction studies. Heats of formation and detonation performances were calculated using Gaussian 03 and EXPLO5 v6.01 programs, respectively. Initial studies show that this new approach is promising for synthesizing less sensitive energetic compounds with fine-tuned properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon isotopic fractionation in lipids from methanotrophic bacteria: relevance for interpretation of the geochemical record of biomarkers

NASA Technical Reports Server (NTRS)

Summons, R. E.; Jahnke, L. L.; Roksandic, Z.

1994-01-01

Experiments with cultured aerobic methane oxidising bacteria confirm that their biomarker lipids will be significantly depleted in 13C compared to the substrate. The methanotrophic bacteria Methylococcus capsulatus and Methylomonas methanica, grown on methane and using the RuMP cycle for carbon assimilation, show maximum 13C fractionation of approximately 30% in the resultant biomass. In M. capsulatus, the maximum fractionation is observed in the earliest part of the exponential growth stage and decreases to approximately 16% as cells approach stationary phase. This change may be associated with a shift from the particulate form to the soluble form of the methane monooxygenase enzyme. Less than maximum fractionation is observed when cells are grown with reduced methane availability. Biomass of M. capsulatus grown on methanol was depleted by 9% compared to the substrate. Additional strong 13C fractionation takes place during polyisoprenoid biosynthesis in methanotrophs. The delta 13C values of individual hopanoid and steroid biomarkers produced by these organisms were as much as l0% more negative than total biomass. In individual cultures, squalene was 13C-enriched by as much as 14% compared to the triterpane skeleton of bacteriohopaneaminopentol. Much of the isotopic dispersion in lipid metabolites could be attributed to shifts in their relative abundances, combined with an overall reduction in fractionation during the growth cycle. In cells grown on methanol, where there was no apparent effect of growth stage on overall fractionation there were still significant isotopic differences between closely related lipids including a 5.3% difference between the hopane and 3 beta-methylhopane skeletons. Hopane and sterane polyisoprenoids were also 13C-depleted compared to fatty acids. These observations have significant implications for the interpretation of specific compound isotopic signatures now being measured for hydrocarbons and other lipids present in sediments and petroleum. In particular, biomarker lipids produced by a single organism do not necessarily have the same carbon isotopic composition.

Microbial carbon turnover in the plant-rhizosphere-soil continuum

NASA Astrophysics Data System (ADS)

Malik, Ashish; Dannert, Helena; Griffiths, Robert; Thomson, Bruce; Gleixner, Gerd

2014-05-01

Soil microbial biomass contributes significantly to maintenance of soil organic matter (SOM). It is well known that biochemical fractions of soil microorganisms have varying turnover and therefore contribute differentially to soil C storage. Here we compare the turnover rates of different microbial biochemical fractions using a pulse chase 13CO2 plant labelling experiment. The isotope signal was temporally traced into rhizosphere soil microorganisms using the following biomarkers: DNA, RNA, fatty acids and chloroform fumigation extraction derived microbial biomass size classes. C flow into soil microbial functional groups was assessed through phospholipid and neutral lipid fatty acid (PLFA/NLFA) analyses. Highest 13C enrichment was seen in the low molecular weight (LMW) size class of microbial biomass (Δδ13C =151) and in nucleic acids (DNA: 38o RNA: 66) immediately after the pulse followed by a sharp drop. The amount of 13C in the high molecular weight (HMW) microbial biomass (17-81) and total fatty acids (32-54) was lower initially and stayed relatively steady over the 4 weeks experimental period. We found significant differences in turnover rates of different microbial biochemical and size fractions. We infer that LMW cytosolic soluble compounds are rapidly metabolized and linked to respiratory C fluxes, whereas mid-sized products of microbial degradation and HMW polymeric compounds have lower renewal rate in that order. The turnover of cell wall fatty acids was also very slow. DNA and RNA showed faster turnover rate; and as expected RNA renewal was the fastest due to its rapid production by active microorganisms independent of cell replication. 13C incorporation into different functional groups confirmed that mutualistic arbuscular mycorrhizal fungi rely on root C and are important in the initial plant C flux. We substantiated through measurements of isotope incorporation into bacterial RNA that rhizosphere bacteria are also important in the initial C conduit from plants. Other saprophytic fungi and bacteria show a delayed 13C incorporation pattern which could suggest secondary 13C assimilation often indicative of trophic interactions. Thus, different soil microbial biochemical fractions as well as functional groups show differential C turnover which could have implications on soil C storage.

Methyl 3-amino-4-butanamido-5-methyl­benzoate

PubMed Central

Li, Xiang; Yuan, Lian-shan; Wang, Dan; Yao, Cheng

2008-01-01

The title compound, C13H18N2O3, is an inter­mediate in the synthesis of compounds with medicinial applications. The crystal structure is stabilized by inter­molecular N—H⋯O, C—H⋯N and C—H⋯O hydrogen bonds. PMID:21202582

Hydrogen bonds directed 2D → 3D interdigitated Cd(II) compound: Synthesis, crystal structure and dual-emission luminescent properties

NASA Astrophysics Data System (ADS)

Yu, Yuanyuan

2017-06-01

A new Cd(II) compound, namely [Cd2(btc)(phen)2Cl]n·n(H2O)·n(DMA) (1, H3btc = 1, 3, 5-benzenetricarboxylic acid, phen = 1,10-phenanthroline, DMA = N,N'-dimethylacetamide) has been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. This compound crystallizes in monoclinic P21/n space group with a = 13.5729(7) Å, b = 20.1049(7) Å, c = 13.9450(6) Å, β = 104.671(4)°, Z = 4. Single-crystal X-ray diffraction analysis reveals that compound 1 features a 2D → 3D interdigitated framework directed by the intermolecular hydrogen bonds. In addition, the luminescent properties of compound 1 were also investigated in the solid state at room temperature.

Cytotoxic grifolin derivatives isolated from the wild mushroom Boletus pseudocalopus (Basidiomycetes).

PubMed

Song, Junsik; Manir, Md Maniruzzaman; Moon, Surk-Sik

2009-09-01

Activity-guided purification of a MeOH extract of the Korean wild mushroom Boletus pseudocalopus afforded three new grifolin derivatives, 1-3, along with four known phenolic compounds 4-7. Their structures were established by a combination of 1H- and 13C-NMR, NOESY, and extensive two-dimensional NMR spectroscopic experiments such as gCOSY, gHSQC, gHMBC, and ROESY. The major metabolites 4 and 5 were subjected to reduction to provide the side chain-reduced compounds 8 and 9 for biological testing. All of the compounds except compound 6 showed anticancer activities in the range of IC(50) 3.5-11.0 microg/ml against human lung carcinoma A549 and mouse melanoma B16F1 cell lines. In addition, all compounds showed moderate radical-scavenging activities determined by DPPH assay.

13C NMR investigation of nonenzymatic glucosylation of protein. Model studies using RNase A.

PubMed

Neglia, C I; Cohen, H J; Garber, A R; Ellis, P D; Thorpe, S R; Baynes, J W

1983-12-10

Nonenzymatic glucosylation of protein is initiated by the reversible condensation of glucose in its open chain form with the amino groups on the protein. The initial product is an aldimine (Schiff base) which cyclizes to the glycosylamine derivative. The aldimine can undergo a slow Amadori rearrangement to yield the relatively stable ketoamine adduct which is structurally analogous to fructose. 13C NMR has been used to characterize these early products of nonenzymatic glucosylation, using RNase A as a model protein. C-1 of the beta-pyranose anomer of the glycosylamine was identified at 88.8 ppm in the spectrum of RNase glucosylated approximately 1:1 with D-[1-13C]glucose. C-1 of the Amadori product was also apparent in this spectrum, resonating as a pair of intense peaks at 52.7 and 53.1 ppm. The anomeric (C-2) resonances of the Amadori adduct were seen in the spectrum of RNase glucosylated approximately 1:1 with [U-13C]glucose. This spectrum was interpreted by comparison to the spectra of reference compounds: D-fructose, fructose-glycine, N alpha-formyl-N epsilon-fructose-lysine, and glucosylated poly-L-lysine. In the protein spectrum, the most intense of the C-2 resonances was that of the beta-fructopyranose anomer at 95.8 ppm. The alpha- and beta-fructofuranose anomers were also observed at 101.7 and 99.2 ppm, respectively. One unidentified signal in the anomeric region was observed in the spectra of poly-L-lysine and RNase, both glucosylated with [U-13C]glucose; no comparable resonances were observed in the spectra of the model compounds.

In-vacuum thermolysis of ethane 1,2-diamineborane for the synthesis of ternary borocarbonitrides

NASA Astrophysics Data System (ADS)

Massimi, Lorenzo; Grazia Betti, Maria; Caramazza, Simone; Postorino, Paolo; Mariani, Carlo; Latini, Alessandro; Leardini, Fabrice

2016-10-01

High-temperature (1000 °C) thermolytic decomposition of ethane 1,2-diamineborane (BH3NH2CH2CH2NH2BH3) deposited onto a Cu foil has been performed in an ultra-high-vacuum environment. A combined thermolytic, structural (x-ray diffraction), microscopic (scanning electron microscopy) and spectroscopic (Raman, x-ray photoemission spectroscopy) analysis, has identified a ternary borocarbonitride (BCN) compound as a result of the process. The obtained BCN compound is nanocrystalline, surrounded by crystallites of ammonium hydroxide borate hydrate. The ternary compound presents a 0.2:0.6:0.2 B:C:N composition in the bulk and 0.11:0.76:0.13 stoichiometry at the very surface, richer in C-C networks with respect to the bulk. Furthermore, the resulting BCN compound does not show oxidation at the surface due to the in-vacuum thermolysis of the single precursor.

In-vacuum thermolysis of ethane 1,2-diamineborane for the synthesis of ternary borocarbonitrides.

PubMed

Massimi, Lorenzo; Betti, Maria Grazia; Caramazza, Simone; Postorino, Paolo; Mariani, Carlo; Latini, Alessandro; Leardini, Fabrice

2016-10-28

High-temperature (1000 °C) thermolytic decomposition of ethane 1,2-diamineborane (BH3NH2CH2CH2NH2BH3) deposited onto a Cu foil has been performed in an ultra-high-vacuum environment. A combined thermolytic, structural (x-ray diffraction), microscopic (scanning electron microscopy) and spectroscopic (Raman, x-ray photoemission spectroscopy) analysis, has identified a ternary borocarbonitride (BCN) compound as a result of the process. The obtained BCN compound is nanocrystalline, surrounded by crystallites of ammonium hydroxide borate hydrate. The ternary compound presents a 0.2:0.6:0.2 B:C:N composition in the bulk and 0.11:0.76:0.13 stoichiometry at the very surface, richer in C-C networks with respect to the bulk. Furthermore, the resulting BCN compound does not show oxidation at the surface due to the in-vacuum thermolysis of the single precursor.

Development and validation of a liquid chromatography isotope dilution mass spectrometry method for the reliable quantification of alkylphenols in environmental water samples by isotope pattern deconvolution.

PubMed

Fabregat-Cabello, Neus; Sancho, Juan V; Vidal, Andreu; González, Florenci V; Roig-Navarro, Antoni Francesc

2014-02-07

We present here a new measurement method for the rapid extraction and accurate quantification of technical nonylphenol (NP) and 4-t-octylphenol (OP) in complex matrix water samples by UHPLC-ESI-MS/MS. The extraction of both compounds is achieved in 30min by means of hollow fiber liquid phase microextraction (HF-LPME) using 1-octanol as acceptor phase, which provides an enrichment (preconcentration) factor of 800. On the other hand we have developed a quantification method based on isotope dilution mass spectrometry (IDMS) and singly (13)C1-labeled compounds. To this end the minimal labeled (13)C1-4-(3,6-dimethyl-3-heptyl)-phenol and (13)C1-t-octylphenol isomers were synthesized, which coelute with the natural compounds and allows the compensation of the matrix effect. The quantification was carried out by using isotope pattern deconvolution (IPD), which permits to obtain the concentration of both compounds without the need to build any calibration graph, reducing the total analysis time. The combination of both extraction and determination techniques have allowed to validate for the first time a HF-LPME methodology at the required levels by legislation achieving limits of quantification of 0.1ngmL(-1) and recoveries within 97-109%. Due to the low cost of HF-LPME and total time consumption, this methodology is ready for implementation in routine analytical laboratories. Copyright © 2013 Elsevier B.V. All rights reserved.

Trangmolins A-F with an Unprecedented Structural Plasticity of the Rings A and B: New Insight into Limonoid Biosynthesis.

PubMed

Li, Wanshan; Shen, Li; Bruhn, Torsten; Pedpradab, Patchara; Wu, Jun; Bringmann, Gerhard

2016-08-08

The absolute stereostructures of trangmolins A-F (1-6), limonoids with three new and one known topologies of the rings A and B, were unambiguously determined by NMR spectroscopic investigations, single-crystal XRD analysis, and quantum-chemical electronic circular dichroism calculations. Compounds 1-3 contain a hexahydro-1H-inden-4-one motif, compound 4 comprises a hexahydro-2,6-methanobenzofuran-7-one cage, and compound 5 consists of a hexahydro-2H-2,8-epoxychromene scaffold. The C1-C30 linkage in 1-3 and the C3-C30 connection in 4 form two unprecedented types of ring A/B-fused carbobicyclic cores: viii and ix. The oxidative cleavage of the C2-C3 bond in 5 and heterocyclization in 4 and 5 constitute the unprecedented tricyclic 6/6/5 ring A/B(1) /B(2) - and 6/5/6 ring A(1) A(2) /B-fused topologies, respectively, which are uncovered, for the first time, in the construction of limonoid architectures. The diverse cyclization patterns of 1-6 reveal an unparalleled structural plasticity of rings A and B in limonoid biosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence of polycyclic aromatic hydrocarbon biodegradation in a contaminated aquifer by combined application of in situ and laboratory microcosms using (13)C-labelled target compounds.

PubMed

Bahr, Arne; Fischer, Anko; Vogt, Carsten; Bombach, Petra

2015-02-01

The number of approaches to evaluate the biodegradation of polycyclic aromatic hydrocarbons (PAHs) within contaminated aquifers is limited. Here, we demonstrate the applicability of a novel method based on the combination of in situ and laboratory microcosms using (13)C-labelled PAHs as tracer compounds. The biodegradation of four PAHs (naphthalene, fluorene, phenanthrene, and acenaphthene) was investigated in an oxic aquifer at the site of a former gas plant. In situ biodegradation of naphthalene and fluorene was demonstrated using in situ microcosms (BACTRAP(®)s). BACTRAP(®)s amended with either [(13)C6]-naphthalene or [(13)C5/(13)C6]-fluorene (50:50) were incubated for a period of over two months in two groundwater wells located at the contaminant source and plume fringe, respectively. Amino acids extracted from BACTRAP(®)-grown cells showed significant (13)C-enrichments with (13)C-fractions of up to 30.4% for naphthalene and 3.8% for fluorene, thus providing evidence for the in situ biodegradation and assimilation of those PAHs at the field site. To quantify the mineralisation of PAHs, laboratory microcosms were set up with BACTRAP(®)-grown cells and groundwater. Naphthalene, fluorene, phenanthrene, or acenaphthene were added as (13)C-labelled substrates. (13)C-enrichment of the produced CO2 revealed mineralisation of between 5.9% and 19.7% for fluorene, between 11.1% and 35.1% for acenaphthene, between 14.2% and 33.1% for phenanthrene, and up to 37.0% for naphthalene over a period of 62 days. Observed PAH mineralisation rates ranged between 17 μg L(-1) d(-1) and 1639 μg L(-1) d(-1). The novel approach combining in situ and laboratory microcosms allowed a comprehensive evaluation of PAH biodegradation at the investigated field site, revealing the method's potential for the assessment of PAH degradation within contaminated aquifers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemistry of decomposition of freshwater wetland sedimentary organic material during ramped pyrolysis

NASA Astrophysics Data System (ADS)

Williams, E. K.; Rosenheim, B. E.

