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Sample records for acid isomers present

  1. Determination of the D and L isomers of some protein amino acids present in soils

    NASA Technical Reports Server (NTRS)

    Pollock, G. E.; Cheng, C.-N.; Cronin, S. E.

    1977-01-01

    The D and L isomers of some protein amino acids present in soils were measured by using a gas chromatographic technique. The results of two processing procedures were compared to determine the better method. Results of the comparison indicated that the determination of D and L percentages requires amino acid purification if one is to obtain accurate data. It was found that very significant amounts of D-alanine, D-aspartic acid, and D-glutamic acid were present in the contemporary soils studied. Valine, isoleucine, leucine, proline, and phenylalanine generally contained only a trace to very small amounts of the D isomer. It is probable that the D-amino acids from the alanine, aspartic, and glutamic acids are contributed to the soil primarily via microorganisms. The finding of very significant quantities of some D-amino acids (about 5-16%) in present-day soils may alert some investigators of geological sediments to a possible problem in using amino acid racemization as an age-dating technique.

  2. Electropolymerization mechanisms of hydroxyphenylacetic acid isomers

    NASA Astrophysics Data System (ADS)

    Rodrigues, Luciano P.; Ferreira, Deusmaque C.; Sonoda, Milton Taidi; Madurro, Ana Graci B.; Abrahão, Odonírio; Madurro, João M.

    2014-08-01

    Three different films of conducting polymers with free carboxylic functional groups were obtained from 2,3 and 4-hydroxyphenylacetic acid isomers (HPA) and the respective electropolymerization mechanisms were elucidated by DFT calculations. The different properties observed at these new material characterizations, obtained by means of cyclic voltammetry on graphite, are in agreement with theoretical interpretation presented for each reaction mechanisms, which involves the different radical cation coupling and formation of aromatic polyethers with free carboxyl groups, characterized by FTIR spectrometry and electrochemical tests. The computational chemistry analysis of the radical cations spin densities and partial atomic charges variation during the monomer oxidations, indicates the most probably reactive sites for their coupling, allowing the proposition of HPA electropolymerization mechanisms. The poly(2-HPA) had the largest yield in the electropolymerization reaction and the lowest electron transfer. The poly(4-HPA) displayed the lowest yield and the largest electron transfer coefficient, with poly(3-HPA) presenting intermediate values between the former two. Therefore, poly(3-HPA) is a very promising polymer for the platform development for electronic systems, which require materials with good electronic conductivity allied to intrinsic flexibility of polymeric materials.

  3. Conjugated linoleic acid isomers: differences in metabolism and biological effects.

    PubMed

    Churruca, Itziar; Fernández-Quintela, Alfredo; Portillo, Maria Puy

    2009-01-01

    The term conjugated linoleic acid (CLA) refers to a mixture of linoleic acid positional and geometric isomers, characterized by having conjugated double bonds, not separated by a methylene group as in linoleic acid. CLA isomers appear as a minor component of the lipid fraction, found mainly in meat and dairy products from cows and sheep. The most abundant isomer is cis-9,trans-11, which represents up to 80% of total CLA in food. These isomers are metabolized in the body through different metabolic pathways, but important differences, that can have physiological consequences, are observed between the two main isomers. The trans-10,cis-12 isomer is more efficiently oxidized than the cis-9,trans-11 isomer, due to the position of its double bounds. Interest in CLA arose in its anticarcinogenic action but there is an increasing amount of specific scientific literature concerning the biological effects and properties of CLA. Numerous biological effects of CLA are due to the separate action of the most studied isomers, cis-9,trans-11 and trans-10,cis-12. It is also likely that some effects are induced and/or enhanced by these isomers acting synergistically. Although the cis-9,trans-11 isomer is mainly responsible for the anticarcinogenic effect, the trans-10,cis-12 isomer reduces body fat and it is referred as the most effective isomer affecting blood lipids. As far as insulin function is concerned, both isomers seem to be responsible for insulin resistance in humans. Finally, with regard to the immune system it is not clear whether individual isomers of CLA could act similarly or differently.

  4. Focal point analysis of torsional isomers of acrylic acid

    NASA Astrophysics Data System (ADS)

    Alev Çiftçioğlu, Gökçen; Trindle, Carl; Yavuz, Ilhan

    2010-10-01

    The thermochemistry of acrylic acid has presented challenges owing to its high reactivity, tendency to dimerize in the gas phase, and the existence of two very nearly equal energy conformational isomers. Well-tested thermochemical schemes including G2, G3, G4, and CBS-QB3 agree in the prediction that the s-cis syn structure is the most stable of the torsional isomers, with the s-cis anti form lying 3 kJ mol-1 or less higher in energy. Microwave spectra suggest a value of 0.63 kJ mol-1. The energy barrier between these forms is in the neighbourhood of 25 kJ mol-1 according to a MP2/cc-pVDZ calculation. We present estimates of the relative energies of all four torsional isomers and the rotational barrier based on a variant of the Focal Point Analysis developed by Császár and co-workers. These calculations, extending to the CCSD(T)/cc-pV5Z level, predict that the s-cis anti torsional isomer is the most stable form, in contrast to prior estimates. The s-cis syn form lies about 2.9 kJ mol-1 higher, while the s-trans syn and anti forms lie at about 21.7 and 23.3 kJ mol-1, respectively. We estimate the rotational barrier between the s-cis trans and s-cis anti structures to be about 23.9 kJ mol-1. Error ranges derived from the fit to extrapolation forms suggest that our estimates have an uncertainty of about 0.1 kJ mol-1.

  5. Structure, dynamics, and energetics of lysobisphosphatidic acid (LBPA) isomers.

    PubMed

    Goursot, A; Mineva, T; Bissig, C; Gruenberg, J; Salahub, D R

    2010-12-02

    Lysobisphosphatidic acid (LBPA), or bis(monoacylglycerol)phosphate, is a very interesting lipid, that is mainly found in late endosomes. It has several intriguing characteristics, which differ from those of other animal glycerophospholipids, that may be related to its specific functions, particularly in the metabolism of cholesterol. Its phosphodiester group is bonded at the sn-1 (sn-1') positions of the glycerols rather than at sn-3 (sn-3'); the position of the two fatty acid chains is still under debate but, increasingly, arguments favor the sn-2, sn-2' position in the native molecule, whereas isolation procedures or acidic conditions lead to the thermodynamically more stable sn-3, sn-3' structure. Because of these peculiar features, it can be expected that LBPA shape and interactions with membrane lipids and proteins are related to its structure at the molecular level. We applied quantum mechanical methods to study the structures and stabilities of the 2,2' and 3,3' LBPA isomers, using a step-by-step procedure from glycerol to precursors (in vitro syntheses) and to the final isoforms. The structures of the two positional LBPA isomers are substantially different, showing that the binding positions of the fatty acid chains on the glycerol backbone determine the shape of the LBPA molecule and thus, possibly, its functions. The 3,3' LBPA structures obtained are more stable with respect to the 2,2' form, as expected from experiment. If one argues that the in vivo synthesis starts from the present glycerol conformers and considering the most stable bis(glycero)phosphate structures, the 2,2' isoform should be the most probable isomer.

  6. Gaussian and linear deconvolution of LC-MS/MS chromatograms of the eight aminobutyric acid isomers.

    PubMed

    Vemula, Harika; Kitase, Yukiko; Ayon, Navid J; Bonewald, Lynda; Gutheil, William G

    2017-01-01

    Isomeric molecules present a challenge for analytical resolution and quantification, even with MS-based detection. The eight aminobutyric acid (ABA) isomers are of interest for their various biological activities, particularly γ-aminobutyric acid (GABA) and the d- and l-isomers of β-aminoisobutyric acid (β-AIBA; BAIBA). This study aimed to investigate LC-MS/MS-based resolution of these ABA isomers as their Marfey's (Mar) reagent derivatives. HPLC was able to separate three Mar-ABA isomers l-β-ABA (l-BABA), and l- and d-α-ABA (AABA) completely, with three isomers (GABA, and d/l-BAIBA) in one chromatographic cluster, and two isomers (α-AIBA (AAIBA) and d-BABA) in a second cluster. Partially separated cluster components were deconvoluted using Gaussian peak fitting except for GABA and d-BAIBA. MS/MS detection of Marfey's derivatized ABA isomers provided six MS/MS fragments, with substantially different intensity profiles between structural isomers. This allowed linear deconvolution of ABA isomer peaks. Combining HPLC separation with linear and Gaussian deconvolution allowed resolution of all eight ABA isomers. Application to human serum found a substantial level of l-AABA (13 μM), an intermediate level of l-BAIBA (0.8 μM), and low but detectable levels (<0.2 μM) of GABA, l-BABA, AAIBA, d-BAIBA, and d-AABA. This approach should be useful for LC-MS/MS deconvolution of other challenging groups of isomeric molecules.

  7. Conjugated Linoleic Acids and Inflammation: Isomer and Tissue Specific Responses

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conjugated linoleic acids (CLAs) are a series of geometric and positional isomers of linoleic acid that have been studied for their effects against diabetes, cancer, and atherosclerosis, all conditions with an inflammatory component. Despite the continued interest in CLA, there are many controversi...

  8. The Immunomodulatory Activity of Jacaric Acid, a Conjugated Linolenic Acid Isomer, on Murine Peritoneal Macrophages

    PubMed Central

    Liu, Wai Nam; Leung, Kwok Nam

    2015-01-01

    This study aims at demonstrating the immunomodulatory property of jacaric acid, a conjugated linolenic acid (CLNA) isomer that is present in jacaranda seed oil, on murine peritoneal macrophages. Our results showed that jacaric acid exhibited no significant cytotoxicity on the thioglycollate-elicited murine peritoneal macrophages as revealed by the neutral red uptake assay, but markedly increased their cytostatic activity on the T-cell lymphoma MBL-2 cells as measured by the fluorometric CyQuant® NF Cell Proliferation Assay Kit. Flow cytometric analysis indicated that jacaric acid could enhance the endocytic activity of macrophages and elevated their intracellular production of superoxide anion. Moreover, jacaric acid-treated macrophages showed an increase in the production of nitric oxide which was accompanied by an increase in the expression level of inducible nitric oxide synthase protein. In addition, the secretion of several pro-inflammatory cytokines, including interferon-γ, interleukin-1β and tumor necrosis factor-α, was up-regulated. Collectively, our results indicated that the naturally-occurring CLNA isomer, jacaric acid, could exhibit immunomodulating activity on the murine peritoneal macrophages in vitro, suggesting that this CLNA isomer may act as an immunopotentiator which can be exploited for the treatment of some immunological disorders with minimal toxicity and fewer side effects. PMID:26629697

  9. The Immunomodulatory Activity of Jacaric Acid, a Conjugated Linolenic Acid Isomer, on Murine Peritoneal Macrophages.

    PubMed

    Liu, Wai Nam; Leung, Kwok Nam

    2015-01-01

    This study aims at demonstrating the immunomodulatory property of jacaric acid, a conjugated linolenic acid (CLNA) isomer that is present in jacaranda seed oil, on murine peritoneal macrophages. Our results showed that jacaric acid exhibited no significant cytotoxicity on the thioglycollate-elicited murine peritoneal macrophages as revealed by the neutral red uptake assay, but markedly increased their cytostatic activity on the T-cell lymphoma MBL-2 cells as measured by the fluorometric CyQuant® NF Cell Proliferation Assay Kit. Flow cytometric analysis indicated that jacaric acid could enhance the endocytic activity of macrophages and elevated their intracellular production of superoxide anion. Moreover, jacaric acid-treated macrophages showed an increase in the production of nitric oxide which was accompanied by an increase in the expression level of inducible nitric oxide synthase protein. In addition, the secretion of several pro-inflammatory cytokines, including interferon-γ, interleukin-1β and tumor necrosis factor-α, was up-regulated. Collectively, our results indicated that the naturally-occurring CLNA isomer, jacaric acid, could exhibit immunomodulating activity on the murine peritoneal macrophages in vitro, suggesting that this CLNA isomer may act as an immunopotentiator which can be exploited for the treatment of some immunological disorders with minimal toxicity and fewer side effects.

  10. Hydroxybenzoic acid isomers and the cardiovascular system

    PubMed Central

    2014-01-01

    Today we are beginning to understand how phytochemicals can influence metabolism, cellular signaling and gene expression. The hydroxybenzoic acids are related to salicylic acid and salicin, the first compounds isolated that have a pharmacological activity. In this review we examine how a number of hydroxyphenolics have the potential to ameliorate cardiovascular problems related to aging such as hypertension, atherosclerosis and dyslipidemia. The compounds focused upon include 2,3-dihydroxybenzoic acid (Pyrocatechuic acid), 2,5-dihydroxybenzoic acid (Gentisic acid), 3,4-dihydroxybenzoic acid (Protocatechuic acid), 3,5-dihydroxybenzoic acid (α-Resorcylic acid) and 3-monohydroxybenzoic acid. The latter two compounds activate the hydroxycarboxylic acid receptors with a consequence there is a reduction in adipocyte lipolysis with potential improvements of blood lipid profiles. Several of the other compounds can activate the Nrf2 signaling pathway that increases the expression of antioxidant enzymes, thereby decreasing oxidative stress and associated problems such as endothelial dysfunction that leads to hypertension as well as decreasing generalized inflammation that can lead to problems such as atherosclerosis. It has been known for many years that increased consumption of fruits and vegetables promotes health. We are beginning to understand how specific phytochemicals are responsible for such therapeutic effects. Hippocrates’ dictum of ‘Let food be your medicine and medicine your food’ can now be experimentally tested and the results of such experiments will enhance the ability of nutritionists to devise specific health-promoting diets. PMID:24943896

  11. [Identification of Six Isomers of Dimethylbenzoic Acid by Using Terahertz Time-Domain Spectroscopy Technique].

    PubMed

    Liu, Jian-wei; Shen, Jing-ling; Zhang, Bo

    2015-11-01

    In this paper, the absorption spectra of 6 isomers of dimethylbenzoic acid, which were widely used in chemical and pharmaceutical production as intermediate substance, were measured by using the terahertz time-domain spectroscopy (THz-TDS) system in the range 0.2-2.2 THz at room temperature. The experimental results show that the six measured isomers present apparent different spectral response. However, the results of using infrared spectroscopy indicates that different isomers show high similarity in absorption spectra in the range 1450-1700 cm⁻¹. The vibrational frequencies are calculated by using the density functional theory (DFT), and identification of vibrational modes are given. It is clear that the absorption peaks of the 6 isomers in the range 1450-1700 cm⁻¹ come from the stretching vibration of benzene ring and C==O, while the absorption peaks in the terahertz range are caused by the relative wagging of benzene ring and all the chains out of plane, which lead to the different absorption characteristics of the 6 isomers in the range 0.2-2.2 THz. The results suggest that the difference and similarity of the absorption spectra observed in the two different frequency range are resulted from the difference and similarity of the molecular structures of the six isomers. By using the different absorption characteristics, we can identify the six isomers of dimethylbenzoic acid effectively. Our study indicates that it is feasible to distinguish the isomers by using terahertz and infrared spectroscopy technique. It provides an effective way to identify different isomers and test the purity of the intermediate substance in the process of production quickly and accurately.

  12. Fuel properties of heptadecene isomers prepared via tandem isomerization-decarboxylation of oleic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heptadecene isomers were prepared via tandem isomerization-decarboxylation of oleic acid using catalytic triruthenium dodecacarbonyl [Ru3(CO)12]. Chromatographic and spectroscopic characterization of the isolated heptadecene mixture indicated that it consisted of 96% internal isomers and 4% aromatic...

  13. Incorporation profiles of conjugated linoleic acid isomers in cell membranes and their positional distribution in phospholipids

    PubMed Central

    Subbaiah, Papasani V.; Gould, Ian G.; Lal, Samanta; Aizezi, Buzulagu

    2010-01-01

    Although the conjugated linoleic acids (CLA) have several isomer-specific biological effects including anti-carcinogenic and anti-adipogenic effects, their mechanisms of action remain unclear. To determine their potential effects on membrane structure and function, we studied the incorporation profiles of four CLA isomers (trans-10 cis-12 (A), trans-9 trans-11 (B), cis-9 trans-11 (C), and cis-9 cis-11 (D)) in CHO and HepG2 cells. All four isomers were incorporated into cellular lipids as efficiently as linoleic acid (LA), with the majority of the incorporated CLA present in membrane rafts. Of the four isomers, only CLA-A increased the cholesterol content of the raft fraction. Over 50% of the incorporated CLAs were recovered in phosphatidylcholine of CHO cells, but in HepG2 the neutral lipids contained the majority of CLA. The desaturation index (18:1/18:0 and 16:1/16:0) was reduced by CLA-A, but increased by CLA-B, the effects being apparent mostly in raft lipids. The Δ9 desaturase activity was inhibited by CLAs A and C. Unlike LA, which was mostly found in the sn-2 position of phospholipids, most CLAs were also incorporated significantly into the sn-1 position in both cell types. These studies show that the incorporation profiles of CLA isomers differ significantly from that of LA, and this could lead to alterations in membrane function, especially in the raft-associated proteins. PMID:20920595

  14. Quantitative Analysis of the Distribution of cis-Eicosenoic Acid Positional Isomers in Marine Fishes from the Indian Ocean.

    PubMed

    Senarath, Samanthika; Yoshinaga, Kazuaki; Nagai, Toshiharu; Yoshida, Akihiko; Beppu, Fumiaki; Jayasinghe, Chamila; Devadawson, Chandravathany; Gotoh, Naohiro

    2017-02-01

    This study investigated the occurrence and distribution of cis-eicosenoic acid (c-20:1) positional isomers in fishes from the Indian Ocean and compared to those from the Pacific and Atlantic Ocean. Lipids were extracted from the edible part of the fish and then methylated. The eicosenoic acid methyl ester fraction was separated from total fatty acid methyl esters by reversed-phase HPLC and quantitatively analyzed using a GC-FID fitted with the SLB-IL111 highly polar GC column. c14-20:1 was used as an internal standard. The results indicated that the highest levels of c-20:1 positional isomers were found in fishes from the Pacific Ocean (saury, 166.95±12.4 mg/g of oil), followed by the Atlantic Ocean (capelin, 162.7±3.5 mg/g of oil), and lastly in fishes from the Indian Ocean (goatfish, 34.39 mg/g of oil). With only a few exceptions, the most abundant 20:1 positional isomer found in fishes of the Indian and Atlantic Ocean was the c11-20:1 isomer (>50%) followed by the c13-20:1 isomer (<25%). Unusually, the c7-20:1 isomer was predominantly found in a few fishes such as the tooth ponyfish, longface emperor, and commerson's sole. The c9, c5, and c15-20:1 isomers were the least occurring in fishes from the Indian and Atlantic Ocean. In contrast, the c9-20:1 isomer was the principal isomer identified in fishes from the Pacific Ocean. The results revealed that the content and distribution of c-20:1 positional isomers varied among fishes in different oceans. The data presented in the current study are the first to report on the distribution of c-20:1 positional isomers in fishes from the Indian Ocean.

  15. Dietary conjugated linoleic acid isomers change the unsaturation degree of hepatic fatty acids in neutral lipids but not in polar lipids.

    PubMed

    Martins, Susana V; Lopes, Paula A; Alves, Susana P; Alfaia, Cristina M; Nascimento, Mafalda; Castro, Matilde F; Bessa, Rui J B; Prates, José António Mestre

    2011-03-01

    The fatty acid composition of phospholipids plays a key role in the structural and functional properties of cellular membrane. In this study, it was hypothesized that conjugated linoleic acid (CLA) isomer supplementation changes the unsaturation degree of the fatty acids of neutral lipids (NLs) but not those of polar lipids (PLs). Thus, the main goal was to determine the pattern of fatty acid incorporation into hepatic PL and NL fractions. Wistar male rats were fed cis(c)9,trans(t)11 and t10,c12 CLA isomers, separately or as a mixture. Whereas the t10,c12 isomer incorporation in the PL fraction was similar when supplemented either individually or as a mixture, the c9,t11 isomer reached the highest values of incorporation when combined with t10,c12. In the PL fraction, the linoleic acid did not change; but the arachidonic acid decreased, especially in the rats given the mixture. Also in this fraction, the t10,c12 isomer, either separately or as a mixture, decreased the amounts of n-6 long-chain (LC) polyunsaturated fatty acids (PUFA) and increased those of the n-3 LC PUFA relative to the control. In the NL fraction, linoleic acid incorporation followed the diet composition, whereas the arachidonic acid was similar among treatments. Facing CLA isomer supplementation, the present study suggests that fatty acid incorporation into phospholipids, through the balance between n-6 and n-3 LC PUFA, is dependent upon maintaining the unsaturation degree of cellular membrane.

  16. Are conjugated linolenic acid isomers an alternative to conjugated linoleic acid isomers in obesity prevention?

    PubMed

    Miranda, Jonatan; Arias, Noemi; Fernández-Quintela, Alfredo; del Puy Portillo, María

    2014-04-01

    Despite its benefits, conjugated linoleic acid (CLA) may cause side effects after long-term administration. Because of this and the controversial efficacy of CLA in humans, alternative biomolecules that may be used as functional ingredients have been studied in recent years. Thus, conjugated linolenic acid (CLNA) has been reported to be a potential anti-obesity molecule which may have additional positive effects related to obesity. According to the results reported in obesity, CLNA needs to be given at higher doses than CLA to be effective. However, because of the few studies conducted so far, it is still difficult to reach clear conclusions about the potential use of these CLNAs in obesity and its related changes (insulin resistance, dyslipidemia, or inflammation).

  17. Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

    NASA Technical Reports Server (NTRS)

    Jackson, T. A.

    1971-01-01

    Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

  18. Fuel properties of heptadecene isomers prepared via tandem isomerization-decarboxylation of oleic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heptadecene isomers were prepared via tandem isomerization-decarboxylation of oleic acid using catalytic triruthenium dodecacarbonyl [Ru3(CO)12]. Chromatographic and spectroscopic characterization of the isolated heptadecene mixture indicated that it consisted of 96% internal trans isomers and 4% ar...

  19. Advances in research on cis-9, trans-11 conjugated linoleic acid: a major functional conjugated linoleic acid isomer.

    PubMed

    Wang, Tao; Lee, Hong Gu

    2015-01-01

    Conjugated linoleic acid (CLA) consists of a group of positional and geometric conjugated isomers of linoleic acid. Since the identification of CLA as a factor that can inhibit mutagenesis and carcinogenesis, thousands of studies have been conducted in the last several decades. Among the many isomers discovered, cis-9, trans-11 CLA is the most intensively studied because of its multiple, isomer-specific effects in humans and animals. This paper provides an overview of the available data on cis-9, trans-11 CLA, including its isomer-specific effects, biosynthesis, in vivo/in vitro research models, quantification, and the factors influencing its content in ruminant products.

  20. The trans-10,cis-12 isomer of conjugated linoleic acid reduces hepatic triacylglycerol content without affecting lipogenic enzymes in hamsters.

    PubMed

    Zabala, Amaia; Churruca, Itziar; Macarulla, M Teresa; Rodríguez, Víctor M; Fernández-Quintela, Alfredo; Martínez, J Alfredo; Portillo, María P

    2004-09-01

    Conjugated linoleic acid (CLA) refers to the positional and geometric dienoic isomers of linoleic acid. The dietary intake of CLA has been associated with changes in lipid metabolism. The aim of the present work was to assess the effects of the two main isomers of CLA on sterol regulatory element binding protein (SREBP)-1a and SREBP-1c mRNA levels, as well as on mRNA levels and the activities of several lipogenic enzymes in liver. For this purpose hamsters were fed an atherogenic diet supplemented with 5 g linoleic acid, cis-9,trans-11 or trans-10,cis-12 CLA/kg diet for 6 weeks. The trans-10,cis-12 isomer intake produced significantly greater liver weight, but also significantly decreased liver fat accumulation. No changes in mRNA levels of SREBP-1a, SREBP-1c and lipogenic enzymes, or in the activities of these enzymes, were observed. There was no effect of feeding cis-9,trans-11 CLA. These results suggest that increased fat accumulation in liver does not occur on the basis of liver enlargement produced by feeding the trans-10,cis-12 isomer of CLA in hamsters. The reduction in hepatic triacylglycerol content induced by this isomer was not attributable to changes in lipogenesis.

  1. Isomers/enantiomers of perfluorocarboxylic acids: Method development and detection in environmental samples.

    PubMed

    Naile, Jonathan E; Garrison, A Wayne; Avants, Jimmy K; Washington, John W

    2016-02-01

    Perfluoroalkyl substances are globally distributed in both urban and remote settings, and routinely are detected in wildlife, humans, and the environment. One of the most prominent and routinely detected perfluoroalkyl substances is perfluorooctanoic acid (PFOA), which has been shown to be toxic to both humans and animals. PFOA exists as both linear and branched isomers; some of the branched isomers are chiral. A novel GC-NCI-MS method was developed to allow for isomer/enantiomer separation, which was achieved using two columns working in tandem; a 30-m DB-5MS column and a 30-m BGB-172 Analytik column. Samples were derivatized with diazomethane to form methyl esters of the PFOA isomers. In standards, at least eight PFOA isomers were detected, of which at least four were enantiomers of chiral isomers; one chiral isomer (P3) was sufficiently separated to allow for enantiomer-fraction calculations. Soil, sediment and plant samples from contaminated locations in Alabama and Georgia were analyzed. P3 was observed in most of these environmental samples, and was non-racemic in at least one sediment, suggesting the possibility of chirally selective generation from precursors or enantioselective sorption. In addition, the ratio of P3/linear PFOA was inversely related to distance from source, which we suggest might reflect a higher sorption affinity for the P3 over the linear isomer. This method focuses on PFOA, but preliminary results suggest that it should be broadly applicable to other chiral and achiral perfluorocarboxylic acids (PFCAs); e.g., we detected several other homologous PFCA isomers in our PFCA standards and some environmental samples.

  2. Two new antioxidant malonated caffeoylquinic acid isomers in fruits of wild eggplant relatives.

    PubMed

    Ma, Chunhui; Dastmalchi, Keyvan; Whitaker, Bruce D; Kennelly, Edward J

    2011-09-14

    Fruits of the cultivated eggplant species Solanum melongena and its wild relative Solanum incanum have a high content of hydroxycinnamic acid conjugates, which are implicated in the human health benefits of various fruits and vegetables. Monocaffeoylquinic acid esters, in particular 5-O-(E)-caffeoylquinic acid, are usually predominant in solanaceous fruits and tubers. Two closely related caffeoylquinic acid derivatives with longer C(18) HPLC retention times than those of monocaffeoylquinic acids are minor constituents in cultivated eggplant fruit. In a prior study, the two compounds were tentatively identified as 3-O-acetyl- and 4-O-acetyl-5-O-(E)-caffeoylquinic acids and composed ≤2% of the total hydroxycinnamic acid conjugates in fruit of most S. melongena accessions. It was recently found that the pair of these caffeoylquinic acid derivatives can compose 15-25% of the total hydroxycinnamic acid conjugates in fruits of S. incanum and wild S. melongena. This facilitated C(18) HPLC isolation and structural elucidation using (1)H and (13)C NMR techniques and HR-ToF-MS. The isomeric compounds were identified as 3-O-malonyl-5-O-(E)-caffeoylquinic acid (isomer 1) and 4-O-(E)-caffeoyl-5-O-malonylquinic acid (isomer 2). Both exhibited free radical scavenging activity, albeit about 4-fold lower than that of the flavonol quercetin dihydrate. By contrast, the iron chelation activities of isomers 1 and 2, respectively, were about 3- and 6-fold greater than that of quercetin dihydrate. Reports of malonylhydroxycinnamoylquinic acids are rare, and only a few of these compounds have been structurally elucidated using both NMR and MS techniques. To the authors' knowledge, these two malonylcaffeoylquinic acid isomers have not previously been reported.

  3. Improved synthesis and characterization of saturated branched-chain fatty acid isomers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The development of viable technologies for producing green products from renewable fats and oils is highly desirable since such materials can serve as replacements for non-renewable and poorly biodegradable petroleum-based products. Mixtures of saturated branched-chain fatty acid isomers (sbc-FAs),...

  4. Methyl-branched poly(hydroxyalkanoate) biosynthesis from 13- methyltetradecanoic acid and mixed isostearic acid isomer substrates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pseudomonas resinovorans, a known medium-chain-length (mcl-) poly(hydroxyalkanoate) (PHA) producer, was grown on 13-methyltetradecanoic acid (13-MTDA) and a mixture of isostearic acid (IA) isomers to produce methyl-branched mcl-PHA polymers. Shake flask experiments revealed polymer productivities (...

  5. Screening of multicomponent crystals of L-tryptophan with three isomers of pyridinedicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Das, Babulal

    2016-08-01

    Multicomponent crystallization of L-tryptophan with three different isomers of pyridinedicarboxylic acids, namely, 2,3-pyridinedicarboxylic acid (2,3-PDA), 2,5-pyridinedicarboxylic acid (2,5-PDA) and 2,6-pyridinedicarboxylic acid (2,6-PDA), were screened using conventional solution cocrystallization technique. Whereas the new phases derived from the amino acid with 2,3-PDA or 2,5-PDA were analyzed using powder X-ray diffraction and thermal analysis techniques, the crystalline phase synthesized from 2,6-substituted isomer was further characterized by single crystal X-ray diffraction. Structural analysis revealed that the amino acid exists in the zwitterionic form interacting with the neutral 2,6-PDA by strong intermolecular hydrogen bonding. The components in the co-crystal self-assemble leading to a three dimensional hydrogen bonded closed packed network structure. Isothermal calorimetric titration showed that among the three isomers, 2,6-PDA showed relatively strong binding interaction towards the amino acid in water at 298 K. All the crystals exhibit marginal quenching of fluorescence properties of L-tryptophan in the solid state.

  6. Effects of ingestion of tomatoes, tomato juice and tomato purée on contents of lycopene isomers, tocopherols and ascorbic acid in human plasma as well as on lycopene isomer pattern.

    PubMed

    Fröhlich, Kati; Kaufmann, Karin; Bitsch, Roland; Böhm, Volker

    2006-04-01

    Tomatoes are an important part of the diet. Lycopene, the predominant carotenoid in tomatoes, is hypothesised to mainly mediate the health benefits of tomato products. Anticancer activity of tomato products and lycopene has been suggested by numerous studies. The aim of the present study was to investigate the effect of ingestion of three different tomato-based foodstuffs on plasma contents of lycopene, tocopherols and ascorbic acid. Because isomers of lycopene may have different biological activities, a special interest was to look how the lycopene isomer pattern is changed depending on the matrix of tomato products. Following a 2-week depletion phase volunteers ingested 12.5 mg lycopene/d for 4 weeks comprising tomatoes, tomato juice or tomato purée. The basal levels of lycopene in plasma were comparable for all groups and decreased significantly during the 2 weeks of depletion to approximately half of the basal values. Following intervention, plasma lycopene concentration increased significantly. Conversely, supplementation did not significantly affect levels of tocopherols and ascorbic acid in plasma. Regarding isomers of lycopene, the (Z)-lycopene:(all-E)-lycopene plasma isomer ratio was significantly changed during the study for all groups. A remarkable enrichment of the relative contents of (5Z)-lycopene was observed during the depletion period, which supports the hypothesis that lycopene (Z)-isomers are formed within the human body after ingestion of (all-E)-lycopene. After dietary intervention with lycopene-rich products the isomer ratios returned to those observed at the start of the study. Further investigations will clarify the process of isomerisation in more detail.

  7. Interactions between major chlorogenic acid isomers and chemical changes in coffee brew that affect antioxidant activities.

    PubMed

    Liang, Ningjian; Xue, Wei; Kennepohl, Pierre; Kitts, David D

    2016-12-15

    Coffee bean source and roasting conditions significantly (p<0.05) affected the content of chlorogenic acid (CGA) isomers, several indices of browning and subsequent antioxidant values. Principal component analysis was used to interpret the correlations between physiochemical and antioxidant parameters of coffee. CGA isomer content was positively correlated (p<0.001) to capacity of coffee to reduce nitric oxide and scavenge Frémy's salt. Indices of browning in roasted coffee were positively correlated (p<0.001) to ABTS and TEMPO radical scavenging capacity, respectively. Only the CGA content of coffee corresponded to intracellular antioxidant capacity measured in Caco-2 intestinal cells. This study concluded that the intracellular antioxidant capacity that best describes potential health benefits of coffee positively corresponds best with CGA content.

  8. Micellar and sub-micellar ultra-high performance liquid chromatography of hydroxybenzoic acid and phthalic acid positional isomers.

    PubMed

    Fasciano, Jennifer M; Danielson, Neil D

    2016-03-18

    Micellar liquid chromatography (MLC) has been used primarily for the separation of neutral analytes of varying polarities, most commonly phenols and polyaromatic hydrocarbons, but does not seem to have been used to study aromatic hydroxy acids in detail. We have studied the separation of hydroxybenzoic acid mixtures, including monohydroxybenzoic and dihydroxybenzoic acid positional isomers by MLC. Sodium dodecylsulfate (SDS) is investigated as the modifying surfactant on a C18 ultra-high performance liquid chromatography (UHPLC) column (100 × 2.1mm, 1.8 μm). The addition of only SDS (no organic solvent) to the mobile phase reduced the influence of hydrophobic interactions while improving the retention times, resolution, and peak shapes, even at concentrations below the critical micellization concentration (CMC). The UHPLC separation of 7 hydroxybenzoic acids, including 6 dihydroxybenzoic acid positional isomers and one trihydroxybenzoic acid, is achieved with high efficiency using 0.1% SDS in 1.84 mM sulfuric acid (pH 2.43) mobile phase, in less than 6 min with a flow rate of 0.3 mL min(-1), and in less than four min with a flow rate of 0.7 mL min(-1). Six monohydroxybenzoic acid isomers are also effectively separated by MLC, using a 0.5% SDS mobile phase modifier, in less than 20 min with a flow rate of 0.3 mL min(-1), and in less than 14 min with a flow rate of 0.7 mL min(-1). The 3 phthalic acid isomers could be separated using a similar mobile phase and flow rates in less than 6 and 4 min. Solute-micelle equilibrium constants and partition coefficients are calculated for 6 monohydroxybenzoic acids based on a plot of MLC retention factor vs. mobile phase micelle concentration. All aromatic acid isomers studied can be classified as binding solutes in the MLC retention mechanism. Less effective separations are observed with shorter chain surfactants, leading to higher retention times and poor peak shapes. It is concluded that increasing chain length led to more

  9. [Trans isomers of unsaturated fatty acids increase the risk of atherosclerosis-related circulatory system diseases].

    PubMed

    Perova, N V; Metel'skaia, V A; Boĭtsov, S A

    2013-01-01

    The paper provides a review of the literature on a relevant non-drug prevention problem, namely the negative effect of trans isomers of unsaturated fatty acids (trans-UFA) on the risk of circulatory system diseases (CSD) and other chronic noncommunicable diseases. It gives data on the specific features of the structure and ability of trans-UFA to elevate the plasma levels of atherogenic low-density lipoproteins and to lower those of non/antiatherogenic high-density lipoproteins. The natural sources of their moderate content in the animal fats from ruminants and those of their redundant content in the margarines manufactured by hydrogenation of liquid vegetable oils are described. A new technology for preparing soft margarines (spreads) is presented, which can produce fatty products that do not virtually contain trans-UFA. There is evidence that trans-UFA can considerably raise the risk of CSD and their acute complications. It is concluded that the manufacture of fatty products with low and even no trans-UFA levels should be expanded in Russia to improve its population's health.

  10. Incorporation and metabolism of dietary trans isomers of linolenic acid alter the fatty acid profile of rat tissues.

    PubMed

    Loï, C; Chardigny, J M; Almanza, S; Leclere, L; Ginies, C; Sébédio, J L

    2000-10-01

    To study the influence on lipid metabolism and platelet aggregation of the fatty acid isomerization that occurs during heat treatment, weanling rats were fed for 8 wk a diet enriched with 5% isomerized (experimental group) or normal (control group) canola oil. Geometrical isomers of alpha-linolenic acid representing 0.2 g/100 g of the experimental diet were incorporated into liver, platelets, aorta and heart, at the expense of their cis homologue and of 18:2(n-6). The major isomer, 9c,12c,15t-18:3, was also metabolized to 5c,8c,11c,14c,17t-20:5 and to an unknown compound, found in liver, platelets and aorta, which has been identified tentatively as 7c, 10c,13c,16c,19t-22:5. The greater 20:4(n-6)/18:2(n-6) ratio in the liver, platelets and heart of the experimental group than the control group indicated an enhancement of desaturation activities. This induced a higher content of long-chain (n-6) fatty acids in the experimental group. Platelet aggregation tended to be slightly higher (P: = 0.065) in the experimental group. We conclude that 0.2 g of trans isomers of alpha-linolenic acid per 100 g of diet was sufficient to be incorporated and metabolized, thus altering the fatty acid profile of rat tissues.

  11. Maternal dietary Alpine butter intake affects human milk: fatty acids and conjugated linoleic acid isomers.

    PubMed

    Bertschi, Isabelle; Collomb, Marius; Rist, Lukas; Eberhard, Pius; Sieber, Robert; Bütikofer, Ulrich; Wechsler, Daniel; Folkers, Gerd; von Mandach, Ursula

    2005-06-01

    Consumption of CLA by lactating women affects the composition of their milk, but the pattern of the different CLA isomers is still unknown. We determined the effects of short maternal supplementation with CLA-rich Alpine butter on the occurrence of FA and CLA isomers in human milk. In an open randomized controlled study with a two-period cross-over design, milk FA and CLA isomer concentrations were measured on postpartum days > or = 20 in two parallel groups of lactating women before, during, and after consumption of defined quantities of Alpine butter or margarine with comparable fat content (10 d of butter followed by 10 d of margarine for one group, and vice versa in the other). In the 16 women who completed the study (8/group), Alpine butter supplementation increased the C16 and C18 FA, the sum of saturated FA, the 18:1 trans FA, and the trans FA with CLA. The CLA isomer 18:2 c9,t11 increased by 49.7%. Significant increases were also found for the isomers t9,t11, t7,c9, t11,c13, and t8,c10 18:2. The remaining nine of the total 14 detectable isomers showed no changes, and concentrations were <5 mg/100 g fat. A breastfeeding mother can therefore modulate the FA/CLA supply of her child by consuming Alpine butter. Further studies will show whether human milk containing this FA and CLA isomer pattern acts as a functional food for newborns.

  12. Isomer-specific trophic transfer of perfluorocarboxylic acids in the marine food web of Liaodong Bay, North China.

    PubMed

    Zhang, Zhong; Peng, Hui; Wan, Yi; Hu, Jianying

    2015-02-03

    Trophic transfers of perfluorocarboxylic acids (PFCAs) have been well studied in aquatic food webs; however, most studies examined PFCAs as single compounds without differentiating isomers. In this study, an in-port derivatization GC-MS method was used to determine PFCA (perfluorooctanoic acid, PFOA; perfluorononanoic acid, PFNA; perfluorodecanoate acid, PFDA; perfluoroundecanoate acid, PFUnDA; perfluorododecanoate acid, PFDoDA; perfluorotridecanoate acid, PFTriDA, and perfluorotetradecanoate acid, PFTeDA) structural isomers in 11 marine species including benthic invertebrates, fishes, and gulls collected in November 2006 from Liaodong Bay in China. The total concentrations of linear PFCAs were 0.35-1.10, 0.93-2.61, and 2.13-2.69 ng/g ww, and the corresponding percentages of branched PFCAs to linear PFCAs were 6.6-15.5%, 4.2-9.9%, and 4.5-6.0% in invertebrates, fishes, and birds, respectively. Except for linear PFOA, significant positive relationships were found between the concentrations of all the target linear PFCAs and trophic levels, and the trophic magnification factors (TMFs) ranged from 1.90 to 4.88. Positive correlations between the concentrations of branched PFCAs isomers and trophic levels were also observed but were without statistical significance. The relatively high biomagnification of linear isomers of PFCAs would lead to low percentages of branched PFCAs to total PFCAs in organisms at high trophic levels. This study for the first time clarified isomer-specific trophic transfers of PFCAs in a marine food web.

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

    PubMed

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

    2016-06-01

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

  14. The 10t,12c isomer of conjugated linoleic acid inhibits fatty acid synthase expression and enzyme activity in human breast, colon, and prostate cancer cells.

    PubMed

    Lau, Dominic S Y; Archer, Michael C

    2010-01-01

    The objective of this study was to determine whether downregulation of fatty acid synthase (FAS) expression and/or inhibition of its activity by the two major CLA isomers, 10t,12c and 9c,11t CLA, could contribute to their inhibitory effect on the growth of human breast (MCF-7), colon (HT-29) and prostate (LNCaP) cancer cell lines. We first confirmed and extended the results of others showing that the inhibitory action of CLA on proliferation is dependent on the cell type as well as the structure of the isomer, the 10,12 isomer being a more potent inhibitor than the 9,11 isomer in the concentration range 25-100 microM. By Western analysis, we showed that 10,12 CLA downregulated FAS expression in all of the cell lines in a concentration-dependent manner, but the 9,11 isomer had no effect. Both isomers inhibited FAS enzyme activity, but 10,12 CLA was again more potent than the 9,11 isomer. Our results suggest that downregulation of FAS by 10,12 CLA, but not by the 9,11 isomer, as well as inhibition of FAS enzyme activity by both isomers, may contribute to growth inhibition of cancer cells but only at relatively high concentrations.

  15. Apoptosis- and differentiation-inducing activities of jacaric acid, a conjugated linolenic acid isomer, on human eosinophilic leukemia EoL-1 cells.

    PubMed

    Liu, Wai-Nam; Leung, Kwok-Nam

    2014-11-01

    Conjugated linolenic acids (CLNAs) are a group of naturally occurring positional and geometrical isomers of the C18 polyunsaturated essential fatty acid, linolenic acid (LNA), with three conjugated double bonds (C18:3). Although previous research has demonstrated the growth-inhibitory effects of CLNA on a wide variety of cancer cell lines in vitro, their action mechanisms and therapeutic potential on human myeloid leukemia cells remain poorly understood. In the present study, we found that jacaric acid (8Z,10E,12Z-octadecatrienoic acid), a CLNA isomer which is present in jacaranda seed oil, inhibited the in vitro growth of human eosinophilic leukemia EoL-1 cells in a time- and concentration-dependent manner. Mechanistic studies showed that jacaric acid triggered cell cycle arrest of EoL-1 cells at the G0/G1 phase and induced apoptosis of the EoL-1 cells, as measured by the Cell Death Detection ELISAPLUS kit, Annexin V assay and JC-1 dye staining. Notably, the jacaric acid-treated EoL-1 cells also underwent differentiation as revealed by morphological and phenotypic analysis. Collectively, our results demonstrated the capability of jacaric acid to inhibit the growth of EoL-1 cells in vitro through triggering cell cycle arrest and by inducing apoptosis and differentiation of the leukemia cells. Therefore, jacaric acid might be developed as a potential candidate for the treatment of certain forms of myeloid leukemia with minimal toxicity and few side effects.

  16. Multispectroscopic and docking studies on the binding of chlorogenic acid isomers to human serum albumin: Effects of esteryl position on affinity.

    PubMed

    Tang, Bin; Huang, Yanmei; Ma, Xiangling; Liao, Xiaoxiang; Wang, Qing; Xiong, Xinnuo; Li, Hui

    2016-12-01

    Structural differences among various dietary polyphenols affect their absorption, metabolism, and bioactivities. In this work, chlorogenic acid (CA) and its two positional isomers, neochlorogenic acid (NCA) and cryptochlorogenic acid (CCA), were investigated for their binding reactions with human serum albumin (HSA) using fluorescence, ultraviolet-visible, Fourier transform infrared and circular dichroism spectroscopies, as well as molecular docking. All three isomers were bound to HSA at Sudlow's site I and affected the protein secondary structure. CCA presented the strongest ability of hydrogen-bond formation, and both CA and NCA generated more electrostatic interactions with HSA. The albumin-binding capacity of these compounds decreased in the order CCA>NCA>CA. The compound with 4-esteryl structure showed higher binding affinity and larger conformational changes to HSA than that with 3- or 5-esteryl structures. These comparative studies on structure-affinity relationship contributed to the structural modification and design of phenolic food additives or new polyphenol-like drugs.

  17. Fatty acid profile of Canadian dairy products with special attention to the trans-octadecenoic acid and conjugated linoleic acid isomers.

    PubMed

    Mendis, Sanjaya; Cruz-Hernandez, Cristina; Ratnayake, Walisundera M N

    2008-01-01

    Current scientific evidence indicates that consumption of industrial trans fatty acids (TFA) produced via partial hydrogenation of vegetable oils increases the risk of coronary heart disease. However, some studies have suggested that ruminant TFA, especially vaccenic acid (VA or 11t-18:1) and rumenic acid (RA or 9c,11t-18:2), which is a conjugated linoleic acid (CLA) isomer, may have potential beneficial health effects for humans. To date, no concerted effort has been made to provide detailed isomer composition of ruminant TFA and CLA of Canadian dairy products, information that is required to properly assess their nutritional impacts. To this end, we analyzed the fatty acid profile of popular brands of commercial cheese (n = 17), butter (n = 12), milk (n = 8), and cream (n = 4) sold in retail stores in Ottawa, Canada, in 2006-2007 by silver nitrate thin-layer chromatography and gas liquid chromatography. The average total TFA content of cheese, butter, milk, and cream samples were 5.6, 5.8, 5.8, and 5.5% of total fatty acids, respectively. VA was the major trans-octadecenoic acid (18:1) isomer in all the Canadian dairy samples with average levels of (as % total trans-18:1) 33.9% in cheese, 35.6% in butter, 31.0% milk, and 30.1% in cream. The different dairy products contained very similar levels of CLA, which ranged from 0.5 to 0.9% of total fat. RA was the major CLA isomer of all the dairy products, accounting for 82.4-83.2% of total CLA. There were no significant differences (P > 0.05) in the fatty acid profile between the 4 different dairy groups, which suggests lack of processing effects on the fatty acid profile of dairy fat.

  18. Anti-allergic effect of the naturally-occurring conjugated linolenic acid isomer, jacaric acid, on the activated human mast cell line-1

    PubMed Central

    LIU, WAI NAM; LEUNG, KWOK NAM

    2015-01-01

    The present study aimed to investigate the immunomodulatory effect of jacaric acid, a naturally-occurring conjugated linolenic acid isomer that can be found in jacaranda seed oil, on the activated human mast cell line-1 (HMC-1). Our previous studies have demonstrated that jacaric acid only exerted minimal, if any, cytotoxicity on normal murine cells. In the present study, jacaric acid at concentrations ≤100 µM did not exhibit direct cytotoxicity on human peripheral blood mononuclear cells after 72 h of incubation, as determined by the MTT reduction assay. By contrast, jacaric acid could alleviate the calcium ionophore A23187 and phorbol 12-myristate 13-acetate-triggered allergic response in the HMC-1 cells at concentrations that were non-cytotoxic to the HMC-1 cells. Following pre-treatment with jacaric acid, the secretion of two inflammatory mediators, β-N-acetylglucosaminidase and tryptase, as well as the T helper 2 cytokines [interleukin (IL)-4 and IL-13] was significantly reduced in HMC-1 cells. The alleviation of allergic response was accompanied by downregulation of the matrix metalloproteinase-2 and −9 proteins and upregulation of the tissue inhibitor of metalloproteinase-1 protein. Collectively, the results indicated that the naturally-occurring jacaric acid exhibits a suppressive effect on the allergic response in activated human mast cells in vitro, and this could not be attributed to the direct cytotoxicity of jacaric acid on the treated cells. PMID:26623027

  19. Anti-allergic effect of the naturally-occurring conjugated linolenic acid isomer, jacaric acid, on the activated human mast cell line-1.

    PubMed

    Liu, Wai Nam; Leung, Kwok Nam

    2015-11-01

    The present study aimed to investigate the immunomodulatory effect of jacaric acid, a naturally-occurring conjugated linolenic acid isomer that can be found in jacaranda seed oil, on the activated human mast cell line-1 (HMC-1). Our previous studies have demonstrated that jacaric acid only exerted minimal, if any, cytotoxicity on normal murine cells. In the present study, jacaric acid at concentrations ≤100 µM did not exhibit direct cytotoxicity on human peripheral blood mononuclear cells after 72 h of incubation, as determined by the MTT reduction assay. By contrast, jacaric acid could alleviate the calcium ionophore A23187 and phorbol 12-myristate 13-acetate-triggered allergic response in the HMC-1 cells at concentrations that were non-cytotoxic to the HMC-1 cells. Following pre-treatment with jacaric acid, the secretion of two inflammatory mediators, β-N-acetylglucosaminidase and tryptase, as well as the T helper 2 cytokines [interleukin (IL)-4 and IL-13] was significantly reduced in HMC-1 cells. The alleviation of allergic response was accompanied by downregulation of the matrix metalloproteinase-2 and -9 proteins and upregulation of the tissue inhibitor of metalloproteinase-1 protein. Collectively, the results indicated that the naturally-occurring jacaric acid exhibits a suppressive effect on the allergic response in activated human mast cells in vitro, and this could not be attributed to the direct cytotoxicity of jacaric acid on the treated cells.

  20. Interstellar isomers

    NASA Technical Reports Server (NTRS)

    Defrees, D.; Mclean, D.; Herbst, E.

    1986-01-01

    Both observational and theoretical studies of molecular clouds are hindered by many difficulties. One way to partially circumvent the difficulties of characterizing the chemistry within these objects is to study the relative abundances of isomers which are synthesized from a common set of precursors. Unfortunately, only one such system has been confirmed, the HCN/HNC pair of isomers. While the basic outlines of its chemistry have been known for some years, there are still many aspects of the chemistry which are unclear. Another potential pair of isomers is HCO+/HOC+; HCO+ is an abundant instellar molecule and a tentative identification of HOC+ has been made in Sgr B2. This identification is being challenged, however, based on theoretical and laboratory evidence that HOC+ reacts with H2. Another potential pair of interstellar isomers is methyl cyanide (CH3CN, acetonitrile) and methyl isocyanide (CH3NC). The cyanide is well known, however the isocyanide has yet to be observed despite theoretical predictions that appreciable quantities should be present.

  1. Identification, Tissue Distribution, and Bioaccumulation Potential of Cyclic Perfluorinated Sulfonic Acids Isomers in an Airport Impacted Ecosystem.

    PubMed

    Wang, Yuan; Vestergren, Robin; Shi, Yali; Cao, Dong; Xu, Lin; Cai, Yaqi; Zhao, Xiaoli; Wu, Fengchang

    2016-10-18

    The use of cyclic perfluoroalkyl acids as anticorrosive agents in hydraulic fluids remains a poorly characterized source of organofluorine compounds to the environment. Here, we investigated the presence of perfluoroethylenecyclohexanesulfonate (PFECHS) isomers in environmental samples for the first time using a combination of high resolution and tandem mass spectrometry. Five distinct peaks attributed to different isomers of PFECHS and perfluoropropylcyclopentanesulfonate (PFPCPeS) were identified in environmental samples. The sum of PFECHS and PFPCPeS isomers displayed logarithmically decreasing spatial trends in water (1.04-324 ng/L) and sediment samples (Isomer-specific differences in the tissue/blood distribution ratios and BAFwhole-body indicate that ring structure and position of the sulfonic acid group affect the bioaccumulation potential of cyclic perfluoroalkyl acids. Based on the high mobility and moderate bioaccumulation potential of cyclic perfluorinated acids it is suggested that contamination of aquifers used for drinking water around airports may be a hitherto overlooked problem for this novel class of contaminants.

  2. Bioaccumulation of perfluoroalkyl acids including the isomers of perfluorooctane sulfonate in carp (Cyprinus carpio) in a sediment/water microcosm.

    PubMed

    Fang, Shuhong; Zhang, Yifeng; Zhao, Shuyan; Qiang, Liwen; Chen, Meng; Zhu, Lingyan

    2016-12-01

    Carp (Cyprinus carpio) were exposed to perfluoroalkyl acids (PFAAs) including perfluorooctane sulfonate (PFOS) isomers in an artificially contaminated sediment/water microcosm. The uptake constant of PFAAs increased with increasing carbon chain length, whereas the elimination coefficient displayed the opposite trend, suggesting that carbon chain length plays an important role in the bioaccumulation of PFAAs. When the contribution of suspended particulate matter was taken into account, the bioaccumulation factors (BAFs) became lower (3.61-600 L/kg) compared with BAFs derived from only considering the absorption from free PFAAs in water (3.85-97000 L/kg). The results indicate that suspended particulate matter in water constitutes an important source of exposure for aquatic organisms to long-chain PFAAs. Linear (n-)PFOS was preferentially accumulated compared with branched isomers in carp. Among the branched isomers, 1m-PFOS displayed the greatest bioaccumulation, whereas m2 -PFOS had the lowest. Linear PFOS displayed greater partitioning ability from blood to other tissues over branched PFOS (br-PFOS) isomers, leading to a relatively lower n-PFOS proportion in blood. In summary, suspended particulate matter made a contribution to the accumulation of long-chain PFAAs in aquatic organisms, and n-PFOS was preferentially accumulated compared with br-PFOS isomers. Environ Toxicol Chem 2016;35:3005-3013. © 2016 SETAC.

  3. Regiospecific Distribution of trans-Octadecenoic Acid Positional Isomers in Triacylglycerols of Partially Hydrogenated Vegetable Oil and Ruminant Fat.

    PubMed

    Yoshinaga, Kazuaki; Kawamura, Yoshinori; Kitayama, Takashi; Nagai, Toshiharu; Mizobe, Hoyo; Kojima, Koichi; Watanabe, Yomi; Sato, Shinichi; Beppu, Fumiaki; Gotoh, Naohiro

    2015-01-01

    It is revealed that binding position of fatty acid in triacylglycerol (TAG) deeply relates to the expression of its function. Therefore, we investigated the binding positions of individual trans-octadecenoic acid (trans-C18:1) positional isomers, known as unhealthy fatty acids, on TAG in partially hydrogenated canola oil (PHCO), milk fat (MF), and beef tallow (BT). The analysis was carried out by the sn-1(3)-selective transesterification of Candida antarctica Lipase B and by using a highly polar ionic liquid capillary column for gas chromatography-flame ionization detection. Trans-9-C18:1, the major trans-C18:1 positional isomer, was selectively located at the sn-2 position of TAG in PHCO, although considerable amounts of trans-9-C18:1 were also esterified at the sn-1(3) position. Meanwhile, trans-11-C18:1, the major isomer in MF and BT, was preferentially located at the sn-1(3) position. These results revealed that the binding position of trans-C18:1 positional isomer varies between various fats and oils.

  4. Heterogeneous OH Oxidation of Two Structure Isomers of Dimethylsuccinic Acid Aerosol: Reactivity and Oxidation Products

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Cheng, C. T.; Wilson, K. R.

    2014-12-01

    Organic aerosol contribute a significant mass fraction of ambient aerosol carbon and can continuously undergo oxidation by colliding with gas phase OH radicals. Although heterogeneous oxidation plays a significant role in the chemical transformation of organic aerosol, the effect of molecular structure on the reactivity and oxidation products remains unclear. We investigate the effect of branched methyl groups on the reactivity of two dimethylsuccinic acids (2,2-dimethylsuccinic acid (2,2-DMSA) and 2,3-dimethylsuccinic acid (2,3-DMSA)) toward gas phase OH radicals in an atmospheric pressure aerosol flow tube reactor. The oxidation products formed upon oxidation is characterized in real time by the Direct Analysis in Real Time (DART), an ambient soft ionization source. The 2,2-DMSA and 2,3-DMSA are structural isomers with the same oxidation state (OSC = -0.33) and carbon number (NC = 6), but different branching characteristics (2,2-DMSA has one secondary carbon and 2,3-DMSA has two tertiary carbons). The difference in molecular distribution of oxidation products observed in these two structural isomers would allow one to assess the sensitivity of kinetics and chemistry to the position of branched methyl group in the DMSA upon oxidation. We observe that the reactivity of 2,3-DMSA toward OH radicals is about 2 times faster than that of 2,2-DMSA. This difference in OH reactivity may attribute to the stability of the carbon-centered radical generated after hydrogen abstraction because an alkyl radical formed from the hydrogen abstraction on a tertiary carbon in 2,3-DMSA is more stable than on a secondary carbon in 2,2-DMSA. For both 2,2-DMSA and 2,3-DMSA, the molecular distribution and evolution of oxidation products is characterized by a predominance of functionalization products at the early oxidation stages. When the oxidation further proceeds, the fragmentation becomes more favorable and the oxidation mainly leads to the reduction of the carbon chain length through

  5. Analysis of histidine and urocanic acid isomers by reversed-phase high-performance liquid chromatography.

    PubMed

    Hermann, K; Abeck, D

    2001-01-05

    The qualitative separation performance of a C18, C8 and C4 reversed-phase column was investigated for the separation of histidine and its metabolites histamine, 1-methyihistamine and trans- and cis-urocanic acid. Trans- and cis-urocanic acid were baseline separated from their precursor histidine on all three columns using isocratic elution with a mobile phase composed of 0.01 M aqueous TEAP pH 3.0 and acetonitrile at a ratio of 98:2 (v/v). However, histidine was not separated from histamine and 1-methyihistamine. Selecting the C8 column and introducing 0.005 M of the ion pairing reagent 1-octanesulfonic acid sodium salt into the aqueous solution and acetonitrile at a ratio of 90:10 (v/v), significantly improved the separation. The separation was also followed by a change in the retention times and the order of elution. The sequence of elution was histidine, cis-urocanic acid, trans-urocanic acid, histamine and 1-methylhistamine with retention times of 5.58 +/- 0.07, 7.03 +/- 0.15, 7.92 +/- 0.18, 18.77 +/- 0.24 and 20.79 +/- 0.21 min (mean +/- SD; n=5). The separation on the C8 column in the presence of the ion-pairing reagent was further improved with gradient elution that resulted in a reduction in the retention times and elution volumes of histamine and 1-methylhistamine. The detection limits of histidine and trans-urocanic acid at a wavelength of 210 nm and an injection volume of 0.05 ml were 5 x 10(-8) mol l(-1) (n=3). The kinetic of the in-vitro conversion of trans- into the cis-isomer after UV irradiation was depending on the time of exposure and the energy of the light source. UVB light induced a significantly faster conversion than UVA light. TUCA and cUCA samples kept at -25 degrees C were stable for up to 50 weeks. Samples, eluted from human skin showed various concentrations of histidine and trans- and cis-urocanic acid with an average of 1.69 +/- 0.33 x 10(-5) mol l(-1), 1.17 +/- 0.43 x 10(-5) mol l(-1) and 1.67 +/- 0.33 x 10(-5) mol l(-1), respectively

  6. Synthesis of hydroxytyrosol, 2-hydroxyphenylacetic acid, and 3-hydroxyphenylacetic acid by differential conversion of tyrosol isomers using Serratia marcescens strain.

    PubMed

    Allouche, Noureddine; Sayadi, Sami

    2005-08-10

    We investigated to develop an effective procedure to produce the potentially high-added-value phenolic compounds through bioconversion of tyrosol isomers. A soil bacterium, designated Serratia marcescens strain, was isolated on the basis of its ability to grow on p-tyrosol (4-hydroxyphenylethanol) as a sole source of carbon and energy. During growth on p-tyrosol, Ser. marcescens strain was capable of promoting the formation of hydroxytyrosol. To achieve maximal hydroxytyrosol yield, the growth state of the culture utilized for p-tyrosol conversion as well as the amount of p-tyrosol that was treated were optimized. The optimal yield of hydroxytyrosol (80%) was obtained by Ser. marcescens growing cells after a 7-h incubation using 2 g/L of p-tyrosol added at the end of the exponential phase to a culture pregrown on 1 g/L of p-tyrosol. Furthermore, the substrate specificity of the developed biosynthesis was investigated using m-tyrosol (3-hydroxyphenylethanol) and o-tyrosol (2-hydroxyphenylethanol) as substrates. Ser. marcescens strain transformed completely m-tyrosol and o-tyrosol into 3-hydroxyphenylacetic acid and 2-hydroxyphenylacetic acid, respectively, via the oxidation of the side chain carbon of the treated substrates. This proposed procedure is an alternative approach to obtain hydroxytyrosol, 2-hydroxyphenylacetic acid, and 3-hydroxyphenylacetic acid in an environmentally friendly way which could encourage their use as alternatives in the search for replacement of synthetic food additives.

  7. Development of an alternative eluent system for Ag+-HPLC analysis of conjugated linoleic acid isomers.

    PubMed

    Müller, André; Düsterloh, Kaja; Ringseis, Robert; Eder, Klaus; Steinhart, Hans

    2006-02-01

    In this study, 13 different eluent systems containing n-hexane, n-heptane and iso-octane as main solvents and ACN, propionitrile (PCN) and butyronitrile (BCN) in concentrations between 0.1 and 0.2% as modifiers were tested for their influence on retention time shifts (RTS) and resolution of conjugated linoleic acid (CLA) methyl esters using two ChromSpher 5 Lipids columns (250 mm x 4.6 mm, 5 microm) in series. The eluent system n-hexane/PCN 0.2% showed the highest stability with an obtained RTS of 0.26 min for the cis/trans-group after 14 consecutive injections of a CLA isomer mix compared to the reference system of n-hexane/ACN 0.15% (RTS of 2.35 min). This enhanced stability is due to better solubility of PCN in n-hexane compared to ACN. The enhanced stability coincided with a negligible loss in resolution for the cis,trans/trans,cis- and the cis,cis-groups. As shown for the analysis of human aortic endothelial cells spiked with t10c12-CLA, data from CLA-analysis by Ag+-HPLC-DAD must be judged very carefully, especially at low concentrations, as coeluting matrix compounds may give false-positive results. Therefore, results should be confirmed by GC-FID and GC-MS.

  8. Differentiation of Sialyl Linkage Isomers by One-Pot Sialic Acid Derivatization for Mass Spectrometry-Based Glycan Profiling.

    PubMed

    Nishikaze, Takashi; Tsumoto, Hiroki; Sekiya, Sadanori; Iwamoto, Shinichi; Miura, Yuri; Tanaka, Koichi

    2017-02-21

    Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has been used for high-throughput glycan profiling analysis. In spite of the biological importance of sialic acids on nonreducing ends of glycans, it is still difficult to analyze glycans containing sialic acid residues due to their instability and the presence of linkage isomers. In this Article, we describe a one-pot glycan purification/derivatization method employing a newly developed linkage-specific sialic acid derivatization for MS-based glycan profiling with differentiation of sialyl linkage isomer. The derivatization, termed sialic acid linkage specific alkylamidation (SALSA), consists of sequential two-step alkylamidations. As a result of the reactions, α2,6- and α2,3-linked sialic acids are selectively amidated with different length of alkyl chains, allowing distinction of α2,3-/α2,6-linkage isomers from given mass spectra. Our studies using N-glycan standards with known sialyl linkages proved high suitability of SALSA for reliable relative quantification of α2,3-/α2,6-linked sialic acids compared with existing sialic acid derivatization approaches. SALSA fully stabilizes both α2,3- and α2,6-linked sialic acids by alkylamidation; thereby, it became possible to combine SALSA with existing glycan analysis/preparation methods as follows. The combination of SALSA and chemoselective glycan purification using hydrazide beads allows easy one-pot purification of glycans from complex biological samples, together with linkage-specific sialic acid stabilization. Moreover, SALSA-derivatized glycans can be labeled via reductive amination without causing byproducts such as amide decomposition. This solid-phase SALSA followed by glycan labeling has been successfully applied to human plasma N-glycome profiling.

  9. Biotransformations of 2-hydroxy-2-(ethoxyphenylphosphinyl)acetic acid and the determination of the absolute configuration of all isomers.

    PubMed

    Majewska, Paulina

    2015-08-01

    2-Hydroxy-2-(ethoxyphenylphosphinyl)acetic acid, a new type of organophosphorus compound possessing two stereogenic centers, was investigated. Racemic 2-butyryloxy-2-(ethoxyphenylphosphinyl)acetic acid was synthesized and hydrolyzed using four bacterial species as biocatalysts. In all cases the reaction was more or less stereoselective and isomers bearing a phosphorus atom with an (SP)-configuration were hydrolyzed preferentially. The observed (1)H and (31)P NMR chemical shifts of Mosher esters of 2-hydroxy-2-(ethoxyphenylphosphinyl)acetic acid were correlated with the configurations of both stereogenic centers of all four stereoisomers.

  10. Estimated pKa values for the environmentally relevant C1 through C8 perfluorinated sulfonic acid isomers.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-10-14

    In order to estimate isomer-specific acidity constants (pKa) for the perfluorinated sulfonic acid (PFSA) environmental contaminants, the parameterization method 6 (PM6) pKa prediction method was extensively validated against a wide range of carbon oxyacids and related sulfonic/sulfinic acids. Excellent pKa prediction performance was observed for the carbon oxyacids using the PM6 method, but this approach was found to have a severe positive bias for sulfonic/sulfinic acids. To overcome this obstacle, a correlation was developed between non-adjusted PM6 pKa values and the corresponding experimentally obtained/estimated acidity constants for a range of representative alkyl, aryl and halogen-substituted sulfonic acids. Application of this correction to the PM6 values allows for extension of this computational method to a new acid functional group. When used to estimate isomer-specific pKa values for the C1 through C8 PFSAs, the modified PM6 approach suggests an adjusted pKa range from -5.3 to -9.0, indicating that all members of this class of well-known environmental contaminants will be effectively completely dissociated in aquatic systems.

  11. Ultrasound in fatty acid chemistry: synthesis of a 1-pyrroline fatty acid ester isomer from methyl ricinoleate.

    PubMed

    Lie Ken Jie, M S; Syed-Rahmatullah, M S; Lam, C K; Kalluri, P

    1994-12-01

    A novel 1-pyrroline fatty acid ester isomer (viz. 8-5-hexyl-1-pyrrolin-2-yl) octanoate) has been synthesized from methyl ricinoleate by two routes with an overall yield of 42 and 30%, respectively. Most of the reactions are carried out under concomitant ultrasonic irradiation (20 KHz, ca. 53 watts/cm2). Under such a reaction condition, the reaction time is considerably shortened, and product yields are high. Dehydrobromination under concomitant ultrasonic irradiation of methyl 9, 10-dibromo-12-hydroxyoctadecanoate with KOH in EtOH furnishes methyl 12-hydroxy-9-octadecynoate (66%) within 15 min. Hydration of the latter under ultrasound with mercury(II)acetate in aqueous tetrahydrofuran yields exclusively methyl 12-hydroxy-9-oxo-octadecanoate (95%) in 30 min. The hydroxy group in the latter compound is transformed to the azido function via the mesylate, and treatment of the azido-oxo intermediate (methyl 12-azido-9-oxooctadecanoate) with Ph3P under ultrasonic irradiation furnishes the requisite 1-pyrroline fatty acid ester (77%). The same azido-oxo intermediate has also been obtained by the oxidation of methyl 12-azido-9-cis-octadecenoate using benzoquinone and a catalytic amount of Pd(II)chloride in aqueous tetrahydrofuran under concomitant ultrasonic irradiation (90 min) to give the product in 45% yield. The latter reaction does not take place even under prolonged silent stirring of the reaction mixture.

  12. Perfluorinated acid isomer profiling in water and quantitative assessment of manufacturing source.

    PubMed

    Benskin, Jonathan P; Yeung, Leo W Y; Yamashita, Nobuyoshi; Taniyasu, Sachi; Lam, Paul K S; Martin, Jonathan W

    2010-12-01

    A method for isomer profiling of perfluorinated compounds (PFCs) in water was developed and applied to quantitatively assess the contributions from electrochemical (ECF) and telomer manufacturing processes around source regions of North America, Asia, and Europe. With the exception of 3 sites in Japan, over 80% of total perfluorooctanoate (PFOA, C(7)F(15)COO(-)) was from ECF, with the balance attributable to strictly linear (presumably telomer) manufacturing source(s). Comparing PFOA isomer profiles in samples from China, with PFOA obtained from a local Chinese manufacturer, indicated <3% difference in overall branched isomer content; thus, exclusive contribution from local ECF production cannot be ruled out. In Tokyo Bay, ECF, linear-telomer, and isopropyl-telomer sources contributed to 33%, 53%, and 14% of total PFOA, respectively. Perfluorooctane sulfonate (PFOS, C(8)F(17)SO(3)(-)) isomer profiles were enriched in branched content (i.e., >50% branched) in the Mississippi River but in all other locations were similar or only slightly enriched in branched content relative to historical ECF PFOS. Isomer profiles of other PFCs are also reported. Overall, these data suggest that, with the exception of Tokyo Bay, ECF manufacturing has contributed to the bulk of contamination around these source regions, but other sources are significant, and remote sites should be monitored.

  13. Power optimization in logic isomers

    NASA Technical Reports Server (NTRS)

    Panwar, Ramesh; Rennels, David; Alkalaj, Leon

    1993-01-01

    Logic isomers are labeled, 2-isomorphic graphs that implement the same logic function. Logic isomers may have significantly different power requirements even though they have the same number of transistors in the implementation. The power requirements of the isomers depend on the transition activity of the input signals. The power requirements of isomorphic graph isomers of n-input NAND and NOR gates are shown. Choosing the less power-consuming isomer instead of the others can yield significant power savings. Experimental results on a ripple-carry adder are presented to show that the implementation using the least power-consuming isomers requires approximately 10 percent less power than the implementation using the most power-consuming isomers. Simulations of other random logic designs also confirm that designs using less power-consuming isomers can reduce the logic power demand by approximately 10 percent as compared to designs using more power-consuming isomers.

  14. Hexadecenoic Fatty Acid Isomers in Human Blood Lipids and Their Relevance for the Interpretation of Lipidomic Profiles

    PubMed Central

    Sansone, Anna; Tolika, Evanthia; Louka, Maria; Sunda, Valentina; Deplano, Simone; Melchiorre, Michele; Anagnostopoulos, Dimitrios; Chatgilialoglu, Chryssostomos; Formisano, Cesare; Di Micco, Rosa; Faraone Mennella, Maria Rosaria; Ferreri, Carla

    2016-01-01

    Monounsaturated fatty acids (MUFA) are emerging health biomarkers, and in particular the ratio between palmitoleic acid (9cis-16:1) and palmitic acid (16:0) affords the delta-9 desaturase index that is increased in obesity. Recently, other positional and geometrical MUFA isomers belonging to the hexadecenoic family (C16 MUFA) were found in circulating lipids, such as sapienic acid (6cis-16:1), palmitelaidic acid (9trans-16:1) and 6trans-16:1. In this work we report: i) the identification of sapienic acid as component of human erythrocyte membrane phospholipids with significant increase in morbidly obese patients (n = 50) compared with age-matched lean controls (n = 50); and ii) the first comparison of erythrocyte membrane phospholipids (PL) and plasma cholesteryl esters (CE) in morbidly obese patients highlighting that some of their fatty acid levels have opposite trends: increases of both palmitic and sapienic acids with the decrease of linoleic acid (9cis,12cis-18:2, omega-6) in red blood cell (RBC) membrane PL were reversed in plasma CE, whereas the increase of palmitoleic acid was similar in both lipid species. Consequentially, desaturase enzymatic indexes gave different results, depending on the lipid class used for the fatty acid content. The fatty acid profile of morbidly obese subjects also showed significant increases of stearic acid (C18:0) and C20 omega-6, as well as decreases of oleic acid (9cis-18:1) and docosahexaenoic acid (C22:6 omega-3) as compared with lean healthy controls. Trans monounsaturated and polyunsaturated fatty acids were also measured and found significantly increased in both lipid classes of morbidly obese subjects. These results highlight the C16 MUFA isomers as emerging metabolic marker provided that the assignment of the double bond position and geometry is correctly performed, thus identifying the corresponding lipidomic pathway. Since RBC membrane PL and plasma CE have different fatty acid trends, caution must also be used in the

  15. Screening of urocanic acid isomers in human basal and squamous cell carcinoma tumors compared with tumor periphery and healthy skin.