2011-12-01

Ramped pyrolysis methodology, such as that used in the programmed-temperature pyrolysis/combustion system (PTP/CS), improves radiocarbon analysis of geologic materials devoid of authigenic carbonate compounds and with low concentrations of extractable authochthonous organic molecules. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves (Rosenheim et al., 2008) and constrained the carbon sequestration potential of suspended sediments in the lower Mississippi River (Roe et al., in review). Although ramped pyrolysis allows for separation of sedimentary organic material based upon relative reactivity, chemical information (i.e. chemical composition of pyrolysis products) is lost during the in-line combustion of pyrolysis products. A first order approximation of ramped pyrolysis/combustion system CO2 evolution, employing a simple Gaussian decomposition routine, has been useful (Rosenheim et al., 2008), but improvements may be possible. First, without prior compound-specific extractions, the molecular composition of sedimentary organic matter is unknown and/or unidentifiable. Second, even if determined as constituents of sedimentary organic material, many organic compounds have unknown or variable decomposition temperatures. Third, mixtures of organic compounds may result in significant chemistry within the pyrolysis reactor, prior to introduction of oxygen along the flow path. Gaussian decomposition of the reaction rate may be too simple to fully explain the combination of these factors. To relate both the radiocarbon age over different temperature intervals and the pyrolysis reaction thermograph (temperature (°C) vs. CO2 evolved (μmol)) obtained from PTP/CS to chemical composition of sedimentary organic material, we present a modeling framework developed based upon the ramped pyrolysis decomposition of simple mixtures of organic compounds (i.e. cellulose, lignin, plant fatty acids, etc.) often found in sedimentary organic material to account for changes in thermograph shape. The decompositions will be compositionally verified by 13C NMR analysis of pyrolysis residues from interrupted reactions. This will allow for constraint of decomposition temperatures of individual compounds as well as chemical reactions between volatilized moieties in mixtures of these compounds. We will apply this framework with 13C NMR analysis of interrupted pyrolysis residues and radiocarbon data from PTP/CS analysis of sedimentary organic material from a freshwater marsh wetland in Barataria Bay, Louisiana. We expect to characterize the bulk chemical composition during pyrolysis and as well as diagenetic changes with depth. Most importantly, we expect to constrain the potential and the limitations of this modeling framework for application to other depositional environments.

Characteristics, sources and evolution of fine aerosol (PM1) at urban, coastal and forest background sites in Lithuania

NASA Astrophysics Data System (ADS)

Masalaite, A.; Holzinger, R.; Remeikis, V.; Röckmann, T.; Dusek, U.

2017-01-01

The chemical and isotopic composition of organic aerosol (OA) samples collected on PM1 filters was determined as a function of desorption temperature to investigate the main sources of organic carbon and the effects of photochemical processing on atmospheric aerosol. The filter samples were collected at an urban (54°38‧ N, 25°18‧ E), coastal (55°55‧ N, 21°00‧ E) and forest (55°27‧ N, 26°00' E) site in Lithuania in March 2013. They can be interpreted as winter-time samples because the monthly averaged temperature was -4 °C. The detailed chemical composition of organic compounds was analysed with a thermal desorption PTR-MS. The mass concentration of organic aerosol at the forest site was roughly by a factor of 30 lower than at the urban and coastal site. This fact could be an indication that in this cold month the biogenic secondary organic aerosol (SOA) formation was very low. Moreover, the organic aerosol collected at the forest site was more refractory and contained a larger fraction of heavy molecules with m/z > 200. The isotopic composition of the aerosol was used to differentiate the two main sources of organic aerosol in winter, i.e. biomass burning (BB) and fossil fuel (FF) combustion. Organic aerosol from biomass burning is enriched in 13C compared to OA from fossil fuel emissions. δ13COC values of the OA samples showed a positive correlation with the mass fraction of several individual organic compounds. Most of these organic compounds contained nitrogen indicating that organic nitrogen compounds formed during the combustion of biomass may be indicative of BB. Other compounds that showed negative correlations with δ13COC were possibly indicative of FF. These compounds included heavy hydrocarbons and were on the average less oxidized than the bulk organic carbon. The correlation of δ13COC and the O/C ratio was positive at low but negative at high desorption temperatures at the forest site. We propose that this might be due to photochemical processing of OA. This processing can lead to accumulation of carbon in the more refractory organic fraction that is depleted in 13C compared with the less refractory organic fraction. Detailed laboratory experiments are necessary to further investigate the aging of aerosol particles before firm conclusions can be drawn.

2D-NMR (HSQC) difference spectra between specifically 13C-enriched and unenriched protolignin of Ginkgo biloba obtained in the solution state of whole cell wall material

Treesearch

Noritsugu Terashima; Takuya Akiyama; Sally Ralph; Dmitry Evtuguin; Carlos Neto Pascoal; Jim Parkas; Magnus Paulsson; Ulla Westermark; John Ralph

2009-01-01

In the structural analysis of lignins by 13C-NMR, signal overlap limits definitive assignment and accurate intensity measurement. Selective labeling by 13C-enrichment of a specific carbon in lignin enhances its signal intensity in the spectrum. Further enhancement of the specifically labeled carbons can be realized via...

Synthesis, X-ray Single Crystal Structure, Molecular Docking and DFT Computations on N-[(1E)-1-(2H-1,3-Benzodioxol-5-yl)-3-(1H-imidazol-1-yl)propylidene]-hydroxylamine: A New Potential Antifungal Agent Precursor.

PubMed

Al-Wabli, Reem I; Al-Ghamdi, Alwah R; Ghabbour, Hazem A; Al-Agamy, Mohamed H; Monicka, James Clemy; Joe, Issac Hubert; Attia, Mohamed I

2017-02-28

Mycoses are serious health problem, especially in immunocompromised individuals. A new imidazole-bearing compound containing an oxime functionality was synthesized and characterized with different spectroscopic techniques to be used for the preparation of new antifungal agents. The stereochemistry of the oxime double bond was unequivocally determined via the single crystal X-ray technique. The title compound 4 , C 13 H 13 N₃O₃·C₃H₈O, crystallizes in the monoclinic space group P 2₁with a = 9.0963(3) Å, b = 14.7244(6) Å, c = 10.7035(4) Å, β = 94.298 (3)°, V = 1429.57(9) ų, Z = 2. The molecules were packed in the crystal structure by eight intermolecular hydrogen bond interactions. A comprehensive spectral analysis of the title molecule 4 has been performed based on the scaled quantum mechanical (SQM) force field obtained by density-functional theory (DFT) calculations. A molecular docking study illustrated the binding mode of the title compound 4 into its target protein. The preliminary antifungal activity of the title compound 4 was determined using a broth microdilution assay.

Analytical pyrolysis and stable isotope analyses reveal past environmental changes in coralloid speleothems from Easter Island (Chile).

PubMed

Miller, Ana Z; De la Rosa, José M; Jiménez-Morillo, Nicasio T; Pereira, Manuel F C; González-Pérez, José A; Calaforra, José M; Saiz-Jimenez, Cesareo

2016-08-26

This study comprises an innovative approach based on the combination of chromatography (analytical pyrolysis and pyrolysis compound-specific isotope analysis (Py-CSIA)), light stable isotopes, microscopy and mineralogy analyses to characterize the internal layering of coralloid speleothems from the Ana Heva lava tube in Easter Island (Chile). This multidisciplinary proxy showed that the speleothems consist of banded siliceous materials of low crystallinity with different mineralogical compositions and a significant contribution of organic carbon. Opal-A constitutes the outermost grey layer of the coralloids, whereas calcite and amorphous Mg hydrate silicate are the major components of the inner whitish and honey-brown layers, respectively. The differences found in the mineralogical, elemental, molecular and isotopic composition of these distinct coloured layers are related to environmental changes during speleothem development. Stable isotopes and analytical pyrolysis suggested alterations in the water regime, pointing to wetter conditions during the formation of the Ca-rich layer and a possible increase in the amount of water dripping into the cave. The trend observed for δ(15)N values suggested an increase in the average temperature over time, which is consistent with the so-called climate warming during the Holocene. The pyrolysis compound-specific isotope analysis of each speleothem layer showed a similar trend with the bulk δ(13)C values pointing to the appropriateness of direct Py-CSIA in paleoenvironmental studies. The δ(13)C values for n-alkanes reinforced the occurrence of a drastic environmental change, indicating that the outermost Opal layer was developed under drier and more arid environmental conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Profiling of Volatile Compounds and Associated Gene Expression and Enzyme Activity during Fruit Development in Two Cucumber Cultivars

PubMed Central

Chen, Shuxia; Zhang, Ranran; Hao, Lining; Chen, Weifeng; Cheng, Siqiong

2015-01-01

Changes in volatile content, as well as associated gene expression and enzyme activity in developing cucumber fruits were investigated in two Cucumis sativus L. lines (No. 26 and No. 14) that differ significantly in fruit flavor. Total volatile, six-carbon (C6) aldehyde, linolenic and linoleic acid content were higher during the early stages, whereas the nine-carbon (C9) aldehyde content was higher during the latter stages in both lines. Expression of C. sativus hydroperoxide lyase (CsHPL) mirrored 13-hydroperoxide lyase (13-HPL) enzyme activity in variety No. 26, whereas CsHPL expression was correlated with 9-hydroperoxide lyase (9-HPL) enzyme activity in cultivar No. 14. 13-HPL activity decreased significantly, while LOX (lipoxygenase) and 9-HPL activity increased along with fruit ripening in both lines, which accounted for the higher C6 and C9 aldehyde content at 0-6 day post anthesis (dpa) and 9-12 dpa, respectively. Volatile compounds from fruits at five developmental stages were analyzed by principal component analysis (PCA), and heatmaps of volatile content, gene expression and enzyme activity were constructed. PMID:25799542

Mechanism studies of the conversion of 13C-labeled n-butane on zeolite H-ZSM-5 by using 13C magic angle spinning NMR spectroscopy and GC-MS analysis.

PubMed

Luzgin, Mikhail V; Stepanov, Alexander G; Arzumanov, Sergei S; Rogov, Vladimir A; Parmon, Valentin N; Wang, Wei; Hunger, Michael; Freude, Dieter

2005-12-23

By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.

Process for producing phenolic compounds from lignins

DOEpatents

Agblevor, F.A.

1998-09-15

A process is described for the production of low molecular weight phenolic compounds from lignins through the pyrolysis of the lignins in the presence of a strong base. In a preferred embodiment, potassium hydroxide is present in an amount of from about 0.1% to about 5% by weight, the pyrolysis temperature is from about 400 C to about 600 C at atmospheric pressure, and the time period for substantial completion of the reaction is from about 1--3 minutes. Examples of low molecular weight phenolic compounds produced include methoxyphenols, non-methoxylated phenols, and mixtures thereof. 16 figs.

Stable carbon isotope ratios of low molecular weight dicarboxylic acids, ketoacids and glyoxal in marine aerosols from the western North Pacific: Long-term trends in Chichijima Island

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.

2012-12-01

Dicarboxylic acids such as oxalic, malonic and succinic acids are the most abundant water-soluble organic compound class in aerosols. To better understand the source and photochemical processes of water-soluble organic aerosols in the remote marine aerosols, we measured stable carbon isotopic composition (δ13C) of dicarboxylic acids and related compounds using a GC/IR/MS technique. The aerosol samples were collected in 2001-2011 at a remote island, Chichijima (27°04'E; 142°13'N) in the western North Pacific. Here we present decadal variations of the isotopic composition of dicarboxylic acids (C2-C9), ketoacids (C2-C8) and glyoxal in summertime aerosols (June, July and August). The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids. Oxalic acid showed higher δ13C values than other species ranging from -18‰ to -2‰ with no clear decadal trend. In contrast, C3 and C4 diacids showed δ13C values of -24 to -5‰ and -40 to -12‰ with a decadal decline. Glyoxal (-60 to -10‰) and ωC7 acid (-34 to -12‰) also showed lower values toward 2011. However, azelaic acid (C9) (-32 to -24‰) stayed relatively constant throughout the observation period. We will discuss the detailed isotopic compositions of these organic species in terms of the photochemical aging and processing in the western North Pacific and the changes in the sources and source regions.

Isotopic and molecular distributions of biochemicals from fresh and buried Rhizophora mangle leaves†

PubMed Central

Smallwood, Barbara J; Wooller, Matthew J; Jacobson, Myrna E; Fogel, Marilyn L

2003-01-01

Rhizophora mangle L. (red mangrove) is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ) red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m). These height differences are coupled with very different stable carbon and nitrogen isotopic values[1] (mean tall δ13C = -28.3‰, δ15N = 0‰; mean tall δ13C = -25.3‰, δ15N = -10‰). To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ13C and δ15N) composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds) in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ13C and δ15N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ13C and δ15N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ15N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in mangrove paleoecosystems.

13C-Breath Tests for Sucrose Digestion in Congenital Sucrase Isomaltase Deficient and Sacrosidase Supplemented Patients

PubMed Central

Robayo-Torres, Claudia C.; Opekun, Antone R.; Quezada-Calvillo, Roberto; Xavier, Villa; Smith, E. O’Brian; Navarrete, Marilyn; Baker, S. Susan; Nichols, Buford L

2008-01-01

Congenital sucrase-isomaltase deficiency (CSID) is characterized by absence or deficiency of the mucosal sucrase-isomaltase enzyme. Specific diagnosis requires upper gastrointestinal biopsy with evidence of low to absent sucrase enzyme activity and normal histology. The hydrogen breath test (BT) is useful but is not specific for confirmation of CSID. We investigated a more specific 13C-sucrose labeled BT. Objectives were to determine if CSID can be detected with the 13C-sucrose BT without duodenal biopsy sucrase assay and if the 13C-sucrose BT can document restoration of sucrose digestion by CSID patients after oral supplementation with sacrosidase (Sucraid®). Methods Ten CSID patients were diagnosed by low biopsy sucrase activity. Ten controls were children who underwent endoscopy and biopsy because of dyspepsia or chronic diarrhea with normal mucosal enzymes activity and histology. Uniformly-labeled 13C-glucose and 13C-sucrose loads were orally administered. 13CO2 breath enrichments were assayed using an infrared spectrophotometer. In CSID patients the 13C-sucrose load was repeated adding Sucraid®. Sucrose digestion and oxidation were calculated as a mean % coefficient of glucose oxidation (% CGO) averaged between 30 and 90 minutes. Results Classification of patients by 13C-sucrose BT % CGO agreed with biopsy sucrase activity. The breath test also documented the return to normal of sucrose digestion and oxidation after supplementation of CSID patients with Sucraid®. Conclusion 13C-sucrose BT is an accurate and specific non-invasive confirmatory test for CSID and for enzyme replacement management. PMID:19330928

Measuring and modeling C flux rates through the central metabolic pathways in microbial communities using position-specific 13C-labeled tracers

NASA Astrophysics Data System (ADS)

Dijkstra, P.; van Groenigen, K.; Hagerty, S.; Salpas, E.; Fairbanks, D. E.; Hungate, B. A.; KOCH, G. W.; Schwartz, E.