    PubMed

    Decara, Juan Manuel; Aguilera, José; Abdala, Roberto; Sánchez, Purificación; Figueroa, Félix L; Herrera, Enrique

    2008-10-01

    Trans-urocanic acid is a major chromophore for ultraviolet (UV) radiation in human epidermis. The UV induces photoisomerization of trans-urocanic acid (tUCA) form to cis-urocanic acid (cUCA) and has been reported as an important mediator in the immunosuppression induced by UV. This immunomodulation has been recognized as an important factor related to skin cancer development. This is the first time that UCA isomers have been measured in epidermis of skin biopsies from patients with squamous cell carcinoma (SCC) and with basal cell carcinoma (BCC) and compared with the tumor periphery and biopsies of healthy photoexposed and non-photoexposed skin as controls. The UCA isomers were separated and quantified by high performance liquid chromatography. Analysis of UCA in healthy skin showed significant increase in total UCA content in non-photoexposed body sites compared with highly exposed skins. In contrast, the percentage of cUCA was higher in photoexposed body sites. Maximal levels of cUCA were found in cheek, forehead and forearm and lower levels in abdomen and thigh. No differences were found in total UCA concentration between the tumor samples and healthy photoexposed skin. However, differences were found in relation between isomers. Higher levels of cUCA were detected in SCC biopsies (44% of total UCA) compared with samples of BCC and that of healthy photoexposed skin (30%). These results suggest that the UV radiation exposure, a main factor in development of SCC can be mediated, apart from direct effect to cells (DNA damage), by immunosuppression pathways mediated by high production of cUCA.

  16. Isolation of isochlorogenic acid isomers in flower buds of Lonicera japonica by high-speed counter-current chromatography and preparative high performance liquid chromatography.

    PubMed

    Guo, Wei; Wang, Liang; Gao, Yan; Zhao, Bonian; Wang, Daijie; Duan, Wenjuan; Yu, Zongyuan

    2015-02-15

    An efficient method was established by HSCCC combined with prep-HPLC for separating isochlorogenic acid isomers from flower buds of Lonicera japonica. The partially purified sample from the methanol extract of flower buds of L. japonica by silica gel column was separated by HSCCC to result in a fraction containing two isochlorogenic acid isomers. The fraction was further isolated by prep-HPLC to yield isochlorogenic acid A and isochlorogenic acid C with purities of 98% and 96%, and the total recoveries at 80.1% and 79.8%, respectively. The chemical structures of isochlorogenic acid isomers were confirmed by electrospray ionization mass spectrometry (ESI-MS) and (1)H nuclear magnetic resonance (NMR).

  17. Thermodynamics of the clusterization process of trans-isomers of unsaturated fatty acids at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vollhardt, D; Fainerman, V B; Miller, R

    2012-02-23

    In the frameworks of the quantum-chemical semiempirical PM3 method, the thermodynamic parameters of trans-isomers of unsaturated carboxylic acids at the air/water interface were studied. Systems with 18-26 carbon atoms in the alkyl chain and different positions of the double bond are considered. Using quantum-chemical semiempirical PM3 method enthalpy, Gibbs' energy of monomers' formation from the elementary compounds and absolute entropy of trans-unsaturated carboxylic acids are calculated. It has been shown that thermodynamic parameters mentioned above for isomers with the same number of carbon atoms in the hydrocarbon chain but different position of double bond are practically the same within the margin of error. For dimers, trimers, and tetramers of the four trans-unsaturated carboxylic acids, the thermodynamic parameters of clusterization were calculated. It is shown that the position of double bond does not significantly affect the values of thermodynamic parameters of formation and clusterization of carboxylic acids with equal alkyl chain lengths. The only exception is the case that the double bond is in the ω-position (extremely distanced from the carboxylic group). In this case, the number of intermolecular interactions between alkyl chains is changed. Spontaneous clusterization of trans- in the standard conditions is possible for molecules that possess more than 16-17 carbon atoms in the alkyl chain. These threshold values exceed the corresponding values that were calculated previously using the quantum-chemical PM3 method for saturated carboxylic acids (12-13 carbon atoms in the alkyl chain) and are a little bit smaller than the corresponding parameters for cis-unsaturated carboxylic acids (18-19 carbon atoms). These values agree with experimental parameters. Also, the calculated structural parameters of trans-unsaturated carboxylic acids' monolayer for the unit cell with a = 6.98 Å, b = 8.30 Å, and for the molecular tilt angle with 64.95° agree with

  18. Application of Attenuated Total Reflectance-Fourier Transformed Infrared (ATR-FTIR) Spectroscopy To Determine the Chlorogenic Acid Isomer Profile and Antioxidant Capacity of Coffee Beans.

    PubMed

    Liang, Ningjian; Lu, Xiaonan; Hu, Yaxi; Kitts, David D

    2016-01-27

    The chlorogenic acid isomer profile and antioxidant activity of both green and roasted coffee beans are reported herein using ATR-FTIR spectroscopy combined with chemometric analyses. High-performance liquid chromatography (HPLC) quantified different chlorogenic acid isomer contents for reference, whereas ORAC, ABTS, and DPPH were used to determine the antioxidant activity of the same coffee bean extracts. FTIR spectral data and reference data of 42 coffee bean samples were processed to build optimized PLSR models, and 18 samples were used for external validation of constructed PLSR models. In total, six PLSR models were constructed for six chlorogenic acid isomers to predict content, with three PLSR models constructed to forecast the free radical scavenging activities, obtained using different chemical assays. In conclusion, FTIR spectroscopy, coupled with PLSR, serves as a reliable, nondestructive, and rapid analytical method to quantify chlorogenic acids and to assess different free radical-scavenging capacities in coffee beans.

  19. Preparative separation of cis- and trans-isomers of unsaturated fatty acid methyl esters contained in edible oils by reversed-phase high-performance liquid chromatography.

    PubMed

    Tsuzuki, Wakako; Ushida, Kaori

    2009-04-01

    In order to measure exactly the trans-fatty acids content in food materials, a preparative group separation of cis- and trans-isomers of unsaturated fatty acid methyl esters (FAMEs) was achieved by an isocratic reversed-phase HPLC (RP-HPLC) method. The trans-isomers of 16:1, 18:1, 18:2, 18:3, 20:1 and 22:1 FAMEs were readily separated from the corresponding cis-isomers by a COSMOSIL Cholester C18 column (4.6 mm I.D. x 250 mm, Nacalai Tesque) or a TSKgel ODS-100Z column (4.6 mm I.D. x 250 mm, TOSOH), using acetonitrile as the mobile phase. This method was applied for determining the trans-18:1 fatty acid content in partially hydrogenated rapeseed oil. The methyl esters of cis- and trans-18:1 isomers of the oil were collected as two separate fractions by the developed RP-HPLC method. Each fraction was analyzed by gas chromatography (GC) for both qualitative and quantitative information on its positional isomers. By a combination of RP-HPLC and GC methods, a nearly complete separation of cis- and trans-18:1 positional isomers was achieved and the trans-18:1 fatty acid content was able to be evaluated more precisely than is possible by the direct GC method. The reproducibility of cis- and trans-18:1 isomers fractionated by the RP-HPLC method was better than 98%. These results suggested that the preparative RP-HPLC method developed in this study could be a powerful tool for trans-fatty acid analysis in edible oils and food products as an alternative to silver-ion chromatography.

  20. trans-Fatty acid isomers in two sesame (Sesamum indicum L.) seed byproducts under processing.

    PubMed

    Dhibi, Madiha; Mechri, Beligh; Cheraif, Imed; Hammami, Mohamed

    2010-12-08

    The present study has been inspired by the growing need for rigorously controlling the nutritional quality and safety of food products. The impact of application in the food industry on fatty acids composition, trans-fatty acids (TFAs), and conjugated linoleic acid (CLA) profiles were investigated in a highly consumed candy byproduct of sesame seed (chamia) in comparison to fresh sesame seed oil (SSO) and heated SSO under simulated frying experiments. The effect of treatment on SSO was studied by determining the TFA and CLA changes. Results showed significant differences between the two byproducts in TFA and CLA amounts. Total TFAs were found to be significantly higher in chamia than fresh SSO (1.31 versus 0.066%, respectively; p < 0.05) and even higher than all heated SSO from 2 to 10 h at 180 °C (1.31 versus 0.33%, respectively; p < 0.05). A significant linear relationship was found between trans-monounsaturated fatty acid (MUFA), trans-polyunsaturated fatty acid (PUFA), and total TFA and the time of processing, with a correlation coefficient (R(2)) greater than 0.9 for TFA and PUFA, with a higher correlation assigned to PUFA (r = 0.988; p < 0.001), followed by TFA (r = 0.959; p < 0.01) and MUFA (r = 0.844; p < 0.05). Principal component analysis of the fatty acid (FA) profiles showed discrimination between chamia and both fresh and heated SSO. A high stability of SSO against isomerization reactions as compared to their chamia sample counterpart has been noted. These findings suggest that the food industry engenders relatively higher changes in fatty acid configurations than the frying process.

  1. Three 2D Ag(I)-framework isomers with helical structures controlled by the chirality of camphor-10-sulfonic acid.

    PubMed

    Guo, Peng

    2011-02-28

    Three 2D Ag(I)-framework isomers were constructed from enantiopure camphor-10-sulfonic acids or racemic camphor-10-sulfonic acids, together with achiral 4-aminobenzoic acids. In complex 1, (+)-camphor-10-sulfonic acids bridge the single left-handed helices that are made up of Ag ions and 4-aminobenzoic acids, generating a homochiral 2D layer. In such a structure, the interweaving of triple left-handed homohelices was also found. It is worth noting that the helicity of complex 2 could be controlled by the handedness of the camphor-10-sulfonic acid. In complex 2, there are right-handed helical structures, including single right-handed and triple right-handed helical structures connected by (-)-camphor-10-sulfonic acids. For a comparative study, (±)-camphor-10-sulfonic acids were utilized to synthesize complex 3, in which equal numbers of right-handed or left-handed double-helical chains are created. All the complexes were characterized by single-crystal X-ray structure determination, powder X-ray diffraction, IR, TGA and element analysis. Circular dichroism spectra of complexes 1 and 2 were been studied to confirm the fact that enantiopure bridging ligands do not racemize.

  2. Trans-18:1 isomers in rat milk fat as effective biomarkers for the determination of individual isomeric trans-18:1 acids in the dams' diet.

    PubMed

    Wolff, Robert L

    2003-11-01

    Female rats were fed a diet containing by weight 10% partially hydrogenated sunflower oil, 2% sunflower oil, and 1% rapeseed oil during gestation and lactation. The trans-18:1 isomer profile of the fat supplement was (in % of total trans 18:1 acids in the fat supplement): delta4, 0.5; delta5, 1.0; delta6-delta8, 18.0; delta9 (elaidic), 13.5; delta10, 22.2; delta11 (vaccenic), 16.0; delta12, 11.3; delta13-delta14, 12.8; delta15, 2.5; and delta16, 2.2 (total trans 18:1 acids in the fat supplement: 40.6%). The cis 18:1 isomer profile was (in % of total cis-18:1 isomers): delta6-delta8, 2.1; delta9 (oleic), 70.9; delta10, 6.1; delta11, 8.3; delta12, 4.0; delta13, 2.8; delta14, 4.6, and delta15, 1.2 (total cis-18:1 acids in the fat supplement: 32.6%). Suckling rats from four litters were sacrificed at day 17 or 18 after birth, and their stomach content (milk) was analyzed. The trans-18:1 isomer profile of milk was (relative proportions, in % of total): delta4, 0.3; delta5, 1.1; delta6-delta8, 16.8; delta9, 15.3; delta10, 22.0; delta11, 16.7; delta12, 11.8; delta13-14, 11.8; delta15, 2.5, and delta16, 1.9 (total trans 18:1 acids in milk: %). That of cis-18:1 isomers was (proportions in % relative to total cis-18:1 isomers): delta6-delta8, 4.7; delta9, 72.5; delta10, 4.0; delta11, 8.0; delta12, 7.1; delta13, 1.9; delta14, 1.0, and delta15, 0.7 (total cis-18:1 acids in milk: %). These results demonstrate that all isomeric acids, independent of the geometry and the position of the ethylenic bond, are incorporated into milk lipids. With regard to trans-18:1 isomers, the distribution profile in milk is identical to that in the dams' diet, i.e., there is no discrimination against any positional isomer between their ingestion and their deposition into milk lipids. As a consequence, this study indicates that the trans-18:1 isomer profile of milk reflects that in the dams' diet and supports our earlier hypothesis that the profile of trans-18:1 isomers in milk can be used to

  3. The content of conjugated linoleic acid (CLA) isomer groups in milk of two Polish sheep breeds determined by silver ion liquid chromatography (Ag(+)-HPLC).

    PubMed

    Rozbicka-Wieczorek, Agnieszka; Radzik-Rant, Aurelia; Rant, Witold; Czauderna, Marian

    2013-01-01

    Sheep milk is rich in CLA isomers which are biologically active components influencing human health. There are four geometric CLA isomer pairs: cis, trans; trans, cis; trans, trans and cis, cis. The aim of the present study was the analysis of CLA isomer groups content by Ag+-HPLC in milk fat of Zelazneńska (ZS) and Wrzosówka (WS) sheep breeds. The ewes of both breeds were kept under the same environmental and nutritional conditions. Milk samples were collected from 60 suckling ewes (30 from each breed), at the age of 3-4 years and in their 4th week of lactation. A higher total amount of all CLA isomer groups was obtained in milk of ZS ewes, however, this result was statistically insignificant. The percentage of the main c9, t11 isomer in total CLA was higher in Wrzosówka milk (68% vs. 74%). The content of the trans, trans isomer group in milk fat of the studied breeds was similar. The percentage of this group in total CLA in milk of WS and ZS constitutes 7.2% and 7.7%, respectively. The amount of cis,cis isomers in milk fat of ZS was higher thanWS (P < or = 0.01).

  4. Identification of conjugated linoleic acid (CLA) isomers by silver ion-liquid chromatography/in-line ozonolysis/mass spectrometry (Ag+-LC/O3-MS).

    PubMed

    Sun, Chenxing; Black, Brenna A; Zhao, Yuan-Yuan; Gänzle, Michael G; Curtis, Jonathan M

    2013-08-06

    A novel method for the identification of conjugated linoleic acid (CLA) isomers has been developed in which silver ion liquid chromatography is coupled to in-line ozonolysis/mass spectrometry (Ag(+)-LC/O3-MS). The mobile phase containing CLA isomers eluting from the Ag(+)-LC column flows through a length of gas-permeable tubing within an ozone rich environment. Ozone penetrating the tubing wall reacts with the conjugated double bonds forming ozonolysis product aldehydes. These, and their corresponding methanol loss fragment ions formed within the atmospheric pressure photoionization (APPI) source, were detected by in-line MS and used for the direct assignment of double bond positions. Assignment of positional isomers is based entirely on the two pairs of diagnostic ions seen in the in-line O3-MS mass spectra. In this way, de novo identification of CLA positional isomers, i.e. without requiring comparison to CLA standards, was achieved. The Ag(+)-LC/O3-MS method was applied to the analysis of CLA isomers in a commercial CLA supplement, milk fat, and the lipid extract from a Lactobacillus plantarum TMW1460 culture. The results demonstrate how Ag(+)-LC/O3-MS can be used for the direct and fast determination of CLA isomers at low concentrations and in complex lipid mixtures.

  5. Synthesis of framework isomer MOFs containing zinc and 4-tetrazolyl benzenecarboxylic acid via a structure directing solvothermal approach

    SciTech Connect

    Ordonez, Carlos; Kinnibrugh, Tiffany L.; Xu, Hongwu; Lindline, Jennifer; Timofeeva, Tatiana; Wei, Qiang

    2015-04-02

    The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H₂TBC, TBC = 4-tetrazolyl benzenecarboxylate) and zinc. H₂TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs) were obtained by systematically changing the solvents of the H₂TBC-Zn reaction, (1) ZnTBC, 2, which has a non-porous structure; (2) Zn₂(TBC)₂(H2O), 3, which has an amphiphilic pore structure and (3) Zn₂(TBC)₂{guest}, 4, which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.

  6. Synthesis of framework isomer MOFs containing zinc and 4-tetrazolyl benzenecarboxylic acid via a structure directing solvothermal approach

    DOE PAGES

    Ordonez, Carlos; Kinnibrugh, Tiffany L.; Xu, Hongwu; ...

    2015-04-02

    The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H₂TBC, TBC = 4-tetrazolyl benzenecarboxylate) and zinc. H₂TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs) were obtained by systematically changing the solvents of the H₂TBC-Zn reaction, (1) ZnTBC, 2, which has a non-porous structure; (2) Zn₂(TBC)₂(H2O), 3, which has an amphiphilic pore structure and (3) Zn₂(TBC)₂{guest}, 4,more » which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.« less

  7. The conjugated linoleic acid isomer trans-9,trans-11 is a dietary occurring agonist of liver X receptor {alpha}

    SciTech Connect

    Ecker, Josef; Liebisch, Gerhard; Patsch, Wolfgang; Schmitz, Gerd

    2009-10-30

    Conjugated linoleic acid (CLA) isomers are dietary fatty acids that modulate gene expression in many cell types. We have previously reported that specifically trans-9,trans-11 (t9,t11)-CLA induces expression of genes involved in lipid metabolism of human macrophages. To elucidate the molecular mechanism underlying this transcriptional activation, we asked whether t9,t11-CLA affects activity of liver X receptor (LXR) {alpha}, a major regulator of macrophage lipid metabolism. Here we show that t9,t11-CLA is a regulator of LXR{alpha}. We further demonstrate that the CLA isomer induces expression of direct LXR{alpha} target genes in human primary macrophages. Knockdown of LXR{alpha} with RNA interference in THP-1 cells inhibited t9,t11-CLA mediated activation of LXR{alpha} including its target genes. To evaluate the effective concentration range of t9,t11-CLA, human primary macrophages were treated with various doses of CLA and well known natural and synthetic LXR agonists and mRNA expression of ABCA1 and ABCG1 was analyzed. Incubation of human macrophages with 10 {mu}M t9,t11-CLA led to a significant modulation of ABCA1 and ABCG1 transcription and caused enhanced cholesterol efflux to high density lipoproteins and apolipoprotein AI. In summary, these data show that t9,t11-CLA is an agonist of LXR{alpha} in human macrophages and that its effects on macrophage lipid metabolism can be attributed to transcriptional regulations associated with this nuclear receptor.

  8. Electrochemical destruction of dinitrotoluene isomers and 2,4,6-trinitrotoluene in spent acid from toluene nitration process.

    PubMed

    Chen, Wen-Shing; Liang, Jing-Song

    2009-01-30

    Mineralization of dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid was conducted by in situ electrogenerated hydrogen peroxide. The electrolytic experiments were carried out to elucidate the influence of various operating parameters on the performance of mineralization of total organic compounds (TOC) in spent acid, including electrode potential, reaction temperature, oxygen dosage and concentration of sulfuric acid. It is worth noting that organic compounds could be completely mineralized by hydrogen peroxide obtained from cathodic reduction of oxygen, which was mainly supplied by anodic oxidation of water. Based on the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of 2,4-DNT and/or 2,6-DNT, 2,4,6-TNT results in o-mononitrotoluene (MNT) and 1,3,5-trinitrobenzene, respectively. Due to the removal of TOC and some amount of water, the electrolytic method established is promising for industrial application to regeneration of spent acid from toluene nitration process.

  9. Identification of a dicaffeoylquinic acid isomer from Arctium lappa with a potent anti-ulcer activity.

    PubMed

    Carlotto, Juliane; da Silva, Luisa M; Dartora, Nessana; Maria-Ferreira, Daniele; Sabry, Diego de A; Filho, Arquimedes P S; de Paula Werner, Maria F; Sassaki, Guilherme L; Gorin, Philip A J; Iacomini, Marcello; Cipriani, Thales R; de Souza, Lauro M

    2015-04-01

    Leaves of Arctium lappa contain several mono- and dicaffeoylquinic acids, as evaluated by liquid chromatography-mass spectrometry. In order to investigate the protection on gastric mucosa against ulcers, rats were treated with fractions from leaf extract prior to ethanol-induced ulcers. The original fraction obtained as ethanol soluble fraction from hot aqueous extract was able to protect de gastric mucosa, and this effect was retained in the ethyl acetate fraction, obtained from liquid/liquid fractionation. The main compound in this fraction was isolated and chemically characterized by nuclear magnetic resonance and mass spectrometry, assisted by isopropylidene derivatization which gave rise a mass increment of 40 units. Therefore, the underivatized compound that had m/z 515.119 [M-H](-) was shifted to m/z 555.151, being confirmed as 1,3-O-dicaffeoylquinic acid, which presented an ED50 of 57 µg kg(-1) on gastric protection, lesser than the therapeutic concentration of omeprazole (40 mg kg(-1)).

  10. Temporal trends of perfluoroalkane sulfonic acids and their sulfonamide-based precursors in herring from the Swedish west coast 1991-2011 including isomer-specific considerations.

    PubMed

    Ullah, Shahid; Huber, Sandra; Bignert, Anders; Berger, Urs

    2014-04-01

    A method was developed for simultaneous analysis of perfluoroalkane sulfonic acids (PFSAs) and their sulfonamide-based precursors (perfluoroalkane sulfonamidoacetic acids (FASAAs), sulfonamides (FASAs), and sulfonamidoethanols (FASEs)) in fish muscle. Extraction was performed with acetonitrile followed by a clean-up and fractionation step and instrumental analysis by UPLC/MS/MS and GC/MS. Time trends of PFSAs and their precursors in herring muscle samples originating from the Kattegat at the west coast of Sweden were investigated covering the years 1991-2011. The following analytes were detected, all with decreasing or unchanged trends between 1991 and 2011: Perfluorobutane sulfonic acid (PFBS, below the method detection limit (acid (PFHxS, 9-38pg/g), perfluorooctane sulfonic acid (PFOS, 240-930pg/g), perfluorodecane sulfonic acid (PFDS, acid (MeFOSAA and EtFOSAA, 2-39 and 2-31pg/g, respectively) and perfluorooctane sulfonamide (FOSA, 78-920pg/g). The highest concentrations were found for PFOS and FOSA around the turn of the century. Shorter disappearance half-lives were observed for precursors compared to PFSAs. Assuming that these trend differences are representative for fish consumed by the general Swedish population, this observation suggests that the relative contribution of precursors to total human exposure to PFOS via fish intake has decreased in Sweden over the study period. PFOS precursors in fish may have constituted a significant indirect exposure pathway for PFOS in the 1990s. Isomer-specific analysis of PFOS and FOSA revealed <10% relative contributions of branched isomers to total PFOS and total FOSA. Furthermore, the percentage branched isomers decreased over time for both compounds. These findings are contrary to patterns and temporal trends of PFOS isomers commonly found in human serum. In combination with literature data on isomer patterns

  11. Individual isomers of conjugated linoleic acid reduce inflammation associated with established collagen-induced arthritis in DBA/1 mice.

    PubMed

    Huebner, Shane M; Campbell, James P; Butz, Daniel E; Fulmer, Tyler G; Gendron-Fitzpatrick, Annette; Cook, Mark E

    2010-08-01

    Previously, dietary conjugated linoleic acid [(CLA), an equal mixture of cis-9, trans-11 (c9t11) and trans-10, cis-12 (t10c12) CLA isomers], was found to reduce inflammation in the murine collagen antibody-induced arthritis model, but less so in the murine collagen-induced arthritis (CIA) model, an arthritic model dependent upon acquired immunity. Because CLA is known to alter the acquired immune response, it was hypothesized that feeding CLA after the establishment of arthritis would reduce paw swelling in the CIA model. In this study, upon the establishment of arthritic symptoms, mice were randomized to the following dietary treatments: corn oil (CO) control (n = 6), 0.5% c9t11-CLA (n = 8), 0.5% t10c12-CLA (n = 6), or 1% combined CLA (1:1 c9t11:t10c12-CLA, n = 6). Paws were scored for severity of arthritis and measured for changes in thickness during an 84-d study period. Dietary c9t11- and combined-CLA similarly decreased the arthritic score (29%, P = 0.036, P = 0.049, respectively, when normalized to initial score) and paw thickness (0.11 mm, P = 0.027, P = 0.035, respectively) compared with CO. Dietary t10c12-CLA reduced the arthritic score (41%, P = 0.007 when normalized) and paw thickness (0.12 mm, P = 0.013) relative to CO. Reduced interleukin-1beta on d 7 and 21 for all CLA treatments (n = 3) relative to CO suggested that antiinflammatory effects of CLA isomers might work by common mechanisms of known pathways involved in chronic inflammation. In conclusion, dietary CLA reduced inflammation associated with CIA, and both c9t11-CLA and t10c12-CLA exhibited antiinflammatory effects.

  12. Gas chromatography and silver-ion high-performance liquid chromatography analysis of conjugated linoleic acid isomers in free fatty acid form using sulphuric acid in methanol as catalyst.

    PubMed

    Luna, Pilar; Juárez, Manuela; de la Fuente, Miguel Angel

    2008-09-12

    This study used GC and silver-ion HPLC to examine the effects of temperature and time on methylation of individual and mixtures of conjugated linoleic acid (CLA) isomers in free fatty acid form using sulphuric acid as catalyst. In the conditions tested (temperatures between 20 and 50 degrees C and times between 10 and 60 min) methylation was complete while avoiding isomerization of conjugated dienes and the formation of artefacts that could interfere with chromatographic determinations. An analytical method using solvent extraction of the lipids followed by selective elution of the free fatty acids from aminopropyl bonded phase columns and methylation with H(2)SO(4) in mild conditions was then applied to determine the CLA isomers in free fatty acid form in rumen fluid, and the results were evaluated.

  13. Selective microbial degradation of saturated methyl branched chain fatty acid isomers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Three strains of Pseudomonas bacteria were screened for their capabilities of degrading chemically synthesized saturated branched-chain fatty acids (sbc-FAs). Mixtures of sbc-FAs with the methyl-branch located at various locales along the fatty acid were used as a carbon feedstock in shake-flask cu...

  14. Two new antioxidant malonated caffeoylquinic acid isomers in fruits of wild eggplant relatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fruits of both the cultivated eggplant species Solanum melongena and its wild relative Solanum incanum have a high content of hydroxycinnamic acid conjugates, which along with other phenylpropanoids are implicated in the human health benefits of various fruits and vegetables. Monocaffeoylquinic acid...

  15. Isomers/enantiomers of perfluorocarboxylic acids: Method development and detection in environmental samples

    EPA Science Inventory

    Perfluoroalkyl substances are globally distributed in both urban and remote settings, and routinely are detected in wildlife, humans, and the environment. One of the most prominent and routinely detected perfluoroalkyl substances is perfluorooctanoic acid (PFOA), which has been s...

  16. Important amino acid residues of hexachlorocyclohexane dehydrochlorinases (LinA) for enantioselective transformation of hexachlorocyclohexane isomers.

    PubMed

    Shrivastava, Nidhi; Macwan, Ankit S; Kohler, Hans-Peter E; Kumar, Ashwani

    2017-03-01

    LinA-type1 and LinA-type2 are two well-characterized variants of the enzyme 'hexachlorocyclohexane (HCH)-dehydrochlorinase'. They differ from each other at ten amino acid positions and exhibit differing enantioselectivity for the transformation of the (-) and (+) enantiomers of α-HCH. Amino acids responsible for this enantioselectivity, however, are not known. An in silico docking analysis identified four amino acids (K20, L96, A131, and T133) in LinA-type1 that could be involved in selective binding of the substrates. Experimental studies with constructed mutant enzymes revealed that a combined presence of three amino acid changes in LinA-type1, i.e. K20Q, L96C, and A131G, caused a reversal in its preference from the (-) to the (+) enantiomer of α-HCH. This preference was enhanced by the additional amino acid change T133 M. Presence of these four changes also caused the reversal of enantioselectivity of LinA-type1 for δ-HCH, and β-, γ-, and δ-pentachlorocyclohexens. Thus, the residues K20, L96, A131, and T133 in LinA-type1 and the residues Q20, C96, G131, and M133 in LinA-type 2 appear to be important determinants for the enantioselectivity of LinA enzymes.

  17. Isomer-sensitive deboronation in reductive aminations of aryl boronic acids

    SciTech Connect

    Jones, Brad Howard; Wheeler, David R.; Wheeler, Jill S.; Miller, Lance Lee; Alam, Todd M.; Spoerke, Erik David

    2015-09-05

    Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

  18. Isomer-sensitive deboronation in reductive aminations of aryl boronic acids

    DOE PAGES

    Jones, Brad Howard; Wheeler, David R.; Wheeler, Jill S.; ...

    2015-09-05

    Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

  19. Atlas of Nuclear Isomers

    SciTech Connect

    Jain, Ashok Kumar; Maheshwari, Bhoomika; Garg, Swati; Patial, Monika; Singh, Balraj

    2015-09-15

    We present an atlas of nuclear isomers containing the experimental data for the isomers with a half-life ≥ 10 ns together with their various properties such as excitation-energy, half-life, decay mode(s), spin-parity, energies and multipolarities of emitted gamma transitions, etc. The ENSDF database complemented by the XUNDL database has been extensively used in extracting the relevant data. Recent literature from primary nuclear physics journals, and the NSR bibliographic database have been searched to ensure that the compiled data Table is as complete and current as possible. The data from NUBASE-12 have also been checked for completeness, but as far as possible original references have been cited. Many interesting systematic features of nuclear isomers emerge, some of them new; these are discussed and presented in various graphs and figures. The cutoff date for the extraction of data from the literature is August 15, 2015.

  20. Diversified self-association through O-H⋯O hydrogen bonds in crystals of formylphenylboronic acid isomers

    NASA Astrophysics Data System (ADS)

    Madura, Izabela D.; Adamczyk-Woźniak, Agnieszka; Sporzyński, Andrzej

    2015-03-01

    Numerous applications of formylphenylboronic acid isomers in organic synthesis as well as co-crystals' design and surface immobilization prompted us to study the effect of substituent position on their molecular and crystal structures. It has been found that changes in molecular geometry of ortho, meta and para derivatives are negligible, except differences in a twist of the -B(OH)2 fragment towards phenyl ring. The lability of boronic moiety was attributed to diversified O-H⋯O hydrogen bonding patterns formed by its hydroxyl groups. The analysis of molecular packing was based on elucidation of hierarchical self-associated structural units. The identification of important, directional intermolecular interactions in crystal structures was supported by the Hirshfeld surface analysis. Subsequent supramolecular levels have been distinguished taking into account estimated energy of O-H⋯O bonds, dimensionality of large synthons and their symmetry. The resulting basic O-H⋯O motives are in form of dimers, undulated layers or chains. They are further joined by π⋯π interactions constituting the large synthons such as stacking columns or double layers.

  1. Polyunsaturated fatty acids and conjugated linoleic acid isomers in breast milk are associated with plasma non-esterified and erythrocyte membrane fatty acid composition in lactating women.

    PubMed

    Torres, Alexandre G; Ney, Jacqueline G; Meneses, Flávia; Trugo, Nádia M F

    2006-03-01

    Maternal adipose tissue is a major contributor to breast milk long-chain fatty acids, probably through the pool of plasma NEFA. The fatty acid composition of the erythrocyte membrane (EM) is a biochemical index of the intake of fatty acids not synthesized endogenously and of PUFA and long-chain PUFA fatty acid status. The present study investigated the associations between breast milk fatty acid composition and the composition of plasma NEFA and of EM fatty acids with special reference to PUFA, long-chain PUFA and conjugated linoleic acid (CLA). The detailed fatty acid composition of mature breast milk was also reported. Thirty-three healthy, lactating Brazilian women donated milk samples; of these, twenty-four also donated blood samples in an observational cross-sectional study. Breast milk fatty acid composition presented several associations with NEFA and EM composition, which explained most (> or =50 %) of the variability of selected milk PUFA, long-chain PUFA and CLA. Milk CLA was associated with fatty acids that are markers of dairy fat intake in the diet, NEFA and EM. In general, breast milk n-3 fatty acids and CLA, but not n-6 fatty acids, were associated with EM composition, whereas both the n-6 and n-3 fatty acids and CLA in milk were associated with NEFA composition, possibly owing to its role as a direct source of fatty acids for breast milk. These findings emphasize the contribution of the NEFA pool derived from the adipose tissue to the long-chain fatty acid composition of breast milk.

  2. Isomer-specific effects of conjugated linoleic acid on HDL functionality associated with reverse cholesterol transport.

    PubMed

    Nicod, Nathalie; Parker, Robert S; Giordano, Elena; Maestro, Virginia; Davalos, Alberto; Visioli, Francesco

    2015-02-01

    High-density lipoproteins (HDLs) are atheroprotective because of their role in reverse cholesterol transport. The intestine is involved in this process because it synthesizes HDL, removes cholesterol from plasma and excretes it into the lumen. We investigated the role of selected dietary fatty acids on intestinal cholesterol uptake and HDL functionality. Caco-2 monolayers grown on Transwells were supplemented with either palmitic, palmitoleic, oleic, linoleic, docosahexaenoic, eicosapentaenoic, arachidonic or conjugated linoleic acids (CLAs): c9,t11-CLA; t9,t11-CLA; c10,t12-CLA. Cells synthesized HDL in the basolateral compartment for 24 h in the absence or presence of an antibody to SR-BI (aSR-BI), which inhibits its interaction with HDL. Free cholesterol (FC) accumulated to a greater extent in the presence than in the absence of aSR-BI, indicating net uptake of FC by SR-BI. Uptake's efficiency was significantly decreased when cells were treated with c9,t11-CLA relative to the other fatty acids. These differences were associated with lower HDL functionality, since neither SR-BI protein expression nor expression and alternative splicing of other genes involved lipid metabolism were affected. Only INSIG2 expression was decreased, with no increase of its target genes. Increasing pre-β-HDL synthesis, by inducing ABCA1 and adding APOA1, resulted in reduced uptake of FC by SR-BI after c9,t11-CLA treatment, indicating reduced functionality of pre-β-HDL. Conversely, treatment with c9,t11-CLA resulted in a greater uptake of FC and esterified cholesterol from mature HDL. Therefore, Caco-2 monolayers administered c9,t11-CLA produced a nonfunctional pre-β-HDL but took up cholesterol more efficiently via SR-BI from mature HDL.

  3. Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

    NASA Technical Reports Server (NTRS)

    Okumura, M.; Mollner, A. K.; Fry, J. L.; Feng, L.

    2005-01-01

    Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

  4. A single dose of c9,t11 or t10,c12 conjugated linoleic acid isomers perturbs vitamin A metabolism in mice.

    PubMed

    Giordano, Elena; Banni, Sebastiano; Quadro, Loredana

    2011-11-01

    Conjugated linoleic acid (CLA) is a polyunsaturated fatty acid that has numerous biologic activities. Previous studies in rodents demonstrated that chronic intake of CLA t10,c12 or CLA c9,t11 isomers perturbs the metabolism of retinoids (vitamin A and its derivatives). Specifically, although both isomers increased liver retinoid levels, only CLA t10,c12 also stimulated hepatic retinol secretion into the bloodstream. Given that retinoid homeostasis in mammalian serum and tissues is crucial to maintain health, it is important to gain more insights into the mode of action of this nutrient-nutrient interaction. Here we hypothesized that an acute administration of either CLA isomer may also influence vitamin A metabolism. By gavaging wild-type and retinol-binding protein knockout mice with an oral bolus of radiolabeled retinol containing 1 of these 2 isomers, we showed that both CLA t10,c12 and CLA c9,t11 rapidly enhance hepatic uptake of dietary vitamin A and its resecretion from the liver in the form of retinol bound to retinol-binding protein. Indeed, in mice lacking this protein, the sole specific carrier for retinol in the circulation, this latter effect was blunted. In addition, by using a pharmacologic inhibitor of the clearance of chylomicrons, which distribute recently ingested vitamin A and lipids throughout the body, we provided evidence that CLA intake might rapidly enhance intestinal absorption of dietary vitamin A. These data demonstrate the existence of multiple levels of interaction between dietary CLA and retinoid metabolism and warrant further studies to understand the molecular mechanisms underlying these effects and their implications for human health.

  5. On-line monitoring of in-vitro oral bioaccessibility tests as front-end to liquid chromatography for determination of chlorogenic acid isomers in dietary supplements.

    PubMed

    Kremr, Daniel; Cocovi-Solberg, David J; Bajerová, Petra; Ventura, Karel; Miró, Manuel

    2017-05-01

    A novel fully automated in-vitro oral dissolution test assay as a front-end to liquid chromatography has been developed and validated for on-line chemical profiling and monitoring of temporal release profiles of three caffeoylquinic acid (CQA) isomers, namely, 3-CQA,4-CQA and 5-CQA, known as chlorogenic acids, in dietary supplements. Tangential-flow filtration is harnessed as a sample processing approach for on-line handling of CQA containing extracts of hard gelatin capsules and introduction of protein-free samples into the liquid chromatograph. Oral bioaccessibility/dissolution test assays were performed at 37.0±0.5°C as per US Pharmacopeia recommendations using pepsin with activity of ca. 749,000 USP units/L in 0.1mol/L HCl as the extraction medium and a paddle apparatus stirred at 50rpm. CQA release rates and steady-state dissolution conditions were determined accurately by fitting the chromatographic datasets, namely, the average cumulative concentrations of bioaccessible pools of every individual isomer monitored during 200min, with temporal resolutions of ≥10min, to a first-order dissolution kinetic model. Distinct solid-to-liquid phase ratios in the mimicry of physiological extraction conditions were assessed. Relative standard deviations for intra-day repeatability and inter-day intermediate precision of 5-CQA within the 5-40µg/mL concentration range were <3.4% and <5.5%, respectively. Trueness of the automatic flow method for determination of 5-CQA released from dietary supplements in gastric fluid surrogate was demonstrated by spike recoveries, spanning from 91.5-104.0%, upon completion of the dissolution process. The proposed hyphenated setup was resorted for evaluating potential differences in dissolution profiles and content of the three most abundant chlorogenic acid isomers in dietary supplements from varied manufacturers.

  6. A novel derivatization-based liquid chromatography tandem mass spectrometry method for quantitative characterization of naphthenic acid isomer profiles in environmental waters.

    PubMed

    Woudneh, Million B; Coreen Hamilton, M; Benskin, Jonathan P; Wang, Guanghui; McEachern, Preston; Cosgrove, John R

    2013-06-07

    A method for quantitative characterization of naphthenic acid (NA) isomer groups by carbon number and extent of cyclization was developed and validated with water samples from northern Alberta. Following solid phase extraction, NAs undergo derivatization with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) allowing detection by positive electrospray ionization tandem mass spectrometry (+ESI)-MS/MS. NA-EDC derivatives produce a common product ion by MS/MS, regardless of structure of the starting NA. Thus, approximately constant relative response factors (RRFs) were assumed for the various isomer groups that elute at a given point in the elution gradient (supported by calculated RRFs for individual model NAs), facilitating quantification using a single standard (1-pyrenebutyric acid). To reduce the impact of major background fatty acids on NA data, the method employed an optimized liquid chromatography method that separated straight chain (Z=0) analytes from other NAs. Method validation was performed at two spiking levels (7.72μg and 38.6μg total refined Merichem per 500mL of reagent water) and good accuracy (mean recoveries of 82.4±2.5% and 93.0±2.6%, respectively; range ~50-130%) and precision (<17% RSD) were achieved at both spiking levels for all 60 NA isomer groups. The method also performed well in an independent method comparison study in which method accuracy values of 107%, 120%, and 121% were obtained for 2 spiked reagent waters (1mg/L and 50mg/L NAs) and spiked Athabasca River water (0.035mg/L NAs), respectively. Application of the method to samples from northern Alberta revealed that NA concentrations decreased in the order: process water (52.8mg/L)>tailings pond water (30.6mg/L)>well water (0.086mg/L)>surface water (0.007mg/L), and that samples were distinguishable by NA isomer profile using Principal components analysis.

  7. The Eskimo diet. Prophylactic effects ascribed to the balanced presence of natural cis unsaturated fatty acids and to the absence of unnatural trans and cis isomers of unsaturated fatty acids.

    PubMed

    Booyens, J; Louwrens, C C; Katzeff, I E

    1986-12-01

    In addition to the well recognised roles of eicosapentaenoic acid and possibly docosahexaenoic acid, there are two other major important, but unrecognised, features of the traditional Eskimo staple diet namely that it contains the unsaturated fatty acids (UFA) cis oleic, cis linoleic and cis alpha-linolenic as well as their respective C20 and C22 metabolites in physiologically optimal concentrations and, it is virtually totally devoid of unnatural and potentially hazardous trans and cis isomers of these fatty acids. Large quantities of unnatural trans and cis isomers of UFA are found in the Western diet as partially hydrogenated UFA in many foods. These isomers are formed during the manufacture of margarines and related compounds, as food contaminants during excessive heating of cooking oils for deep-frying and other excessive heat-requiring mass food preparation procedures and it is suggested, as the result of excessive feeding with an unnatural diet of ruminants and non-ruminants for increased meat and/or milk production and of poultry for increased egg and/or meat production. These isomers have been shown to display potentially hazardous metabolic effects which include the competitive inhibition of UFA metabolism at various steps and have been causally implicated in the etiology of ischemic heart disease and cancer. It is suggested that the myth of the safety of trans fatty acids arises from misinterpretation of the observation that increasing dietary cis linoleic acid reduces the toxic effects of trans UFA. It is suggested that the decrease of 20% in the ischemic heart disease mortality in the USA during the past two decades is directly related to a shift in the dietary ratio of unnatural trans and cis UFA isomers: cis linoleic acid in favour of the latter. It is predicted that this ratio will be found to correlate with ischemic heart disease patterns in other countries. Eskimos consume the bulk of their food frozen, raw or dried, seldom boiled, but never deep

  8. Modelling Study of Interstellar Ethanimine Isomers

    NASA Astrophysics Data System (ADS)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    Ethanimine (CH3CHNH) , including both the E- and Z- isomers, were detected towards the star-forming region Sgr B2(N) using the GBT PRIMOS data (Loomis et al 2013), and were recently imaged by the ACTA (Corby et al. 2015). These aldimines can serve as precursors of biological molecules such as amino acids thus are considered prebiotic molecules in interstellar medium. In this study, we present chemical simulations of ethanimine with various physical conditions. From models for Sgr B2(N) and environs, calculated ethanimine abundances show reasonable agreement with observed values, while the translucent cloud models yield much lower abundances. These results agree with locations suggested by observations that ethanimine isomers were detected in the foreground of the shells of the hot core.

  9. Nuclear shape isomers

    NASA Astrophysics Data System (ADS)

    Möller, P.; Sierk, A. J.; Bengtsson, R.; Sagawa, H.; Ichikawa, T.

    2012-03-01

    We calculate potential-energy surfaces as functions of spheroidal (ɛ2), hexadecapole (ɛ4), and axial-asymmetry (γ) shape coordinates for 7206 nuclei from A=31 to A=290. We tabulate the deformations and energies of all minima deeper than 0.2 MeV and of the saddles between all pairs of minima. The tabulation is terminated at N=160. Our study is based on the FRLDM macroscopic-microscopic model defined in ATOMIC DATA AND NUCLEAR DATA TABLES [P. Möller, J.R. Nix, W.D. Myers, W.J. Swiatecki, At. Data Nucl. Data Tables 59 (1995) 185]. We also present potential-energy contour plots versus ɛ2 and γ for 1224 even-even nuclei in the region studied. We can identify nuclei for which a necessary condition for shape isomers occurs, namely multiple minima in the calculated potential-energy surface. We find that the vast majority of nuclear shape isomers occur in the A=80 region, the A=100 region, and in a more extended region centered around 208Pb. A calculated region of shape isomers that has so far not been extensively explored is the region of neutron-deficient actinides "north-east" of 208Pb.

  10. In-house validation of an improved sample extraction and clean-up method for GC determination of isomers of nervonic acid in meat products.

    PubMed

    Agazzi, Marie-Elisabeth; Bau, Andrea; Barcarolo, Robertino; Luecker, Ernst; Barrero-Moreno, Josefa; Anklam, Elke

    2003-06-01

    An improved extraction and clean-up method for determination of brain-specific fatty acids, in particular lignoceric acid (C24:0) and the cis/ trans isomers of nervonic acid (15 c-t C24:1), in meat products has been developed. The method is based on isolation of the polar lipids of interest from the bulk lipids by solid-phase extraction. The fatty acids, derivatised to their fatty acid methyl esters, are quantified by GC in a DB5 column. Fresh meat samples were extracted by using a mixture of n-butanol:hexane (1:9) as solvent. The extract was loaded in a silica gel cartridge column previously equilibrated with hexane. The first fraction containing the major part of the fat was eluted with hexane while acetone and methanol allowed the elution of fatty acids bound to polar moieties such as nervonic and lignoceric acids. This second fraction containing the analyte was methylated and injected into the GC for quantification after addition octacosane (C(28)) as internal standard.

  11. Moderate doses of conjugated linoleic acid isomers mix contribute to lowering body fat content maintaining insulin sensitivity and a noninflammatory pattern in adipose tissue in mice.

    PubMed

    Parra, Pilar; Serra, Francisca; Palou, Andreu

    2010-02-01

    Conjugated linoleic acid (CLA) modulates body composition, especially by reducing adipose tissue. However, despite the increasing knowledge about CLA's beneficial effects on obesity management, the mechanism of action is not yet fully understood. Furthermore, in some human studies fat loss is accompanied by impairment in insulin sensitivity, especially when using the trans-10,cis-12 isomer. The aim of this work was to study the effects of moderate doses of CLA on body fat deposition, cytokine profile and inflammatory markers in mice. Mice were orally treated with a mixture of CLA isomers, cis-9,trans-11 and trans-10,cis-12 (50:50), for 35 days with doses of CLA1 (0.15 g CLA/kg body weight) and CLA2 (0.5 g CLA/kg body weight). CLA had discrete effects on body weight but caused a clear reduction in fat mass (retroperitoneal and mesenteric as the most sensitive depots), although no other tissue weights were affected. Glucose and insulin were not altered by CLA treatment, and maintenance of glucose homeostasis was observed even under insulin overload. The study of gene expression (Emr1, MCP-1, IL-6, TNFalpha, PPARgamma2 and iNOS) either in adipocytes and/or in the stromal vascular fraction indicated that CLA does not lead to the infiltration of macrophages in adipose tissue or to the induction of expression of pro-inflammatory cytokines. The use of a mixture of both isomers, as well as moderate doses of CLA, is able to induce a reduction of fat gain without an impairment of adipose tissue function while preserving insulin sensitivity.

  12. Dachtal Isomers and Acidic Herbicides and Pesticides in Eggs of Osprey (Pandion haliaetus) from the Seattle and Everett Areas, Washington, U.S.A

    USGS Publications Warehouse

    Chu, S.; Henny, Charles J.; Kaiser, James L.; Drouillard, K.G.; Haffner, G.D.; Letcher, R.J.

    2007-01-01

    Current-use chlorophenoxy herbicides including 2,4-dichlorophenoxyacetic acid, dicamba, triclopyr, dicamba, dimethyl tetrachloroterephthalate (DCPA or dacthal), and the metabolite of pyrethroids, 3-phenoxybenzoic acid (3-PBA), and the fungicide, chlorothalonil, were investigated in the eggs of osprey (Pandion haliaetus) that were collected from 15 sites from five study areas Puget Sound/Seattle area of Washington State, USA. DCPA differs from acidic chlorophenoxy herbicides, and is not readily hydrolyzed to free acid or acid metabolites, and thus we developed a new method. Of the 12 chlorophenoxy herbicides and chlorothalonil analyzed only DCPA could be quantified at six of these sites (2.0 to 10.3 pg/g fresh weight). However, higher levels (6.9 to 85.5 pg/g fresh weight) of the unexpected DCPA structural isomer, dimethyl tetrachlorophthalate (diMe-TCP) were quantified in eggs from all sites. diMe-TCP concentrations tended to be higher in eggs from the Everett Harbor area. As diMe-TCP is not an industrial product, and not commercially available, the source of diMe-TCP is unclear. Regardless, these findings indicate that DCPA and diMe-TCP can be accumulated in the food chain of fish-eating osprey, and transferred in ovo to eggs, and thus may be of concern to the health of the developing chick and the general reproductive health of this osprey population.

  13. Differences in CLA isomer distribution of cow's milk lipids.

    PubMed

    Kraft, Jana; Collomb, Marius; Möckel, Peter; Sieber, Robert; Jahreis, Gerhard

    2003-06-01

    The uniqueness of ruminant milk lipids is based on their high concentration of CLA. Maximal CLA concentrations in milk lipids require optimal conditions of ruminal fermentation and substrate availability, conditions like those present in pasture-fed cows. Our previous work showed that farm management (indoor feeding vs. pasture feeding) markedly influenced the CLA concentration. In this study, the objective was to evaluate the influence of the farm management system as dependent on different locations. Milk samples from different locations (Thuringia and the Alps, representing diverse altitudes) were collected during the summer months and analyzed for FA profile and CLA isomer distribution. The proportion of PUFA and total CLA in milk fat was significantly lower in milk from indoor cows compared with the pasture cows in the Alps. The trans-11 18:1 in milk fat of Alpine cows was elevated, in contrast to lower values for trans-10 18:1. Milk from cows grazing pasture in the Alps was higher in EPA and lower in arachidonic acid than milk from indoor-fed cows. The proportion of cis,trans/trans,cis isomers of CLA was 10 times higher from the indoor cows than from the Alpine cows. In addition to the major isomer cis-9,trans-11, this difference also occurred for the trans-11,cis-13 isomer, which represented more than a fourth of the total CLA present in milk fat. This is the first report showing a special isomer distribution in the milk fat of cows living under very natural conditions. We hypothesize that the CLA isomer trans-11,cis-13 is formed in large quantity as a result of grazing mountain pasture, which is rich in alpha-linolenic acid.

  14. Present Global Situation of Amino Acids in Industry.

    PubMed

    Tonouchi, Naoto; Ito, Hisao

    2016-11-11

    At present, amino acids are widely produced and utilized industrially. Initially, monosodium glutamate (MSG) was produced by extraction from a gluten hydrolysate. The amino acid industry started using the residual of the lysate. The discovery of the functions of amino acids has led to the expansion of their field of use. In addition to seasoning and other food use, amino acids are used in many fields such as animal nutrients, pharmaceuticals, and cosmetics. On the other hand, the invention of the glutamate fermentation process, followed by the development of fermentation methods for many other amino acids, is no less important. The supply of these amino acids at a low price is very essential for their industrial use. Most amino acids are now produced by fermentation. The consumption of many amino acids such as MSG or feed-use amino acids is still rapidly increasing.

  15. High spin isomer beam line at RIKEN

    SciTech Connect

    Kishida, T.; Ideguchi, E.; Wu, H.Y.

    1996-12-31

    Nuclear high spin states have been the subject of extensive experimental and theoretical studies. For the production of high spin states, fusion reactions are usually used. The orbital angular momentum brought in the reaction is changed into the nuclear spin of the compound nucleus. However, the maximum induced angular momentum is limited in this mechanism by the maximum impact parameter of the fusion reaction and by the competition with fission reactions. It is, therefore, difficult to populate very high spin states, and as a result, large {gamma}-detector arrays have been developed in order to detect subtle signals from such very high spin states. The use of high spin isomers in the fusion reactions can break this limitation because the high spin isomers have their intrinsic angular momentum, which can bring the additional angular momentum without increasing the excitation energy. There are two methods to use the high spin isomers for secondary reactions: the use of the high spin isomers as a target and that as a beam. A high spin isomer target has already been developed and used for several experiments. But this method has an inevitable shortcoming that only {open_quotes}long-lived{close_quotes} isomers can be used for a target: {sup 178}Hf{sup m2} (16{sup +}) with a half-life of 31 years in the present case. By developing a high spin isomer beam, the authors can utilize various short-lived isomers with a short half-life around 1 {mu}s. The high spin isomer beam line of RIKEN Accelerator Facility is a unique apparatus in the world which provides a high spin isomer as a secondary beam. The combination of fusion-evaporation reaction and inverse kinematics are used to produce high spin isomer beams; in particular, the adoption of `inverse kinematics` is essential to use short-lived isomers as a beam.

  16. Analysis of neurotoxin 3-N-oxalyl-L-2,3-diaminopropionic acid and its alpha-isomer in Lathyrus sativus by high-performance liquid chromatography with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatization.

    PubMed

    Chen, X; Wang, F; Chen, Q; Qin, X C; Li, Z

    2000-08-01

    A method was developed for the quantitative determination of the neurotoxic nonprotein amino acid, 3-N-oxalyl-L-2,3-diaminopropionic acid (beta-ODAP), and its nontoxic alpha-isomer, 2-N-oxalyl-L-2, 3-diaminopropionic acid (alpha-ODAP), in the plant samples of Lathyrus sativus after derivatization with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) by reversed-phase high-performance liquid chromatography (HPLC). Hippuric acid was used as an internal standard. A linear response was recorded in the concentration rang 0.32-32 nmol with r > 0.999. The RP HPLC detection limit for both isomers is 1.8 ng. According to different experimental needs, a ternary gradient system can be used to determine toxin and other nonprotein amino acids. The RP HPLC method and a colorimetric method were compared for measuring ODAP.

  17. Development and Optimization of an UPLC-QTOF-MS/MS Method Based on an In-Source Collision Induced Dissociation Approach for Comprehensive Discrimination of Chlorogenic Acids Isomers from Momordica Plant Species

    PubMed Central

    Madala, N. E.; Tugizimana, F.; Steenkamp, P. A.

    2014-01-01

    Chlorogenic acids (CGA) have been profiled in the leaves of Momordica balsamina, Momordica charantia, and Momordica foetida. All three species were found to contain the trans and cis isomers of 4-acyl para-coumaroylquinic acid (pCoQA), caffeoylquinic acid (CQA), and feruloylquinic acid (FQA). To the best of our knowledge, this is the first report of pCoQA and FQA and their cis isomers in these Momordica species. These profiles were obtained by a newly developed UPLC-qTOF-MS method based on the in-source collision induced dissociation (ISCID) method optimized to mimic the MS2 and MS3 fragmentation of an ion trap-based MS. The presence of the cis isomers is believed to be due to high UV exposure of these plants. Furthermore, the absence of the 3-acyl and 5-acyl CGA molecules points to a metabolic mark that is unusual and represents a very interesting biochemical phenotype of these species. Our optimized ISCID method was also shown to be able to distinguish between the geometrical isomers of all three forms of CGA, a phenomenon previously deemed impossible with other common mass spectrometry systems used for CGA analyses. PMID:25295221

  18. Modulation of oxidative stress by γ-glutamylcysteine (GGC) and conjugated linoleic acid (CLA) isomer mixture in human umbilical vein endothelial cells.

    PubMed

    Nakamura, Yukiko K; Dubick, Michael A; Omaye, Stanley T

    2012-06-01

    Individually, γ-glutamylcysteine (GGC), a dipeptide and precursor of glutathione (GSH), and conjugated linoleic acid (CLA), a trans-fatty acid, exhibit antioxidant properties. The objective of this study was to compare effects of co-administration of GGC and CLA to treatment with GGC alone on oxidative stress and GSH synthesis in human endothelial cells. Changes in levels of 8-epi-PGF2α, thiobarbituric acid reactive substances (TBARS), GSH, total antioxidants, GSH synthetase (GSS) expression, and transcription factor DNA binding were assessed in human umbilical vein endothelial cells (HUVEC) treated with GGC alone (100 μmol/L) or combined with CLA isomer mixture (10, 50, 100 μmol/L) for 24h. Significantly higher levels of TBARS, 8-epi-PGF2α, GSH, and GSS protein were found in cells treated with GGC and 10 μmol/L CLA, compared to cells treated with GGC alone, indicative of prooxidant effects of CLA. Approximately 40% cell death was microscopically observed in cells incubated with GGC and 100 μmol/L CLA. Despite lower levels of GSH, treatment with GGC and 50 μmol/L CLA appeared to be protective from oxidative stress similar to treatment with GGC alone, as indicated by lower levels of TBARS, compared to control cells not treated with GGC and CLA.

  19. A tandem mass spectrometric study of bile acids: interpretation of fragmentation pathways and differentiation of steroid isomers.

    PubMed

    Qiao, Xue; Ye, Min; Liu, Chun-fang; Yang, Wen-zhi; Miao, Wen-juan; Dong, Jing; Guo, De-an

    2012-02-01

    Bile acids are steroids with a pentanoic acid substituent at C-17. They are the terminal products of cholesterol excretion, and play critical physiological roles in human and animals. Bile acids are easy to detect but difficult to identify by using mass spectrometry due to their poly-ring structure and various hydroxylation patterns. In this study, fragmentation pathways of 18 free and conjugated bile acids were interpreted by using tandem mass spectrometry. The analyses were conducted on ion trap and triple quadrupole mass spectrometers. Upon collision-induced dissociation, the conjugated bile acids could cleave into glycine or taurine related fragments, together with the steroid skeleton. Fragmentations of free bile acids were further elucidated, especially by atmospheric pressure chemical ionization mass spectrometry in positive ion mode. Aside from universally observed neutral losses, eliminations occurred on bile acid carbon rings were proposed for the first time. Moreover, four isomeric 5β-cholanic acid hydroxyl derivatives (3α,6α-, 3α,7β-, 3α,7α-, and 3α,12α-) were differentiated using electrospray ionization in negative ion mode: 3α,7β-OH substituent inclined to eliminate H(2)O and CH(2)O(2) groups; 3α,6α-OH substituent preferred neutral loss of two H(2)O molecules; 3α,12α-OH substituent apt to lose the carboxyl in the form of CO(2) molecule; and 3α,7α-OH substituent exhibited no further fragmentation after dehydration. This study provided specific interpretation for mass spectra of bile acids. The results could contribute to bile acid analyses, especially in clinical assays and metabonomic studies.

  20. Distinguishing the cyanobacterial neurotoxin beta-N-methylamino-L-alanine (BMAA) from its structural isomer 2,4-diaminobutyric acid (2,4-DAB).

    PubMed

    Banack, S A; Downing, T G; Spácil, Z; Purdie, E L; Metcalf, J S; Downing, S; Esterhuizen, M; Codd, G A; Cox, P A

    2010-11-01

    The cyanobacterial neurotoxin beta-N-methylamino-L-alanine (BMAA) has been associated with certain forms of progressive neurodegenerative disease, including sporadic Amyotrophic Lateral Sclerosis and Alzheimer's disease. Reports of BMAA in cyanobacterial blooms from lakes, reservoirs, and other water resources continue to be made by investigators in a variety of laboratories. Recently it was suggested that during analysis BMAA may be confused with its structural isomer 2,4-diaminobutyric acid (2,4-DAB), or that current detection methods may mistake other compounds for BMAA. We here review the evidence that BMAA can be consistently and reliably separated from 2,4-DAB during reversed-phase HPLC, and that BMAA can be confidently distinguished from 2,4-DAB during triple quadrupole LC-MS/MS analysis by i) different retention times, ii) diagnostic product ions resulting from collision-induced dissociation, and iii) consistent ratios between selected reaction monitoring (SRM) transitions. Furthermore, underivatized BMAA can be separated from 2,4-DAB with an amino acid analyzer with post-column visualization using ninhydrin. Other compounds that may be theoretically confused with BMAA during chloroformate derivatization during GC analysis are distinguished due to their different retention times.

  1. Differential adsorption of complex organic molecule isomers on interstellar ice surfaces

    NASA Astrophysics Data System (ADS)

    Bertin, M.; Michaut, X.; Lattelais, M.; Mokrane, H.; Pauzat, F.; Pilmé, J.; Minot, C.; Ellinger, Y.; Romanzin, C.; Jeseck, P.; Fillion, J.-H.; Chaabouni, H.; Congiu, E.; Dulieu, F.; Baouche, S.; Lemaire, J.-L.

    2012-02-01

    We present a combined theoretical and experimental study of the adsorption of two pairs of organic isomers, (i) acetic acid AA (CH3COOH) and methyl formate MF (HCOOCH3), and (ii) ethanol EtOH (CH3CH2OH) and dimethyl ether DME (CH3OCH3), onto crystalline water ice surfaces at low temperatures. Both approaches show that, for each pair, the most stable isomer from a thermodynamical point of view, i.e. AA and EtOH, is also the one which is the more tightly bound to the water ice surface compared to the less stable isomers (MF and DME). This finding, which can be explained by the ability of AA or EtOH to efficiently interact with the ice surface via hydrogen bondings, may have important consequences in an astrophysical context, since it could explain why the most stable isomer is not the most abundant observed in the interstellar gas phase.

  2. E/Z Isomers and Isomerization

    NASA Astrophysics Data System (ADS)

    Liaaen-Jensen, Synnøve; Lutnœes, Bjart Frode

    The natural occurrence of several carotenoid cis isomers and their biological significance were not anticipated in 1962, when the classical monograph on cis-trans isomeric carotenoids [1] was published. More recent research has demonstrated that various cis isomers occur naturally in bacteria plants, algae and invertebrate animals, and are present in human blood and tissues. The participation of cis isomers in the biosynthethic route to coloured carotenoids is well established (Volume 3, Chapter 2). Important biological functions of (15Z)-carotenoids in photosynthesis have been revealed [2]. In relation to health aspects of carotenoids, the bioavailability of cis isomers may be higher than that of the all-trans isomer [3], and accumulated evidence suggests that cis/trans isomerization may occur in biological tissues, particularly of lycopene (31) in human serum [4] (Volume 5, Chapter 7).

  3. Separation and identification of underivatized plasma acylcarnitine isomers using liquid chromatography-tandem mass spectrometry for the differential diagnosis of organic acidemias and fatty acid oxidation defects.

    PubMed

    Peng, Minzhi; Fang, Xiefan; Huang, Yonglan; Cai, Yanna; Liang, Cuili; Lin, Ruizhu; Liu, Li

    2013-12-06

    A simple HPLC-MS/MS method has been established to separate and identify underivatized acylcarnitine isomers. Human plasma samples were deproteinized and concentrated. Acylcarnitines were separated on a reverse phase column and detected with triple quadrupole linear ion trap mass spectrometry. Deuterium-labeled internal standards were used for quantitation. To identify acylcarnitines without pure standards, information-dependent acquisition linking to enhanced product ion scan mode was used. 112 acylcarnitines, including stereoisomers, were found in samples of patients. Dicarboxylic acylcarnitines, such as methylmalonylcarnitine and glutarylcarnitine, were detected with high sensitivity. Three stereoisomers of (R,S)2-methyl-3-hydroxy butyrylcarnitine were detected in samples of patients with β-ketothiolase deficiency. Validation results revealed excellent precision and accuracy of the method. In general the within- and between-run coefficients of variation (CV%) were less than 15%, and recoveries were in the range of 92.7-117.5%. In addition, the reference intervals of acylcarnitines for children aged 3-day to13-year old were established. Using the new method and reference intervals, we have correctly diagnosed 49 patients with fatty acid oxidation defects or organic acidemias in 176 high-risk patients.

  4. The antiproliferative activity of all-trans-retinoic acid catabolites and isomers is differentially modulated by liarozole-fumarate in MCF-7 human breast cancer cells.

    PubMed

    Van heusden, J; Wouters, W; Ramaekers, F C; Krekels, M D; Dillen, L; Borgers, M; Smets, G

    1998-04-01

    The clinical use of all-trans-retinoic acid (ATRA) in the treatment of cancer is significantly hampered by the prompt emergence of resistance, believed to be caused by increased ATRA catabolism. Inhibitors of ATRA catabolism may therefore prove valuable for cancer therapy. Liarozole-fumarate is an anti-tumour drug that inhibits the cytochrome P450-dependent catabolism of ATRA. ATRA, but also its naturally occurring catabolites, 4-oxo-ATRA and 5,6-epoxy-ATRA, as well as its stereoisomers, 9-cis-RA and 13-cis-RA, show significant antiproliferative activity in MCF-7 human breast cancer cells. To further elucidate its mechanism of action, we investigated whether liarozole-fumarate was able to enhance the antiproliferative activity of ATRA catabolites and isomers. Liarozole-fumarate alone up to a concentration of 10(-6) M had no effect on MCF-7 cell proliferation. However, in combination with ATRA or the ATRA catabolites, liarozole-fumarate (10(-6) M) significantly enhanced their antiproliferative activity. On the contrary, liarozole-fumarate (10(-6) M) was not able to potentiate the antiproliferative activity of the ATRA stereoisomers, most probably because of the absence of cytochrome P450-dependent catabolism. Together, these findings show that liarozole-fumarate acts as a versatile inhibitor of retinoid catabolism in that it not only blocks the breakdown of ATRA, but also inhibits the catabolic pathway of 4-oxo-ATRA and 5,6-epoxy-ATRA, thereby enhancing their antiproliferative activity.

  5. Effects of milk supplementation with conjugated linoleic acid (isomers cis-9, trans-11 and trans-10, cis-12) on body composition and metabolic syndrome components.

    PubMed

    Laso, Nuria; Brugué, Emma; Vidal, Josep; Ros, Emilio; Arnaiz, Joan Albert; Carné, Xavier; Vidal, Sergi; Mas, Sergi; Deulofeu, Ramon; Lafuente, Amalia

    2007-10-01

    The effects of conjugated linoleic acid (CLA) on body weight and body composition in man are controversial. The aim of this study was to investigate the effects of milk supplementation with CLA on body composition and on the biochemical parameters of the metabolic syndrome. This was a randomised, double-blind, placebo-controlled trial. Subjects were randomised to a daily intake of 500 ml milk supplemented with 3 g CLA (using a mixture of the bioactive isomers cis-9, trans-11 and trans-10, cis-12, marketed as Tonalin, Naturlinea; Central Lechera Asturiana) or placebo for 12 weeks. Sixty healthy men and women (aged 35-65 years) with signs of the metabolic syndrome participated (BMI 25-35 kg/m2). Dual-energy X-ray absorptiometry was used to measure body composition (week 0 baseline and week 12). Total fat mass in the CLA-milk subgroup with a BMI < or = 30 kg/m2 decreased significantly while no changes were detected in the placebo group (approximately 2 %, P = 0.01). Trunk fat mass showed a trend towards reduction (approximately 3 %, P = 0.05). CLA supplementation had no significant effect on the parameters of the metabolic syndrome, nor was it associated with changes in haematological parameters or renal function. The supplementation of milk with 3 g CLA over 12 weeks results in a significant reduction of fat mass in overweight but not in obese subjects. CLA supplementation was not associated with any adverse effects or biological changes.

  6. Multiple Uric Acid Bladder Stones: Clinical Presentation and Endoscopic Management

    PubMed Central

    Torricelli, Fabio Cesar Miranda; Chueh, Shih-Chieh Jeff; Shen, Shujane

    2017-01-01

    Abstract Background: Bladder urinary calculi occur in 3%–8% of men with bladder outlet obstruction, and although most of them are composed of calcium, in a few cases uric acid bladder stones are diagnosed. Case Presentation: We present clinical images and therapeutic management of a 65-year-old diabetic man with significant prostate enlargement and >30 bladder stones, the largest being 17 mm. Despite the large stone burden, the patient was managed by cystolithotripsy. Remarkably, stone composition analysis revealed 100% uric acid stone. Intraoperative and postoperative course were uneventfully. Conclusion: Uric acid bladder stone pathogenesis seems to be multifactorial with local and systemic factors contributing in different manners and even large stone burdens may be cystoscopically managed. PMID:28265592

  7. [Ni(PPh2NBn2)2(CH3CN)]2+ as an Electrocatalyst for H2 Production: Dependence on Acid Strength and Isomer Distribution

    SciTech Connect

    Appel, Aaron M.; Pool, Douglas H.; O'Hagan, Molly J.; Shaw, Wendy J.; Yang, Jenny Y.; Rakowski DuBois, Mary; DuBois, Daniel L.; Bullock, R. Morris

    2011-07-01

    [Ni(PPh2NBz2)2(CH3CN)](BF4)2, Ni(PPh2NBz2)22+ (where PPh2NBz2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) has been studied as an electrocatalyst for the production of hydrogen in acetonitrile. Using strong acids, such as p cyanoanilinium, Ni(PPh2NBz2)22+ has been shown to be protonated under catalytic conditions prior to reduction, with an effective pKa of 6.7±0.4. Through multinuclear NMR spectroscopy studies, the nickel(II) complex was found to be doubly protonated without any observed singly protonated species. In the doubly protonated complex, both protons are positioned exo with respect to the metal center and are stabilized by an N-H-N hydrogen bond. The formation of exo protonated isomers is proposed to limit the rate of hydrogen production because the protons are unable to gain suitable proximity to the reduced metal center to generate dihydrogen. Pre-protonation of Ni(PPh2NBz2)22+ has been found to shift the catalytic operating potential to more positive potentials by up to 440 mV, depending upon the conditions. The catalytic rate was found to increase by an order of magnitude by increasing the solution pH or through the addition of water. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

  8. Ultrasensitive analysis of lysergic acid diethylamide and its C-8 isomer in hair by capillary zone electrophoresis in combination with a stacking technique and laser induced fluorescence detection.

    PubMed

    Airado-Rodríguez, Diego; Cruces-Blanco, Carmen; García-Campaña, Ana M

    2015-03-25

    This article deals with the development and validation of a novel capillary zone electrophoresis (CZE) with laser induced fluorescence detection method for the analysis of lysergic acid diethylamide (LSD) and its isomer iso-LSD in hair samples. The separation of both analytes has been achieved in less than 13 min in a 72-cm effective length capillary with 75-μm internal diameter. As running buffer 25 mM citrate, pH 6.0 has been employed and separation temperature and voltage of 20 °C and 13 kV respectively, were applied. Field amplified sample injection (FASI) has been employed for on-line sample preconcentration, using ultrapure water containing 117 μM H3PO4 as optimum injection medium. Injection voltage and time have been optimized by means of experimental design, obtaining values of 7 kV and 15s, respectively. Methylergonovine has been employed as internal standard in order to compensate irreproducibility from electrokinetic injection. The analytical method has been applied to hair samples, previous extraction of the target analytes by ultrasound assisted solid-liquid extraction at 40 °C for 2.5 h, employing acetonitrile as extracting solvent. Linear responses were found for LSD and iso-LSD in matrix-matched calibrations from around 0.400 up to 50.0 pg mg(-1). LODs (3 S/N) in the order of 0.100 pg mg(-1) were calculated for both analytes, obtaining satisfactory recovery percentages for this kind of sample.

  9. The antiproliferative activity of all-trans-retinoic acid catabolites and isomers is differentially modulated by liarozole-fumarate in MCF-7 human breast cancer cells.

    PubMed Central

    Van heusden, J.; Wouters, W.; Ramaekers, F. C.; Krekels, M. D.; Dillen, L.; Borgers, M.; Smets, G.

    1998-01-01

    The clinical use of all-trans-retinoic acid (ATRA) in the treatment of cancer is significantly hampered by the prompt emergence of resistance, believed to be caused by increased ATRA catabolism. Inhibitors of ATRA catabolism may therefore prove valuable for cancer therapy. Liarozole-fumarate is an anti-tumour drug that inhibits the cytochrome P450-dependent catabolism of ATRA. ATRA, but also its naturally occurring catabolites, 4-oxo-ATRA and 5,6-epoxy-ATRA, as well as its stereoisomers, 9-cis-RA and 13-cis-RA, show significant antiproliferative activity in MCF-7 human breast cancer cells. To further elucidate its mechanism of action, we investigated whether liarozole-fumarate was able to enhance the antiproliferative activity of ATRA catabolites and isomers. Liarozole-fumarate alone up to a concentration of 10(-6) M had no effect on MCF-7 cell proliferation. However, in combination with ATRA or the ATRA catabolites, liarozole-fumarate (10(-6) M) significantly enhanced their antiproliferative activity. On the contrary, liarozole-fumarate (10(-6) M) was not able to potentiate the antiproliferative activity of the ATRA stereoisomers, most probably because of the absence of cytochrome P450-dependent catabolism. Together, these findings show that liarozole-fumarate acts as a versatile inhibitor of retinoid catabolism in that it not only blocks the breakdown of ATRA, but also inhibits the catabolic pathway of 4-oxo-ATRA and 5,6-epoxy-ATRA, thereby enhancing their antiproliferative activity. PMID:9579827

  10. Using One's Hands for Naming Optical Isomers and Other Stereochemical Positions.

    ERIC Educational Resources Information Center

    Mezl, Vasek A.