2012-12-01

The production of energy and metabolic precursors occurs in well-known processes such as glycolysis and Krebs cycle. We use position-specific 13C-labeled metabolic tracers, combined with models of microbial metabolic organization, to analyze the response of microbial community energy production, biosynthesis, and C use efficiency (CUE) in soils, decomposing litter, and aquatic communities. The method consists of adding position-specific 13C -labeled metabolic tracers to parallel soil incubations, in this case 1-13C and 2,3-13C pyruvate and 1-13C and U-13C glucose. The measurement of CO2 released from the labeled tracers is used to calculate the C flux rates through the various metabolic pathways. A simplified metabolic model consisting of 23 reactions is solved using results of the metabolic tracer experiments and assumptions of microbial precursor demand. This new method enables direct estimation of fundamental aspects of microbial energy production, CUE, and soil organic matter formation in relatively undisturbed microbial communities. We will present results showing the range of metabolic patterns observed in these communities and discuss results from testing metabolic models.

Antiprotozoal activity of extracts and isolated triterpenoids of 'carnauba' (Copernicia prunifera) wax from Brazil.

PubMed

de Almeida, Buana C; Araújo, Bruno Q; Carvalho, Adonias A; Freitas, Sâmya Danielle L; Maciel, Dayany da S Alves; Ferreira, Ari José S; Tempone, Andre G; Martins, Ligia F; Alexandre, Tatiana R; Chaves, Mariana H; Lago, João Henrique G

2016-12-01

'Carnauba' wax is a natural product obtained from the processing of the powder exuded from Copernicia prunifera (Miller) H. E. Moore (Arecaceae). This material is widely used in the Brazilian folk medicine, including the treatment of rheumatism and syphilis. To investigate the antiprotozoal activity of hexane and EtOH extracts from the 'carnauba' wax as well as from the isolated compounds from the bioactive extracts. Two different samples of 'carnauba' (C. prunifera) waxes - types 1 and 4 - were individually extracted using hexane (EH) and EtOH (EE). Aliquots of hexane (type 1 - EH-1 and EH-4) and EtOH (type 4 - EE-1 and EE-4) extracts were tested against promastigote (2-200 μg/mL in DMSO during 48 h at 24 °C) and amastigote (3-150 μg/mL in DMSO during 120 h at 37 °C) forms of Leishmania infantum as well as against trypomastigote (3-150 μg/mL in DMSO during 24 h at 37 °C) forms of Trypanosoma cruzi. Bioactive extracts EH-1 and EE-4 were subjected to a bioactivity-guided fractionation to afford three dammarane-type triterpenoids (1-3). The in vitro antiprotozoal activities of the obtained compounds were evaluated as described above. Additionally, the cytotoxicity activity of compounds 1-3 against mammalian conjunctive cells (NCTC - 2-200 μg/mL in DMSO during 48 h at 37 °C) was determined. From the bioactive hexane and EtOH extracts from the 'carnauba' (C. prunifera) wax, were isolated three dammarane-type triterpenoids: (24R*)-methyldammar-25-ene-3β,20-diol (carnaubadiol, 1), (24R*)-methyldammara-20,25-dien-3-one (2) and (24R*)-methyldammara-20,25-dien-3α-ol (3). These compounds were identified based on the analysis of NMR and MS spectroscopic data. Compounds 1-3 were effective against the intracellular amastigotes of L. infantum, with IC 50 values ranging from 8 to 52 μM, while compounds 1 and 3 displayed activity against trypomastigote forms of T. cruzi with IC 50 values of 15 and 35 μM, respectively. The mammalian cytotoxicity assay demonstrated no damage to NCTC conjunctive cells up to 200 μM, except for compound 1, which demonstrated a CC 50 value of 34 μM. Based on the results, it was possible to conclude that the detected antiprotozoal bioactivity of 'carnauba' (C. prunifera) wax extracts could be related to the presence of the natural dammarane triterpenoid derivatives. The results suggested that these compounds could be used as promising scaffolds for drug design studies for leishmaniasis and Chagas disease.

Carbon stable isotope (δ13C) and elemental (TOC, TN, C/N) geochemistry in salt marsh surface sediments (Western Brittany, France): Adequate proxies for relative sea-level reconstruction?

NASA Astrophysics Data System (ADS)

Goslin, Jerome; Sans-jofre, Pierre; Van Vliet Lanoë, Brigitte; Delacourt, Christophe

2017-04-01

Reconstructing a dense network of precise and reliable records of Holocene relative sea-level (RSL) changes is still a major challenge for the paleo climate scientific community. In some regions, the use of traditional foraminifera-based transfer function is prevented by micro-fauna scarcity (e.g. Stéphan et al., 2014, Goslin et al., 2015), thus fostering the need for alternative proxies to be developed and used. Rather recently, isotopic and elemental geochemistry tools have been shown to form promising alternative proxies for RSL reconstruction (e.g. Wilson et al., 2005, Engelhart et al., 2013, Khan et al., 2015). Questions remain nonetheless open regarding the possibility for such markers to allow (i) distinguishing between freshwater and brackish to marine domains (this condition being needed if RSL index-points are to be derived from sedimentary markers) and (ii) to adequately identify the source of the organic matter preserved in the sediment. Concerns about the preservation of carbon and nitrogen compounds during diagenesis have also arose questioning the reliability of such markers for paleo-environmental reconstruction purposes (Wilson et al., 2005; Lamb et al., 2006). We analyzed stable carbon isotope ratios (δ13C), Total Organic Carbon (TOC), and Total Nitrogen (TN) values within 94 surface sediments sampled across two C-3 plants dominated saltmarshes (Brittany, France). The distributions of δ13C, TOC, TN and C/N values is observed to follow clear and strong elevation-dependent trends. Some slight local variability appears between the studied sites that can be easily explained by the different morphological configuration and functioning of these latter. An indicator is found that allows sediments from below and above the high-tide level to be discriminated. This finding forms an interesting advance in the field as it permits to ensure that samples formed under saline conditions and thus suggests that these can be used as stand-alone proxies for RSL reconstruction. This dataset is then used as a modern referential for Holocene RSL reconstruction. Statistical clustering analyses, conducted on the combined regional dataset allow for the identification of several intertidal elevation-dependent groups, characterized by specific values of δ13C, TOC, and TN. Our study thus confirm that δ13C, TOC, TN can act as direct RSL indicators in the context of C-3 plants dominated salt-marshes. Nonetheless, potential preservation issues are observed for the nitrogen compounds within the ancient sediments that deposited in the upper-tidal domain. This eventually challenges the reliable positioning of these latter on the former tidal frame, and thus introduces some uncertainty in the RSL positions that can be derived from them.

Silent information regulator 1 modulator resveratrol increases brain lactate production and inhibits mitochondrial metabolism, whereas SRT1720 increases oxidative metabolism.

PubMed

Rowlands, Benjamin D; Lau, Chew Ling; Ryall, James G; Thomas, Donald S; Klugmann, Matthias; Beart, Philip M; Rae, Caroline D

2015-07-01

Silent information regulators (SIRTs) have been shown to deacetylate a range of metabolic enzymes, including those in glycolysis and the Krebs cycle, and thus alter their activity. SIRTs require NAD(+) for their activity, linking cellular energy status to enzyme activity. To examine the impact of SIRT1 modulation on oxidative metabolism, this study tests the effect of ligands that are either SIRT-activating compounds (resveratrol and SRT1720) or SIRT inhibitors (EX527) on the metabolism of (13)C-enriched substrates by guinea pig brain cortical tissue slices with (13)C and (1)H nuclear magnetic resonance spectroscopy. Resveratrol increased lactate labeling but decreased incorporation of (13)C into Krebs cycle intermediates, consistent with effects on AMPK and inhibition of the F0/F1-ATPase. By testing with resveratrol that was directly applied to astrocytes with a Seahorse analyzer, increased glycolytic shift and increased mitochondrial proton leak resulting from interactions of resveratrol with the mitochondrial electron transport chain were revealed. SRT1720, by contrast, stimulated incorporation of (13)C into Krebs cycle intermediates and reduced incorporation into lactate, although the inhibitor EX527 paradoxically also increased Krebs cycle (13)C incorporation. In summary, the various SIRT1 modulators show distinct acute effects on oxidative metabolism. The strong effects of resveratrol on the mitochondrial respiratory chain and on glycolysis suggest that caution should be used in attempts to increase bioavailability of this compound in the CNS. © 2015 Wiley Periodicals, Inc.

Production of rosamicin derivatives in Micromonospora rosaria by introduction of D-mycinose biosynthetic gene with PhiC31-derived integration vector pSET152.

PubMed

Anzai, Yojiro; Iizaka, Yohei; Li, Wei; Idemoto, Naoki; Tsukada, Shu-ichi; Koike, Kazuo; Kinoshita, Kenji; Kato, Fumio

2009-08-01

Some of the polyketide-derived bioactive compounds contain sugars attached to the aglycone core, and these sugars often impart specific biological activity to the molecule or enhance this activity. Mycinamicin II, a 16-member macrolide antibiotic produced by Micromonospora griseorubida A11725, contains a branched lactone and two different deoxyhexose sugars, D-desosamine and D-mycinose, at the C-5 and C-21 positions, respectively. The D-mycinose biosynthesis genes, mycCI, mycCII, mycD, mycE, mycF, mydH, and mydI, present in the M. griseorubida A11725 chromosome were introduced into pSET152 under the regulation of the promoter of the apramycin-resistance gene aac(3)IV. The resulting plasmid pSETmycinose was introduced into Micromonospora rosaria IFO13697 cells, which produce the 16-membered macrolide antibiotic rosamicin containing a branched lactone and D-desosamine at the C-5 position. Although the M. rosaria TPMA0001 transconjugant exhibited low rosamicin productivity, two new compounds, IZI and IZII, were detected in the ethylacetate extract from the culture broth. IZI was identified as a mycinosyl rosamicin derivative, 23-O-mycinosyl-20-deoxo-20-dihydro-12,13-deepoxyrosamicin (MW 741), which has previously been synthesized by a bioconversion technique. This is the first report on production of mycinosyl rosamicin-derivatives by a engineered biosynthesis approach. The integration site PhiC31attB was identified on M. rosaria IFO13697 chromosome, and the site lay within an ORF coding a pirin homolog protein. The pSETmycinose could be useful for stimulating the production of "unnatural" natural mycinosyl compounds by various actinomycete strains using the bacteriophage PhiC31 att/int system.

Beckmann rearrangement within the ring C of oleanolic acid lactone: Synthesis, structural study and reaction mechanism analysis

NASA Astrophysics Data System (ADS)

Froelich, Anna; Bednarczyk-Cwynar, Barbara; Zaprutko, Lucjusz; Gzella, Andrzej

2017-05-01

Synthesis, spectral and X-ray analysis of three compounds, i.e. 3β-acetoxy-12-hydroxyimino-18β-oleanan-28,13β-olide (substrate) and 3β-acetoxy-12-nitrile-12,13-seco-15(14 → 13)-abeoolean-14(27)-en-28,13β-olide and 3β-acetoxy-12-oxo-12a-aza-C-homoolean-13(18)-en-28-oic acid (Beckmann rearrangement reaction products) are described. Structural analysis revealed that the oxime group in the ring C in substrate molecule had an E-configuration. The nitrile product with retained lactone group was a result of major transformations within rings C and D of oleanane skeleton. In lactam product free carboxyl group and a double bond in ring D instead of lactone system were formed in Beckmann rearrangement reaction.

A fluorometric determination of urinary 17-hydroxycorticosteroids using benzamidine.

PubMed

Yamaguchi, Y; Seki, T

1984-10-01

A fluorometric determination of urinary 17-hydroxycorticosteroids using a reaction of benzamidine with compounds carrying the dihydroxyacetone side chain is described. The fluorescent compounds have excitation and emission maxima at 370 and 480 nm, respectively. The method includes enzymatic hydrolysis with beta-glucuronidase (EC 3.2.1.31, from Escherichia coli) and extraction with methylene chloride and generation of fluorescence in alkaline solution (pH 13.4). The specificity of the reaction was examined and the results were compared with those of an accepted method based on the Porter-Silber reaction (C. C. Porter and R. H. Silber, 1950, J. Biol. Chem. 185, 201-207). The coefficient of correlation was 0.945 with regression line of y = 0.91x + 0.7 mg/day (y, present method; x, Porter-Silber reaction method). Sensitivity of the reaction was 0.5 microgram/ml of standard or sample, mean recovery of cortisol added to five urine samples (5-micrograms addition) was 95%, and the coefficient of variation of the method (five repeated assays of sample with a value of 5.2 mg/liter) was 6.2%.

Terpenoids from Curcuma wenyujin increased glucose consumption on HepG2 cells.

PubMed

Zhou, Chang-Xin; Zhang, Li-Sha; Chen, Fei-Fei; Wu, Hao-Shu; Mo, Jian-Xia; Gan, Li-She

2017-09-01

Thirty four terpenoids, including two new cadinane-type sesquiterpenoids containing conjugated aromatic-ketone moieties, curcujinone A (1) and curcujinone B (2), were isolated from 95% ethanol extract of the root tubers of Curcuma wenyujin. Their structures were determined by spectroscopic methods, especially 2D NMR and HRMS techniques. The relative and absolute configurations of 1 and 2 were identified by quantum chemical DFT and TDDFT calculations of the 13 C NMR chemical shifts, ECD spectra, and specific optical rotations. All compounds and extracts were evaluated for their anti-diabetic activities with a glucose consumption model on HepG2 Cells. The petroleum fraction CWP (10μg/mL) and compounds curcumenol (4), 7α,11α-epoxy-5β-hydroxy-9-guaiaen-8-one (5), curdione (17), (1S, 4S, 5S 10S)-germacrone (18), zederone (20), a mixture of curcumanolide A (25) and curcumanolide B (26), gajutsulactone B (27), and wenyujinin C (30) showed promising activities with over 45% increasing of glucose consumption at 10μM. Copyright © 2017. Published by Elsevier B.V.

Site-Specific Carbon Isotopes in Organics

NASA Astrophysics Data System (ADS)

Piasecki, A.; Eiler, J. M.

2012-12-01

Natural organic molecules exhibit a wide range of internal site-specific isotope variation (i.e., molecules with same isotopic substitution type but different site). Such variations are generally unconstrained by bulk isotopic measurements. If known, site-specific variations might constrain temperatures of equilibrium, mechanisms of formation or consumption reactions, and possibly other details. For example, lipids can exhibit carbon isotope differences of up to 30‰ between adjacent carbon sites as a result of fractionations arising during decarboxylation of pyruvate and other steps in lipid biosynthesis(1). We present a method for site-specific carbon isotope analysis of propane, based on high-resolution, multi-collector gas source mass spectrometry, using a novel prototype instrument - the Thermo MAT 253 Ultra. This machine has an inlet system and electron bombardment ion source resembling those in conventional stable isotope gas source mass spectrometers, and the energy filter, magnet, and detector array resembling those in multi-collector ICPMS and TIMS. The detector array has 7 detector positions, 6 of which are movable, and each of which can collect ions with either a faraday cup (read through amplifiers ranging from 107-1012 ohms) or an SEM. High mass resolving power (up to 27,000, MRP = M/dM definition) is achieved through a narrow entrance slit, adjustable from 250 to 5 μm. Such resolution can cleanly separate isobaric interferences between isotopologues of organic molecules having the same cardinal mass (e.g., 13CH3 and 12CH2D). We use this technology to analyze the isotopologues and fragments of propane, and use such data to solve for the site-specific carbon isotope fractionation. By measuring isotopologues of both the one-carbon (13CH3) and the two-carbon (13C12CH4) fragment ion, we can solve for both bulk δ13C and the difference in δ13C between the terminal and central carbon position. We tested this method by analyzing mixtures between natural propane and labeled propane (13CH3-12CH2-12CH3). Results are consistent with the expected relative fractionations between the two fragments, indicating limited 'scrambling' of carbon positions of less than 2% in the source. The limits of precision of this method are currently ~0.5 ‰, sufficient to resolve known or suspected position-specific isotope effects in propane. We have explored the expected temperature-dependent equilibrium isotopic distributions of propane using density functional theory and quantum mechanical models of vibrational isotope effects. These models predict the homogeneous isotope exchange equilibria among the various isotopologues of propane, which include several of a wide range of effects that should be measurable by our methods. At 300 K we predict that the central carbon site is 15‰ higher in δ13C and 95 ‰ higher in δD than the terminal carbon site; similarly the molecule containing both a 13C and D in the central site is enriched by ~120 ‰ relative to a random isotopic distribution at 300 K. These predictions present targets for future experimental and empirical studies of the temperature dependence of isotopic ordering in propane. More generally, the methods we are developing for the study of intramolecular isotopic distributions in propane will serve as a model for future study of similar effects in other organic compounds. [1]DeNiro, Epstein (1977) Science Volume 197, 261-263.

Degradation and environmental risk of surfactants after the application of compost sludge to the soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonzalez, M.M.; Martin, J.; Camacho-Munoz, D.

2012-07-15

Highlights: Black-Right-Pointing-Pointer Degradation of surfactants in soil amended with sewage sludge during 100 days. Black-Right-Pointing-Pointer Temperature influences on the degradation of the studied compounds. Black-Right-Pointing-Pointer Overall, the LAS degradation is faster than the NP compounds degradation. Black-Right-Pointing-Pointer Therefore, the LAS presented lower environmental risk than the NP compounds. - Abstract: In this work, the degradation of anionic and non-ionic surfactants in agricultural soil amended with sewage sludge is reported. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10-13 carbon alkylic chain, and nonylphenolic compounds (NPE), including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EOmore » and NP2EO). The degradation studies were carried out under winter (12.7 Degree-Sign C) and summer (22.4 Degree-Sign C) conditions in Andalusia region. The concentration of LAS was reduced to 2% of the initial concentration 100 day after sludge-application to the soil. The half-life time measured for LAS homologues were ranged between 4 and 14 days at 12.7 Degree-Sign C and between 4 and 7 days at 22.4 Degree-Sign C. With regard to NPE compounds, after 8 and 4 days from the beginning of the experiment at 12.7 and 22.4 Degree-Sign C, respectively, their concentration levels were increased to 6.5 and 13.5 mg/kg dm (dry matter) as consequence of the degradation of nonylphenol polyethoxylates. These concentration levels were reduced to 5% after 63 and 70 days for 12.7 Degree-Sign C and 22.4 Degree-Sign C, respectively. The half-life times measured for NPEs were from 8 to 16 days at 12.7 Degree-Sign C and from 8 to 18 days at 22.4 Degree-Sign C. Environmental risk assessment revealed that for LAS homologues no environment risk could be expected after 7 and 8 days of sludge application to the soil for 22.4 and 12.7 Degree-Sign C, respectively; however, potential toxic effects could be observed for the nonylphenolic compounds during the first 56 days after sludge application to the soil.« less

Trichorenins A-C, Algicidal Tetracyclic Metabolites from the Marine-Alga-Epiphytic Fungus Trichoderma virens Y13-3.

PubMed

Shi, Zhen-Zhen; Miao, Feng-Ping; Fang, Sheng-Tao; Yin, Xiu-Li; Ji, Nai-Yun

2018-04-27

Three novel polyketide-like metabolites, trichorenins A-C (1-3), with a unique tetracyclic carbon skeleton were obtained from the culture of Trichoderma virens Y13-3, an epiphyte of the marine red alga Gracilaria vermiculophylla. Their structures and relative configurations were established by analysis of 1D/2D NMR and MS data, and their absolute configurations were unequivocally assigned by X-ray diffraction and ECD spectra aided by quantum chemical calculations. Compounds 1-3 exhibited potent inhibition against two marine phytoplankton species, Chattonella marina and Karlodinium veneficum.

A protocol for pressurized liquid extraction and processing methods to isolate modern and ancient bone cholesterol for compound-specific stable isotope analysis.

PubMed

Laffey, Ann O; Krigbaum, John; Zimmerman, Andrew R

2017-02-15

Bone lipid compound-specific isotope analysis (CSIA) and bone collagen and apatite stable isotope ratio analysis are important sources of ecological and paleodietary information. Pressurized liquid extraction (PLE) is quicker and utilizes less solvent than traditional methods of lipid extraction such as soxhlet and ultrasonication. This study facilitates dietary analysis by optimizing and testing a standardized methodology for PLE of bone cholesterol. Modern and archaeological bones were extracted by PLE using varied temperatures, solvent solutions, and sample weights. The efficiency of PLE was assessed via quantification of cholesterol yields. Stable isotopic ratio integrity was evaluated by comparing isotopic signatures (δ 13 C and δ 18 O values) of cholesterol derived from whole bone, bone collagen and bone apatite. Gas chromatography/mass spectrometry (GC/MS) and gas chromatography isotope ratio mass spectrometry (GC/IRMS) were conducted on purified collagen and lipid extracts to assess isotopic responses to PLE. Lipid yield was optimized at two PLE extraction cycles of 75 °C using dichloromethane/methanol (2:1 v/v) as a solvent with 0.25-0.75 g bone sample. Following lipid extraction, saponification combined with the derivatization of the neutral fraction using trimethylsilylation yielded nearly twice the cholesterol of non-saponified or non-derivatized samples. It was also found that lipids extracted from purified bone collagen and apatite could be used for cholesterol CSIA. There was no difference in the bulk δ 13 C values of collagen extracted from bone with or without lipid. However, there was a significant depletion in 18 O of bone apatite due to lipid presence or processing. These results should assist sample selection and provide an effective, alternative extraction method for bone cholesterol that may be used for isotopic and paleodietary analysis. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Antitumor Compounds from the Stout Camphor Mushroom Taiwanofungus camphoratus (Higher Basidiomycetes) Spent Culture Broth.

PubMed

Jia, Wei; Bai, Yan-Yan; Zhang, Zhong; Feng, Na; Feng, Jie; Yan, Meng-Qiu; Zhu, Li-Na; Jia, Xin-Cheng; Wang, Ming-Dao; Zhang, Jing-song; Fan, Hua

2015-01-01

A known compound, 5-(hydroxymethyl) furan-2-carbaldehyde, and a novel compound, 3-isobutyl-1-methoxy-4-(4'-(3-methylbut-2-enyloxy)phenyl)-1H-pyrrole-2,5-dione were isolated from spent broth from submerged cultures of Taiwanofungus camphoratus. Their structures were elucidated by nuclear magnetic resonance (1H, 13C, and 2D) and mass spectra. These compounds inhibited the proliferation of K562 and HepG2 tumor cells in vitro.

Structure elucidation of organic compounds from natural sources using 1D and 2D NMR techniques

NASA Astrophysics Data System (ADS)

Topcu, Gulacti; Ulubelen, Ayhan

2007-05-01

In our continuing studies on Lamiaceae family plants including Salvia, Teucrium, Ajuga, Sideritis, Nepeta and Lavandula growing in Anatolia, many terpenoids, consisting of over 50 distinct triterpenoids and steroids, and over 200 diterpenoids, several sesterterpenoids and sesquiterpenoids along with many flavonoids and other phenolic compounds have been isolated. For Salvia species abietanes, for Teucrium and Ajuga species neo-clerodanes for Sideritis species ent-kaurane diterpenes are characteristic while nepetalactones are specific for Nepeta species. In this review article, only some interesting and different type of skeleton having constituents, namely rearranged, nor- or rare diterpenes, isolated from these species will be presented. For structure elucidation of these natural diterpenoids intensive one- and two-dimensional NMR techniques ( 1H, 13C, APT, DEPT, NOE/NOESY, 1H- 1H COSY, HETCOR, COLOC, HMQC/HSQC, HMBC, SINEPT) were used besides mass and some other spectroscopic methods.

Virgatolides A-C, benzannulated spiroketals from the plant endophytic fungus Pestalotiopsis virgatula.

PubMed

Li, Jian; Li, Li; Si, Yikang; Jiang, Xuejun; Guo, Liangdong; Che, Yongsheng

2011-05-20

Virgatolides A-C (1-3), unique metabolites with a 3',4',5',6'-tetrahydrospiro[chroman-2,2'-pyran] core, were isolated from cultures of the plant endophytic fungus Pestalotiopsis virgatula. Compounds 1-3 possess two previously undescribed skeletons originating from a benzannulated 6,6-spiroketal and one (2 and 3) and two (1) γ-lactone units, respectively. The structure of 1 was secured by X-ray crystallography.

One new and six known triterpene xylosides from Cimicifuga racemosa: FT-IR, Raman and NMR studies and DFT calculations

NASA Astrophysics Data System (ADS)

Jamróz, Marta K.; Jamróz, Michał H.; Cz. Dobrowolski, Jan; Gliński, Jan A.; Gleńsk, Michał

One new and six known triterpene xylosides were isolated from Cimicifuga racemosa (black cohosh, Actaea racemosa). The structure of a new compound, designated as isocimipodocarpaside (1), was established to be (24S)-3β-hydroxy-24,25-oxiirane-16,23-dione-9,10-seco-9,19-cyclolanost-1(10),7(8),9(11)-trien 3-O-β-D-xylopyranoside, by means of 1H and 13C NMR, IR and Raman spectroscopies and Mass Spectrometry. The six known compounds are: 23-epi-26-deoxycimicifugoside (2), 23-epi-26-deoxyactein (3), 25-anhydrocimigenol xyloside (4), 23-O-acetylshengmanol xyloside (5), 25-O-acetylcimigenol xyloside (6) and 3'-O-acetylcimicifugoside H-1 (7). On the basis of NMR data supported by DFT calculations of NMR shielding constants of (2), its structure, previously described as 26-deoxycimicifugoside was corrected and determined as 23-epi-26-deoxycimicifugoside. The 13C CPMAS NMR spectra of the studied compounds (1)-(7) provided data on their solid-state interactions. The IR and Raman spectra in the Cdbnd O, Cdbnd C, and Csbnd H stretching vibration regions clearly discriminate different triterpenes found in C. racemosa.

Trivalent metal ions based on inorganic compounds with in vitro inhibitory activity of matrix metalloproteinase 13.

PubMed

Wen, Hanyu; Qin, Yuan; Zhong, Weilong; Li, Cong; Liu, Xiang; Shen, Yehua

2016-10-01

Collagenase-3 (MMP-13) inhibitors have attracted considerable attention in recent years and have been developed as a therapeutic target for a variety of diseases, including cancer. Matrix metalloproteinases (MMPs) can be inhibited by a multitude of compounds, including hydroxamic acids. Studies have shown that materials and compounds containing trivalent metal ions, particularly potassium hexacyanoferrate (III) (K3[Fe(CN)6]), exhibit cdMMP-13 inhibitory potential with a half maximal inhibitory concentration (IC50) of 1.3μM. The target protein was obtained by refolding the recombinant histidine-tagged cdMMP-13 using size exclusion chromatography (SEC). The secondary structures of the refolded cdMMP-13 with or without metal ions were further analyzed via circular dichroism and the results indicate that upon binding with metal ions, an altered structure with increased domain stability was obtained. Furthermore, isothermal titration calorimetry (ITC) experiments demonstrated that K3[Fe(CN)6]is able to bind to MMP-13 and endothelial cell tube formation tests provide further evidence for this interaction to exhibit anti-angiogenesis potential. To the best of our knowledge, no previous report of an inorganic compound featuring a MMP-13 inhibitory activity has ever been reported in the literature. Our results demonstrate that K3[Fe(CN)6] is useful as a new effective and specific inhibitor for cdMMP-13 which may be of great potential for future drug screening applications. Copyright © 2016. Published by Elsevier Inc.

Bursaphelenchus xylophilus is killed by homologues of 2-(1-undecyloxy)-1-ethanol

NASA Astrophysics Data System (ADS)

Kim, Junheon; Lee, Sang-Myeong; Park, Chung Gyoo

2016-07-01

2-(1-Undecyloxy)-1-ethanol, monochamol, is a male-produced aggregation pheromone of the Monochamus species, which are efficient vectors of the pine wood nematode (PWN), Bursaphelenchus xylophilus, which cause devastating damage to pines worldwide. The nematicidal activity of synthetic monochamol and its homologues (ROEtOH: R = C7-C13) were investigated to find potential alternatives to the currently used PWN control agents abamectin and emamectin. Compounds with C7-C13 chain length alkyl groups exhibited 100% nematicidal activity at a concentration of 1000 mg/L. At a concentration of 100 mg/L, 2-(1-nonyloxy)-1-ethanol (C9OEtOH), 2-(1-decyloxy)-1-ethanol (C10OEtOH), 2-(1-undecyloxy)-1-ethanol (C11OEtOH), and 2-(1-dodecyloxy)-1-ethanol (C12OEtOH) showed 100% nematicidal activity, but the others showed weaker activities. C11OEtOH showed similar nematicidal activity to abamectin in terms of LD90 values, which were 13.30 and 12.53 mg/L, respectively. However, C9OEtOH, C10OEtOH, and C12OEtOH (LC90 values: 53.63, 38.18, and 46.68 mg/L, respectively) were less effective than C11OEtOH and abamectin. These results indicate that monochamol could be an effective alternative agent against PWN. The relationship of insecticidal and nematicidal activity to different carbon chain lengths in compounds is discussed.

The Reactivity of Transition Metal-Silicon Compounds

DTIC Science & Technology

1988-08-08

light, and appear to follow both thermal and photochemical pathways. Compounds 9 and 10 are efficient acetylene polymerization catalysts . The scandium...containing both silicon and an early-transition- metal, Previously this field was quite undeveloped, therefore we surveyed a number ( approaches to...15- C5Me5)Ta(SiMe 3)C13 ," J Arnold and T D Tilley, J Am Chem Soc, 107, 6409 (1985) "Tetrahedral Lewis Base Adducts of an Acyl. Preparation and X-ray

29 CFR 1926.55 - Gases, vapors, fumes, dusts, and mists.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Nitrous oxide 10024-97-2 E Octachloronaphthalene 2234-13-1 — 0.1 X Octane 111-65-9 400 1900 — Oil mist... — Uranium (as U) 7440-61-1 Soluble compounds — 0.2 — Insoluble compounds — 0.2 — Vanadium 1314-62-1 Respirable dust (as V2 O5) — (C)0.5 — Fume (as V2 O5) — (C)0.1 — Vegetable oil mist Total dust — — Respirable...

29 CFR 1926.55 - Gases, vapors, fumes, dusts, and mists.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Nitrous oxide 10024-97-2 E Octachloronaphthalene 2234-13-1 — 0.1 X Octane 111-65-9 400 1900 — Oil mist... — Uranium (as U) 7440-61-1 Soluble compounds — 0.2 — Insoluble compounds — 0.2 — Vanadium 1314-62-1 Respirable dust (as V2 O5) — (C)0.5 — Fume (as V2 O5) — (C)0.1 — Vegetable oil mist Total dust — — Respirable...

29 CFR 1915.1000 - Air contaminants.

Code of Federal Regulations, 2012 CFR

2012-07-01

... E Octachloronaphthalene 2234-13-1 — 0.1 X Octane 111-65-9 400 1900 — Oil mist, mineral 8012-95-1 — 5... — Turpentine 8006-64-2 100 560 — Uranium (as U) 7440-61-1 Soluble compounds — 0.2 — Insoluble compounds — 0.2 — Vanadium 1314-62-1 Respirable dust (as V2 O5) — (C)0.5 — Fume (as V2 O5) — (C)0.1 — Vegetable oil mist...