    1996-01-01

    Presents a method that allows students to use their hands to obtain the stereochemistry of chiral centers without redrawing the structure. Discusses the use of the model in: determining the configurations of amino acids, determining if sugars are D or L isomers, the sequence rule procedure, prochirality, naming the sides of trigonal carbons, and…

  11. Energetic and Structural Study of Diphenylpyridine Isomers

    NASA Astrophysics Data System (ADS)

    Rocha, Marisa A. A.; Gomes, Lígia R.; Low, John N.; Santos, Luís M. N. B. F.

    2009-09-01

    The energetic and structural study of three diphenylpyridine isomers is presented in detail. The three isomers, 2,6-, 2,5-, and 3,5-diphenylpyridines, were synthesized via Suzuki-Miyaura methodology based on palladium catalysis, and the crystal structures of the isomers were obtained by X-ray diffraction. The relative energetic stabilities in the condensed and gaseous phases as well as volatilities and structures of the three studied isomers were evaluated, regarding the position of the phenyl groups relative to the nitrogen atom of the pyridine ring. The temperature, standard molar enthalpies, and entropies of fusion were measured and derived by differential scanning calorimetry. The vapor pressures of the considered isomers were determined by a static apparatus based on a MKS capacitance diaphragm manometer. The standard molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived, and the phase diagram near the triple point coordinates were determined for all isomers. The standard (p° = 0.1 MPa) molar enthalpies of combustion of all crystalline isomers were determined, at T = 298.15 K, by static bomb combustion calorimetry. The standard molar enthalpies of formation, in the crystalline and gaseous phases, at T = 298.15 K, were derived. The experimental results for the energetics in the gaseous phase of the three compounds were compared and assessed with the values obtained by ab initio calculations at different levels of theory (DFT and MP2) showing that, at this level of theory, the computational methods underestimate the energetic stability, in the gaseous phase, for these molecules. In order to understand the aromaticity in the central ring of each isomer, calculations of NICS (B3LYP/6-311G++(d,p) level of theory) values on the pyridine ring were also performed.

  12. Preparation of 3R- and 3S-methyl isomers of the myocardial imaging agent 15-(p-IODOPHENYL)-3-methylpentadecanoic acid ({open_quotes}BMIPP{close_quotes})

    SciTech Connect

    Lin, Q. |; Luo, J.; Mokler, F.

    1996-10-01

    Iodine-123-labeled racemic BMIPP is used for clinical evaluation of heart disease. To evaluate the expected importance of configuration of the asymmetric C-3 center, we have synthesized the 3R-isomer. 6-Phenylhexanoyl chloride was condensed with thiophene (Friedel-Crafts), followed by Wolff-Kishner reduction and subsequent acylation with the ethyl-3-R-methylglutaroyl chloride, Wolff-Kishner reduction and Raney-Ni ring opening. Para Thallation (TTFA)/KI provided 3R-BMIPP, m.p. 51-52{degrees}C, [{alpha}{sub D}] = +0.74{degrees}. The diastereomeric amide mixture was prepared by reaction of racemic 3-R,S-BMIPP with (S)-(-)-{alpha}-methylbenzylamine. Chromatographic separation and HCl hydrolysis (at 175{degrees}C) provided the 3R- and 3S- (m.p. 45-46{degrees}C, [{alpha}{sub D}] = -1.67{degrees}) BMIPP isomers. The more polar amide (m.p. 93-94{degrees}C) was identical with the amide from the synthetic 3R-BMIPP (m.p., HPLC, NMR). Availability of the 3R- and 3S-BMIPP isomers will permit preparation of the radioiodinated isomers and animal evaluation to determine the effects of the methyl group configuration on myocardial uptake and metabolism.

  13. Infrared spectroscopy of the bent isomer of N 2O-HF

    NASA Astrophysics Data System (ADS)

    Dayton, D. C.; Miller, R. E.

    1988-02-01

    We report the infrared spectrum of the bent isomer of N 2O-HF in which the HF subnit is hydrogen bonded to the oxygen. This isomer was previously observed using microwave spectroscopy, while recent infrared measurements by Lovejoy and Nesbitt have shown that a linear (or slightly bent) ONNHF isomer also exists. We find that the linear ONNHF isomer is present under identical beam conditions to those used to record the spectrum of the bent isomer.

  14. Vaccenic acid and trans fatty acid isomers from partially hydrogenated oil both adversely affect LDL cholesterol: a double-blind, randomized controlled trial

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Evidence of the adverse effects of industrially-produced trans fatty acids (iTFA) on risk of cardiovascular disease is consistent and well documented in the scientific literature; however, the cardiovascular effects of naturally-occurring TFA synthesized in ruminant animals (rTFA), such as vaccenic ...

  15. Simultaneous ozonation kinetics of phenolic acids present in wastewaters

    SciTech Connect

    Benitez, F.J.; Beltran-Heredia, J.; Acero, J.L.; Pinilla, M.L.

    1996-12-31

    Among the several chemical processes conducted for the removal of organic matter present in wastewaters coming from some agro-industrial plants (wine distilleries, olive oil mills, etc), the oxidation by ozone has shown a great effectiveness in the destruction of specially refractory pollutants: it is demonstrated that the biodegradability of those wastewaters increases aflcer an ozonation pretreatment. Their great pollutant character is imputed to the presence of some organic compounds, like phenols and polyphenols, which are toxic and inhibit the latter biological treatments. In this research, a competitive kinetic procedure reported by Clurol and Nekouinaini is applied to determine the degradation rate constants by ozone of several phenolic acids which are present in the wastewaters from the olive oil obtaining process. The resulting kinetic expressions for the ozonation reactions are useful for the successful design and operation of ozone reactors in water and wastewaters treatment plants.

  16. The interstellar chemistry of H2C3O isomers.

    PubMed

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-03-11

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects.

  17. The interstellar chemistry of H2C3O isomers

    PubMed Central

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-01-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects. PMID:27013768

  18. Potential antifertility agents. 6. Synthesis and biological activities of optical isomers of 4 beta-(p-methozyphenyl)-2 beta-methylcyclohexane-alpha-carboxylic acid and related compounds.

    PubMed

    Crenshaw, R R; Jenks, T A; Luke, G M; Bialy, G

    1974-12-01

    The optical isomers of the title compound were synthesized and the biological potencies of the two enantiomers were compared. There was essentially no difference in their hypocholesterolemic activities, as had been predicted, and little or no difference between their uterotropic potencies. The approximately equal uterotropic activities seen with the enantiomers is explained in terms of stereochemical requirements at the receptor level for an estrogenic response. A working model of an estrogenic receptor is proposed. An accompanying paper provides support for the proposed model.

  19. The proportion of lycopene isomers in human plasma is modulated by lycopene isomer profile in the meal but not by lycopene preparation.

    PubMed

    Richelle, Myriam; Lambelet, Pierre; Rytz, Andreas; Tavazzi, Isabelle; Mermoud, Anne-France; Juhel, Christine; Borel, Patrick; Bortlik, Karlheinz

    2012-05-01

    Dietary lycopene consists mostly of the (all-E) isomer. Upon absorption, (all-E) lycopene undergoes isomerisation into various (Z)-isomers. Because these isomers offer potentially better health benefits than the (all-E) isomer, the aim of the present study was to investigate if the profile of lycopene isomers in intestinal lipoproteins is affected by the profile of lycopene isomers in the meal and by the tomato preparation. Six postprandial, crossover tests were performed in healthy men. Three meals provided about 70 % of the lycopene as (Z)-isomers, either mainly as 5-(Z) or 13-(Z), or as a mixture of 9-(Z) and 13-(Z) lycopene, while three tomato preparations provided lycopene mainly as the (all-E) isomer. Consumption of the 5-(Z) lycopene-rich meal led to a high (60 %) proportion of this isomer in TAG-rich lipoproteins (TRL), indicating a good absorption and/or a low intestinal conversion of this isomer. By contrast, consumption of meals rich in 9-(Z) and 13-(Z) lycopene isomers resulted in a low level of these isomers but high amounts of the 5-(Z) and (all-E) isomers in TRL. This indicates that the 9-(Z) and 13-(Z) isomers were less absorbed or were converted into 5-(Z) and (all-E) isomers. Dietary (Z)-lycopene isomers were, therefore, differently isomerised and released in TRL during their intestinal absorption in men. Consuming the three meals rich in (all-E) lycopene resulted in similar proportions of lycopene isomers in TRL: 60 % (all-E), 20 % 5-(Z), 9 % 13-(Z), 2 % 9-(Z) and 9 % unidentified (Z)-isomers. These results show that the tomato preparation has no impact on the lycopene isomerisation occurring during absorption in humans.

  20. Stereospecific Synthesis of the Geometrical Isomers of a Natural Product

    ERIC Educational Resources Information Center

    Grove, T.; DiLella, D.; Volker, E.

    2006-01-01

    Stereospecific synthesis of a geometrical isomer is not a common topic for the introductory organic chemistry laboratory. We have developed and tested an experiment for the synthesis of (Z) and (E) isomers that has been performed successfully by undergraduate students. The experiment is presented to the students as a puzzle in which they must…

  1. Cerebrospinal Fluid Steroidomics: Are Bioactive Bile Acids Present in Brain?*

    PubMed Central

    Ogundare, Michael; Theofilopoulos, Spyridon; Lockhart, Andrew; Hall, Leslie J.; Arenas, Ernest; Sjövall, Jan; Brenton, A. Gareth; Wang, Yuqin; Griffiths, William J.

    2010-01-01

    In this study we have profiled the free sterol content of cerebrospinal fluid by a combination of charge tagging and liquid chromatography-tandem mass spectrometry. Surprisingly, the most abundant cholesterol metabolites were found to be C27 and C24 intermediates of the bile acid biosynthetic pathways with structures corresponding to 7α-hydroxy-3-oxocholest-4-en-26-oic acid (7.170 ± 2.826 ng/ml, mean ± S.D., six subjects), 3β-hydroxycholest-5-en-26-oic acid (0.416 ± 0.193 ng/ml), 7α,x-dihydroxy-3-oxocholest-4-en-26-oic acid (1.330 ± 0.543 ng/ml), and 7α-hydroxy-3-oxochol-4-en-24-oic acid (0.172 ± 0.085 ng/ml), and the C26 sterol 7α-hydroxy-26-norcholest-4-ene-3,x-dione (0.204 ± 0.083 ng/ml), where x is an oxygen atom either on the CD rings or more likely on the C-17 side chain. The ability of intermediates of the bile acid biosynthetic pathways to activate the liver X receptors (LXRs) and the farnesoid X receptor was also evaluated. The acidic cholesterol metabolites 3β-hydroxycholest-5-en-26-oic acid and 3β,7α-dihydroxycholest-5-en-26-oic acid were found to activate LXR in a luciferase assay, but the major metabolite identified in this study, i.e. 7α-hydroxy-3-oxocholest-4-en-26-oic acid, was not an LXR ligand. 7α-Hydroxy-3-oxocholest-4-en-26-oic acid is formed from 3β,7α-dihydroxycholest-5-en-26-oic acid in a reaction catalyzed by 3β-hydroxy-Δ5-C27-steroid dehydrogenase (HSD3B7), which may thus represent a deactivation pathway of LXR ligands in brain. Significantly, LXR activation has been found to reduce the symptoms of Alzheimer disease (Fan, J., Donkin, J., and Wellington C. (2009) Biofactors 35, 239–248); thus, cholesterol metabolites may play an important role in the etiology of Alzheimer disease. PMID:19996111

  2. Gas-grain Modeling of Isocyanic Acid (HNCO), Cyanic Acid (HOCN), Fulminic Acid (HCNO), and Isofulminic Acid (HONC) in Assorted Interstellar Environments

    NASA Astrophysics Data System (ADS)

    Quan, Donghui; Herbst, Eric; Osamura, Yoshihiro; Roueff, Evelyne

    2010-12-01

    Isocyanic acid (HNCO) is a well-known interstellar molecule. Evidence also exists for the presence of two of its metastable isomers in the interstellar medium: HCNO (fulminic acid) and HOCN (cyanic acid). Fulminic acid has been detected toward cold and lukewarm sources, while cyanic acid has been detected both in these sources and in warm sources in the Galactic Center. Gas-phase models can reproduce the abundances of the isomers in cold sources, but overproduce HCNO in the Galactic Center. Here we present a detailed study of a gas-grain model that contains these three isomers, plus a fourth isomer, isofulminic acid (HONC), for four types of sources: hot cores, the warm envelopes of hot cores, lukewarm corinos, and cold cores. The current model is partially able to rationalize the abundances of HNCO, HOCN, and HCNO in cold and warm sources. Predictions for HONC in all environments are also made.

  3. Diagnostic fragment-ion-based and extension strategy coupled to DFIs intensity analysis for identification of chlorogenic acids isomers in Flos Lonicerae Japonicae by HPLC-ESI-MS(n).

    PubMed

    Zhang, Jia-Yu; Zhang, Qian; Li, Ning; Wang, Zi-Jian; Lu, Jian-Qiu; Qiao, Yan-Jiang

    2013-01-30

    A method of modified diagnostic fragment-ion-based extension strategy (DFIBES) coupled to DFIs (diagnostic fragmentation ions) intensity analysis was successfully established to simultaneously screen and identify the chlorogenic acids (CGAs) in Flos Lonicerae Japonicae (FLJ) by HPLC-ESI-MS(n). DFIs, such as m/z 191 [quinic acid-H](-), m/z 179 [caffeic acid-H](-) and m/z 173 [quinic acid-H-H2O](-) were determined or proposed from the fragmentation patterns analysis of corresponding reference substances for every chemical family of CGAs. A "structure extension" method was then proposed based on the well-demonstrated fragmentation patterns and was successively applied into the rapid screening of CGAs in FLJ. Considering that substitution isomerism is a common phenomenon, a full ESI-MS(n) fragmentation analysis according to the intensity of DFIs has been performed to identify the CGA isomers. Based on the DFIs and intensity analysis, 41 peaks attributed to CGAs including 4 caffeoylquinic acids (CQA), 7 CQA glycosides, 6 dicaffeoylquinic acids (DiCQA), 10 DiCQA glycosides, 1 tricaffeoylquinic acids (TriCQA), 4p-coumaroylquinic acids (pCoQA), 3 feruloylquinic acids (FQA) and 6 caffeoylferuloylquinic acids (CFQA) were identified preliminarily in a 65-min chromatographic run. It was the first time to systematically report the presence of CGAs in FLJ, especially for CQA glycosides, DiCQA glycosides, TriCQA, pCoQA and CFQA. All the results indicated that the method of developed DFIBES coupled to DFIs analysis was feasible, reliable and universal for screening and identifying the constituents with the same carbon skeletons especially the isomeric compounds from the complex extract of TCMs.

  4. Crystal structures and spectroscopic properties of zinc(II) ternary complexes of vitamin L, H' and their isomer m-aminobenzoic acid with bipyridine.

    PubMed

    Wang, Yue; Okabe, Nobuo

    2005-06-01

    The crystal structures of the three Zn(II) complexes, [Zn(bpy)(o-AB)2] (1) (bpy=2,2'-bipyridine, o-AB=o-aminobenzoic acid=Vitamin L), [Zn(bpy)(m-AB)Cl]2 (2) (m-AB=m-aminobenzoic acid), [Zn(bpy)(p-AB)Cl]*p-AB*H2O (3) (p-AB=p-aminobenzoic acid=Vitamin H'), have been determined and the basic coordination geometries and architectures organized by hydrogen-bonds and pi-pi interactions also characterized. The substitute amine group at ortho-, meta-, and para-position of AB plays an important role to produce completely different coordination motif of these complexes, further, in all complexes, aromatic amines are not coordinated to Zn(II) atom. While two different types of coordination modes of the carboxylate O atoms are present in these complexes: one mode consists of the usual Zn-O bond lengths (2.009(2)-2.251(2) A) in complex 1, 2 and 3; another consists of a very long Zn-O bond lengths (2.422(2) A) in complex 1. Each of the complexes has the characteristic UV absorption bands around 250-310 nm region, and the intense fluorescence band at near 325 nm.

  5. Nutritional quality of fresh and heated Aleppo pine (Pinus halepensis Mill.) seed oil: trans-fatty acid isomers profiles and antioxidant properties.

    PubMed

    Dhibi, Madiha; Issaoui, Manel; Brahmi, Faten; Mechri, Beligh; Mnari, Amira; Cheraif, Imed; Skhiri, Fathia; Gazzah, Noureddine; Hammami, Mohamed

    2014-08-01

    Numerous studies have focused on trans fatty acids (TFA) technologically produced by partial hydrogenation of oils. However, TFA can also be present in fresh oils. For this reason, cis fatty acid (CFA), TFA and conjugated linoleic acid (CLA) of fresh and heated Aleppo pine seed oil (APSO) at frying temperature (180 °C) were evaluated and correlated with the antioxidant characteristics. Results showed that fresh APSO had a low oleic/linoleic ratio O/L (0.4). Total TFA in fresh APSO reached 1%. The predominant TFA was 18:2 n-6 (t9, t12) in both fresh and heated APSO. Individual TFA increased with significant differences (p < 0.05) with heating time. CLA occurred after 4 h and significantly increased (p < 0.05) accounting 10% of total TFA after 10 h. Total TFA are negatively correlated with α-tocopherol, γ-tocopherol (p < 0.05) and carotenoïds (p < 0.01) and positively correlated with remaining DPPH. Oil stability index (OSI) showed significant negative correlation with TFA (r = -0.925; p = 0.008). A principal component analysis (PCA) showed a clear discrimination between fresh and heated oils. Temperature, heating time, unsaturation degree and antioxidants are combined factors which significantly affect the isomerization rate and nutritional quality of APSO.

  6. Azaphthalocyanines with fused triazolo rings: formation of sterically stressed constitutional isomers.

    PubMed

    Novakova, Veronika; Roh, Jaroslav; Gela, Petr; Kuneš, Jiří; Zimcik, Petr

    2012-05-07

    The presented work deals with synthesis and isolation of constitutional isomers of triazolo-fused azaphthalocyanines. Distribution of the isomers did not follow the statistical calculations due to steric effects of the substituents preferring the least sterically stressed C(4h) isomer.

  7. Quantification of Triacylglycerol Positional Isomers in Rat Milk.

    PubMed

    Watanabe, Natsuko; Nagai, Toshiharu; Mizobe, Hoyo; Yoshinaga, Kazuaki; Yoshida, Akihiko; Kitamura, Yohei; Shimizu, Takashi; Beppu, Fumiaki; Gotoh, Naohiro

    2016-12-01

    The absolute amount of triacylglycerol (TAG) positional isomers was analyzed in rat milk fat, a representative of non-ruminant milk fat, using a HPLC-UV-atmospheric pressure chemical ionization-MS/MS system equipped with an octacosyl silylation column or polymeric ODS column. TAGs consisting of two oleic acids (O) and one palmitic acid (P) were the most abundant. In particular, β-OPO, a TAG binding P at the β-position (sn-2) and two Os at the α-positions (sn-1/3), was prominent. The β-OPO content decreased over time, while a TAG consisting of two Ps and one capric acid, a medium-chain fatty acid, increased. TAGs consisting of two Ps and one docosahexaenoic acid were present in small amounts and decreased with time. These results indicated that the recombination of fatty acids in TAGs in milk fat occurs in the mother, and is thought to depend on the infant's stage of growth, in response to their nutritional needs. It was also demonstrated that medium-chain fatty acids were mainly located at the α-position (sn-3), while Ps were mainly located at the β-position (sn-2). Therefore, the combination and binding positions of fatty acids of TAG are considered very important in infant nutrition.

  8. Biodegradation of cresol isomers in anoxic aquifers.

    PubMed Central

    Smolenski, W J; Suflita, J M

    1987-01-01

    The biodegradation of o-, m-, and p-cresol was examined in material obtained from a shallow anaerobic alluvial sand aquifer. The cresol isomers were preferentially metabolized, with p-cresol being the most easily degraded. m-Cresol was more persistent than the para-isomer, and o-cresol persisted for over 90 days. Biodegradation of cresol isomers was favored under sulfate-reducing conditions (SRC) compared with that under methanogenic conditions (MC). Slurries that were acclimated to p-cresol metabolism transformed this substrate at 18 and 330 nmol/h per g (dry weight) for MC and SRC, respectively. Inhibition of electron flow to sulfate reduction with 2.0 mM molybdate reduced p-cresol metabolism in incubations containing sulfate. When methanogenesis was blocked with 5 mM bromoethanesulfonic acid in incubations lacking sulfate, p-cresol catabolism was retarded. Under SRC 3.4 mol of sulfate was consumed per mol of p-cresol metabolized. The addition of sulfate to methanogenic incubations stimulated p-cresol degradation. Simultaneous adaptation studies in combination with spectrophotometric and chromatographic analysis of metabolites indicated that p-cresol was oxidized under SRC to p-hydroxybenzoate via the corresponding alcohol and aldehyde. This series of reactions was inhibited under sulfate-limited or aerobic conditions. Therefore, the primary catabolic event for p-cresol decomposition under SRC appears to involve the hydroxylation of the aryl methyl group. PMID:3579279

  9. Chemical Simulations of Prebiotic Molecules: Interstellar Ethanimine Isomers

    NASA Astrophysics Data System (ADS)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    The E- and Z-isomers of ethanimine (CH3CHNH) were recently detected toward the star-forming region Sagittarius (Sgr) B2(N) using the Green Bank Telescope PRIMOS cm-wave spectral data, and imaged by the Australia Telescope Compact Array. Ethanimine is not reported in the hot cores of Sgr B2, but only in gas that absorbs at +64 and +82 km s-1 in the foreground of continuum emission generated by H ii regions. The ethanimine isomers can serve as precursors of the amino acid alanine and may play important roles in forming biological molecules in the interstellar medium. Here we present a study of the chemistry of ethanimine using a gas-grain simulation based on rate equations, with both isothermal and warm-up conditions. In addition, the density, kinetic temperature, and cosmic ray ionization rate have been varied. For a variety of physical conditions in the warm-up models for Sgr B2(N) and environs, the simulations show reasonable agreement with observationally obtained abundances. Isothermal models of translucent clouds along the same line of sight yield much lower abundances, so that ethanimine would be much more difficult to detect in these sources despite the fact that other complex molecules have been detected there.

  10. [The positional isomers of triglycerides in oils, fats and apoB-100 lipoproteins: palmitic and oleic modes of metabolism of fatty acids-substrates for energy acquiring].

    PubMed

    Kotkina, T I; Titov V N

    2014-01-01

    Even total resemblance of content of fatty acids in triglycerides has both no standing for their functional unity nor even identity of their physical chemical characteristics. The etherification of fatty acids in various positions of three-atomic glycerin separates triglycerides on palmitic and oleic substrates for energy acquiring by cells. The kinetic parameters of biochemical reactions under palmitic mode of metabolism of fatty acids are always low. The myocytes in biological reaction of exotrophy experience deficiency of exogenous fatty acids which in vivo is to permanently supply through activation of biological reaction of endotrophy--enhancement of lipolysis in adipocytes. The biological role of insulin is to prevent formation in vivo of palmitic mode of metabolism of saturated and monoenic fatty acids. Under this condition, the necessity to activate lipolysis and to increase in blood plasma concentration of unesteritied fatty acids forms syndrome of resistance to insulin. The surplus of palmitic fatty acid in food and deficiency of insulin show in vivo unidirectional a physiologic action. The formation of palmitic mode of metabolism of energy substrates--portion of pathogenesis of atherosclerosis, metabolic syndrome, obesity, non-alcoholic fatty infiltration of liver and partiallly essential arterial hypertension.

  11. Porphycenes and Related Isomers: Synthetic Aspects.

    PubMed

    Anguera, Gonzalo; Sánchez-García, David

    2017-02-22

    Porphyrins, called the pigments of life, have been studied for decades. However, the first constitutional isomer of porphyrin, porphycene, was not synthesized until 1986. This milestone marked the beginning of a new era in the field of porphyrinoids and presented opportunities for the creation of an abundance of new pigments. The unique structural and electronic features of these compounds give rise to interesting physical and optical properties with applications in biomedicine and materials science. This review focuses on the synthetic methodologies available for the preparation of porphycenes (functionalized porphycenes, extended porphycenes, benzoporphycenes, naphthoporphycenes, and heteroanalogues) and the other known isomers, namely, corrphycene, hemiporphycene, and isoporphycene. Although the classical synthetic approaches are discussed, particular emphasis is placed on improvements to the known methodologies and recent advances in the field.

  12. Isomer-specific biodegradation of nonylphenol in river sediments and structure-biodegradability relationship.

    PubMed

    Lu, Zhijiang; Gan, Jay

    2014-01-21

    Nonylphenol (NP), a well-known environmental estrogen with numerous isomers, is frequently found in surface water and sediments. Recent studies showed that NP isomers exhibited different estrogenicity. However, at present little information is available on its isomer-specific degradation in the bed sediment, which is the primary sink of NP in surface aquatic systems. In this study, we investigated the biodegradability of 19 NP isomers in two river sediments under oxic and anoxic conditions. Under oxic conditions, the half-lives of NP isomers in an upper river sediment ranged from 0.9 to 13.2 d. Under reduced conditions, the persistence of NP isomers generally increased, with negligible dissipation under strongly reduced conditions. In the well-aerated sediment, NP isomers with short side chain and/or bulky α-substituents were found to be more recalcitrant to degradation. Moreover, when a total of 57 molecular descriptors were examined, the degree of branching as quantified by IDWbar was found to result in the best linear correlation with half-lives of NP isomers (R(2) = 0.88). These results indicated that the isomer-specificity of NP in environmental processes should be considered, and that simple molecular descriptors may be used to identify the more recalcitrant isomers, thus allowing prioritization in the evaluation of environmental fate and risks of NP isomers.

  13. Carotenoids and their isomers: color pigments in fruits and vegetables.

    PubMed

    Khoo, Hock-Eng; Prasad, K Nagendra; Kong, Kin-Weng; Jiang, Yueming; Ismail, Amin

    2011-02-18

    Fruits and vegetables are colorful pigment-containing food sources. Owing to their nutritional benefits and phytochemicals, they are considered as 'functional food ingredients'. Carotenoids are some of the most vital colored phytochemicals, occurring as all-trans and cis-isomers, and accounting for the brilliant colors of a variety of fruits and vegetables. Carotenoids extensively studied in this regard include β-carotene, lycopene, lutein and zeaxanthin. Coloration of fruits and vegetables depends on their growth maturity, concentration of carotenoid isomers, and food processing methods. This article focuses more on several carotenoids and their isomers present in different fruits and vegetables along with their concentrations. Carotenoids and their geometric isomers also play an important role in protecting cells from oxidation and cellular damages.

  14. Polymerization of the cis- and trans-isomers of bis(triethoxysilyl)-2-butene and comparison of their structural properties

    SciTech Connect

    Shaltout, R.M.; Loy, D.A.; Carpenter, J.P.; Dorhout, K.; Shea, K.J.

    1998-09-01

    The cis and trans isomers of bis-(triethoxysilyl)-2-butene were polymerized by the sol-gel method under various conditions. The trans isomer formed gels under all conditions. The cis isomer formed gels only under basic conditions. Under acidic conditions it formed soluble resins of molecular weight ranging from 88,000 to 180,000 Daltons. Solid state and solution {sup 29}Si NMR revealed that the trans isomer formed condensed gels, and that the resins formed by the cis isomer contained cyclic monomers and/or ordered oligomers.

  15. LC/MS/MS determination and pharmacokinetic study of iridoid glycosides monotropein and deacetylasperulosidic acid isomers in rat plasma after oral administration of Morinda officinalis extract.

    PubMed

    Li, Chunmin; Dong, Jian; Tian, Jingchang; Deng, Zhipeng; Song, Xiujing

    2016-02-01

    Morinda officinalis is a famous traditional Chinese medicine containing iridoid glycoside compounds, such as monotropein and deacetylasperulosidic acid. The aim of the study was to develop a novel and sensitive liquid chromatography-tandem mass spectrometry (LC/MS/MS) method for the simultaneous determination of the two isomeric iridoid glycosides and then evaluate their pharmacokinetic properties in rats. Selected-reaction monitoring mode was employed for quantification of two analytes in rat plasma. The calibration curves were linear over their respective concentration range with correlation coefficient >0.995 for both analytes. Precision for monotropein and deacetylasperulosidic acid ranged from 2.5 to 11.9% relative standard deviation, and the accuracy of two analytes was -2.0-3.7 and -6.4-10.7% relative error, respectively. This method was successfully applied in pharmacokinetic study after oral administration of M. officinalis extract in rats. The results provided a basis for further research on the bioactivity of M. officinalis.

  16. Dynamic Kinetic Asymmetric Amination of Alcohols: From A Mixture of Four Isomers to Diastereo- and Enantiopure α-Branched Amines.

    PubMed

    Rong, Zi-Qiang; Zhang, Yao; Chua, Raymond Hong Bing; Pan, Hui-Jie; Zhao, Yu

    2015-04-22

    The first dynamic kinetic asymmetric amination of alcohols via borrowing hydrogen methodology is presented. Under the cooperative catalysis by an iridium complex and a chiral phosphoric acid, α-branched alcohols that exist as a mixture of four isomers undergo racemization by two orthogonal mechanisms and are converted to diastereo- and enantiopure amines bearing adjacent stereocenters. The preparation of diastereo- and enantiopure 1,2-amino alcohols is also realized using this catalytic system.

  17. Ab initio study of cyanoguanidine isomers

    NASA Astrophysics Data System (ADS)

    Arbuznikov, A. V.; Sheludyakova, L. A.; Burgina, E. B.

    1995-06-01

    An ab initio quantum chemical study of the geometric structure and stability of cyanoguanidine isomers was carried out at the Hartree-Fock and Møller-Plesset levels of theory. Two stable separable isomers ('cyanioime' and 'cyanoamine') are found. This gives evidence in favour of the vibrational spectroscopy data showing the existence of both isomers.

  18. Ab initio study of cyanoguanidine isomers

    NASA Astrophysics Data System (ADS)

    Arbuznikov, A. V.; Sheludyakova, L. A.; Burgina, E. B.

    1995-06-01

    An ab initio quantum chemical study of the geometric structure and stability of cyanoguanidine isomers was carried out at the Hartree-Fock and Møller-Plesset levels of theory. Two stable separable isomers (‘cyanioime' and ‘cyanoamine') are found. This gives evidence in favour of the vibrational spectroscopy data showing the existence of both isomers.

  19. Selective LC-MS/MS method for the identification of BMAA from its isomers in biological samples.

    PubMed

    Jiang, Liying; Aigret, Benoit; De Borggraeve, Wim M; Spacil, Zdenek; Ilag, Leopold L

    2012-06-01

    Algal blooms are well-known sources of acute toxic agents that can be lethal to aquatic organisms. However, one such toxin, β-N-methylamino-L-alanine (BMAA) is also believed to cause amyotrophic lateral sclerosis, also known as Lou Gehrig's disease. The detection and identification of BMAA in natural samples were challenging until the recent introduction of reliable methods. However, the issue of potential interference from unknown isomers of BMAA present in samples has not yet been thoroughly investigated. Based on a systematic database search, we generated a list of all theoretical BMAA structural isomers, which was subsequently narrowed down to seven possible interfering compounds for further consideration. The seven possible candidates satisfied the requirements of chemical stability and also shared important structural domains with BMAA. Two of the candidates, 2,4-diaminobutyric acid (DAB) and N-(2-aminoethyl) glycine (AEG) have recently been studied in the context of BMAA. A further isomer, β-amino-N-methyl-alanine (BAMA), has to be considered because it can potentially yield the fragment ion, which is diagnostic for BMAA. Here, we report the synthesis and analysis of BAMA, together with AEG, DAB, and other isomers that are of interest in the separation and detection of BMAA in biological samples by using either high-performance liquid chromatography or ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. We detected for the first time BAMA in blue mussel and oyster samples. This work extends the previously developed liquid chromatography-tandem mass spectrometry platform Spacil et al. (Analyst 135:127, 2010) to allow BMAA isomers to be distinguished, improving the detection and identification of this important amino acid.

  20. Evidence for two interconverting protein isomers in the methotrexate complex of dihydrofolate reductase from Escherichia coli

    SciTech Connect

    Falzone, C.J.; Benkovic, S.J. ); Wright, P.E. )

    1991-02-26

    Two-dimensional {sup 1}H NMR methods and a knowledge of the X-ray crystal structure have been used to make resonance assignments for the amino acid side chains of dihydrofolate reductase from Escherichia coli complexed with methotrexate. The H7 proton on the pteridine ring of methotrexate was found to have NOEs to the methyl protons of Leu-28 which were assigned by using the L28F mutant. These NOEs indicated that the orientation of the methotrexate pteridine ring is similar in both solution and crystal structures. During the initial assignment process, it became evident that many of the resonances in this complex, unlike those of the folate complex, are severally broadened or doubled. The observation of two distinct sets of resonances in a ratio of approximately 2:1 was attributed to the presence of two protein isomers. Many of the side chains with clearly doubled resonances were located in the {beta}-sheet and the active site. Preliminary studies on the apoprotein also revealed doubled resonances in the absence of the inhibitor, indicating the existence of the protein isomers prior to methotrexate binding. In contrast to the methotrexate complex, the binary complex with folate and the ternary MTX-NADPH-DHFR complex presented a single enzyme form. These results are proposed to reflect the ability of folate and NADPH to bind predominantly to one protein isomer.

  1. Comparative pharmacological activity of optical isomers of phenibut.

    PubMed

    Dambrova, Maija; Zvejniece, Liga; Liepinsh, Edgars; Cirule, Helena; Zharkova, Olga; Veinberg, Grigory; Kalvinsh, Ivars

    2008-03-31

    Phenibut (3-phenyl-4-aminobutyric acid) is a GABA (gamma-aminobutyric acid)-mimetic psychotropic drug which is clinically used in its racemic form. The aim of the present study was to compare the effects of racemic phenibut and its optical isomers in pharmacological tests and GABAB receptor binding studies. In pharmacological tests of locomotor activity, antidepressant and pain effects, S-phenibut was inactive in doses up to 500 mg/kg. In contrast, R-phenibut turned out to be two times more potent than racemic phenibut in most of the tests. In the forced swimming test, at a dose of 100 mg/kg only R-phenibut significantly decreased immobility time. Both R-phenibut and racemic phenibut showed analgesic activity in the tail-flick test with R-phenibut being slightly more active. An GABAB receptor-selective antagonist (3-aminopropyl)(diethoxymethyl)phosphinic acid (CGP35348) inhibited the antidepressant and antinociceptive effects of R-phenibut, as well as locomotor depressing activity of R-phenibut in open field test in vivo. The radioligand binding experiments using a selective GABAB receptor antagonist [3H]CGP54626 revealed that affinity constants for racemic phenibut, R-phenibut and reference GABA-mimetic baclofen were 177+/-2, 92+/-3, 6.0+/-1 microM, respectively. We conclude that the pharmacological activity of racemic phenibut relies on R-phenibut and this correlates to the binding affinity of enantiomers of phenibut to the GABAB receptor.

  2. LAS bioconcentration is isomer specific

    SciTech Connect

    Tolls, J.; Haller, M.; Graaf, I. de; Thijssen, M.H.C.; Sijm, D.T.H.M.

    1995-12-31

    The authors measured parent compound specific bioconcentration data for linear alkylbenzene sulfonates in Pimephales promelas. They did so by using cold, custom synthesized sulfophenyl alkanes. They observed that, within homologous series of isomers, the uptake rate constants (k{sub 1}) and the bioconcentration factor (BCF) increase with increasing number of carbon atoms in the alkyl chain (n{sub C-atoms}). In contrast, the elimination rate constant k{sub 2} appears to be independent of the alkyl chain length. Regressions of log BCF vs n{sub C-atoms} yielded different slopes for the homologous groups of the 5- and the 2-sulfophenyl alkane isomers. Regression of all log BCF-data vs log 1/CMC yielded a good description of the data. However, when regressing the data for both homologous series separately again very different slopes are obtained. The results therefore indicate that hydrophobicity-bioconcentration relationships may be different for different homologous groups of sulfophenyl alkanes.