29 CFR 1915.1000 - Air contaminants.

Code of Federal Regulations, 2014 CFR

2014-07-01

... E Octachloronaphthalene 2234-13-1 — 0.1 X Octane 111-65-9 400 1900 — Oil mist, mineral 8012-95-1 — 5... — Turpentine 8006-64-2 100 560 — Uranium (as U) 7440-61-1 Soluble compounds — 0.2 — Insoluble compounds — 0.2 — Vanadium 1314-62-1 Respirable dust (as V2 O5) — (C)0.5 — Fume (as V2 O5) — (C)0.1 — Vegetable oil mist...

29 CFR 1926.55 - Gases, vapors, fumes, dusts, and mists.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Nitrous oxide 10024-97-2 E Octachloronaphthalene 2234-13-1 — 0.1 X Octane 111-65-9 400 1900 — Oil mist... — Uranium (as U) 7440-61-1 Soluble compounds — 0.2 — Insoluble compounds — 0.2 — Vanadium 1314-62-1 Respirable dust (as V2 O5) — (C)0.5 — Fume (as V2 O5) — (C)0.1 — Vegetable oil mist Total dust — — Respirable...

29 CFR 1915.1000 - Air contaminants.

Code of Federal Regulations, 2013 CFR

2013-07-01

... E Octachloronaphthalene 2234-13-1 — 0.1 X Octane 111-65-9 400 1900 — Oil mist, mineral 8012-95-1 — 5... — Turpentine 8006-64-2 100 560 — Uranium (as U) 7440-61-1 Soluble compounds — 0.2 — Insoluble compounds — 0.2 — Vanadium 1314-62-1 Respirable dust (as V2 O5) — (C)0.5 — Fume (as V2 O5) — (C)0.1 — Vegetable oil mist...

Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments

USGS Publications Warehouse

Oremland, R.S.; Whiticar, Michael J.; Strohmaier, F.E.; Kiene, R.P.

1988-01-01

Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12C-enriched values of ??13CH4 (-62 to -86%.), ??13C2H6 (-35 to -55%.) and high ratios (720 to 140,000) of CH4 [C2H6 + C3H8]. Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively. ?? 1988.

Benzene and Naphthalene Degrading Bacterial Communities in an Oil Sands Tailings Pond

PubMed Central

Rochman, Fauziah F.; Sheremet, Andriy; Tamas, Ivica; Saidi-Mehrabad, Alireza; Kim, Joong-Jae; Dong, Xiaoli; Sensen, Christoph W.; Gieg, Lisa M.; Dunfield, Peter F.

2017-01-01

Oil sands process-affected water (OSPW), produced by surface-mining of oil sands in Canada, is alkaline and contains high concentrations of salts, metals, naphthenic acids, and polycyclic aromatic compounds (PAHs). Residual hydrocarbon biodegradation occurs naturally, but little is known about the hydrocarbon-degrading microbial communities present in OSPW. In this study, aerobic oxidation of benzene and naphthalene in the surface layer of an oil sands tailings pond were measured. The potential oxidation rates were 4.3 μmol L−1 OSPW d−1 for benzene and 21.4 μmol L−1 OSPW d−1 for naphthalene. To identify benzene and naphthalene-degrading microbial communities, metagenomics was combined with stable isotope probing (SIP), high-throughput sequencing of 16S rRNA gene amplicons, and isolation of microbial strains. SIP using 13C-benzene and 13C-naphthalene detected strains of the genera Methyloversatilis and Zavarzinia as the main benzene degraders, while strains belonging to the family Chromatiaceae and the genus Thauera were the main naphthalene degraders. Metagenomic analysis revealed a diversity of genes encoding oxygenases active against aromatic compounds. Although these genes apparently belonged to many phylogenetically diverse taxa, only a few of these taxa were predominant in the SIP experiments. This suggested that many members of the community are adapted to consuming other aromatic compounds, or are active only under specific conditions. 16S rRNA gene sequence datasets have been submitted to the Sequence Read Archive (SRA) under accession number SRP109130. The Gold Study and Project submission ID number in Joint Genome Institute IMG/M for the metagenome is Gs0047444 and Gp0055765. PMID:29033909

Long-enduring primary hepatocyte-based co-cultures improve prediction of hepatotoxicity.

PubMed

Novik, Eric I; Dwyer, Jacquelyn; Morelli, James K; Parekh, Amit; Cho, Cheul; Pludwinski, Eitan; Shrirao, Anil; Freedman, Robert M; MacDonald, James S; Jayyosi, Zaid

2017-12-01

The failure of drug candidates during clinical trials and post-marketing withdrawal due to Drug Induced Liver Injury (DILI), results in significant late-stage attrition in the pharmaceutical industry. Animal studies have proven insufficient to definitively predict DILI in the clinic, therefore a variety of in vitro models are being tested in an effort to improve prediction of human hepatotoxicity. The model system described here consists of cryopreserved primary rat, dog or human hepatocytes co-cultured together with a fibroblast cell line, which aids in the hepatocytes' maintenance of more in vivo-like characteristics compared to traditional hepatic mono-cultures, including long term viability and retention of activity of cytochrome P450 isozymes. Cell viability was assessed by measurement of ATP following treatment with 29 compounds having known hepatotoxic liabilities. Hμrelrat™, Hμreldog™, and Hμrelhuman™ hepatic co-cultures were treated for 24h, or under repeat-dosing for 7 or 13days, and compared to rat and human hepatic mono-cultures following single-dose exposure for 24h. The results allowed for a comparison of cytotoxicity, species-specific responses and the effect of repeat compound exposure on the prediction of hepatotoxic potential in each model. Results show that the co-culture model had greater sensitivity compared to that of the hepatic mono-cultures. In addition, "time-based ratios" were determined by dividing the compounds' 24-hour TC 50 /C max values by TC 50 /C max values measured after dosing for either 7 or 13days. The results suggest that this approach may serve as a useful adjunct to traditional measurements of hepatotoxicity, improving the predictive value of early screening studies. Copyright © 2017 Elsevier Inc. All rights reserved.

Structural diversity of anti-pancreatic cancer capsimycins identified in mangrove-derived Streptomyces xiamenensis 318 and post-modification via a novel cytochrome P450 monooxygenase

PubMed Central

Yu, He-Lin; Jiang, Shu-Heng; Bu, Xu-Liang; Wang, Jia-Hua; Weng, Jing-Yi; Yang, Xiao-Mei; He, Kun-Yan; Zhang, Zhi-Gang; Ao, Ping; Xu, Jun; Xu, Min-Juan

2017-01-01

Polycyclic tetramate macrolactams (PTMs) were identified as distinct secondary metabolites of the mangrove-derived Streptomyces xiamenensis 318. Together with three known compounds—ikarugamycin (1), capsimycin (2) and capsimycin B (3)—two new compounds, capsimycin C (4) with trans-diols and capsimycin D (5) with trans-configurations at C-13/C-14, have been identified. The absolute configurations of the tert/tert-diols moiety was determined in 4 by NMR spectroscopic analysis, CD spectral comparisons and semi-synthetic method. The post-modification mechanism of the carbocyclic ring at C-14/C-13 of compound 1 in the biosynthesis of an important intermediate 3 was investigated. A putative cytochrome P450 superfamily gene, SXIM_40690 (ikaD), which was proximally localized to the ikarugamycin biosynthetic pathway, was characterized. In vivo gene inactivation and complementation experiment confirmed that IkaD catalysed the epoxide-ring formation reaction and further hydroxylation of ethyl side chain to form capsimycin G (3′). Binding affinities and kinetic parameters for the interactions between ikarugamycin (1) and capsimycin B (3) with IkaD were measured with Surface Plasmon Resonance. The intermediate compound 3′ was isolated and identified as 30-hydroxyl-capsimycin B. The caspimycins 2 and 3, were transferred to methoxyl derivatives, 6 and 7, under acidic and heating conditions. Compounds 1–3 exhibited anti-proliferative activities against pancreatic carcinoma with IC50 values of 1.30–3.37 μM. PMID:28098172

Synthesis, characterization and antibacterial studies of 2-chloro-5-fluoro-N-[dibenzyl carbamothioyl] benzamide thiourea

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sapari, Suhaila; Yamin, Bohari M.; Hasbullah, Aishah

Synthesis, characterization and antibacterial studies of 2-chloro-5-fluoro-N-[dibenzyl carbamothioyl] benzamide thiourea has been reported. The compound characterized by using elementary analysis CHNS, IR, {sup 1}H NMR and {sup 13}C NMR spectroscopies. The compounds have been screened for their antibacterial studies.

Highly enriched multiply-labeled stable isotopic compounds as atmospheric tracers

DOEpatents

Goldblatt, M.; McInteer, B.B.

1974-01-29

Compounds multiply-labeled with stable isotopes and highly enriched in these isotopes are readily capable of detection in tracer experiments involving high dilutions. Thus, for example, /sup 13/C/sup 18/O/sub 2/ provides a useful tracer for following atmospheric pol lution produced as a result of fossil fuel burning. (Official Gazette)

Absence of a long-range ordered magnetic ground state in Pr3Rh4Sn13 studied through specific heat and inelastic neutron scattering

NASA Astrophysics Data System (ADS)

Nair, Harikrishnan S.; Ogunbunmi, Michael O.; Ghosh, S. K.; Adroja, D. T.; Koza, M. M.; Guidi, T.; Strydom, A. M.

2018-04-01

Signatures of absence of a long-range ordered magnetic ground state down to 0.36 K are observed in magnetic susceptibility, specific heat, thermal/electrical transport and inelastic neutron scattering data of the quasi-skutterudite compound Pr3Rh4Sn13 which crystallizes in the Yb3Rh4Sn13-type structure with a cage-like network of Sn atoms. In this structure, Pr3+ occupies a lattice site with D 2d point symmetry having a ninefold degeneracy corresponding to J  =  4. The magnetic susceptibility of Pr3Rh4Sn13 shows only a weak temperature dependence below 10 K otherwise remaining paramagnetic-like in the range, 10 K-300 K. From the inelastic neutron scattering intensity of Pr3Rh4Sn13 recorded at different temperatures, we identify excitations at 4.5(7) K, 5.42(6) K, 10.77(5) K, 27.27(5) K, 192.28(4) K and 308.33(3) K through a careful peak analysis. However, no signatures of long-range magnetic order are observed in the neutron data down to 1.5 K, which is also confirmed by the specific heat data down to 0.36 K. A broad Schottky-like peak is recovered for the magnetic part of the specific heat, C 4f, which suggests the role of crystal electric fields of Pr3+ . A crystalline electric field model consisting of 7 levels was applied to C 4f which leads to the estimation of energy levels at 4.48(2) K, 6.94(4) K, 11.23(8) K, 27.01(5) K, 193.12(6) K and 367.30(2) K. The CEF energy levels estimated from the heat capacity analysis are in close agreement with the excitation energies seen in the neutron data. The Sommerfeld coefficient estimated from the analysis of magnetic specific heat is γ = 761(6) mJ K-2 mol-Pr which suggests the formation of heavy itinerant quasi-particles in Pr3Rh4Sn13. Combining inelastic neutron scattering results, analysis of the specific heat data down to 0.36 K, magnetic susceptibility and, electrical and thermal transport, we establish the absence of long-range ordered magnetic ground state in Pr3Rh4Sn13.

Total Synthesis of Marine Cyclic Enol-Phosphotriester Salinipostin Compounds

NASA Astrophysics Data System (ADS)

Zhao, Mingliang; Wei, Xianfeng; Liu, Xuemeng; Dong, Xueyang; Yu, Rilei; Wan, Shengbiao; Jiang, Tao

2018-06-01

Due to their structural diversity and variety of biological activities, marine natural products have been the subject of extensive study. These compounds, especially phospholipid polycyclic aromatic hydrocarbons, have a wide range of pharmacological applications, including embedded DNA and central nervous system, anti-tumor, anti-virus, anti-parasite, anti-bacterial, and antithrombotic effects. Unfortunately, the insufficient drug sources have limited the development of these compounds. In this study, we isolated salinpostin compounds from a fermentation solution of marine-derived Salinospora sp., which has a common bicyclic enol-phosphotriester core framework, as well as potent and selective antimalarial activities against P. falciparum with EC50 = 50 nmol L-1. The chemical synthesis of these compounds in greater quantities is necessary for their use in bioactivity studies. Thus we explored a short route with high yields and mild reaction conditions, which can generate combinatorial libraries for drug discovery and lead optimization. We developed a new total synthesis method for six cyclic enol-phosphotriester salinipotin compounds and their diastereomers. For the total synthesis of cyclipostin P, we prepared cyclic enol-phosphotriester salinipostin compounds in 10 steps from a readily accessible starting material, 1,3-dihydroxyacetone, and obtained an overall yield of 1.29%. We fully characterized these compounds by proton nuclear magnetic resonance (1H-NMR), carbon-13 NMR (13C-NMR), and high-resolution mass spectrometry (HRMS) analyses, and found they coincide absolutely with the same compounds reported previously.

Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

NASA Technical Reports Server (NTRS)

Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

2014-01-01

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

Biotransformation of furfural and 5-hydroxymethyl furfural (HMF) by Clostridium acetobutylicum ATCC 824 during butanol fermentation.

PubMed

Zhang, Yan; Han, Bei; Ezeji, Thaddeus Chukwuemeka

2012-02-15

The ability of fermenting microorganisms to tolerate furan aldehyde inhibitors (furfural and 5-hydroxymethyl furfural (HMF)) will enhance efficient bioconversion of lignocellulosic biomass hydrolysates to fuels and chemicals. The effect of furfural and HMF on butanol production by Clostridium acetobutylicum 824 was investigated. Whereas specific growth rates, μ, of C. acetobutylicum in the presence of furfural and HMF were in the range of 15-85% and 23-78%, respectively, of the uninhibited Control, μ increased by 8-15% and 23-38% following exhaustion of furfural and HMF in the bioreactor. Using high performance liquid chromatography and spectrophotometric assays, batch fermentations revealed that furfural and HMF were converted to furfuryl alcohol and 2,5-bis-hydroxymethylfuran, respectively, with specific conversion rates of 2.13g furfural and 0.50g HMF per g (biomass) per hour, by exponentially growing C. acetobutylicum. Biotransformation of these furans to lesser inhibitory compounds by C. acetobutylicum will probably enhance overall fermentation of lignocellulosic hydrolysates to butanol. Copyright © 2011 Elsevier B.V. All rights reserved.

Preparation and structural characterization of corn starch-aroma compound inclusion complexes.

PubMed

Zhang, Shu; Zhou, Yibin; Jin, Shanshan; Meng, Xin; Yang, Liping; Wang, Haisong

2017-01-01

Six corn starch inclusion complexes were synthesized using small nonpolar or weak polar aroma compounds (heptanolide, carvone and menthone) and small polar aroma compounds (linalool, heptanol and menthol). The objectives of this study were to (a) investigate the ability of corn starch to form inclusion complexes with these aroma compounds and (b) characterize the structure of the corn starch inclusion complexes. The resulting inclusion ratios were 75.6, 36.9, 43.8, 91.9, 67.2 and 54.7% for heptanolide, carvone, menthone, linalool, heptanol and menthol respectively. The inclusion complexes had laminated structures with a certain amount of holes or blocky constructions. Compared with gelatinized corn starch, the transition temperatures, peak temperatures and enthalpies of the inclusion complexes were significantly different. The major peak of CO at 1771 cm -1 and significant peak shifts revealed the formation of inclusion complexes. X-ray diffractometry (XRD) analyses revealed that the crystallinity of corn starch-polar aroma compound inclusion complexes increased. Based on cross-polarization magic angle spinning 13 C nuclear magnetic resonance (CP-MAS 13 C NMR) results, novel peaks and chemical shifts were attributed to the presence of small aroma compounds, thereby confirming the formation of corn starch inclusion complexes. Small nonpolar and polar aroma compounds can be complexed to corn starch. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Analysis of the specificity of sialyltransferases toward mucin core 2, globo, and related structures. identification of the sialylation sequence and the effects of sulfate, fucose, methyl, and fluoro substituents of the carbohydrate chain in the biosynthesis of selectin and siglec ligands, and novel sialylation by cloned alpha2,3(O)sialyltransferase.