  3. Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging

    PubMed Central

    Ablikim, Utuq; Bomme, Cédric; Xiong, Hui; Savelyev, Evgeny; Obaid, Razib; Kaderiya, Balram; Augustin, Sven; Schnorr, Kirsten; Dumitriu, Ileana; Osipov, Timur; Bilodeau, René; Kilcoyne, David; Kumarappan, Vinod; Rudenko, Artem; Berrah, Nora; Rolles, Daniel

    2016-01-01

    An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C2H2Br2). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model. PMID:27910943

  4. Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging

    NASA Astrophysics Data System (ADS)

    Ablikim, Utuq; Bomme, Cédric; Xiong, Hui; Savelyev, Evgeny; Obaid, Razib; Kaderiya, Balram; Augustin, Sven; Schnorr, Kirsten; Dumitriu, Ileana; Osipov, Timur; Bilodeau, René; Kilcoyne, David; Kumarappan, Vinod; Rudenko, Artem; Berrah, Nora; Rolles, Daniel

    2016-12-01

    An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C2H2Br2). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model.

  5. Preferential hydrophobic interactions are responsible for a preference of D-amino acids in the aminoacylation of 5'-AMP with hydrophobic amino acids

    NASA Technical Reports Server (NTRS)

    Lacey, J. C. Jr; Wickramasinghe, N. S.; Sabatini, R. S.

    1992-01-01

    We have studied the chemistry of aminoacyl AMP to model reactions at the 3' terminus of aminoacyl tRNA for the purpose of understanding the origin of protein synthesis. The present studies relate to the D, L preference in the esterification of 5'-AMP. All N-acetyl amino acids we studied showed faster reaction of the D-isomer, with a generally decreasing preference for D-isomer as the hydrophobicity of the amino acid decreased. The beta-branched amino acids, Ile and Val, showed an extreme preference for D-isomer. Ac-Leu, the gamma-branched amino acid, showed a slightly low D/L ratio relative to its hydrophobicity. The molecular basis for these preferences for D-isomer is understandable in the light of our previous studies and seems to be due to preferential hydrophobic interaction of the D-isomer with adenine. The preference for hydrophobic D-amino acids can be decreased by addition of an organic solvent to the reaction medium. Conversely, peptidylation with Ac-PhePhe shows a preference for the LL isomer over the DD isomer.

  6. Metastable isomers - A new class of interstellar molecules

    NASA Technical Reports Server (NTRS)

    Green, S.; Herbst, E.

    1979-01-01

    The abundances of a variety of metastable isomers of small organic molecules, analogous to HNC/HCN, in dense interstellar clouds are considered. These metastable species, some of which are thought to exist as intermediates in laboratory organic chemical reactions, are of considerable interest to chemists. Current ideas of gas-phase, ion-molecule chemistry are utilized to demonstrate that such metastable species should often be present in dense clouds in sufficient abundance to be observed. Unfortunately, the spectral constants of metastable isomers have rarely been determined in the laboratory, and quantum chemical calculations of a varying degree of accuracy must be utilized; results are included of some new quantum chemical calculations. The interstellar chemistry and expected microwave spectra of a representative sample of possibly important interstellar metastable isomers are discussed.

  7. Interconversion of diborane(4) isomers

    NASA Technical Reports Server (NTRS)

    Stanton, John F.; Gauss, Juergen; Bartlett, Rodney J.; Helgaker, Trygve; Jorgensen, Poul; Jensen, Hans J. A.; Taylor, Peter R.

    1992-01-01

    Highly correlated electronic structure computations using many-body perturbation theory and coupled-cluster gradient techniques are used to study the reaction pathway that links the two forms (C2u and D2d) of diborane(4). The results obtained indicate that a low-energy pathway exists for interconversion of the two low-lying isomers of diborane(4). The proposed mechanism consists of a single concerted but nonsynchronous rotation of the BH2 groups. The pathway first follows an idealized reaction coordinate which preserves C2 symmetry, but then bifurcates at a branch point, leading to two equivalent transition states which lack nontrivial elements of symmetry.

  8. Isomer-Specific Distribution of Perfluoroalkyl Substances in Blood.

    PubMed

    Jin, Hangbiao; Zhang, Yifeng; Jiang, Weiwei; Zhu, Lingyan; Martin, Jonathan W

    2016-07-19

    Perfluoroalkyl substances (PFASs) such as perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS) and PFOS-precursors are routinely measured in human plasma and serum, but their relative abundance in the blood cell fraction has not been carefully examined, particularly at the isomer-specific level. Human plasma and whole blood were collected and partitioning behaviors of PFASs and their isomers between plasma and blood cells were investigated. In human samples, mass fraction in plasma (Fp) for PFASs increased among perfluoroalkyl carboxylates as the carbon chain length increased from C6 (mean 0.24) to C11 (0.87), indicating preference for the plasma fraction with increasing chain length. However, among perfluoroalkyl sulfonates, PFHxS (mean 0.87) had a slightly higher Fp than PFOS (0.85). In vitro assays with spiked Sprague-Dawley rat blood were also conducted, and the results showed that PFOS-precursors had lower Fp values than perfluoroalkyl acids, with perfluoroctanesulfonamide having the lowest Fp (mean 0.24). Consistently, linear isomers of PFOS and PFOS-precursors had lower mean Fp than their corresponding total branched isomers. Multiplying by a factor of 2 is not a reasonable method to convert from whole blood to plasma PFAS concentrations, and current ratios could be used as more accurate conversion factors.

  9. Spectroscopic and computational study of a new isomer of salinomycin

    NASA Astrophysics Data System (ADS)

    Pankiewicz, Radosław

    2013-09-01

    A new derivative of polyether ionophore salinomycin was obtained as a result of a rearrangement catalysed by sulphuric acid in two-phase medium of water/methylene chloride solution. The new isomer was fully characterized by multinuclear 2D NMR, NOESY and MALDI-TOF. The properties of the new compound were additionally study by semiempirical (PM5) and DFT (B3LYP) methods. A potential mechanism of the rearrangement was also proposed.

  10. Ozonation kinetics of phenolic acids present in wastewaters from olive oil mills

    SciTech Connect

    Benitez, F.J.; Beltran-Heredia, J.; Acero, J.L.; Pinilla, M.L.

    1997-03-01

    A kinetic study of the degradation by ozone of eight phenolic acids present in wastewaters from olive oil mills has been performed by using a competition kinetic method. The selected phenolic acids are: caffeic, p-coumaric, syringic, vanillic, 3,4,5-trimethoxybenzoic, veratric, p-hydroxy-benzoic, and protocatechuic. The influence of the operating variables (temperature, pH, and ozone partial pressure in the gas stream) is established, and the stoichiometric ratios for the individual direct reactions between ozone and each acid are determined. Once the reaction rate constants are evaluated, they are correlated as a function of temperature and pH into kinetic expressions which are provided for every phenolic acid. The global process occurs in the fast and pseudo-first-order kinetic regime of absorption, a condition required by the competition model to be used.

  11. The molecular properties of nitrobenzanthrone isomers and their mutagenic activities.

    PubMed

    Ostojić, Bojana D; Stanković, Branislav; Ðorđević, Dragana S

    2014-06-01

    The mutagenic activity of five mono-substituted nitrobenzanthrones (NBA) has been determined in the Ames assay (Takamura-Enya et al., 2006). In the present study, a theoretical investigation of the electronic properties of all mono-substituted NBA isomers and their relation to mutagenic activity are presented. Equilibrium geometries, vertical ionization potentials (VIP), vertical electron affinities (VEA), relative energies, dipole moments and electronic dipole polarizabilities, and the IR and Raman spectra of NBA isomers calculated by Density Functional Theory (DFT) methods are presented. The position of the nitro group affects the spectral features of the IR and Raman spectra of the NBA isomers. The results show that a good linear relationship exists between the summation of Raman activities (∑ARaman) over all the 3N-6 vibrational modes and the mutagenic activity of the NBA isomers in Salmonella typhimurium strains. The spectroscopic results suggest that the unknown mutagenic activities of 4-NBA, 5-NBA, 6-NBA, 8-NBA and 10-NBA are predicted to follow the order 4-NBA>10-NBA>5-NBA>8-NBA>6-NBA.

  12. Presentation of opsoclonus myoclonus ataxia syndrome with glutamic acid decarboxylase antibodies.

    PubMed

    Bhandari, Hanul Srinivas

    2012-08-08

    In this rare case, the patient presented with opsoclonus, myoclonus and ataxia. Serological and imaging studies revealed high glutamic acid decarboxylase antibody (GAD-Ab) levels. High-dose corticosteroids were of no benefit and subsequent intravenous immunoglobulin (IVIg) administration proved resolution of the condition. Levetiracetam proved useful in symptomatically controlling the myoclonus. Follow-up GAD-Ab levels were within normal limits.

  13. Effectiveness of Iron Ethylenediamine-N,N'-bis(hydroxyphenylacetic) Acid (o,o-EDDHA/Fe(3+)) Formulations with Different Ratios of Meso and d,l-Racemic Isomers as Iron Fertilizers.

    PubMed

    Alcañiz, Sara; Jordá, Juana D; Cerdán, Mar

    2017-01-18

    Two o,o-EDDHA/Fe(3+) formulations (meso, 93.5% w/w of meso isomer; and d,l-racemic, 91.3% w/w of d,l-racemic mixture) were prepared, and their efficacy to avoid or to relieve iron deficiency in Fe-sufficient and Fe-deficient tomato plants grown on hydroponic solution was compared with that of the current o,o-EDDHA/Fe(3+) formulations (50% of meso and d,l-racemic isomers). The effectiveness of the three o,o-EDDHA/Fe(3+) formulations was different depending on the iron nutritional status of plants. The three o,o-EDDHA/Fe(3+) formulations tested were effective in preventing iron chlorosis in healthy plants. However, the higher the meso concentration in the formulations, the higher the effectiveness in the recovery of iron chlorotic plants from iron deficiency. Accordingly, o,o-EDDHA/Fe(3+) formulations rich in meso isomer are recommended in hydroponic systems.

  14. Complete Hexose Isomer Identification with Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Nagy, Gabe; Pohl, Nicola L. B.

    2015-04-01

    The first analytical method is presented for the identification and absolute configuration determination of all 24 aldohexose and 2-ketohexose isomers, including the D and L enantiomers for allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, and tagatose. Two unique fixed ligand kinetic method combinations were discovered to create significant enough energetic differences to achieve chiral discrimination among all 24 hexoses. Each of these 24 hexoses yields unique ratios of a specific pair of fragment ions that allows for simultaneous determination of identification and absolute configuration. This mass spectrometric-based methodology can be readily employed for accurate identification of any isolated monosaccharide from an unknown biological source. This work provides a key step towards the goal of complete de novo carbohydrate analysis.

  15. Static and Dynamic Nanosheets from Selective Assembly of Geometric Macrocycle Isomers.

    PubMed

    Wang, Yanqiu; Kim, Yongju; Lee, Myongsoo

    2016-10-10

    In contrast to the significant advances that have been made in the construction of two-dimensional (2D) nanostructures, the rational modification from static to dynamic 2D sheets remains a great challenge. Static and dynamic sheets formed from selective self-assembly of geometric macrocycle isomers based on anthracene units are presented. The self-assembly of the cis isomer generates static planar sheets, whereas the trans isomer forms dynamic rolled sheets which are reversibly unrolled upon stimulation by a thermal signal. Furthermore, the mixed solution of the two isomers exhibits self-sorting behavior, generating the coexistence of the two independent self-assembled structures, the planar sheets and the folded scrolls. The self-sorted supramolecular objects with considerable shape and size differences are able to be readily separated, one isomer from the other.

  16. Anomalously large difference in dipole moment of isomers with nearly identical thermodynamic stability.

    PubMed

    Nadykto, Alexey B; Yu, Fangqun

    2008-08-07

    Sulfuric acid is a primary atmospheric nucleation precursor, with the ability to form stable aqueous hydrogen-bonded clusters/complexes. The electrical dipole moment of such clusters/complexes is important for ion-induced nucleation, largely controlled by dipole-charge interaction of airborne ions with vapor monomers and pre-existing clusters. Although experiments typically trace a single lowest energy conformer at low temperatures, the present study shows that the immediate vicinity (<1 kcal mol (-1)) of the global minima may be populated with a number of isomers of nearly identical spectral characteristics and drastically different dipole moments. The difference in the dipole moment of mono-, di-, and trihydrates of the sulfuric acid exceeds 1.3-1.5 Debyes ( approximately 50-60%), 1.4-2.6 Debyes ( approximately 50-90%), and 3.8-4.2 Debyes ( approximately 370-550%), respectively. Being driven by the temperature dependence of the Boltzmann distribution, the difference between the Boltzmann-Gibbs average dipole moment and the dipole moment of the most stable isomer increases with the ambient temperature, leading to large variations in the dipole-ion interaction strength, which may have important implications for the ion-mediated production of ultrafine aerosol particles associated with various climatic and health impacts.

  17. Fermentation of five sucrose isomers by human dental plaque bacteria.

    PubMed

    Matsuyama, J; Sato, T; Hoshino, E; Noda, T; Takahashi, N

    2003-01-01

    Sucrose has five structural isomers: palatinose, trehalulose, turanose, maltulose and leucrose. Although these isomers have been reported to be noncariogenic disaccharides, which cannot be utilized by mutans streptococci, there is no information about their fermentability by other bacteria in dental plaque. The purpose of the present study was to examine whether these isomers were fermented by predominant bacteria in human dental plaque. Clinical bacterial isolates obtained from dental plaque from 3 children aged 22 months to 50 months (146 strains) were inoculated into 3 ml of peptone-yeast extract (PY medium) containing glucose for 1 day, then an aliquot of 20 microl of culture medium was inoculated into 1 ml of PY medium containing 1% (w/v) of the respective test carbohydrates. After incubation for 1 day, the pH values and the optical density at 660 nm of the cultures were measured. Fermentation ability was measured by pH or=0.5. Of the clinical isolates, 33% fermented palatinose, and 69% of these were Actinomyces species. All of the palatinose-fermenting bacterial strains fermented trehalulose, 25% fermented turanose, 70% fermented maltulose and 23% fermented leucrose. We therefore conclude that, in human dental plaque, there are significant numbers of bacteria that are able to ferment sucrose isomers.

  18. How are the Concepts and Theories of Acid-Base Reactions Presented? Chemistry in Textbooks and as Presented by Teachers

    ERIC Educational Resources Information Center

    Furio-Mas, Carlos; Calatayud, Maria Luisa; Guisasola, Jenaro; Furio-Gomez, Cristina

    2005-01-01

    This paper investigates the views of science and scientific activity that can be found in chemistry textbooks and heard from teachers when acid-base reactions are introduced to grade 12 and university chemistry students. First, the main macroscopic and microscopic conceptual models are developed. Second, we attempt to show how the existence of…

  19. Conjugated linoleic acid isomers and their precursor fatty acids regulate peroxisome proliferator-activated receptor subtypes and major peroxisome proliferator responsive element-bearing target genes in HepG2 cell model.

    PubMed

    Benjamin, Sailas; Flotho, Silke; Börchers, Torsten; Spener, Friedrich

    2013-02-01

    The purpose of this study was to examine the induction profiles (as judged by quantitative reverse transcription polymerase chain reaction (qRT-PCR)) of peroxisome proliferator-activated receptor (PPAR) α, β, γ subtypes and major PPAR-target genes bearing a functional peroxisome proliferator responsive element (PPRE) in HepG2 cell model upon feeding with cis-9,trans-11-octadecadienoic acid (9-CLA) or trans-10,cis-12-octadecadienoic acid (10-CLA) or their precursor fatty acids (FAs). HepG2 cells were treated with 100 μmol/L 9-CLA or 10-CLA or their precursor FAs, viz., oleic, linoleic, and trans-11-vaccenic acids against bezafibrate control to evaluate the induction/expression profiles of PPAR α, β, γ subtypes and major PPAR-target genes bearing a functional PPRE, i.e., fatty acid transporter (FAT), glucose transporter-2 (GLUT-2), liver-type FA binding protein (L-FABP), acyl CoA oxidase-1 (ACOX-1), and peroxisomal bifunctional enzyme (PBE) with reference to β-actin as house keeping gene. Of the three housekeeping genes (glyceraldehyde 3-phosphate dehydrogenase (GAPDH), β-actin, and ubiquitin), β-actin was found to be stable. Dimethyl sulfoxide (DMSO), the common solubilizer of agonists, showed a significantly higher induction of genes analyzed. qRT-PCR profiles of CLAs and their precursor FAs clearly showed upregulation of FAT, GLUT-2, and L-FABP (~0.5-2.0-fold). Compared to 10-CLA, 9-CLA decreased the induction of the FA metabolizing gene ACOX-1 less than did PBE, while 10-CLA decreased the induction of PBE less than did ACOX-1. Both CLAs and precursor FAs upregulated PPRE-bearing genes, but with comparatively less or marginal activation of PPAR subtypes. This indicates that the binding of CLAs and their precursor FAs to PPAR subtypes results in PPAR activation, thereby induction of the target transporter genes coupled with downstream lipid metabolising genes such as ACOX-1 and PBE. To sum up, the expression profiles of these candidate genes showed that

  20. Reversed Phase High-Performance Liquid Chromatographic Ultra-violet (Photo Diode Array) Quantification of Oleanolic Acid and its Isomer Ursolic Acid for Phytochemical Comparison and Pharmacological Evaluation of Four Leucas Species Used in Ayurveda

    PubMed Central

    Shukla, Pushpendra Kumar; Misra, Ankita; Srivastava, Sharad; Rawat, Ajay K. S.

    2016-01-01

    Content: Different Leucas species are well known as “Dronpushpi,” a well-known herb of Ayurveda, used in the treatment of various ailments. Objective: Evaluation of four industrially important Leucas species for their in vitro antidiabetic potential and radical scavenging effect along with high-performance liquid chromatographic quantification of the bioactive triterpenes. Materials and Methods: The quantification of triterpenes was carried out on C-18 column with acetonitrile and water (90:10) as the solvent system at a detection wavelength of 210 nm. In vitro antidiabetic activity was evaluated by α-amylase inhibition assay based on starch–iodine and 3,5 dinitrosalicylic acid (DNS) method. Antioxidant activity was calculated by five different models, namely total phenolic and total flavonoid content, free radical scavenging activity by 1-1-diphenyl-2-pic-rylhydrazyl (DPPH), ferric-reducing power assay, and the total antioxidant capacity. Results: Maximum concentration of oleanolic acid was found in Leucas cristata, followed by Leucas mollissima, Leucas Aspera, and Leucas biflora. Ursolic acid was highest in L. mollissima and then in L. biflora, L. cristata, and L. aspera, respectively. In in vitro antidiabetic activity, IC50 of L. aspera (1.56 ± 0.01 mg/ml) and L. mollissima (0.75 ± 0.005 mg/ml) were found to be highest in DNS and iodine starch assay. IC50 in DPPH assay ranges from 0.6 ± 0.011 to 1.68 ± 0.011 mg/ml. Antioxidant capacity follows the order; L. aspera > L. mollissima > L. biflora > L. cristata. Conclusion: Promising activities were observed in targeted species, thus L. mollissima, L. biflora, and L. cristata can be used alternatively as a substitute to L. aspera. SUMMARY Physicochemical parameters are within the limit as per the Ayurvedic Pharmacopoeia of IndiaMaximum concentration of oleanolic acid was found in Leucas cristata; however, ursolic acid was highest in Leucas mollissimaIn vitro antidiabetic activity of Leucas aspera and L

  1. Studies of multi-quasiparticle k-isomers in rare-earth and trans-fermium nuclei.

    SciTech Connect

    Kondev, F. G.; Dracoulis, G. D.; Khoo, T. L.; Lane, G. J.; Byrne, A. P.; Kibedi, T.; Ahmad, I.; Carpenter, M. P.; Janssens, R. V. F.; Lauritzen, T.; Lister, C. J.; Seweryniak, D.; Zhu, S.; Chowdhury, P.; Tandel, S. K.; Australian National Univ.; Univ. of Massachusetts Lowell

    2007-01-01

    Nuclear K-isomers play an important role in understanding the structure of deformed axially symmetric nuclei. Examples are presented of recent studies in the rare-earth region (A {approx} 180) using deep-inelastic and multi-nucleon transfer reactions, and in the trans-fermium region (A {approx} 250) using fusion-evaporation reactions. A specific two-level mixing scenario is invoked to explain the unusual decay of the K{sup {pi}} = 13{sup +} isomer in {sup 174}Lu. The identification of 2- and 4-quasiparticle isomers in {sup 254}No is discussed and predictions of similar isomers in neighboring No and Rf nuclei are presented.

  2. Utilization of Lactate Isomers by Propionibacterium freudenreichii subsp. shermanii: Regulatory Role for Intracellular Pyruvate

    PubMed Central

    Crow, Vaughan L.

    1986-01-01

    Five strains of Propionibacterium freudenreichii subsp. shermanii utilized the l-(+) isomer of lactate at a faster rate than they did the d-(−) isomer when grown with a mixture of lactate isomers under a variety of conditions. ATCC 9614, grown anaerobically in defined medium containing 160 mM dl-lactate, utilized only 4 and 15% of the d-(−)-lactate by the time 50 and 90%, respectively, of the l-(+)-lactate was used. The intracellular pyruvate concentration was high (>100 mM) in the initial stages of lactate utilization, when either dl-lactate or the l-(+) isomer was the starting substrate. The concentration of this intermediate dropped during dl-lactate fermentation such that when only d-(−)-lactate remained, the concentration was <20 mM. When only the d-(−) isomer was initially present, a similar relatively low concentration of intracellular pyruvate was present, even at the start of lactate utilization. The NAD+-independent lactate dehydrogenase activities in extracts showed different kinetic properties with regard to pyruvate inhibition, depending upon the lactate isomer present. Pyruvate gave a competitive inhibitor pattern with l-(+)-lactate and a mixed-type inhibitor pattern with d-(−)-lactate. It is suggested that these properties of the lactate dehydrogenases and the intracellular pyruvate concentrations explain the preferential use of the l-(+) isomer. PMID:16347134

  3. Roles of the tyrosine isomers meta-tyrosine and ortho-tyrosine in oxidative stress.

    PubMed

    Ipson, Brett R; Fisher, Alfred L

    2016-05-01

    The damage to cellular components by reactive oxygen species, termed oxidative stress, both increases with age and likely contributes to age-related diseases including Alzheimer's disease, atherosclerosis, diabetes, and cataract formation. In the setting of oxidative stress, hydroxyl radicals can oxidize the benzyl ring of the amino acid phenylalanine, which then produces the abnormal tyrosine isomers meta-tyrosine or ortho-tyrosine. While elevations in m-tyrosine and o-tyrosine concentrations have been used as a biological marker of oxidative stress, there is emerging evidence from bacterial, plant, and mammalian studies demonstrating that these isomers, particularly m-tyrosine, directly produce adverse effects to cells and tissues. These new findings suggest that the abnormal tyrosine isomers could in fact represent mediators of the effects of oxidative stress. Consequently the accumulation of m- and o-tyrosine may disrupt cellular homeostasis and contribute to disease pathogenesis, and as result, effective defenses against oxidative stress can encompass not only the elimination of reactive oxygen species but also the metabolism and ultimately the removal of the abnormal tyrosine isomers from the cellular amino acid pool. Future research in this area is needed to clarify the biologic mechanisms by which the tyrosine isomers damage cells and disrupt the function of tissues and organs and to identify the metabolic pathways involved in removing the accumulated isomers after exposure to oxidative stress.

  4. Kinetics of Non-Catalytic Esterification of Free Fatty Acids Present in Jatropha Oil.

    PubMed

    Prasanna Rani, Karna Narayana; Ramana Neeharika, Tulasi Sri Venkata; Kumar, Thella Prathap; Satyavathi, Bankupalli; Sailu, Chintha

    2016-05-01

    Non-catalytic esterfication of free fatty acids (FFA) present in vegetable oils is an alternative pretreatment process for the biodiesel production. Biodiesel, consists of long-chain fatty acid methyl esters (FAME) and is obtained from renewable sources such as vegetable oils or animal fat. This study presents kinetics of thermal esterification of free fatty acids present in jatropha oil with methanol. The effect of process parameters like reaction time (1-5 h), temperature (170-190°C) and oil to methanol ratio (1:3-1:5) at constant pressure was investigated. The optimal conditions were found to be oil to methanol ratio of 1:4, 190°C, at 27.1 bar and 5 h which gave a maximum conversion of 95.1%. A second order kinetic model for both forward and backward reactions was proposed to study the reaction system. A good agreement was observed between the experimental data and the model values. The activation energy for forward reaction and the heat of reaction were found to be 36.364 Kcal/mol and 1.74 Kcal/mol respectively.

  5. The optical nature of methylsuccinic acid in human urine

    NASA Technical Reports Server (NTRS)

    Zeitman, B.; Lawless, J. G.

    1975-01-01

    Methylsuccinic acid was isolated from human urine, derivatized as the di-S-(+)-2-butyl ester, and analyzed using a gas chromatographic system capable of separating the enantiomers of the derivative. The R-(+)-isomer was found to be present. Methylsuccinic acid is potentially important as a criterion for abiogenicity, having been obtained as a racemic mixture from sources known to be abiotic.

  6. Isomer-specific combustion chemistry in allene and propyne flames

    SciTech Connect

    Hansen, Nils; Miller, James A.; Westmoreland, Phillip R.; Kasper, Tina; Kohse-Hoeinghaus, Katharina; Wang, Juan; Cool, Terrill A.

    2009-11-15

    A combined experimental and modeling study is performed to clarify the isomer-specific combustion chemistry in flames fueled by the C{sub 3}H{sub 4} isomers allene and propyne. To this end, mole fraction profiles of several flame species in stoichiometric allene (propyne)/O{sub 2}/Ar flames are analyzed by means of a chemical kinetic model. The premixed flames are stabilized on a flat-flame burner under a reduced pressure of 25 Torr (=33.3 mbar). Quantitative species profiles are determined by flame-sampling molecular-beam mass spectrometry, and the isomer-specific flame compositions are unraveled by employing photoionization with tunable vacuum-ultraviolet synchrotron radiation. The temperature profiles are measured by OH laser-induced fluorescence. Experimental and modeled mole fraction profiles of selected flame species are discussed with respect to the isomer-specific combustion chemistry in both flames. The emphasis is put on main reaction pathways of fuel consumption, of allene and propyne isomerization, and of isomer-specific formation of C{sub 6} aromatic species. The present model includes the latest theoretical rate coefficients for reactions on a C{sub 3}H{sub 5} potential [J.A. Miller, J.P. Senosiain, S.J. Klippenstein, Y. Georgievskii, J. Phys. Chem. A 112 (2008) 9429-9438] and for the propargyl recombination reactions [Y. Georgievskii, S.J. Klippenstein, J.A. Miller, Phys. Chem. Chem. Phys. 9 (2007) 4259-4268]. Larger peak mole fractions of propargyl, allyl, and benzene are observed in the allene flame than in the propyne flame. In these flames virtually all of the benzene is formed by the propargyl recombination reaction. (author)

  7. The sealed lead-acid battery: performance and present aircraft applications

    NASA Astrophysics Data System (ADS)

    Timmons, John; Kurian, Raju; Goodman, Alan; Johnson, William R.

    The United States Navy has flown valve-regulated lead-acid batteries (VRLA) for approximately 22 years. The first VRLA aircraft batteries were of a cylindrical cell design and these evolved to a prismatic design to save weight, volume, and to increase rate capability. This paper discusses the evolution of the VRLA aircraft battery designs, present VRLA battery performance, and battery size availability along with their aircraft applications (both military and commercial). The paper provides some of the reliability data from present applications. Finally, the paper discusses what future evolution of the VRLA technology is required to improve performance and to remain the technology of choice over other sealed aircraft battery designs.

  8. Determination by GC×GC of fatty acid and conjugated linoleic acid (CLA) isomer profiles in six selected tissues of lambs fed on pasture or on indoor diets with and without rumen-protected CLA.

    PubMed

    Pellattiero, Erika; Cecchinato, Alessio; Tagliapietra, Franco; Schiavon, Stefano; Bittante, Giovanni

    2015-01-28

    In this study GC×GC was used to study the effects of pasture, hay, concentrate (indoor), and indoor plus 8 g/day of a rumen-protected conjugated linoleic acid (indoor-CLA) diets on the detailed fatty acid (FA) profiles of six tissues (muscles, fatty tissues, and liver) collected from 36 lambs. This powerful technique allowed the quantification of 128 FAs, of which 21 SFAs, 16 MUFAs, 19 PUFAs were identified by reference standards. The diets had similar, but not identical, effects on FA profiles (g/100 g FA) in the various tissues, as both indoor diets reduced total PUFAs (from 8.91 ± 6.27 to 8.06 ± 5.97; p < 0.05) and n-3 PUFAs (from 2.70 ± 2.37 to 1.50 ± 1.69; p < 0.01) and increased n-6 PUFA (from 3.76 ± 2.46 to 4.58 ± 3.42; p < 0.01), branched (from 2.37 ± 2.05 to 3.23 ± 0.54; p < 0.01), odd-chain FAs (from 5.88 ± 5.33 to 7.07 ± 1.51; p < 0.01) compared to pasture. Indoor-CLA increased CLAc9,t11 (from 0.42 ± 0.13 to 0.53 ± 0.19; p < 0.01), CLAt10,c12 (from 0.07 ± 0.06 to 0.12 ± 0.22; p < 0.05), and CLAc11,t13 (from 0.02 ± 0.04 to 0.05 ± 0.04; p < 0.05) compared to indoor.

  9. Differential adsorption of CHON isomers at interstellar grain surfaces

    NASA Astrophysics Data System (ADS)

    Lattelais, M.; Pauzat, F.; Ellinger, Y.; Ceccarelli, C.

    2015-06-01

    Context. The CHON generic chemical formula covers different isomers such as isocyanic acid (HNCO), cyanic acid (HOCN), fulminic acid (HCNO), and isofulminic acid (HONC); the first three have been identified in a large variety of environments in the interstellar medium (ISM). Several phenomena could be at the origin of the observed abundances, such as different pathways of formation and destruction involving gas phase reactions with different possible activation barriers and/or surface processes depending on the local temperature and the nature of the support. Aims: The scope of this article is to shed some light on the interaction of the CHON isomers with interstellar grains as a function of the nature of the surface and to determine the corresponding adsorption energies in order to find whether this phenomenon could play a role in the abundances observed in the ISM. Methods: The question was addressed by means of numerical simulations using first principle periodic density functional theory (DFT) to represent the grain support as a solid of infinite dimension. Results: Regardless of the nature of the model surface (water ice, graphene, silica), two different classes of isomers were identified: weakly bound (HNCO and HCNO) and strongly bound (HOCN and HONC), with the adsorption energies of the latter group being about twice those of the former. The range of the adsorption energies is (from highest to lowest) HOCN > HONC > HNCO > HCNO. They are totally disconnected from the relative stabilities, which range from HNCO > HOCN > HCNO > HONC. Conclusions: The possibility of hydrogen bonding is the discriminating factor in the trapping of CHON species on grain surfaces. Whatever the environment, differential adsorption is effective and its contribution to the molecular abundances should not be ignored. The theoretical adsorption energies provided here could be profitably used for a more realistic modeling of molecule-surfaces interactions.

  10. Spectral identification of fullerene C82 isomers

    NASA Astrophysics Data System (ADS)

    Gao, Bin; Liu, Lei; Wang, ChunRu; Wu, ZiYu; Luo, Yi

    2007-10-01

    Ultraviolet photoelectron spectra (UPS) of C82 isomers have been calculated using hybrid density functional theory in combination with the Gelius model [Proceedings of the International Conference on Electron spectroscopy, edited by D. A. Shirley (North-Holland, Amsterdam, 1972), p. 311; J. Electron Spectrosc. Relat. Phenom. 5, 985 (1974)]. The calculated UPS spectra are found to be isomer dependent and in good agreement with the experimental counterparts. Near-edge x-ray absorption fine structure (NEXAFS), x-ray photoelectron spectroscopy (XPS), x-ray emission spectroscopy, and the resonant inelastic x-ray scattering (RIXS) spectra of three important isomers [3(C2), 6(Cs), and 9(C2v)] have also been simulated. Strong isomer dependence has also been found for NEXAFS, XPS, and RIXS spectra.

  11. Highly Stable trans-Cyclooctene Amino Acids for Live-Cell Labeling.

    PubMed

    Hoffmann, Jan-Erik; Plass, Tilman; Nikić, Ivana; Aramburu, Iker Valle; Koehler, Christine; Gillandt, Hartmut; Lemke, Edward A; Schultz, Carsten

    2015-08-24

    trans-Cyclooctene groups incorporated into proteins via non-canonical amino acids (ncAAs) are emerging as specific handles for bioorthogonal chemistry. Here, we present a highly improved synthetic access to the axially and the equatorially linked trans-cyclooct-2-ene isomers (1 a,b). We further show that the axially connected isomer has a half-life about 10 times higher than the equatorial isomer and reacts with tetrazines much faster, as determined by stopped-flow experiments. The improved properties resulted in different labeling performance of the insulin receptor on the surface of intact cells.

  12. Periodicity of monoisotopic mass isomers and isobars in proteomics.

    PubMed

    Yu, Long; Xiong, Yan-Mei; Polfer, Nick C

    2011-10-15

    We report trends in the theoretically derived number of compositionally distinct peptides (i.e., peptides made up of different amino acid residues) up to a nominal mass of 1000. A total of 21 amino acid residues commonly found in proteomics studies are included in this study, 19 natural, nonisomeric amino acid residues as well as oxidated methione and acetamidated cysteine. The number of possibilities is found to increase in an exponential fashion with increasing nominal mass, and the data show a periodic oscillation that starts at mass ~200 and continues throughout to 1000. Note that similar effects are reported in the companion article on fragment ions from electron capture/transfer dissociation (ECD/ETD) (Mao et al. Anal. Chem.2011, DOI: 10.1021/ac201619t). The spacing of this oscillation is ~15 mass units at lower masses and ~14 mass units at higher nominal masses. This correlates with the most common mass differences between the amino acid building blocks. In other words, some mass differences are more common than others, thus determining the periodicity in this data. From an analytical point of view, nominal masses with a larger number of compositionally distinct peptides include a substantial number of isomers, which cannot be separated based on mass. Consequently, even ultrahigh mass accuracy (i.e., 0.5 ppm) does not lead to a substantially enhanced rate of identification. Conversely, for adjacent nominal masses with a lower number of isomers, moderately accurate mass (i.e., 10 ppm) gives a higher degree of certainty in identification. These effects are limited to the mass range between 200 and 500 Da. At higher masses, the percentage of uniquely identified peptides drops off to close to zero, independent of nominal mass, due the inherently high number of isomers. While the exact number of isobars/isomers at each nominal mass depends on the amino acid building blocks that are considered, the periodicity in the data is found to be remarkably robust; for

  13. Isomer effects on polyimide properties

    NASA Technical Reports Server (NTRS)

    Stump, B. L.

    1974-01-01

    The polymerization of 2,4'-methylene-dianiline with benzophenone tetracarboxylic acid dianhydride yields high molecular weight polyamic acid. Polyimide is formed when films of the polyamic acid are cured between 200 - 300 C. A lower molecular weight polyamic acid is obtained from 2,2'-MDA with BTDA, but it appears that a lowering of the reaction temperature will yield high molecular weight polymer. Evaluation of these polymers is underway. Continued efforts to synthesize 2,3'- MDA and 2,3'-diaminobenzophenone have met with little success.

  14. Identification of RNA sequence isomer by isotope labeling and LC-MS/MS.

    PubMed

    Li, Siwei; Limbach, Patrick A

    2014-11-01

    Recently, we developed a method for modified ribonucleic acid (RNA) analysis based on the comparative analysis of RNA digests (CARD). Within this CARD approach, sequence or modification differences between two samples are identified through differential isotopic labeling of two samples. Components present in both samples will each be labeled, yielding doublets in the CARD mass spectrum. Components unique to only one sample should be detected as singlets. A limitation of the prior singlet identification strategy occurs when the two samples contain components of unique sequence but identical base composition. At the first stage of mass spectrometry, these sequence isomers cannot be differentiated and would appear as doublets rather than singlets. However, underlying sequence differences should be detectable by collision-induced dissociation tandem mass spectrometry (CID MS/MS), as y-type product ions will retain the original enzymatically incorporated isotope label. Here, we determine appropriate instrumental conditions that enable CID MS/MS of isotopically labeled ribonuclease T1 (RNase T1) digestion products such that the original isotope label is maintained in the product ion mass spectrum. Next, we demonstrate how y-type product ions can be used to differentiate singlets and doublets from isomer sequences. We were then able to extend the utility of this approach by using CID MS/MS for the confirmation of an expected RNase T1 digestion product within the CARD analysis of an Escherichia coli mutant strain even in the presence of interfering and overlapping digestion products from other transfer RNAs.