PubMed

Chandrasekaran, E V; Xue, Jun; Xia, Jie; Chawda, Ram; Piskorz, Conrad; Locke, Robert D; Neelamegham, Sriram; Matta, Khushi L

2005-11-29

Sialic acids are key determinants in many carbohydrates involved in biological recognition. We studied the acceptor specificities of three cloned sialyltransferases (STs) [alpha2,3(N)ST, alpha2,3(O)ST, and alpha2,6(N)ST] and another alpha2,3(O)ST present in prostate cancer cell LNCaP toward mucin core 2 tetrasaccharide [Galbeta1,4GlcNAcbeta1,6(Galbeta1,3)GalNAcalpha-O-Bn] and Globo [Galbeta1,3GalNAcbeta1,3Galalpha-O-Me] structures containing sialyl, fucosyl, sulfo, methyl, or fluoro substituents by identifying the products by electrospray ionization tandem mass spectral analysis and other biochemical methods. The Globo precursor was an efficient acceptor for both alpha2,3(N)ST and alpha2,3(O)ST, whereas only alpha2,3(O)ST used its deoxy analogue (d-Fucbeta1,3GalNAcbeta1,3-Gal-alpha-O-Me); 2-O-MeGalbeta1,3GlcNAc and 4-OMeGalbeta1,4GlcNAc were specific acceptors for alpha2,3(N)ST. Other major findings of this study include: (i) alpha2,3 sialylation of beta1,3Gal in mucin core 2 can proceed even after alpha1,3 fucosylation of beta1,6-linked LacNAc. (ii) Sialylation of beta1,3Gal must precede the sialylation of beta1,4Gal for favorable biosynthesis of mucin core 2 compounds. (iii) alpha2,3 sialylation of the 6-O-sulfoLacNAc moiety in mucin core 2 (e.g., GlyCAM-1) is facilitated when beta1,3Gal has already been alpha2,3 sialylated. (iv) alpha2,6(N)ST was absolutely specific for the beta1,4Gal in mucin core 2. Either alpha1,3 fucosylation or 6-O-sulfation of the GlcNAc moiety reduced the activity. Sialylation of beta1,3Gal in addition to 6-O-sulfation of GlcNAc moiety abolished the activity. (v) Prior alpha2,3 sialylation or 3-O-sulfation of beta1,3Gal would not affect alpha2,6 sialylation of Galbeta1,4GlcNAc of mucin core 2. (vi) A 3- or 4-fluoro substituent in beta1,4Gal resulted in poor acceptors for the cloned alpha2,6(N)ST and alpha2,3(N)ST, whereas 4-fluoro- or 4-OMe-Galbeta1,3GalNAcalpha was a good acceptor for cloned alpha2,3(O)ST. (vii) 4-O-Methylation of beta1,4Gal abolished the acceptor ability toward alpha2,6(N)ST but increased the acceptor efficiency considerably toward alpha2,3(N)ST. (viii) Just like LNCaPalpha1,2-FT and Gal-3-O-sulfotransferase T2, the cloned alpha2,3(N)ST which modifies terminal Gal in Galbeta1,4GlcNAc also efficiently utilizes the terminal beta1,3Gal in the Globo backbone. Utilization of C-3 blocked compounds such as 3-O-sulfo-Galbeta1,3GalNAcbeta1,3Galalpha-OMe as acceptors by cloned alpha2,3(O)ST and analyses of the resulting products by lectin chromatography and mass spectrometry indicate that alpha2,3(O)ST is capable of attaching NeuAc to another position in C-3-substituted beta1,3Gal.

Identification and bioactivity of compounds from the fungus Penicillium sp. CYE-87 isolated from a marine tunicate.

PubMed

Shaala, Lamiaa A; Youssef, Diaa T A

2015-03-25

In the course of our continuous interest in identifying bioactive compounds from marine microbes, we have investigated a tunicate-derived fungus, Penicillium sp. CYE-87. A new compound with the 1,4-diazepane skeleton, terretrione D (2), together with the known compounds, methyl-2-([2-(1H-indol-3-yl)ethyl]carbamoyl)acetate (1), tryptamine (3), indole-3-carbaldehyde (4), 3,6-diisobutylpyrazin-2(1H)-one (5) and terretrione C (6), were isolated from Penicillium sp. CYE-87. The structures of the isolated compounds were established by spectral analysis, including 1D (1H, 13C) and 2D (COSY, multiplicity edited-HSQC and HMBC) NMR and HRESIMS, as well as comparison of their NMR data with those in the literature. The compounds were evaluated for their antimigratory activity against the human breast cancer cell line (MDA-MB-231) and their antiproliferation activity against HeLa cells. Compounds 2 and 6 showed significant antimigratory activity against MDA-MB-231, as well as antifungal activity against C. albicans.

Identification and Bioactivity of Compounds from the Fungus Penicillium sp. CYE-87 Isolated from a Marine Tunicate

PubMed Central

Shaala, Lamiaa A.; Youssef, Diaa T. A.

2015-01-01

In the course of our continuous interest in identifying bioactive compounds from marine microbes, we have investigated a tunicate-derived fungus, Penicillium sp. CYE-87. A new compound with the 1,4-diazepane skeleton, terretrione D (2), together with the known compounds, methyl-2-([2-(1H-indol-3-yl)ethyl]carbamoyl)acetate (1), tryptamine (3), indole-3-carbaldehyde (4), 3,6-diisobutylpyrazin-2(1H)-one (5) and terretrione C (6), were isolated from Penicillium sp. CYE-87. The structures of the isolated compounds were established by spectral analysis, including 1D (1H, 13C) and 2D (COSY, multiplicity edited-HSQC and HMBC) NMR and HRESIMS, as well as comparison of their NMR data with those in the literature. The compounds were evaluated for their antimigratory activity against the human breast cancer cell line (MDA-MB-231) and their antiproliferation activity against HeLa cells. Compounds 2 and 6 showed significant antimigratory activity against MDA-MB-231, as well as antifungal activity against C. albicans. PMID:25815893

Characterization of Imidazopyridine Compounds as Negative Allosteric Modulators of Proton-Sensing GPR4 in Extracellular Acidification-Induced Responses

PubMed Central

Tobo, Ayaka; Tobo, Masayuki; Nakakura, Takashi; Ebara, Masashi; Tomura, Hideaki; Mogi, Chihiro; Im, Dong-Soon; Murata, Naoya; Kuwabara, Atsushi; Ito, Saki; Fukuda, Hayato; Arisawa, Mitsuhiro; Shuto, Satoshi; Nakaya, Michio; Kurose, Hitoshi; Sato, Koichi; Okajima, Fumikazu

2015-01-01

G protein-coupled receptor 4 (GPR4), previously proposed as the receptor for sphingosylphosphorylcholine, has recently been identified as the proton-sensing G protein-coupled receptor (GPCR) coupling to multiple intracellular signaling pathways, including the Gs protein/cAMP and G13 protein/Rho. In the present study, we characterized some imidazopyridine compounds as GPR4 modulators that modify GPR4 receptor function. In the cells that express proton-sensing GPCRs, including GPR4, OGR1, TDAG8, and G2A, extracellular acidification stimulates serum responsive element (SRE)-driven transcriptional activity, which has been shown to reflect Rho activity, with different proton sensitivities. Imidazopyridine compounds inhibited the moderately acidic pH-induced SRE activity only in GPR4-expressing cells. Acidic pH-stimulated cAMP accumulation, mRNA expression of inflammatory genes, and GPR4 internalization within GPR4-expressing cells were all inhibited by the GPR4 modulator. We further compared the inhibition property of the imidazopyridine compound with psychosine, which has been shown to selectively inhibit actions induced by proton-sensing GPCRs, including GPR4. In the GPR4 mutant, in which certain histidine residues were mutated to phenylalanine, proton sensitivity was significantly shifted to the right, and psychosine failed to further inhibit acidic pH-induced SRE activation. On the other hand, the imidazopyridine compound almost completely inhibited acidic pH-induced action in mutant GPR4. We conclude that some imidazopyridine compounds show specificity to GPR4 as negative allosteric modulators with a different action mode from psychosine, an antagonist susceptible to histidine residues, and are useful for characterizing GPR4-mediated acidic pH-induced biological actions. PMID:26070068

Characterization of Imidazopyridine Compounds as Negative Allosteric Modulators of Proton-Sensing GPR4 in Extracellular Acidification-Induced Responses.

PubMed

Tobo, Ayaka; Tobo, Masayuki; Nakakura, Takashi; Ebara, Masashi; Tomura, Hideaki; Mogi, Chihiro; Im, Dong-Soon; Murata, Naoya; Kuwabara, Atsushi; Ito, Saki; Fukuda, Hayato; Arisawa, Mitsuhiro; Shuto, Satoshi; Nakaya, Michio; Kurose, Hitoshi; Sato, Koichi; Okajima, Fumikazu

2015-01-01

G protein-coupled receptor 4 (GPR4), previously proposed as the receptor for sphingosylphosphorylcholine, has recently been identified as the proton-sensing G protein-coupled receptor (GPCR) coupling to multiple intracellular signaling pathways, including the Gs protein/cAMP and G13 protein/Rho. In the present study, we characterized some imidazopyridine compounds as GPR4 modulators that modify GPR4 receptor function. In the cells that express proton-sensing GPCRs, including GPR4, OGR1, TDAG8, and G2A, extracellular acidification stimulates serum responsive element (SRE)-driven transcriptional activity, which has been shown to reflect Rho activity, with different proton sensitivities. Imidazopyridine compounds inhibited the moderately acidic pH-induced SRE activity only in GPR4-expressing cells. Acidic pH-stimulated cAMP accumulation, mRNA expression of inflammatory genes, and GPR4 internalization within GPR4-expressing cells were all inhibited by the GPR4 modulator. We further compared the inhibition property of the imidazopyridine compound with psychosine, which has been shown to selectively inhibit actions induced by proton-sensing GPCRs, including GPR4. In the GPR4 mutant, in which certain histidine residues were mutated to phenylalanine, proton sensitivity was significantly shifted to the right, and psychosine failed to further inhibit acidic pH-induced SRE activation. On the other hand, the imidazopyridine compound almost completely inhibited acidic pH-induced action in mutant GPR4. We conclude that some imidazopyridine compounds show specificity to GPR4 as negative allosteric modulators with a different action mode from psychosine, an antagonist susceptible to histidine residues, and are useful for characterizing GPR4-mediated acidic pH-induced biological actions.

Benzoquinones and terphenyl compounds as phosphodiesterase-4B inhibitors from a fungus of the order Chaetothyriales (MSX 47445).

PubMed

El-Elimat, Tamam; Figueroa, Mario; Raja, Huzefa A; Graf, Tyler N; Adcock, Audrey F; Kroll, David J; Day, Cynthia S; Wani, Mansukh C; Pearce, Cedric J; Oberlies, Nicholas H

2013-03-22

Three bioactive compounds were isolated from an organic extract of an ascomycete fungus of the order Chaetothyriales (MSX 47445) using bioactivity-directed fractionation as part of a search for anticancer leads from filamentous fungi. Of these, two were benzoquinones [betulinan A (1) and betulinan C (3)], and the third was a terphenyl compound, BTH-II0204-207:A (2). The structures were elucidated using a set of spectroscopic and spectrometric techniques; the structure of the new compound (3) was confirmed via single-crystal X-ray diffraction. Compounds 1-3 were evaluated for cytotoxicity against a human cancer cell panel, for antimicrobial activity against Staphylococcus aureus and Candida albicans, and for phosphodiesterase (PDE4B2) inhibitory activities. The putative binding mode of 1-3 with PDE4B2 was examined using a validated docking protocol, and the binding and enzyme inhibitory activities were correlated.

Gersemiols A-C and Eunicellol A, Diterpenoids from the Arctic Soft Coral Gersemia fruticosa.

PubMed

Angulo-Preckler, Carlos; Genta-Jouve, Grégory; Mahajan, Nipun; de la Cruz, Mercedes; de Pedro, Nuria; Reyes, Fernando; Iken, Katrin; Avila, Conxita; Thomas, Olivier P

2016-04-22

Three new diterpenes named gersemiols A-C (1-3) and a new eunicellane diterpene, eunicellol A (4), have been isolated together with the known sesquiterpene (+)-α-muurolene (5) from the Arctic soft coral Gersemia fruticosa. The name gersemiane was assigned to the rare and unnamed diterpene skeleton of compounds 1-3 corresponding to 4-isopropyl-1,5,8a-trimethyltetradecahydrophenanthrene. The chemical structures were elucidated on the basis of extensive spectroscopic analysis (HR-ESIMS, 1D and 2D NMR) as well as coupling constant calculations for the determination of the relative configurations. All compounds were tested for their antimicrobial activity against several bacteria and fungi and eunicellol A was found to exhibit moderate and selective antibacterial activity.

Bismaleimide compounds

DOEpatents

Adams, J.E.; Jamieson, D.R.

1986-01-14

Bismaleimides of the formula shown in the diagram wherein R[sub 1] and R[sub 2] each independently is H, C[sub 1-4]-alkyl, C[sub 1-4]-alkoxy, Cl or Br, or R[sub 1] and R[sub 2] together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R[sub 1] and R[sub 2] are not t-butyl or t-butoxy; X is O, S or Se; n is 1--3; and the alkylene bridging group, optionally, is substituted by 1--3 methyl groups or by fluorine, form polybismaleimide resins which have valuable physical properties. Uniquely, these compounds permit extended cure times, i.e., they remain fluid for a time sufficient to permit the formation of a homogeneous melt prior to curing.

A NMR study of parasitized Tenebrio molitor and Hymenolepis diminuta cysticercoids.

PubMed

Schoen, J; Modha, A; Maslow, K; Novak, M; Blackburn, B J

1996-07-01

In vivo NMR spectra of uninfected and Hymenolepis diminuta-infected Tenebrio molitor fed D-(1-13C)glucose showed that infected beetles of both sexes had a significantly higher ratio for (glycogen C1/lipid (CH2)n) than the corresponding controls. Quantitative metabolic profiles and the per cent 13C-label in metabolites, based on NMR of perchloric acid extracts, are presented for control and infected beetles fed D-(1-13C)glucose and for H. diminuta cysticercoids. Female beetles, both control and infected, contained more glycogen than their male counterparts and infected beetles of both sexes possessed less glycerophos-phocholine, but more glycogen and a higher percentage label in glucose and trehalose than their respective controls. Label was also incorporated into glycogen, succinate, acetate, alanine and lactate. Extracts of cysticercoids from beetles fed D-(1-13C)glucose contained the following labelled compounds, in order of decreasing per cent 13C label: glucose, trehalose, alanine, succinate, lactate, glycogen and acetate. In vitro cultivation experiments, employing D-(1-13C)glucose, revealed that trehalose found in cysticercoids was of parasite, and not beetle, origin.

Solvent-free dry powder coating process for low-cost manufacturing of LiNi1/3Mn1/3Co1/3O2 cathodes in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Al-Shroofy, Mohanad; Zhang, Qinglin; Xu, Jiagang; Chen, Tao; Kaur, Aman Preet; Cheng, Yang-Tse

2017-06-01

We report a solvent-free dry powder coating process for making LiNi1/3Mn1/3Co1/3O2 (NMC) positive electrodes in lithium-ion batteries. This process eliminates volatile organic compound emission and reduces thermal curing time from hours to minutes. A mixture of NMC, carbon black, and poly(vinylidene difluoride) was electrostatically sprayed onto an aluminum current collector, forming a uniformly distributed electrode with controllable thickness and porosity. Charge/discharge cycling of the dry-powder-coated electrodes in lithium-ion half cells yielded a discharge specific capacity of 155 mAh g-1 and capacity retention of 80% for more than 300 cycles when the electrodes were tested between 3.0 and 4.3 V at a rate of C/5. The long-term cycling performance and durability of dry-powder coated electrodes are similar to those made by the conventional wet slurry-based method. This solvent-free dry powder coating process is a potentially lower-cost, higher-throughput, and more environmentally friendly manufacturing process compared with the conventional wet slurry-based electrode manufacturing method.

Biological Degradation of Black Carbon in Temperate Forest Soils: Effects of Clay Mineralogy and Nitrogen Availability

NASA Astrophysics Data System (ADS)

Bird, J. A.; Santos, F.; Torn, M. S.

2008-12-01

A critical knowledge gap in soil organic carbon (SOC) cycling concerns the SOC portion collectively known as pyrogenic C or black carbon (BC), which is a chemically heterogeneous class of highly reduced compounds produced by incomplete combustion. While the stocks of BC are significant in surface soils worldwide, this SOC pool has been considered to be relatively inert with negligible biologically mediated degradation of BC occurring. We will present findings from a laboratory incubation of dual-labeled (13C/15N) BC and its precursor wood (Pinus ponderosa) in two temperate soils (Haploxeralfs) that differ in their clay mineralogy (granitic versus andesitic parent material) and organic C content. In addition, we used N additions in the granitic soil to investigate the effects of N availability on soil and substrate C and N cycling. Sterile controls were used to demonstrate that the BC turnover observed was biotic. The laboratory incubations were carried out at 25°C and at 55% of soil water holding capacity. We are measuring the flux of mineralized 13C in respired CO2, dissolved organic C, soil microbial biomass, specific microbial groups (13C-phospholipid fatty acids) and density-defined soil organic matter fractions. The overall flux of 15N is being observed in the microbial biomass, soluble organic and inorganic pools, and organic matter fractions. We will present rates of biologically-mediated decomposition of BC and its precursor wood, as well as the effects of soil mineralogy and N availability on these rates and on products of decomposition. We will also present decomposition rates of native SOM in incubations with and without substrate to investigate C priming.

ALLocator: an interactive web platform for the analysis of metabolomic LC-ESI-MS datasets, enabling semi-automated, user-revised compound annotation and mass isotopomer ratio analysis.

PubMed

Kessler, Nikolas; Walter, Frederik; Persicke, Marcus; Albaum, Stefan P; Kalinowski, Jörn; Goesmann, Alexander; Niehaus, Karsten; Nattkemper, Tim W

2014-01-01

Adduct formation, fragmentation events and matrix effects impose special challenges to the identification and quantitation of metabolites in LC-ESI-MS datasets. An important step in compound identification is the deconvolution of mass signals. During this processing step, peaks representing adducts, fragments, and isotopologues of the same analyte are allocated to a distinct group, in order to separate peaks from coeluting compounds. From these peak groups, neutral masses and pseudo spectra are derived and used for metabolite identification via mass decomposition and database matching. Quantitation of metabolites is hampered by matrix effects and nonlinear responses in LC-ESI-MS measurements. A common approach to correct for these effects is the addition of a U-13C-labeled internal standard and the calculation of mass isotopomer ratios for each metabolite. Here we present a new web-platform for the analysis of LC-ESI-MS experiments. ALLocator covers the workflow from raw data processing to metabolite identification and mass isotopomer ratio analysis. The integrated processing pipeline for spectra deconvolution "ALLocatorSD" generates pseudo spectra and automatically identifies peaks emerging from the U-13C-labeled internal standard. Information from the latter improves mass decomposition and annotation of neutral losses. ALLocator provides an interactive and dynamic interface to explore and enhance the results in depth. Pseudo spectra of identified metabolites can be stored in user- and method-specific reference lists that can be applied on succeeding datasets. The potential of the software is exemplified in an experiment, in which abundance fold-changes of metabolites of the l-arginine biosynthesis in C. glutamicum type strain ATCC 13032 and l-arginine producing strain ATCC 21831 are compared. Furthermore, the capability for detection and annotation of uncommon large neutral losses is shown by the identification of (γ-)glutamyl dipeptides in the same strains. ALLocator is available online at: https://allocator.cebitec.uni-bielefeld.de. A login is required, but freely available.

[The secondary metabolites of the mangrove endophytic fungi ZZF13 and Guignardia sp. 4382 from the South China Sea].

PubMed

Xia, Xue-kui; Liu, Chang-heng; Yuan, Wen-peng; Wang, Xiao-jun; Meng, Xiu-mei; Zhang, Mian-song; She, Zhi-gang; Lin, Yong-cheng

2009-09-01

The secondary metabolites of the fungus ZZF13 isolated from the leaves of the mangrove sample Kandelia candel in Zhanjiang and Guignardia sp. 4382 isolated from bark of Kandelia candel (endophyte) of Mai Po, Hong Kong were studied. The compounds were isolated by siliga gel, and their structures were identified by IR, MS and NMR. Four compounds were isolated from the culture of this strain. Their structures were identified as Bacillpsporin C (1), 5-carboxymellein (2), 5-methylmellein (3) and 1-(2,6-dihydroxyphenyl) butanone (4). The compounds 2 - 4 are isolated from the Guignardia sp. of Marine fungi for the first time.

Preparation, Crystal Structure, Dielectric Properties, and Magnetic Behavior of Ba 2Fe 2Ti 4O 13

NASA Astrophysics Data System (ADS)

Vanderah, T. A.; Huang, Q.; Wong-Ng, W.; Chakoumakos, B. C.; Goldfarb, R. B.; Geyer, R. G.; Baker-Jarvis, J.; Roth, R. S.; Santoro, A.

1995-11-01

The preparation, crystal structure, dielectric properties, and magnetic behavior of the new compound Ba2Fe2Ti4O13 are reported. Structural studies carried out by single-crystal X-ray diffraction and neutron powder diffraction show that this phase is isostructural with K2Ti6O13 and Ba2ZnTi5O13 (C2/m (No. 12); a = 15.216(1), b = 3.8979(3), c = 9.1350(6) Å, β = 98.460(7)°; V = 535.90(8) Å3; Z = 2). The cations Fe3+ and Ti4+ are partially ordered among distorted octahedral sites with Ba2+ occupying eleven-coordinated polyhedra. Ba2Fe2Ti4O13 exhibits TE0 resonance near 10 GHz with a dielectric constant of ∼28 and a dielectric loss tangent of 2 × 10-3. The compound displays complex paramagnetic behavior with marked field dependence; the magnetization at 80 kA/m is several orders of magnitude smaller than that of most ferrites. Spin-glass effects have not been observed; however, weak collective interactions are clearly present. No magnetic ordering has been detected by neutron diffraction down to 13 K.

A new 5-alkylresorcinol glucoside derivative from Cybianthus magnus.

PubMed

Cabanillas, B; Vásquez-Ocmín, P; Zebiri, I; Rengifo, E; Sauvain, M; Le, H L; Vaisberg, A; Voutquenne-Nazabadioko, L; Haddad, M

2016-01-01

One new 5-alkylresorcinol glucoside (1) was isolated from leaves of Cybianthus magnus, along with 12 known compounds (2-13), isolated from four plants belonging to Myrsinaceae family. Their structures were determined on the basis of spectroscopic analysis and by comparison of their spectral data with those reported in the literature. Among the tested molecules, only compound 2 displayed a strong cytotoxic activity with IC50 values ranging between 22 and 100 μM for all cell lines tested. One new 5-alkylresorcinol glucoside (1) was isolated from leaves of Cybianthus magnus, along with 12 known compounds, isolated from four plants belonging to Myrsinaceae family (2, 3 isolated from C. magnus; 4-7, 10 and 11 isolated from Myrsine latifolia; 4, 8 and 9 isolated from Myrsine sessiflora; 6, 7, 10, 12 and 13 isolated from Myrsine congesta). Their structures were determined on the basis of spectroscopic analysis and by comparison of their spectral data with those reported in the literature. So far, only nine 5-alkylresorcinol glucosides were isolated from leaves of Grevillea robusta. Since resorcinols are known to exhibit strong cytotoxic activity, compounds 1 and 2 were tested against cell lines 3T3, H460, DU145 and MCF-7 for cytotoxicity in vitro and compounds 3-13 were tested for their antileishmanial activity. Compound 2 displayed a strong cytotoxic activity with IC50 values ranging between 22 and 100 μM for all tested cell lines. Compounds 3-13 were not active against Leishmania amazonensis amastigotes.

Tissue-specific concentrations and patterns of perfluoroalkyl carboxylates and sulfonates in East Greenland polar bears.

PubMed

Greaves, Alana K; Letcher, Robert J; Sonne, Christian; Dietz, Rune; Born, Erik W

2012-11-06

Several perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) of varying chain length are bioaccumulative in biota. However, wildlife reports have focused on liver and with very little examination of other tissues, and thus there is a limited understanding of their distribution and potential effects in the mammalian body. In the present study, the comparative accumulation of C(6) to C(15) PFCAs, C(4), C(6), C(8) and C(10) PFSAs, and select precursors were examined in the liver, blood, muscle, adipose, and brain of 20 polar bears (Ursus maritimus) from Scoresby Sound, Central East Greenland. Overall, PFSA and PFCA concentrations were highest in liver followed by blood > brain > muscle ≈ adipose. Liver and blood samples contained proportionally more of the shorter/medium chain length (C(6) to C(11)) PFCAs, whereas adipose and brain samples were dominated by longer chain (C(13) to C(15)) PFCAs. PFCAs with lower lipophilicities accumulated more in the liver, whereas the brain accumulated PFCAs with higher lipophilicities. The concentration ratios (±SE) between perfluorooctane sulfonate and its precursor perfluorooctane sulfonamide varied among tissues from 9 (±1):1 (muscle) to 36 (±7):1 (liver). PFCA and PFSA patterns in polar bears indicate that the pharmacokinetics of these compounds are to some extent tissue-specific, and are the result of several factors that may include differing protein interactions throughout the body.

The rational design of a novel potent analogue of the 5’-AMP-activated protein kinase inhibitor compound C with improved selectivity and cellular activity

PubMed Central

Machrouhi, Fouzia; Ouhamou, Nouara; Laderoute, Keith; Calaoagan, Joy; Bukhtiyarova, Marina; Ehrlich, Paula J.; Klon, Anthony E.

2010-01-01

We have designed and synthesized analogues of compound C, a non-specific inhibitor of 5’-AMP-activated protein kinase (AMPK), using a computational fragment-based drug design (FBDD) approach. Synthesizing only twenty-seven analogues yielded a compound that was equipotent to compound C in the inhibition of the human AMPK (hAMPK) α2 subunit in the heterotrimeric complex in vitro, exhibited significantly improved selectivity against a subset of relevant kinases, and demonstrated enhanced cellular inhibition of AMPK. PMID:20932747

The dynamics of methane emissions in Alaskan peatlands at different trophic levels

NASA Astrophysics Data System (ADS)

Zhang, L.; Liu, X.; Langford, L.; Chanton, J.; Hines, M. E.

2016-12-01

One major uncertainty in estimating methane (CH4) emission from wetlands is extrapolating from highly heterogeneous and inadequately studied local sites to larger scales. The heterogeneity of peatlands comes from contrasting surface vegetation compositions within short distances that are usually associated with different nutrient sources and trophic status. Different microbial communities and metabolic pathways occur at different trophic levels. Stable isotope C ratios (δ13C) have been used as a robust tool to distinguish methanogenic pathways, but different sources of parent compounds (acetate and CO2) with unique δ13C signatures, and unresolved fractionation factors associated with different methanogens, add complexity. To better understand the relationships between trophic status, surface vegetation compositions and methanogenic pathways, 28 peatland sites were studied in Fairbanks and Anchorage, Alaska in the summer of 2015. These sites were ordinated using multiple factor analysis into 3 clusters based on pH, temp, CH4 and volatile fatty acids production rates, δ13C values, and surface vegetation composition. In the low-pH trophic cluster (pH 4.2), Sphagnum fuscum was the dominant species with specific sedges (Ledum decumbens), and primary fermentation rates was slow with no CH4 detected. In the intermediate trophic level (pH 5.3), in which Sphagnum magellanicum was largely present, both hydrogenotrophic (HM) and acetoclastic methanogenesis (AM) were very active. Syntrophy was present at certain sites, which may provide CO2 and acetate with unique δ13C for CH4 production. At the highest pH trophic cluster examined in this study (pH 5.8), Carex tenuiflora, Carex aquatilis, and Sphagnum Squarrosum dominated. CH4 production rates were higher than those in the intermediate cluster and the apparent fractionation factor a was lower.

Identification of 4-oxo-13-cis-retinoic acid as the major metabolite of 13-cis-retinoic acid in human blood.

PubMed

Vane, F M; Buggé, C J

1981-01-01

The metabolites of 13-cis-retinoic acid (Accutane) were investigated in blood samples from human volunteers on chronic treatment for dermatological disorders. The major metabolite was isolated by reverse-phase high-pressure liquid chromatography and identified as 4-oxo-13-cis-retinoic acid by comparison of its mass and NMR spectra to the spectra of the reference compound. 4-Oxo-all-trans-retinoic acid was also identified, but the extent to which this compound was a metabolite of 13-cis-retinoic acid or an artifactual isomerization product of the major metabolite is unknown. Chromatographic data suggested that small amounts of 13-cis-retinoic acid, 4-hydroxy-13-cis-retinoic acid, and dioxygenated metabolites of 13-cis-retinoic acid may also be present in the blood. This study indicates that a major metabolic pathway of 13-cis-retinoic acid in humans is oxidation at C4 of the cyclohexenyl group.

40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

Code of Federal Regulations, 2010 CFR

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...

40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 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...

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity.

PubMed

Mayr, Monika; Wurst, Klaus; Ongania, Karl-Hans; Buchmeiser, Michael R

2004-03-05

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2) (2+)(Ag(2)Br(2)Cl(4) (4-))(1/2) (15) and Pd[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]Cl(2) (16). Complex 15 crystallizes in the monoclinic space group P2(1)/c, and 16 in the monoclinic space group C(2)/c. The catalytic activity of 15 and 16 in Heck-type reactions was studied in detail. Both compounds are highly active in the coupling of aliphatic and aromatic vinyl compounds with aryl bromides and chlorides with turnover numbers (TONs) up to 2000000. Stabilities of 15 and 16 under Heck-couplings conditions were correlated with their molecular structure. Finally, selected kinetic data for these couplings are presented.

Five new diarylheptanoids from the rhizomes of Curcuma kwangsiensis and their antiproliferative activity.

PubMed

Chen, Shao-Dan; Gao, Jin-Tao; Liu, Jing-Gong; Liu, Bo; Zhao, Rui-Zhi; Lu, Chuan-Jian

2015-04-01

Five new diarylheptanoids (1-5), along with nine known ones (6-14), were isolated from the rhizomes of Curcuma kwangsiensis. Their structures were established on the basis of spectroscopic analyses. Compounds 1-3 were cyclic diarylheptanoids rarely discovered from C. kwangsiensis. Of all the isolated compounds, compound 4 showed moderate antiproliferative activity on HH and HaCaT cells. Copyright © 2015. Published by Elsevier B.V.