  15. Search for the isomers of C2H3NO and C2H3NS in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Etim, Emmanuel; Chakrabarti, Sandip Kumar; Das, Ankan; Gorai, Prasanta; Arunan, Elangannan

    2016-07-01

    With about 40% of all the known interstellar and circumstellar molecules having their isomeric analogues as known astromolecules, isomerism remains one of the leading themes in interstellar chemistry. In this regard, the recent detection of methyl isocyanate (with a number of isomeric analogues) in the Sgr B2(N) giant molecular cloud opens a new window for the possible astronomical detection of other C_2H_3NO isomers. The present work looks at the possibility of detecting other isomers of methyl isocyanate by considering different factors such as thermodynamic stability of the different isomers with respect to the Energy, Stability and Abundance (ESA) relationship, effect of interstellar hydrogen bonding with respect to the formation these isomers on the surface of the interstellar dust grains, possible formation routes for these isomers, spectroscopic parameters for potential astromolecules among these isomers, chemical modeling among other studies. The same studies are repeated for the C_2H_3NS isomers which are the isoelectroninc analogues of the C_2H_3NO isomers taking into account the unique chemistry of S and O-containing interstellar molecular species. Among the C_2H_3NS isomers, methyl isothiocyanate remains the most potential candidate for astronomical observation.

  16. Low-energy electron scattering from C{sub 4}H{sub 9}OH isomers

    SciTech Connect

    Bettega, M. H. F.; Winstead, C.; McKoy, V.

    2010-12-15

    We present differential, integral, and momentum-transfer cross sections for elastic scattering of low-energy electrons by three butanol isomers, isobutanol, t-butanol, and 2-butanol. Our results were calculated with the Schwinger multichannel method in the static-exchange plus polarization approximation for collision energies from 1 to 50 eV. The present results are compared with previous calculations and measurements for the remaining C{sub 4}H{sub 9}OH isomer, n-butanol [Khakoo et al., Phys. Rev. A 78, 062714 (2008)]. Distinctive behavior is observed in the differential cross sections at collision energies between 5 and 10 eV. In particular, whereas n-butanol exhibits an f-wave scattering pattern, the other isomers exhibit d-wave behavior. A similar pattern is found in the related alkanes when comparing straight-chain versus branched isomers. We discuss the possible connection of this behavior to shape resonances that influence the scattering.

  17. Structural isomers of C2N(+) - A selected-ion flow tube study

    NASA Technical Reports Server (NTRS)

    Knight, J. S.; Petrie, S. A. H.; Freeman, C. G.; Mcewan, M. J.; Mclean, A. D.

    1988-01-01

    Reactivities of the structural isomers CCN(+) and CNC(+) were examined in a selected-ion flow tube at 300 + or - 5 K. The less reactive CNC(+) isomer was identified as the product of the reactions of C(+) + HCN and C(+) + C2N2; in these reactions only CNC(+) can be produced because of energy constraints. Rate coefficients and branching ratios are reported for the reactions of each isomer with H2, CH4, NH3, H2O, C2H2, HCN, N2, O2, N2O, and CO2. Ab initio calculations are presented for CCN(+) and CNC(+); a saddle point for the reaction CCN(+) yielding CNC(+) is calculated to be 195 kJ/mol above CNC(+). The results provide evidence that the more reactive CCN(+) isomer is unlikely to be present in measurable densities in interstellar clouds.

  18. Allantoin, the oxidation product of uric acid is present in chicken and turkey plasma.

    PubMed

    Simoyi, Melvin F; Falkenstein, Elizabeth; Van Dyke, Knox; Blemings, Kenneth P; Klandorf, Hillar

    2003-06-01

    Urate oxidase is not present in birds yet allantoin, a product of this enzyme, has been measured in birds. Studies were designed to compare the concentrations of plasma purine derivatives in chickens and turkeys fed inosine-supplemented diets. The first study consisted of 12 male chicks that were fed diets supplemented with 0.6 mol inosine or hypoxanthine per kilogram diet from 3- to 6-week-old. Study 2 consisted of 12 turkey poults (toms) fed inosine-supplemented diets (0.7 mol/kg) from 6- to 8-week-old. Plasma allantoin and oxypurines concentrations were measured weekly using high performance liquid chromatography. Plasma uric acid (PUA) in chickens fed inosine-supplemented diets increased from 0.31 to 1.34 mM (P<0.05) at the end of week 2. In turkeys, those fed control diet had 0.17 mM PUA concentration compared to 0.3 mM in those fed the inosine diet at week 2 (P<0.05). Allantoin concentration increased in chickens from week 1 to 2 while a decrease was observed in turkeys (P<0.005) for both treatments. These data show that allantoin is present in turkey and chicken plasma. The presence of allantoin in avian plasma is consistent with uric acid acting as an antioxidant in these species.

  19. A Case of Mania Presenting with Hypersexual Behavior and Gender Dysphoria that Resolved with Valproic Acid

    PubMed Central

    Heare, Michelle R.; Barsky, Maria; Faziola, Lawrence R.

    2016-01-01

    Hypersexuality and gender dysphoria have both been described in the literature as symptoms of mania. Hypersexuality is listed in the Diagnostic and Statistical Manual of Mental Disorders 5 as part of the diagnostic criteria for bipolar disorder. Gender dysphoria is less often described and its relation to mania remains unclear. This case report describes a young homosexual man presenting in a manic episode with co-morbid amphetamine abuse whose mania was marked by hypersexuality and the new onset desire to be a woman. Both of these symptoms resolved with the addition of valproic acid to antipsychotics. This case report presents the existing literature on hypersexuality and gender dysphoria in mania and describes a treatment option that has not been previously reported. PMID:27994833

  20. Hyaluronic acid-coated chitosan nanoparticles: molecular weight-dependent effects on morphology and hyaluronic acid presentation.

    PubMed

    Almalik, Abdulaziz; Donno, Roberto; Cadman, Christopher J; Cellesi, Francesco; Day, Philip J; Tirelli, Nicola

    2013-12-28

    Chitosan nanoparticles are popular carriers for the delivery of macromolecular payloads, e.g. nucleic acids. In this study, nanoparticles were prepared via complexation with triphosphate (TPP) anions and were successively coated with hyaluronic acid (HA). Key variables of the preparative process (e.g. chitosan and HA molecular weight) were optimised in view of the maximisation of loading with DNA, of the Zeta potential and of the dimensional stability, and the resulting particles showed excellent storage stability. We have focused on the influence of chitosan molecular weight on nanoparticle properties. Larger molecular weight increased their porosity (=decreased cross-link density), and this caused also larger dimensional changes in response to variations in osmotic pressure or upon drying. The dependency of nanoparticle porosity on chitosan molecular weight had a profound effect on the adsorption of HA on the nanoparticles; HA was apparently able to penetrate deeply into the more porous high molecular weight (684 kDa) chitosan nanoparticles, while it formed a corona around those composed of more densely cross-linked low molecular weight (25 kDa) chitosan. Atomic Force Microscopy (AFM) allowed not only to highlight the presence of this corona, but also to estimate its apparent thickness to about 20-30 nm (in a dry state). The different morphology has a significant effect on the way HA is presented to biomolecules, and this has specific relevance in relation to interactions with HA receptors (e.g. CD44) that influence kinetics and mechanism of nanoparticle uptake. Finally, it is worth to mention that chitosan molecular weight did not appear to greatly affect the efficiency of nanoparticle loading with DNA, but significantly influenced its chitosanase-triggered release, with high molecular chitosan nanoparticles seemingly more prone to degradation by this enzyme.

  1. Isomer-specific accumulation of perfluorooctane sulfonate in the liver of chicken embryos exposed in ovo to a technical mixture.

    PubMed

    O'Brien, Jason M; Kennedy, Sean W; Chu, Shaogang; Letcher, Robert J

    2011-01-01

    Prior to its recent phaseout, perfluorooctane sulfonate (PFOS) was produced by electrochemical fluorination processes, which yielded technical mixtures composed of linear isomer (∼65-79%) and several branched isomers (∼21-35%). Because PFOS can biomagnify in wildlife, birds that occupy higher trophic levels are at increased risk of exposure. We hypothesized that the pharmacokinetic properties of PFOS are isomer-specific in developing chicken (Gallus gallus domesticus) embryos exposed to technical grade PFOS (T-PFOS). In the present study, T-PFOS was composed of 62.7% linear isomer (L-PFOS), and 37.3% branched isomer, including six mono(trifluoromethyl)-branched isomers and four bis(trifluoromethyl)-branched isomers. Concentrations of 0.1, 5, or 100 µg/g of T-PFOS were injected into the air cell of chicken eggs prior to incubation. After pipping, compared with T-PFOS, the PFOS isomer profile in embryonic liver tissue for the 0.1 µg/g dose group showed 21% enrichment in the proportion of L-PFOS with a corresponding decrease in the proportion of branched isomers. Not all branched isomers were discriminated against at equal rates. The proportion of two mono(trifluoromethyl)-branched isomers and three bis(trifluoromethyl)-branched isomers decreased to a greater degree than other branched isomers. In contrast, the mono-branched isomer, P6MHpS, was overrepresented in the low-dose group. In the higher dose groups, L-PFOS was still enriched but only by approximately 10%, which indicated a dose-dependent change in isomer composition relative to T-PFOS. These results show that accumulation of PFOS in chicken embryo livers is dependent on the presence and position of branches on the alkyl backbone. This supports the hypothesis that the pharmacokinetics of PFOS are isomer-specific in biota, and may help explain why wildlife PFOS burdens are dominated by L-PFOS relative to T-PFOS mixtures.

  2. High-harmonic spectroscopy of molecular isomers

    SciTech Connect

    Wong, M. C. H.; Brichta, J.-P.; Bhardwaj, V. R.; Spanner, M.; Patchkovskii, S.

    2011-11-15

    We demonstrate that high-order-harmonic generation (HHG) spectroscopy can be used to probe stereoisomers of randomly oriented 1,2-dichloroethylene (C{sub 2}H{sub 2}Cl{sub 2}) and 2-butene (C{sub 4}H{sub 8}). The high-harmonic spectra of these isomers are distinguishable over a range of laser intensities and wavelengths. Time-dependent numerical calculations of angle-dependent ionization yields for 1,2-dichloroethylene suggest that the harmonic spectra of molecular isomers reflect differences in their strong-field ionization. The subcycle ionization yields for the cis isomer are an order of magnitude higher than those for the trans isomer. The sensitivity in discrimination of the harmonic spectra of cis- and trans- isomers is greater than 8 and 5 for 1,2-dichloroethylene and 2-butene, respectively. We show that HHG spectroscopy cannot differentiate the harmonic spectra of the two enantiomers of the chiral molecule propylene oxide (C{sub 3}H{sub 6}O).

  3. Determination of ortho-cresyl phosphate isomers of tricresyl phosphate used in aircraft turbine engine oils by gas chromatography and mass spectrometry.

    PubMed

    De Nola, G; Kibby, J; Mazurek, W

    2008-07-25

    Tricresyl phosphate (TCP) is used as an anti-wear additive in aircraft turbine engine oil. Concerns about its toxicity are largely based on the tri-o-cresyl phosphate isomer content. However, the presence of other and more toxic isomers has been previously suggested. In this work, the structural isomers of TCP have been determined by two methods (experimental and semi-theoretical). First, the TCP isomers were separated by gas chromatography (GC) and identified by mass spectrometry (MS). Second, after base cleavage of TCP, GC was used to quantify the cresol precursors. These results were used to calculate the TCP isomer distribution based on the assumption of a statistical distribution of the TCP isomers. The results from the two determinations showed reasonable agreement for three of the four oils studied. The o-cresyl isomers were found to be present almost exclusively as the more toxic mono-o-cresyl isomers in the concentration range 13-150 mg/L. The ability to analyse for the mono-o-cresyl isomers allows the toxicity of TCP to be based on the latter isomers rather than on the less toxic tri-o-cresyl phosphate isomer.

  4. Actual ratio of triacylglycerol positional isomers in milk and cheese.

    PubMed

    Gotoh, Naohiro; Matsumoto, Yumiko; Nagai, Toshiharu; Mizobe, Hoyo; Yoshinaga, Kazuaki; Kojima, Koichi; Kuroda, Ikuma; Kitamura, Yohei; Shimizu, Takashi; Ishida, Hiroki; Wada, Shun

    2012-01-01

    Actual ratios of triacylglycerol (TAG) positional isomers in human, rat, and cow milk fat and cow, buffalo, goat, and sheep cheese fat were analyzed using HPLC-UV-atmospheric pressure chemical ionization-MS/MS system equipped with an octacosyl silylation column or polymeric ODS column. We substituted cheese fats for milk fats in parts of our study because milks from ruminants, with the exception of cows, are difficult to get in Japan. The actual ratio of β-PPC (the TAG consisting of two palmitic acids (P) and one capric acid (C), with the palmitic acid located at the β position) and β-PCP in human milk was different from those in ruminants, with more than half of the medium-chain fatty acids located at the β position even though other fats possessed it mainly at the α position. Palmitic acid was mainly located at the β position for human milk and rat milk; however, the location in ruminant cheese fat was mainly at the α position. The location of fatty acids is thought to be very important for infant nutrition. Particularly, the location of palmitic acid in case of human milk and of medium-chain fatty acids in case of ruminant milk was very characteristic and is considered to be very important to the fatty acids in milk fat.

  5. A Novel Method for Presenting the Amino Acids in an Introductory Biochemistry Course.

    ERIC Educational Resources Information Center

    Kuehl, LeRoy

    1978-01-01

    Introduces an approach to teaching amino acids that employs the use of a poem containing information on the structure and properties of amino acids, and of slides illustrating the poem. Student response to the method was positive. (MA)

  6. An isomer-specific high-energy collision-induced dissociation MS/MS database for forensic applications: a proof-of-concept on chemical warfare agent markers.

    PubMed

    Subramaniam, Raja; Östin, Anders; Nygren, Yvonne; Juhlin, Lars; Nilsson, Calle; Åstot, Crister

    2011-09-01

    Spectra database search has become the most popular technique for the identification of unknown chemicals, minimizing the need for authentic reference chemicals. In the present study, an isomer-specific high-energy collision-induced dissociation (CID) MS/MS spectra database of 12 isomeric O-hexyl methylphosphonic acids (degradation markers of nerve agents) was created. Phosphonate anions were produced by the electrospray ionization of phosphonic acids or negative-ion chemical ionization of their fluorinated derivatives and were analysed in a hybrid magnetic-sector-time-of-flight tandem mass spectrometer. A centre-of-mass energy (E(com)) of 65 eV led to an optimal sequential carbon-carbon bond breakage, which was interpreted in terms of charge remote fragmentation. The proposed mechanism is discussed in comparison with the routinely used low-energy CID MS/MS. Even-mass (odd-electron) charge remote fragmentation ion series were diagnostic of the O-alkyl chain structure and can be used to interpret unknown spectra. Together with the odd-mass ion series, they formed highly reproducible, isomer-specific spectra that gave significantly higher database matches and probability factors (by 1.5 times) than did the EI MS spectra of the trimethylsilyl derivatives of the same isomers. In addition, ionization by negative-ion chemical ionization and electrospray ionization resulted in similar spectra, which further highlights the general potential of the high-energy CID MS/MS technique.

  7. Cis and Trans Isomers of Cycloalkenes

    NASA Astrophysics Data System (ADS)

    Barrows, Susan E.; Eberlein, Thomas H.

    2005-09-01

    As a rule, a trans disubstituted alkene is more stable than the corresponding cis isomer. For cycloalkenes of fewer than eleven members, cis isomers are more stable than their trans counterparts. Although this exception to the normal rule is occasionally noted in beginning organic chemistry textbooks, it is often done without a careful analysis of the reasons behind it. The purpose of this article is to provide that analysis. In order for a cycloalkene to accommodate a trans double bond one or more of the following nonideal geometries must occur: a twisted π bond; pyramidal sp 2 -carbon atoms; nonideal sp 3 bond angles; or longer than normal C C single and double bonds. This article provides a list of experimentally determined relative energies of the cis and trans isomers within the series cycloheptene cycloundecene, along with computationally derived energies at several levels of theory. It also examines the geometric distortions through which cycloalkenes relieve the strain introduced by a trans double bond.

  8. K isomers as probes of nuclear structure

    SciTech Connect

    Tandel, S. K.

    2014-08-14

    K isomers are studied in Pu and Cm isotopes, and also in Hf and W nuclei. Many high-K states, several of which are isomeric, are identified. Lifetime measurements spanning the ns-s range have been performed, and decay paths of isomers established. Rotational bands built on high-K states are also identified in many cases. Isomer decays are considerably hindered in many instances, both in the A≈180 and 250 regions indicating that K is an approximately conserved quantum number. High-K states become the favored excitation mode at high spins in the A≈180 region. The energies of the 2-quasiparticle high-K states in Cm isotopes suggest the presence of a deformed subshell gap at N=152.

  9. Nuclear isomer suitable for gamma ray laser

    NASA Technical Reports Server (NTRS)

    Jha, S.

    1979-01-01

    The operation of gamma ray lasers (gasers) are studied. It is assumed that the nuclear isomers mentioned in previously published papers have inherent limitations. It is further assumed that the judicious use of Bormann effect or the application of the total external reflection of low energy gamma radiation at grazing angle of incidence may permit the use of a gaser crystal sufficiently long to achieve observable stimulated emission. It is suggested that a long lived 0(+) isomer decaying by low energy gamma ray emission to a short lived 2(+) excited nuclear state would be an attractive gaser candidate. It is also suggested that the nuclear isomer be incorporated in a matrix of refractory material having an electrostatic field gradient whose principal axis lies along the length of the medium. This results in the preferential transmission of electric quadrupole radiation along the length of the medium.

  10. An Assessment of Nuclear Isomers as an Energy Storage Medium

    SciTech Connect

    Hartouni, E P

    2008-12-08

    Nuclear Isomers have been suggested as a potential high energy density medium that might be used to store energy. This talk assesses the state of the science supporting key elements of using nuclear isomers in energy storage applications. The focus is on the nuclear isomer {sup 178m2}Hf which has been most widely suggested for energy storage applications. However, the science issues apply to all nuclear isomer. The assessment addresses the production of the nuclear isomer, and inducing the release of the isomer. Also discussed are novel speculations on photon and/or neutron chain reactions, both as a 'pure' material as well as mixed with other materials.

  11. New Millisecond Isomer Lifetime Measurements at LANSCE

    SciTech Connect

    Devlin, M. Nelson, R.O.; Fotiades, N.; O'Donnell, J.M.

    2014-06-15

    New half-life measurements have been made of the millisecond isomers {sup 71m}Ge, {sup 114m2}I, {sup 208m}Bi, {sup 88m1}Y, {sup 88m2}Y, and {sup 75m}As populated in neutron-induced reactions. These measurements were made using the unique time structure of the LANSCE/WNR neutron source, by observing the γ-ray decays of the isomers during the time between the LANSCE proton macropulses. Two different LANSCE proton beam time structures were used. The GEANIE array of HPGe detectors was used to detect the γ-ray decays.

  12. 'Melatonin isomer' in wine is not an isomer of the melatonin but tryptophan-ethylester.

    PubMed

    Gardana, Claudio; Iriti, Marcello; Stuknytė, Milda; De Noni, Ivano; Simonetti, Paolo

    2014-11-01

    Melatonin is a neurohormone, chronobiotic, and antioxidant compound found in wine and deriving directly from grapes and/or synthesized by yeast during alcoholic fermentation. In addition, a melatonin isomer has been detected in different foods, wine among them. The special interest for melatonin isomer related to the fact that it was found in greater quantities than melatonin and probably shares some of its biological properties. Despite this, its chemical structure has not yet been defined; although some researchers hypothesize, it could be melatonin with the ethylacetamide group shifted into position N1. Thus, the aim of our study was to identify the structures of the melatonin isomer. For this purpose, melatonin and melatonin isomer in Syrah wine were separated chromatographically by a sub-2 μm particle column and detected by tandem mass spectrometry. The sample was then purified and concentrated by solid-phase extraction, hydrolyzed with alkali or esterase, and substrates and products quantified by UPLC-MS/MS. Moreover, melatonin, melatonin isomer, and their product ions were evaluated by high-resolution mass spectrometry. The amount of melatonin isomer and melatonin in the wine was 84 ± 4 and 3 ± 0 ng/mL, respectively. In the solutions, containing diluted alkali or esterase, melatonin isomer was hydrolyzed in about 8 min. Correspondingly, tryptophan was detected, and its amount increased and reached the maximum concentration in about 8 min. Melatonin concentration was not affected by diluted alkali or esterase. The fragmentation pattern of melatonin isomer was different from that of melatonin but comparable to that of tryptophan-ethylester. Finally, the so-called melatonin isomer identity was verified by cochromatography with authentic standard of tryptophan-ethylester.

  13. Isomer Tagging with a Dual Multi-Wire Proportional Counter and a Differential Plunger

    SciTech Connect

    Cullen, D. M.; Mason, P. J. R.; Khan, S.; Kishada, A. M.; Varley, B. J.; Rigby, S. V.; Scholey, C.; Greenlees, P.; Rahkila, P.; Jones, P. M.; Julin, R.; Juutinen, S.; Leino, M.; Leppaenen, A. P.; Nyman, M.; Uusitalo, J.; Grahn, T.; Pakarinen, J.; Nieminen, P.

    2008-05-12

    This report details the status of an experimental research programme which has studied isomeric states in the mass 130-160 region of the nuclear chart. Several new isomers have been established and characterised near the proton drip line using a recoil isomer tagging technique at the University of Jyvaeskylae, Finland. The latest experiments have been performed with a modified setup where the standard GREAT focal-plane double-sided silicon-strip detector was changed to a dual multi-wire proportional-counter arrangement. This new setup has improved capability for short-lived isomer studies where large focal-plane rates can be tolerated. The results of key recent experiments for nuclei situated above ({sup 153}Yb, {sup 152}Tm) and below ({sup 144}Ho, {sup 142}Tb) the N = 82 shell gap were presented. These studies have charted the evolution of isomeric states across the neutron shell from K-Isomers at N = 74, to shape isomers at N = 77 and shell-model isomers at N = 82, 83. The excitation energies for some of the lowest-lying excited states in these isomeric nuclei show behaviour which is characteristic of an X(5) symmetry falling midway between the limits expected for pure vibrational and rotational behaviour. The future prospects for studies of these nuclei were discussed using an isomer-tagged differential-plunger setup. This technique will be capable of establishing the deformation of the states above the isomers and will aid in determining whether their behaviour is indeed well described by the X(5) symmetry limit.

  14. Isomer Studies for Nuclei near the Proton Drip Line in the Mass 130-160 Region

    SciTech Connect

    Cullen, D. M.; Mason, P. J. R.; Khan, S.; Kishada, A. M.; Varley, B. J.; Rigby, S. V.; Scholey, C.; Greenlees, P.; Rahkila, P.; Jones, P. M.; Julin, R.; Juutinen, S.; Leino, M.; Leppaenen, A. P.; Nyman, M.; Uusitalo, J.; Grahn, T.; Nieminen, P.; Pakarinen, J.

    2007-11-30

    This report details the status of an experimental research programme which has studied isomeric states in the mass 130-160 region of the nuclear chart. Several new isomers have been established and characterised near the proton drip line using a recoil isomer tagging technique at the University of Jyvaeskylae, Finland. The latest experiments have been performed with a modified setup where the standard GREAT focal-plane double-sided silicon-strip detector was changed to a dual multi-wire proportional-counter arrangement. This new setup has improved capability for short-lived isomer studies where high focal-plane rates can be tolerated. The results of key recent experiments for nuclei situated above ({sup 153}Yb,{sup 152}Tm) and below ({sup 136}Pm,{sup 142}Tb) the N = 82 shell gap were presented along with an interpretation for the isomers. Finally, the future prospects of the technique, using an isomer-tagged differential-plunger setup, were discussed. This technique will be capable of establishing the deformation of the states above the isomers and will aid in the process of assigning underlying single-particle configurations to the isomeric states.

  15. Kinetics of the reaction between ozone and phenolic acids present in agro-industrial wastewaters.

    PubMed

    Beltran-Heredia, J; Torregrosa, J; Dominguez, J R; Peres, J A

    2001-03-01

    The kinetics of the ozonation of three phenolic acids is investigated from ozone absorption experiments in a semi-continuous reactor. After the evaluation of stoichiometric ratios for the individual reactions between ozone and each phenolic acid, the oxidation of p-hydroxybenzoic acid by ozone is performed in a first stage. The influence of the operating variables on the degradation process is established, and the application of a mass transfer with chemical reaction model based on the film theory leads to the determination of the reaction orders and kinetic rate constants. The experimental absorption rates obtained agree well with those calculated theoretically. In the second stage, a mixture of ferulic acid (4-hydroxy-3-methoxycinnamic acid), beta-resorcylic acid (2,4-dihydroxybenzoic acid) and p-hydroxybenzoic acid is ozonated under different experimental conditions. The kinetic study is performed by means of a competitive method that takes p-hydroxybenzoic acid as reference compound. The application of this model allows to determine the kinetic rate constants for each compound, which are correlated as a function of pH and temperature. The results obtained support that the kinetic regime of absorption is fast and pseudo-first order with respect to ozone, a condition required by the competitive method used.

  16. Energetics of the S2 State Spin Isomers of the Oxygen-Evolving Complex of Photosystem II.

    PubMed

    Vinyard, David J; Khan, Sahr; Askerka, Mikhail; Batista, Victor S; Brudvig, Gary W

    2017-02-09

    The S2 redox intermediate of the oxygen-evolving complex in photosystem II is present as two spin isomers. The S = 1/2 isomer gives rise to a multiline electron paramagnetic resonance (EPR) signal at g = 2.0, whereas the S = 5/2 isomer exhibits a broad EPR signal at g = 4.1. The electronic structures of these isomers are known, but their role in the catalytic cycle of water oxidation remains unclear. We show that formation of the S = 1/2 state from the S = 5/2 state is exergonic at temperatures above 160 K. However, the S = 1/2 isomer decays to S1 more slowly than the S = 5/2 isomer. These differences support the hypotheses that the S3 state is formed via the S2 state S = 5/2 isomer and that the stabilized S2 state S = 1/2 isomer plays a role in minimizing S2QA(-) decay under light-limiting conditions.

  17. Energetics of the S2 state spin isomers of the oxygen-evolving complex of Photosystem II

    DOE PAGES

    Vinyard, David J.; Khan, Sahr; Askerka, Mikhail; ...

    2017-01-12

    Here, the S2 redox intermediate of the oxygen-evolving complex in Photosystem II is present as two spin isomers. The S = 1/2 isomer gives rise to a multiline EPR signal at g = 2, while the S = 5/2 isomer exhibits a broad EPR signal at g = 4.1. The electronic structures of these isomers are known, but their role in the catalytic cycle of water oxidation remains unclear. We show that formation of the S = 1/2 state from the S = 5/2 state is exergonic at temperatures above 160 K. However, the S = 1/2 isomer decays tomore » S1 more slowly than the S = 5/2 isomer. These differences support the hypotheses that the S3 state is formed via the S2 state S = 5/2 isomer and that the stabilized S2 state S = 1/2 isomer plays a role in minimizing S2QA- decay in light-limiting conditions.« less

  18. Structural Elucidation of cis/trans Dicaffeoylquinic Acid Photoisomerization Using Ion Mobility Spectrometry-Mass Spectrometry.

    PubMed

    Zheng, Xueyun; Renslow, Ryan S; Makola, Mpho M; Webb, Ian K; Deng, Liulin; Thomas, Dennis G; Govind, Niranjan; Ibrahim, Yehia M; Kabanda, Mwadham M; Dubery, Ian A; Heyman, Heino M; Smith, Richard D; Madala, Ntakadzeni E; Baker, Erin S

    2017-04-06

    Due to the recently uncovered health benefits and anti-HIV activities of dicaffeoylquinic acids (diCQAs), understanding their structures and functions is of great interest for drug discovery efforts. DiCQAs are analytically challenging to identify and quantify since they commonly exist as a diverse mixture of positional and geometric (cis/trans) isomers. In this work, we utilized ion mobility spectrometry coupled with mass spectrometry to separate the various isomers before and after UV irradiation. The experimental collision cross sections were then compared with theoretical structures to differentiate and identify the diCQA isomers. Our analyses found that naturally the diCQAs existed predominantly as trans/trans isomers, but after 3 h of UV irradiation, cis/cis, cis/trans, trans/cis, and trans/trans isomers were all present in the mixture. This is the first report of successful differentiation of cis/trans diCQA isomers individually, which shows the great promise of IMS coupled with theoretical calculations for determining the structure and activity relationships of different isomers in drug discovery studies.

  19. Organometallic chemistry: Heavyweight isomer brings stability

    NASA Astrophysics Data System (ADS)

    Scheschkewitz, David

    2016-11-01

    Due to its high reactivity, vinylidene -- the sole 'electron-precise' isomer of acetylene -- is only known to exist in the gas phase. Now, a stable base-free digermanium version of a vinylidene has been isolated by the clever use of suitable substituents.

  20. Introduction of Branching Degrees of Octane Isomers.

    PubMed

    Perdih, Anton

    2016-01-01

    The concept of branching degrees is introduced. In the case of octane isomers it is derived from the values of a set of their physicochemical properties, calculating for each isomer the average of the normalized values and these averages are defined as branching degrees of octane isomers. The sequence of these branching degrees of octane isomers does not differ much from the »regular« one defined earlier. 2,2-Dimethylhexane appears to be less branched than 3,4-dimethylhexane and 3-ethyl, 2-methylpentane, whereas 2,3,4-trimethylpentane appears to be less branched than 3-ethyl, 3-methylpentane. While the increasing number of branches gives rise to increasing branching degrees, the peripheral position of branches and the separation between branches decreases the value of the branching degree. The central position of branches increases it. A bigger branch increases it more than a smaller one. The quantification of these structural features and their correlations with few indices is given as well.

  1. Microbial oxidation of dimethylnaphthalene isomers

    SciTech Connect

    Miyachi, Nobuya; Tanaka, Tohru; Suzuki, Takaya; Hotta, Yasushi ); Omori, Toshio )

    1993-05-01

    Few studies have focused on the microbial oxidation and metabolism of dimethylnaphthalenes (DMNs), which are supplied from the light oil fraction of crude oil. This report describes the isolation of 2,6-DMN-utilizing bacteria, the identification of the isolates (Alcaligenes sp. strain D-59, Pseudomonas sp. strains D-87 and D-186), the accumulation of 2,6-naphthalene dicarboxylic acid (NDCA) from 2,6-DMN, the identification of some metabolic intermediates of 2,6-DMN, and a proposal of a metabolic pathway of 2,6-DMN. 11 refs., 2 figs.

  2. Dietary Trans Fatty Acids and Cardiovascular Disease Risk: Past and Present

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dietary trans double bond fatty acids have been associated with increased risk of cardiovascular disease. There are two main sources of dietary trans fatty acids: meat and dairy fats, and partially-hydrogenated oils. Due to a number of factors, including changes in federal labeling requirements fo...

  3. Isomer discrimination of polycyclic aromatic hydrocarbons in the Murchison meteorite by resonant ionization.

    PubMed

    Callahan, Michael P; Abo-Riziq, Ali; Crews, Bridgit; Grace, Louis; de Vries, Mattanjah S

    2008-12-15

    We have used two-color resonant two-photon ionization (2C-R2PI) mass spectrometry to discriminate between isomers of polycyclic aromatic hydrocarbons in the Murchison meteorite. We measured the 2C-R2PI spectra of chrysene and triphenylene seeded in a supersonic jet by laser desorption. Since each isomer differs in its R2PI spectrum, we can distinguish between isomers using wavelength dependent ionization and mass spectrometry. We found both chrysene and triphenylene in sublimates from carbonaceous residue obtained by acid demineralization of the Murchison meteorite. Their R2PI mass spectra show only the molecular ion, even though these samples contain a complex inventory of organic molecules.

  4. Isomer profiles of perfluoroalkyl substances in water and soil surrounding a chinese fluorochemical manufacturing park.

    PubMed

    Jin, Hangbiao; Zhang, Yifeng; Zhu, Lingyan; Martin, Jonathan W

    2015-04-21

    Despite that China is the largest global manufacturer of perfluoroalkyl substances (PFASs), the manufacturing methods and isomer purity of these chemicals are generally unknown. Here, sampling was conducted around a major fluorochemical manufacturing park in China in 2012, including soil and water collection inside the park, including from a wastewater treatment plant (WWTP), as well as in surrounding rivers and soil (∼15 km radius). Perfluoroalkyl sulfonates (PFSAs) were lower than perfluoroalkyl carboxylates (PFCAs) in all samples, and short-chain (C4-C6) PFCAs were predominant. Perfluoroalkyl phosphonates and phosphate diesters were occasionally detected, but at low detection frequency. Branched isomers of perfluorobutanesulfonate (PFBS) are reported for the first time, accounting for 15-27% of total PFBS in water. An enrichment of isopropyl-PFOA (28%) was found in WWTP influent, suggesting its manufacturing primarily by isopropyl telomerization. More numerous branched isomers were observed for the longer C9-C13 PFCAs (e.g., C12 PFCA had 16 branched isomers), including high proportions of one major branched isomer (likely isopropyl), possibly as impurities from isopropyl-PFOA manufacturing. Overall, short-chain perfluorinated acids were the predominant PFASs being released, but PFOA was still a major chemical in use at this site, primarily from isopropyl telomerization.

  5. Webinar Presentation: Suspect Screening of Environmental Organic Acids in Human Serum Using High-resolution Mass Spectrometry (HRMS)

    EPA Pesticide Factsheets

    This presentation, Suspect Screening of Environmental Organic Acids in Human Serum Using High-resolution Mass Spectrometry (HRMS), was given at the NIEHS/EPA Children's Centers 2016 Webinar Series: Exposome held on May 11, 2016.

  6. Excitation of nuclear isomers by X rays from laser plasma

    SciTech Connect

    Andreev, Aleksandr A; Karpeshin, F; Trzhaskovskaya, M B; Platonov, Konstantin Yu; Rozhdestvenskii, Yu V

    2010-06-23

    The possibility of obtaining isomer nuclei is studied by the example of the molybdenum isomer {sup 93}Mo upon irradiation of a niobium {sup 93}Nb target by {approx}50-J, 100-fs laser pulses. It is shown that the modern laser technique allows production of isomer nuclei by accelerated protons and radiative de-excitation of isomer nuclear states by thermal or line X-rays from laser plasma. (interaction of laser radiation with matter. laser plasma)

  7. Computational Study of the Malonic Acid Tautomerization Products in Highly Concentrated Particles.

    PubMed

    Dick-Pérez, Marilú; Windus, Theresa L

    2017-03-23

    Knowing the tautomeric form of malonic acid (MA) in concentrated particles is critical to understanding its effect on the atmosphere. Energies and vibrational modes of hydrated MA particles were calculated using density functional theory (DFT) at the B3LYP/6-31G(d,p) level and the effective fragment potential (EFP) method. Visualization of the keto and enol isomer vibrational modes enabled the assignment of keto isomer peaks in the 1710-1750 cm(-1) range, and previously unidentified experimental IR peaks in the 1690-1710 cm(-1) can now be attributed to the enol isomer. Comparison of calculated spectra of pure hydrated enol or keto isomers confirm recent experimental evidence, presented by Ghorai et al. ( J. Phys. Chem. A 2011 , 115 , 4373 - 4380 ) of a shift in the keto-enol tautomer equilibrium when MA exists as concentrated particles.

  8. Search for a ''3.5-eV isomer'' in {sup 229}Th in a hollow-cathode electric discharge

    SciTech Connect

    Inamura, T. T.; Haba, H.