Woody Plant Invasion of Grassland: Lignin and Aliphatic Biopolymer Chemistry and Carbon Isotope Composition in Physical Fractions

NASA Astrophysics Data System (ADS)

Gamblin, D.; Boutton, T.; Liao, J.; Jastrow, J.; Filley, T.

2003-12-01

Significant changes in the apportionment of organic carbon in grassland and savanna soils have been document as a result of woody plant encroachment. In the Rio Grande Plains of Texas, C4 grasslands (d13C = -14 0/00) have undergone succession to trees and shrubs of a subtropical thorn woodland (d13C = -27 0/00) over the past 150 y which has resulted in increased soil organic carbon storage. Large differences in the turnover times of physical fractions in this system indicate selective preservation mechanisms which may include physical protection or inherent biochemical recalcitrance. To elucidate mechanisms of SOC sequestration during woody plant succession in this system, we are investigating the chemistry and compound-specific stable carbon isotope composition of lignin and aliphatic biopolymers in specific physical (size, density) soil fractions within a chronosequence that includes remnant grasslands (Time 0) and woody plant stands ranging in age from 10-130 y. The soil fraction data is being compared to biopolymer and isotope chemistry of the root, stem and/or leaf tissue of 20 of the dominant genus of plants in the system. Lignin phenols and suberin and cutin-derived hydroxyfatty acids are being isolated using alkaline CuO oxidation and tetramethylammonium hydroxide thermochemolysis. A comparison of the macroaggregate (greater than 250 um), microaggregate (53-250 um), and free silt and clay fractions in the oldest stand indicates that lignin is the most concentrated (organic carbon normalized values) in macroaggregates and is significantly less degraded, as determined by relative yields of oxidized and reduced lignin phenols. Additionally, the intra-aggregate silt and clay fraction from the macroaggregates contains less than half of the organic carbon normalized lignin phenols and is relatively more oxidized than what is found in the total macroaggregate pool. From these preliminary results it appears that the bulk macroaggregate pool contains the least degraded/freshest lignin of the physical fractions. This is consistent with the relatively shorter residence times determined for this fraction in this system. Continuing work includes compound specific isotope analysis of isolated lignin and hydroxyl fatty acids to elucidate biopolymer-specific turnover times which will provide important clues into the mechanisms of SOM storage and biopolymer recalcitrance.

Carbon transfer from plant roots to soil - NanoSIMS analyses of undisturbed rhizosphere samples

NASA Astrophysics Data System (ADS)

Vidal, Alix; Hirte, Juliane; Bender, S. Franz; Mayer, Jochen; Gattinger, Andreas; Mueller, Carsten W.

2017-04-01

Soils are composed of a wide diversity of organic and mineral compounds, interacting to form complex mosaics of microenvironments. Roots and microorganisms are both key sources of organic carbon (OC). The volume of soil around living roots, i.e. the rhizosphere, is a privileged area for soil microbial activity and diversity. The microscopic observation of embedded soil sections has been applied since the 1950´s and has enabled observation of the rhizosphere at the smallest scale of organism interaction, i.e. at the level of root cells and bacteria (Alexander and Jackson, 1954). However, the observation of microorganisms in their intact environment, especially in soil, remains challenging. Existing microscopic images do not provide clear evidence of the chemical composition of compounds observed in the rhizosphere. Nano-scale secondary ion mass spectrometry (NanoSIMS) is a high spatial resolution method providing elemental and isotopic maps of organic and mineral materials. This technic has been increasingly used in soil science during the last decade (Hermann et al., 2007; Vogel et al., 2014) and more specifically for undisturbed soil sample observations (Vidal et al., 2016). In the present study, NanoSIMS was used to illustrate the biological, physical and chemical processes occurring in the rhizosphere at the microscale. To meet this objective, undisturbed rhizosphere samples were collected from a field experiment in Switzerland where wheat plants were pulse-labelled with 99% 13C-CO2 in weekly intervals throughout the growing season and sampled at flowering. Samples were embedded, sectioned, polished and analyzed with NanoSIMS, obtaining secondary ion images of 12C, 13C, 12C14N, 16O, 31P16O2, and 32S. The δ13C maps were obtained thanks to 12C and 13C images. 13C labelled root cells were clearly distinguished on images and presented highly variable δ13C values. Labelled spots (< 1 µm), identified as bacteria, were located at the root cell surroundings. These microorganisms were intimately associated with soil particles, forming microaggregates tightly bound to root cells. Finally, some images revealed the presence of larger labelled spots (> 4 µm) potentially assignable to arbuscular fungal hyphae. These results illustrate the transfer of carbon from the root tissues towards the microbial communities and the direct fate as organo-mineral associated OC at mineral soil particles. Alexander, F., Jackson, R., 1954. Examination of soil micro-organisms in their natural environment. Nature. 174, 750-751. Herrmann, A.M., Ritz, K., Nunan, N., Clode, P.L., Pett-Ridge, J., Kilburn, M.R., Murphy, D.V., O'Donnell, A.G., Stockdale, E.A., 2007. Nano-scale secondary ion mass spectrometry — A new analytical tool in biogeochemistry and soil ecology: A review article. Soil Biology and Biochemistry. 39, 1835-1850. Vidal, A., Remusat, L., Watteau, F., Derenne, S., Quenea K., 2016. Incorporation of 13C labelled shoot residues in Lumbricus terrestris casts: A combination of Transmission Electron Microscopy and Nanoscale Secondary Ion Mass Spectrometry. Soil Biology and Biochemistry. 93, 8-16. Vogel, C., Mueller, C.W., Höschen, C., Buegger, F., Heister, K., Schulz, S., Schloter, M., Kögel-Knabner, I., 2014. Submicron structures provide preferential spots for carbon and nitrogen sequestration in soils. Nature Communications 5.

Synthesis and evaluation of triazole linked glycosylated 18β-glycyrrhetinic acid derivatives as anticancer agents.

PubMed

Parida, Pravat Kumar; Sau, Abhijit; Ghosh, Tamashree; Jana, Kuladip; Biswas, Kaushik; Raha, Sanghamitra; Misra, Anup Kumar

2014-08-15

A series of glycosyl triazol linked 18β-glycyrrhetinic acid (GA) derivatives have been synthesized using 1,3-dipolar cycloaddition reaction of per-O-acetylated glycosyl azide derivatives (4a-h) with propargyl ester of 18β-glycyrrhetinic acid (GA) (2 and 3) following the concept of 'Click chemistry'. The synthesized triazole derivatives were de-O-acetylated to furnish compounds (7a-h and 8a-c) with free hydroxyl groups in the carbohydrate moieties, which were evaluated for their anticancer potential against human cervical cancer cells (HeLa) and normal kidney epithelial (NKE) cells. GA (1), compound 7d, compound 7g and compound 8c showed promising anticancer activities. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Geology of Liberia: A Selected Bibliography of Liberian Geology, Geography and Earth Science

DTIC Science & Technology

2006-05-01

acerca do Sistema do Oendolongo e da Serie do Sansicua ( Sistema do Congo Ocidental).” Translated title: “The marked orogenesis in the Cariango region...Nitrogen ratio; Chemistry, organic compounds; Chemistry, sediment; Components, terrigeneous; d13C Corg; delta 13C, organic carbon; Dinost/ TOC ...for Geosciences, Christian Albrechts University, Kiel; Isotopes, stable, general; Ketone/ TOC ; M6/5; M65; Mass spectrometer Finnigan MAT 251; Meteor

Crystal structures of 2-meth­oxy­isoindoline-1,3-dione, 1,3-dioxoisoindolin-2-yl methyl carbonate and 1,3-dioxo-2,3-di­hydro-1H-benzo[de]isoquinolin-2-yl methyl carbonate: three anti­convulsant compounds

PubMed Central

Ezemobi, Fortune; North, Henry; Scott, Kenneth R.; Wutoh, Anthohy K.; Butcher, Ray J.

2014-01-01

The title compounds, C9H7NO3, (1), C10H7NO5, (2), and C14H9NO5, (3), are three potentially anti­convulsant compounds. Compounds (1) and (2) are isoindoline derivatives and (3) is an iso­quinoline derivative. Compounds (2) and (3) crystallize with two independent mol­ecules (A and B) in their asymmetric units. In all three cases, the isoindoline and benzoiso­quinoline moieties are planar [r.m.s. deviations are 0.021 Å for (1), 0.04 and 0.018 Å for (2), and 0.033 and 0.041 Å for (3)]. The substituents attached to the N atom are almost perpendicular to the mean planes of the heterocycles, with dihedral angles of 89.7 (3)° for the N—O—Cmeth­yl group in (1), 71.01 (4) and 80.00 (4)° for the N—O—C(=O)O—Cmeth­yl groups in (2), and 75.62 (14) and 74.13 (4)° for the same groups in (3). In the crystal of (1), there are unusual inter­molecular C=O⋯C contacts of 2.794 (1) and 2.873 (1) Å present in mol­ecules A and B, respectively. There are also C—H⋯O hydrogen bonds and π–π inter­actions [inter-centroid distance = 3.407 (3) Å] present, forming slabs lying parallel to (001). In the crystal of (2), the A and B mol­ecules are linked by C—H⋯O hydrogen bonds, forming slabs parallel to (10-1), which are in turn linked via a number of π–π inter­actions [the most significant centroid–centroid distances are 3.4202 (7) and 3.5445 (7) Å], forming a three-dimensional structure. In the crystal of (3), the A and B mol­ecules are linked via C—H⋯O hydrogen bonds, forming a three-dimensional structure, which is consolidated by π–π inter­actions [the most significant inter-centroid distances are 3.575 (3) and 3.578 (3) Å]. PMID:25552964

Microsporols A-C from the Plant Endophytic Fungus Pestalotiopsis microspore.

PubMed

Wu, Xianfu; Wang, Yadan; Liu, Shuchun; Liu, Xinzhong; Guo, Liangdong

2015-10-01

Three new ambuic acid derivatives, microsporols A-C (1-3) and the known compound ambuic acid (4), were isolated from the solid-substrate fermentation cultures of the plant endophytic fungus Pestalotiopsis microspora. Their structures were elucidated primarily by NMR experiments. The absolute configurations of the 6,7-diol moiety in 1 and 2 were assigned using the Snatzke's method, whereas that of 3 was deduced by circular dichroism (CD) exciton chirality method. Compounds 1, 3, and 4 showed moderate 5-lipoxygenase (5-LOX) inhibitory effects.

Synthesis, characterization and antioxidant study of N,N’-bis(2-chlorobenzamidothiocarbonyl)hydrazine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Firdausiah, Syadza; Hasbullah, Siti Aishah; Yamin, Bohari M.

2015-09-25

N,N’-bis(2-chlorobenzamidothiocarbonyl)hydrazine was synthesized from 2-chlorobenzoylisothiocyanate and hydrazine in acetone. The compound was characterized by infrared, {sup 1}H and {sup 13}C NMR, and UV-Vis spectroscopies. X-ray crystallography study showed the molecule adopt trans configuration at both N-N and C-N bonds. The compound showed high antioxidant activity, EC{sub 50} of 374.89 µM, compared to ascorbic acid (EC{sub 50} of 561.36 µM)

Lactone Derivatives Produced by a Phaeoacremonium sp., an Endophytic Fungus from Senna spectabilis.

PubMed

Silva, Geraldo H; Zeraik, Maria L; de Oliveira, Camila M; Teles, Helder L; Trevisan, Henrique C; Pfenning, Ludwig H; Nicolli, Camila P; Young, Maria C M; Mascarenhas, Yvonne P; Abreu, Lucas M; Saraiva, Amanda C; Medeiros, Alexandra I; Bolzani, Vanderlan da S; Araujo, Angela R

2017-05-26

Three new isoaigialones, A, B, and C (1-3), along with aigialone (4), were isolated from the crude EtOAc extract of a Phaeoacremonium sp., an endophytic fungus obtained from the leaves of Senna spectabilis. The structures of these compounds were elucidated based on the analysis of spectroscopic data. Compounds 2 and 4 were active against the phytopathogenic fungi Cladosporium cladosporioides and C. sphaerospermum. This is the first report of metabolites produced by an Phaeoacremonium sp., associated with S. spectabilis.

Antibacterial and Hypoglycemic Diterpenoids from Salvia chamaedryoides.

PubMed

Bisio, Angela; De Mieri, Maria; Milella, Luigi; Schito, Anna M; Parricchi, Anita; Russo, Daniela; Alfei, Silvana; Lapillo, Margherita; Tuccinardi, Tiziano; Hamburger, Matthias; De Tommasi, Nunziatina

2017-02-24

A surface extract of the aerial parts of Salvia chamaedryoides afforded 13 diterpenes (1-13), with seven compounds (1, 3, 4, 7-9, 12) described for the first time. The structures of the new compounds were established using 1D and 2D NMR spectroscopic methods, HRESIMS, and ECD data. The potential hypoglycemic effects of the crude extract, fractions, and pure compounds from S. chamaedryoides were investigated by inhibition of α-glucosidase and α-amylase enzymes. The extract and its fractions showed a moderate dose-dependent inhibition; the pure compounds exhibited differential inhibitory activity against these two enzymes. Molecular modeling studies were also performed to suggest the interaction mode of compound 3 in the α-glucosidase enzyme active site. The antimicrobial activity of the purified compounds was investigated against 26 clinical pathogens. No activity was detected for the Gram-negative species tested nor on Candida albicans and C. glabrata, while variable susceptibilities were observed using Gram-positive staphylococcal and enterococcal species.

Contrasting dual (C, Cl) isotope fractionation offers potential to distinguish reductive chloroethene transformation from breakdown by permanganate.

PubMed

Doğan-Subaşı, Eylem; Elsner, Martin; Qiu, Shiran; Cretnik, Stefan; Atashgahi, Siavash; Shouakar-Stash, Orfan; Boon, Nico; Dejonghe, Winnie; Bastiaens, Leen

2017-10-15

cis-1,2-Dichloroethene (cis-DCE) and trichloroethene (TCE) are persistent, toxic and mobile pollutants in groundwater systems. They are both conducive to reductive dehalogenation and to oxidation by permanganate. In this study, the potential of dual element (C, Cl) compound specific isotope analyses (CSIA) for distinguishing between chemical oxidation and anaerobic reductive dechlorination of cis-DCE and TCE was investigated. Well-controlled cis-DCE degradation batch tests gave similar carbon isotope enrichment factors ε C (‰), but starkly contrasting dual element isotope slopes Δδ 13 C/Δδ 37 Cl for permanganate oxidation (ε C =-26‰±6‰, Δδ 13 C/Δδ 37 Cl≈-125±47) compared to reductive dechlorination (ε C =-18‰±4‰, Δδ 13 C/Δδ 37 Cl≈4.5±3.4). The difference can be tracked down to distinctly different chlorine isotope fractionation: an inverse isotope effect during chemical oxidation (ε Cl =+0.2‰±0.1‰) compared to a large normal isotope effect in reductive dechlorination (ε Cl =-3.3‰±0.9‰) (p≪0.05). A similar trend was observed for TCE. The dual isotope approach was evaluated in the field before and up to 443days after a pilot scale permanganate injection in the subsurface. Our study indicates, for the first time, the potential of the dual element isotope approach for distinguishing cis-DCE (and TCE) concentration drops caused by dilution, oxidation by permanganate and reductive dechlorination both at laboratory and field scale. Copyright © 2017. Published by Elsevier B.V.