    2009-03-15

    A hollow-cathode electric discharge, a well-established source in optical spectroscopy, was used to populate the ''3.5-eV isomer'' in {sup 229}Th with use of nuclear excitation by electron transition (NEET). The radiochemically purest {sup 229}Th sample was loaded into the hollow cathode in which the electric discharge excited the {sup 229}Th to atomic states some of which could be expected to lie close to the excitation energy of the sought isomer. Although there remain some uncertainties, our experiments indicate that the isomer was populated by NEET and its {alpha} decay observed after switching off the electric discharge with a corresponding isomer half-life 1 min < or approx. T{sub 1/2}{sup m} < or approx. 3 min. From the present NEET condition, the isomer appears to lie between 3 eV and 7 eV. The probability of the isomer population by NEET is discussed.

  9. INVESTIGATING THE MINIMUM ENERGY PRINCIPLE IN SEARCHES FOR NEW MOLECULAR SPECIES—THE CASE OF H{sub 2}C{sub 3}O ISOMERS

    SciTech Connect

    Loomis, Ryan A.; McGuire, Brett A.; Remijan, Anthony J.; Shingledecker, Christopher; Johnson, Chelen H.; Blair, Samantha; Robertson, Amy

    2015-01-20

    Recently, Lattelais et al. have interpreted aggregated observations of molecular isomers to suggest that there exists a ''minimum energy principle'', such that molecular formation will favor more stable molecular isomers for thermodynamic reasons. To test the predictive power of this principle, we have fully characterized the spectra of the three isomers of C{sub 3}H{sub 2}O toward the well-known molecular region Sgr B2(N). Evidence for the detection of the isomers cyclopropenone (c-C{sub 3}H{sub 2}O) and propynal (HCCCHO) is presented, along with evidence for the non-detection of the lowest zero-point energy isomer, propadienone (CH{sub 2}CCO). We interpret these observations as evidence that chemical formation pathways, which may be under kinetic control, have a more pronounced effect on final isomer abundances than thermodynamic effects such as the minimum energy principle.

  10. Pairing correlations in high-spin isomers

    SciTech Connect

    Odahara, A.; Gono, Y.; Fukuchi, T.; Wakabayashi, Y.; Sagawa, H.; Satula, W.; Nazarewicz, W.

    2005-12-15

    High-spin isomers with J{sup {pi}}=49/2{sup +} and 27{sup +} have been systematically observed in a number of N=83 isotones with 60{<=}Z{<=}67 at excitation energies {approx}9 MeV. Based on experimental excitation energies, an odd-even binding energy staggering has been extracted for the first time for these multi-quasiparticle states. Surprisingly, the magnitude of the odd-even effect in high-spin isomers turned out to be very close to that in ground states, thus challenging conventional wisdom that pairing correlations are reduced in highly excited states. Theoretical analysis based on mean-field theory explains the observed proton number dependence of the odd-even effect as a manifestation of strong pairing correlations in the highly excited states. Mean-field effects and the proton-neutron residual interaction on the odd-even staggering are also examined.

  11. Measurements of Short-Lived Fission Isomers

    NASA Astrophysics Data System (ADS)

    Finch, Sean; Bhike, Megha; Howell, Calvin; Krishichayan, Fnu; Tornow, Werner

    2016-09-01

    Fission yields of the short lived isomers 134mTe (T1 / 2 = 162 ns) and 136mXe (T1 / 2 = 2 . 95 μs) were measured for 235U and 238U. The isomers were detected by the γ rays associated with the decay of the isomeric states using high-purity germanium detectors. Fission was induced using both monoenergetic γ rays and neutrons. At TUNL's High-Intensity Gamma-ray Source (HI γS), γ rays of 9 and 11 MeV were produced . Monoenergetic 8 MeV neutrons were produced at TUNL's tandem accelerator laboratory. Both beams were pulsed to allow for precise time-gated spectroscopy of both prompt and delayed γ rays following fission. This technique offers a non-destructive probe of special nuclear materials that is sensitive to the isotopic identity of the fissile material.

  12. K Isomer in {sup 252}No

    SciTech Connect

    Sulignano, B.; Theisen, Ch.; Drouart, A.; Goergen, A.; Korten, W.; Obertelli, A.; Ackermann, D.; Hessberger, F. P.; Hofmann, S.; Antalic, S.; Venhart, M.; Dorvaux, O.; Piot, J.; Greenlees, P. T.; Jakobsson, U.; Jones, P.; Julin, R.; Juutinen, S.

    2010-04-30

    In this paper we discuss the discovery of an isomeric state in {sup 252}No and a recent experiment studying the rotational band built upon this isomeric state. Results from the later experiment help to assign the structure of the isomer on the basis of purely experimental data, and to disentangle between different theoretical interpretations. Comparison with similar states in {sup 250}Fm and {sup 254}No provides important information and helps the development of self -consistent theories.

  13. Accurate ab initio Quartic Force Fields of Cyclic and Bent HC2N Isomers

    NASA Technical Reports Server (NTRS)

    Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J.

    2012-01-01

    Highly correlated ab initio quartic force field (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC2N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T). Dunning s correlation-consistent basis sets cc-pVXZ, X=3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schr dinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by perturbation theory). On the other hand, this procedure (a QFF together with either perturbation theory or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC2N. All three isomers possess significant dipole moments, 3.05D, 3.06D, and 1.71D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.

  14. Isomers of perfluorooctanesulfonate (PFOS) in cord serum and birth outcomes in China: Guangzhou Birth Cohort Study.

    PubMed

    Li, Meng; Zeng, Xiao-Wen; Qian, Zhengmin Min; Vaughn, Michael G; Sauvé, Sébastien; Paul, Gunther; Lin, Shao; Lu, Long; Hu, Li-Wen; Yang, Bo-Yi; Zhou, Yang; Qin, Xiao-Di; Xu, Shu-Li; Bao, Wen-Wen; Zhang, Ya-Zhi; Yuan, Ping; Wang, Jia; Zhang, Chuan; Tian, Yan-Peng; Nian, Min; Xiao, Xiang; Fu, Chuanxi; Dong, Guang-Hui

    2017-03-12

    Prior investigations on the associations of polyfluoroalkyl substances (PFASs) with fetal growth are mixed. Moreover, little research has accrued pertaining to the association between isomers of PFASs with gestational age and birth weight. To address this gap and present novel information, we conducted a study including 321 pairs of mothers and their infants recruited from Guangzhou, China. High performance liquid chromatography-mass spectrometry was utilized to analyze isomers of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) along with other PFAS levels in cord serum samples. Mothers' and infants' characteristics were gathered from medical records. The resulting data revealed that higher PFOS, PFOA and isomers of PFOS were associated with lower birth weight. Per ln-unit (ng/mL) increase in cord serum total branched PFOS isomers was associated with a 126.3g (95% CI: -195.9, -56.8) reduction in the weight of infants at birth, while an ln-unit (ng/mL) increase of serum linear PFOS isomers (n-PFOS) was associated with a 57.2g (95% CI: -103.1, -11.3) reduction in the weight of infants at birth upon the subsequent adjustment for potential confounding variables. Notably, the association between cord PFAS level and birth weight was more pronounced in male infants. Furthermore, a positive association among branched PFOS isomers (1m-PFOS and 3+4+5m-PFOS) and gestational age was found. No associations could be found among other PFASs in conjunction with gestational age or birth weight. In conclusion, this investigation suggests that higher PFAS concentrations are associated with lower birth weight, and branched PFOS isomers show greater impact on infant birth weight than linear PFOS.

  15. Accurate ab initio quartic force fields of cyclic and bent HC2N isomers.

    PubMed

    Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J

    2011-12-28

    Highly correlated ab initio quartic force fields (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC(2)N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted as CCSD(T). Dunning's correlation-consistent basis sets cc-pVXZ, X = 3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (PT) (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schrödinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by PT). On the other hand, this procedure (a QFF together with either PT or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC(2)N. All three isomers possess significant dipole moments, 3.05 D, 3.06 D, and 1.71 D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.

  16. Idiopathic bile acid malabsorption--a review of clinical presentation, diagnosis, and response to treatment.

    PubMed Central

    Williams, A J; Merrick, M V; Eastwood, M A

    1991-01-01

    Between 1982 and 1989, the seven day retention of 75SeHCAT was measured in 181 patients with chronic diarrhoea that remained unexplained after full investigation. Altogether 121 of the 181 had a seven day 75SeHCAT retention greater than or equal to 15% and thus had no evidence of abnormal bile acid turnover. Twenty one had a seven day 75SeHCAT retention greater than or equal to 10% but less than 15%. Their clinical features were typical of the irritable bowel syndrome, and none of eight treated with cholestyramine showed symptomatic improvement. Sixteen patients had a seven day retention greater than or equal to 5% and less than 10%, six of whom had improved symptoms after treatment with bile acid chelating agents. The remaining 23 patients had a 75SeHCAT retention of less than 5% at seven days and responded to bile acid chelators. This group had a characteristic illness with intermittent watery diarrhoea, but no constitutional upset. It was not possible to distinguish the patients with bile acid malabsorption exclusively on the basis of the clinical symptoms and investigations, other than 75SeHCAT retention. We conclude that the measurement of 75SeHCAT retention is useful, appropriate, and necessary in patients with unexplained chronic diarrhoea. PMID:1916479

  17. Isomer effects on polyimide properties

    NASA Technical Reports Server (NTRS)

    Stump, B. L.

    1978-01-01

    Thermally stable polyimide polymers were prepared. Parameters explored include asymmetry of substitution, addition of alkyl substituents to an aromatic ring, and an increase in the number of aromatic rings present in the diamine monomer. It is shown that the use of an asymmetrical diamine in the preparation of a polyimide produces a polymer with a markedly lowered glass transition temperature. This is achieved with little or no sacrifice of thermal stability. An alternate approach taken was to prepare imide monomers which are capable of addition-type polymerization.

  18. Biohydrogenation of Linoleic Acid by Lactic Acid Bacteria for the Production of Functional Cultured Dairy Products: A Review

    PubMed Central

    Kuhl, Gabriela Christina; De Dea Lindner, Juliano

    2016-01-01

    Conjugated linoleic acid (CLA) isomers have attracted significant attention due to their important physiological properties, which have been observed in humans. Many lactic acid bacteria (LAB) demonstrate the ability to produce CLA isomers (C18:2 cis-9, trans-11 and C18:2 trans-10, cis-12) from the linoleic acid (LA) present in milk or in synthetic media. CLA isomers can be synthesized in vitro by LAB using vegetable oils rich in LA. The aim of this review is to present an update on the studies that have been conducted on the production of CLA isomers from LA mainly by LAB and of the factors that influence this conversion (source and concentration of LA and fermentation conditions). In addition, this review presents the relationship between the consumption of CLA isomers and their health benefits in humans such as anti-atherosclerosis and anti-carcinogenic effects. There is considerable variation between the studies concerning the beneficial effects of CLA in animal models, which have not been reflected in human studies. This can be attributed to the differences in the doses of CLA isomers used and to the different sources of CLA. Furthermore, the regulatory and scientific information classifying the physiological properties of CLA, which serve as support for the claims of its potential as a functional ingredient, are presented. More research is needed to determine whether CLA production by LAB can be enhanced and to determine the optimal requirements for these microbial cultures. Furthermore, safety and efficacy of CLA consumption have to be investigated in the future. PMID:28231108

  19. Label-free direct surface-enhanced Raman scattering (SERS) of nucleic acids (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Guerrini, Luca; Morla-Folch, Judit; Gisbert-Quilis, Patricia; Xie, Hainan; Alvarez-Puebla, Ramon

    2016-03-01

    Recently, plasmonic-based biosensing has experienced an unprecedented level of attention, with a particular focus on the nucleic acid detection, offering efficient solutions to engineer simple, fast, highly sensitive sensing platforms while overcoming important limitations of PCR and microarray techniques. In the broad field of plasmonics, surface-enhanced Raman scattering (SERS) spectroscopy has arisen as a powerful analytical tool for detection and structural characterization of biomolecules. Today applications of SERS to nucleic acid analysis largely rely on indirect strategies, which have been demonstrated very effective for pure sensing purposes but completely dismiss the exquisite structural information provided by the direct acquisition of the biomolecular vibrational fingerprint. Contrarily, direct label-free SERS of nucleic acid shows an outstanding potential in terms of chemical-specific information which, however, remained largely unexpressed mainly because of the inherent poor spectral reproducibility and/or limited sensitivity. To address these limitations, we developed a fast and affordable high-throughput screening direct SERS method for gaining detailed genomic information on nucleic acids (DNA and RNA) and for the characterization and quantitative recognition of DNA interactions with exogenous agents. The simple strategy relies on the electrostatic adhesion of DNA/RNA onto positively-charged silver colloids that promotes the nanoparticle aggregation into stable clusters yielding intense and reproducible SERS spectra at picogram level (i.e. the analysis can be performed without the necessity of amplification steps thus providing realistic direct information of the nucleic acid in its native state). We anticipate this method to gain a vast impact and set of applications in different fields, including medical diagnostics, genomic screening, drug discovery, forensic science and even molecular electronics.

  20. Interstellar Isomers: The Importance of Bonding Energy Differences

    NASA Technical Reports Server (NTRS)

    Remijan, Anthony J.; Hollis, J. M.; Lovas, F. J.; Plusquellic, D. F.; Jewell, P. R.

    2005-01-01

    We present strong detections of methyl cyanide (CH3CN), vinyl cyanide (CH2CHCN), ethyl cyanide (CH3CH2CN) and cyanodiacetylene (HC4CN) molecules with the Green Bank Telescope (GBT) toward the Sgr B2(N) molecular cloud. Attempts to detect the corresponding isocyanide isomers were only successful in the case of methyl isocyanide (CH3NC) for its J(sub K) = 1(sub 0) - 0(sub 0) transition, which is the first interstellar report of this line. To determine the spatial distribution of CH3NC, we used archival Berkeley-Illinois-Maryland Association (BIMA) array data for the J(sub K) = 1(sub 0) - 0(sub 0) transitions but no emission was detected. From ab initio calculations, the bonding energy difference between the cyanide and isocyanide molecules is greater than 8500 per centimeter (greater than 12,000 K). Thus, cyanides are the more stable isomers and would likely be formed more preferentially over their isocyanide counterparts. That we detect CH3NC emission with a single antenna (Gaussian beamsize(omega(sub B))=1723 arcsec(sup 2)) but not with an interferometer (omega(sub b)=192 arcsec(sup 2)), strongly suggests that CH3NC has a widespread spatial distribution toward the Sgr B2(N) region. Other investigators have shown that CH3CN is present both in the LMH hot core of Sgr B2(N) and in the surrounding medium, while we have shown that CH3NC appears to be deficient in the LMH hot core. Thus, largescale, non-thermal processes in the surrounding medium may account for the conversion of CH3CN to CH3NC while the LMH hot core, which is dominated by thermal processes, does not produce a significant amount of CH3NC. Ice analog experiments by other investigators have shown that radiation bombardment of CH3CN can produce CH3NC, thus supporting our observations. We conclude that isomers separated by such large bonding energy differences are distributed in different interstellar environments, making the evaluation of column density ratios between such isomers irrelevant unless it can

  1. Experimental investigation of the low temperature oxidation of the five isomers of hexane.

    PubMed

    Wang, Zhandong; Herbinet, Olivier; Cheng, Zhanjun; Husson, Benoit; Fournet, René; Qi, Fei; Battin-Leclerc, Frédérique

    2014-07-31

    The low-temperature oxidation of the five hexane isomers (n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethylbutane, and 2,3-dimethylbutane) was studied in a jet-stirred reactor (JSR) at atmospheric pressure under stoichiometric conditions between 550 and 1000 K. The evolution of reactant and product mole fraction profiles were recorded as a function of the temperature using two analytical methods: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Experimental data obtained with both methods were in good agreement for the five fuels. These data were used to compare the reactivity and the nature of the reaction products and their distribution. At low temperature (below 800 K), n-hexane was the most reactive isomer. The two methyl-pentane isomers have about the same reactivity, which was lower than that of n-hexane. 2,2-Dimethylbutane was less reactive than the two methyl-pentane isomers, and 2,3-dimethylbutane was the least reactive isomer. These observations are in good agreement with research octane numbers given in the literature. Cyclic ethers with rings including 3, 4, 5, and 6 atoms have been identified and quantified for the five fuels. While the cyclic ether distribution was notably more detailed than in other literature of JSR studies of branched alkane oxidation, some oxiranes were missing among the cyclic ethers expected from methyl-pentanes. Using SVUV-PIMS, the formation of C2-C3 monocarboxylic acids, ketohydroperoxides, and species with two carbonyl groups have also been observed, supporting their possible formation from branched reactants. This is in line with what was previously experimentally demonstrated from linear fuels. Possible structures and ways of decomposition of the most probable ketohydroperoxides were discussed. Above 800 K, all five isomers have about the same reactivity, with a larger formation from branched alkanes of some unsaturated species, such as allene and propyne, which

  2. Free fatty acid and triacylglycerol forms of CLA isomers are not incorporated equally in the liver but do not lead to differences in bone density and biomarkers of bone metabolism.

    PubMed

    DeGuire, Jason R; Weiler, Hope A

    2013-05-01

    Few studies have compared differences between conjugated linoleic acid (CLA) in triacylglycerol (TG) and free fatty acid (FFA) form. This study assessed differences in liver incorporation, mineral mass balance, bone density, and biomarkers of bone metabolism between FFA and TG CLA diets. Rats (n=36) were fed a control (CTRL) or 1% CLA diet in FFA or TG form (1:1 mixture c9, t11: t10, c12). Liver content of c9, t11 CLA from FFA was greater than TG form and CTRL (FFA: 0.05±0.01 vs. TG: 0.02±0.01 vs. CTRL: 0.001±0.001% total fatty acids, P<0.0001). Liver t10, c12 CLA did not differ among groups (P=0.11). No diet differences among groups for growth, bone biomarkers or mass nor mineral balance were found. These findings suggest that c9, t11 CLA in FFA form is preferentially incorporated in the liver but fatty acid forms of CLA do not affect bone or mineral outcomes.

  3. Triterpenic Acids Present in Hawthorn Lower Plasma Cholesterol by Inhibiting Intestinal ACAT Activity in Hamsters.

    PubMed

    Lin, Yuguang; Vermeer, Mario A; Trautwein, Elke A

    2011-01-01

    Hawthorn (Crataegus pinnatifida) is an edible fruit used in traditional Chinese medicine to lower plasma lipids. This study explored lipid-lowering compounds and underlying mechanisms of action of hawthorn. Hawthorn powder extracts inhibited acylCoA:cholesterol acyltransferase (ACAT) activity in Caco-2 cells. The inhibitory activity was positively associated with triterpenic acid (i.e., oleanolic acid (OA) and ursolic acid (UA)) contents in the extracts. Cholesterol lowering effects of hawthorn and its potential additive effect in combination with plant sterol esters (PSE) were further studied in hamsters. Animals were fed a semi-synthetic diet containing 0.08% (w/w) cholesterol (control) or the same diet supplemented with (i) 0.37% hawthorn dichloromethane extract, (ii) 0.24% PSE, (iii) hawthorn dichloromethane extract (0.37%) plus PSE (0.24%) or (iv) OA/UA mixture (0.01%) for 4 weeks. Compared to the control diet, hawthorn, PSE, hawthorn plus PSE and OA/UA significantly lowered plasma non-HDL (VLDL + LDL) cholesterol concentrations by 8%, 9%, 21% and 6% and decreased hepatic cholesterol ester content by 9%, 23%, 46% and 22%, respectively. The cholesterol lowering effects of these ingredients were conversely associated with their capacities in increasing fecal neutral sterol excretion. In conclusion, OA and UA are responsible for the cholesterol lowering effect of hawthorn by inhibiting intestinal ACAT activity. In addition, hawthorn and particularly its bioactive compounds (OA and UA) enhanced the cholesterol lowering effect of plant sterols.

  4. A Type II Pathway for Fatty Acid Biosynthesis Presents Drug Targets in Plasmodium falciparum

    PubMed Central

    Waller, Ross F.; Ralph, Stuart A.; Reed, Michael B.; Su, Vanessa; Douglas, James D.; Minnikin, David E.; Cowman, Alan F.; Besra, Gurdyal S.; McFadden, Geoffrey I.

    2003-01-01

    It has long been held that the malaria parasite, Plasmodium sp., is incapable of de novo fatty acid synthesis. This view has recently been overturned with the emergence of data for the presence of a fatty acid biosynthetic pathway in the relict plastid of P. falciparum (known as the apicoplast). This pathway represents the type II pathway common to plant chloroplasts and bacteria but distinct from the type I pathway of animals including humans. Specific inhibitors of the type II pathway, thiolactomycin and triclosan, have been reported to target this Plasmodium pathway. Here we report further inhibitors of the plastid-based pathway that inhibit Plasmodium parasites. These include several analogues of thiolactomycin, two with sixfold-greater efficacy than thiolactomycin. We also report that parasites respond very rapidly to such inhibitors and that the greatest sensitivity is seen in ring-stage parasites. This study substantiates the importance of fatty acid synthesis for blood-stage parasite survival and shows that this pathway provides scope for the development of novel antimalarial drugs. PMID:12499205

  5. Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products.

    PubMed

    Ye, Feng; Zushi, Yasuyuki; Masunaga, Shigeki

    2015-05-01

    Perfluoroalkyl acids (PFAAs) and their precursors have been used in various consumer products. However, limited information regarding their occurrence and concentration levels in products is available. In this study, we investigated 18 PFAAs and 14 PFAA precursors in various categories of consumer products purchased in Japan. Relatively high total concentrations of PFAAs and their precursors were found in sprays for fabrics and textiles (acid (PFOS), N-methyl perfluorooctane sulfonamidoethanol (MeFOSE) was detected in a higher frequency (8%) and in greater concentrations (acids (PFCAs) (carbon chain length⩾7) were also detected in greater concentrations than short chain PFCAs (⩽6). This result suggests that consumer products are one of the important sources of long-chain PFCAs in the environment.

  6. Elucidation of Drug Metabolite Structural Isomers Using Molecular Modeling Coupled with Ion Mobility Mass Spectrometry.

    PubMed

    Reading, Eamonn; Munoz-Muriedas, Jordi; Roberts, Andrew D; Dear, Gordon J; Robinson, Carol V; Beaumont, Claire

    2016-02-16

    Ion mobility-mass spectrometry (IM-MS) in combination with molecular modeling offers the potential for small molecule structural isomer identification by measurement of their gas phase collision cross sections (CCSs). Successful application of this approach to drug metabolite identification would facilitate resource reduction, including animal usage, and may benefit other areas of pharmaceutical structural characterization including impurity profiling and degradation chemistry. However, the conformational behavior of drug molecules and their metabolites in the gas phase is poorly understood. Here the gas phase conformational space of drug and drug-like molecules has been investigated as well as the influence of protonation and adduct formation on the conformations of drug metabolite structural isomers. The use of CCSs, measured from IM-MS and molecular modeling information, for the structural identification of drug metabolites has also been critically assessed. Detection of structural isomers of drug metabolites using IM-MS is demonstrated and, in addition, a molecular modeling approach has been developed offering rapid conformational searching and energy assessment of candidate structures which agree with experimental CCSs. Here it is illustrated that isomers must possess markedly dissimilar CCS values for structural differentiation, the existence and extent of CCS differences being ionization state and molecule dependent. The results present that IM-MS and molecular modeling can inform on the identity of drug metabolites and highlight the limitations of this approach in differentiating structural isomers.

  7. Probiotic potential of lactic acid bacteria present in home made curd in southern India

    PubMed Central

    Balamurugan, Ramadass; Chandragunasekaran, Aarthi Sophia; Chellappan, Gowri; Rajaram, Krithika; Ramamoorthi, Gayathri; Ramakrishna, Balakrishnan S.

    2014-01-01

    Background & objectives: The human gut microbiota play a significant role in nutritional processes. The concept of probiotics has led to widespread consumption of food preparations containing probiotic microbes such as curd and yogurt. Curd prepared at home is consumed every day in most homes in southern India. In this study the home-made curd was evaluated for lactic acid bacteria (LAB) with probiotic potential. Methods: Fifteen LAB (12 lactobacilli, 1 Lactococcus, 2 Leuconostoc) and one yeast isolated from home-made curd were evaluated for resistance to acid, pepsin, pancreatin and bile salts; antimicrobial resistance; intrinsic antimicrobial activity; adherence to Caco-2 epithelial cells; ability to block pathogen adherence to Caco-2 cells; ability to inhibit interleukin (IL)-8 secretion from HT-29 epithelial cells in response to Vibrio cholerae; and ability to induce anti-inflammatory cytokine expression in THP-1 monocyte cells. Results: Lactobacillus abundance in fermenting curd peaked sharply at 12 h. Nine of the strains survived exposure to acid (pH 3.0) for at least one hour, and all strains survived in the presence of pancreatin or bile salts for 3 h. None showed haemolytic activity. All were resistant to most antimicrobials tested, but were sensitive to imipenem. Most strains inhibited the growth of Salmonella Typhimurium while five inhibited growth of V. cholerae O139. Seven strains showed adherence to Caco-2 cells ranging from 20-104 per cent of adherence of an adherent strain of Escherichia coli, but all inhibited V. cholerae adherence to Caco-2 cells by 20-100 per cent. They inhibited interleukin-8 secretion from HT-29 cells, in response to V. cholerae, by 50-80 per cent. Two strains induced IL-10 and IL-12 messenger ribonucleic acid (mRNA) expression in THP-1 cells. Interpretation & conclusions: LAB in curd had properties consistent with probiotic potential, but these were not consistent across species. LAB abundance in curd increased rapidly at 12 h

  8. Perfluorooctane sulfonate toxicity, isomer-specific accumulation, and maternal transfer in zebrafish (Danio rerio) and rainbow trout (Oncorhynchus mykiss).

    PubMed

    Sharpe, Rainie L; Benskin, Jonathan P; Laarman, Anne H; Macleod, Sherri L; Martin, Jonathan W; Wong, Charles S; Goss, Greg G

    2010-09-01

    Perfluorooctane sulfonate (PFOS; C(8)F(17)SO(3) (-)) bioaccumulation and toxicity have been demonstrated in both aquatic and terrestrial organisms. The majority of investigations have examined total PFOS concentrations in wildlife and in toxicity testing, but isomer-specific monitoring studies are less common, and no laboratory-based study of PFOS isomer accumulation in fish has been reported. The present study examined accumulation and maternal transfer of PFOS isomers in zebrafish and tissue-specific accumulation of PFOS isomers in trout parr. A median lethal dose (LC50) of 22.2 and 2.5 mg/L was calculated for adult zebrafish and trout parr, respectively. A two-week PFOS exposure resulted in tissue-specific PFOS accumulation in trout, with maximum concentrations identified in the liver tissue (>50 microg/g). Prior exposure to PFOS as alevin did not affect the accumulation of PFOS in tissues later in life. In both species, accumulation of branched PFOS isomers generally occurred to a lesser extent than linear PFOS, which may explain the relative deficiency of branched PFOS isomers in some aquatic species in the field. Analysis of exposed trout tissues indicated that isomer discrimination may occur at the level of elimination or uptake and elimination processes in the kidney or gill, respectively. When zebrafish underwent a reproductive cycle in the presence of PFOS, approximately 10% (wt) of the adult PFOS body burden was transferred to the developing embryos, resulting in a higher total PFOS concentration in eggs (116 +/- 13.3 microg/g) than in the parent fish (72.1 +/- 7.6 microg/g). The isomer profile in eggs was not significantly different from that of adults, suggesting that the maternal transfer of branched and linear PFOS isomers in fish is largely nonisomer specific.

  9. Acid rain monitoring in East-Central Florida from 1977 to present

    NASA Technical Reports Server (NTRS)

    Madsen, B. C.; Kheoh, T.; Hinkle, C. R.; Dreschel, T. W.

    1990-01-01

    Rainfall has been collected on the University of Central Florida campus and at the Kennedy Space Center over a 12 year period. The chemical composition has been determined and summarized by monthly, annual periods, and for the entire 12 year period at both locations. The weighted average pH at each site is 4.58; however, annual weighted average pH has been equal to or above the 12 year average during six of the past eight years. Nitrate concentrations have increased slightly during recent years while excess sulfate concentrations have remained below the 12 year weighted average during six of the past seven years. Stepwise regression suggests that sulfate, nitrate, ammonium ion and calcium play major roles in the description of rainwater acidity. Annual acid deposition and annual rainfall have varied from 20 to 50 meg/(m(exp 2) year) and 100 to 180 cm/year, respectively. Sea salt comprises at least 25 percent of the total ionic composition.

  10. Reduction of MTT to Purple Formazan by Vitamin E Isomers in the Absence of Cells.

    PubMed

    Lim, Su-Wen; Loh, Hwei-San; Ting, Kang-Nee; Bradshaw, Tracey Dawn; Allaudin, Zeenathul Nazariah

    2015-04-01

    The yellow tetrazolium salt 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is widely used to determine cell viability in cell proliferation and cytotoxic assays. MTT is reduced by metabolically active cells to form an insoluble purple formazan product that is quantifiable by spectrophotometry. It is the most common and direct assay for cell viability. However, in this present study, we demonstrated that the vitamin E isomers α-β-γ-δ-tocotrienols and α-tocopherol were able to reduce MTT into a formazan product, despite the absence of living cells. For comparison, a second method for determining cell viability, which is the neutral red uptake assay, was used in parallel with the MTT assay. The results showed that neutral red did not interact with the vitamin E isomers. Our findings suggest that the MTT assay is not suitable for studying the proliferative effects of vitamin E isomers on cell growth.

  11. Reduction of MTT to Purple Formazan by Vitamin E Isomers in the Absence of Cells

    PubMed Central

    Lim, Su-Wen; Loh, Hwei-San; Ting, Kang-Nee; Bradshaw, Tracey Dawn; Allaudin, Zeenathul Nazariah

    2015-01-01

    The yellow tetrazolium salt 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is widely used to determine cell viability in cell proliferation and cytotoxic assays. MTT is reduced by metabolically active cells to form an insoluble purple formazan product that is quantifiable by spectrophotometry. It is the most common and direct assay for cell viability. However, in this present study, we demonstrated that the vitamin E isomers α-β-γ-δ-tocotrienols and α-tocopherol were able to reduce MTT into a formazan product, despite the absence of living cells. For comparison, a second method for determining cell viability, which is the neutral red uptake assay, was used in parallel with the MTT assay. The results showed that neutral red did not interact with the vitamin E isomers. Our findings suggest that the MTT assay is not suitable for studying the proliferative effects of vitamin E isomers on cell growth. PMID:26868595

  12. Studies on the metabolism and the detectability of 4-methyl-amphetamine and its isomers 2-methyl-amphetamine and 3-methyl-amphetamine in rat urine using GC-MS and LC-(high-resolution)-MSn.

    PubMed

    Welter, Jessica; Meyer, Markus R; Kavanagh, Pierce; Maurer, Hans H

    2014-03-01

    4-Methyl-amphetamine (1-(4-methylphenyl)propane-2-amine; 4-MA) and its isomers 2-methyl-amphetamine (2-MA) and 3-methyl-amphetamine (3-MA) belong to the group of amphetamine-type stimulants and of new psychoactive substances. Several studies showed similar potencies in releasing noradrenalin and dopamine, but higher potencies in releasing serotonin than amphetamine. In March 2013, the EU Council decided on an EU-wide control based on the European Monitoring Centre for Drugs and Drug Addiction risk assessment report documenting that 4-MA was sold as amphetamine on the illicit market and detected in several fatal cases. Therefore, 4-MA and its isomers should be covered by drug testing in clinical and forensic toxicology. The aims of the presented work were to study the metabolism and detectability of each isomer in urine samples. For metabolism studies, rat urine samples were isolated by solid-phase extraction without and after enzymatic cleavage of conjugates. The phase I metabolites were separated and identified after acetylation by gas chromatography-mass spectrometry (GC-MS) and/or liquid chromatography-high resolution-linear ion trap mass spectrometry (LC-HR-MS(n)) and the phase II metabolites by LC-HR-MS(n). From the identified phase I and II metabolites, the following main metabolic pathways were deduced: aromatic hydroxylation, hydroxylation of the phenylmethyl group followed by oxidation to the corresponding carboxylic acid, hydroxylation of the side chain, and glucuronidation and/or sulfation of the hydroxy and carboxy groups. CYP2D6 was involved in the aromatic hydroxylation. Finally, the intake of a commonly used dose of the MAs could be confirmed in rat urine using the authors' GC-MS and the LC-MS(n) standard urine screening approaches. Differentiation of the isomers to confirm the intake of a specific isomer was possible with an additional workup in rat urine.

  13. Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Moini, Mehdi; Rollman, Christopher M.

    2016-03-01

    We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

  14. Conformational preferences and synthesis of isomers Z and E of oxazole-dehydrophenylalanine.

    PubMed

    Staś, Monika; Bujak, Maciej; Broda, Małgorzata A; Siodłak, Dawid

    2016-05-01

    Dehydrophenylalanine, ΔPhe, is the most commonly studied α,β-dehydroamino acid. In nature, further modifications of the α,β-dehydroamino acids were found, for example, replacement of the C-terminal amide group by oxazole ring. The conformational properties of oxazole-dehydrophenylalanine residue (ΔPhe-Ozl), both isomers Z and E, were investigated. To determine all possible conformations, theoretical calculations were performed using Ac-(Z/E)-ΔPhe-Ozl(4-Me) model compounds at M06-2X/6-31++G(d,p) level of theory. Ac-(Z/E)-ΔPhe-Ozl-4-COOEt compounds were synthesized and the conformational preferences of each isomer, Z and E, were investigated using FTIR and NMR-NOE in solutions of increasing polarity (CHCl3 , DMSO-d6). The solid-state low-temperature structures of Ac-(Z)-ΔPhe-Ozl-4-COOEt and its intermediate analog Ac-(Z)-ΔPhe-Ozn(4-OH)-4-COOEt were also determined. In a weakly polar environment, the ΔPhe-Ozl residue has a tendency to adopt the conformation β2 with the calculated φ and ψ angles of -127° and 0° for the isomer Z and -170° and 26° for the isomer E. The increase of environment polarity favors the helical conformation α and the beta-turn like conformation β, but the conformation β2 seems to be still accessible. The (E)-ΔPhe-Ozl residue can be obtained from the isomer Z in photoisomerization reaction. However, hydroxyl-oxazoline-dehydrophenylalanine ΔPhe-Ozn(4-OH) decomposes in such conditions. Alternatively, (E)-ΔPhe-NH2 can be applied as a substrate in the Hantzsch reaction. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 283-294, 2016.

  15. Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry.

    PubMed

    Moini, Mehdi; Rollman, Christopher M

    2016-03-01

    We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

  16. Gamma-ray spectroscopy of the ^238U shape isomer.

    NASA Astrophysics Data System (ADS)

    Hauschild, K.; Bauer, R. W.; Becker, J. A.; Bernstein, L. A.; Britt, H. C.; Younes, W.; Fotiades, N.

    1997-04-01

    The γ--rays de--exciting the fission isomers ^236U and ^238U are very different despite similar excitation energies, lifetimes and low--lying yrast structures. The predominant γ--ray decay branch for ^236U^m is a 1.783 MeV E1 transition (J. Schirmer, et al., Phys. Rev. Lett. 63), 2196 (1989); and Refs. therein., while ^238U^m is depopulated by a 2.513 MeV E2 γ-ray (J. Kantele, et al., Phys. Rev. C 29), 1693 (1984); and Refs. therein.. Approximately 65% of the γ--branch de-exciting ^238U^m remains to be identified. To determine the multipolarity of the remaining γ-branch out of ^238U^m we used the Gammasphere array at LBNL and the ^238U(d,pn) reaction at Ed = 20 MeV. A search for excited states in the 2^nd well has also been conducted. Preliminary results will be presented, and the γ--decay of the shape isomers discussed in context with the recent A ~190 SD decay--out results (T. L. Khoo, et al., Phys. Rev. Lett. 76), 1583 (1996); A. Lopez-Martens, et al., Phys. Lett. B380, 18 (1996); K. Hauschild, et al., submitted to Phys. Rev. C (1996)..

  17. The rapid identification of lactic acid bacteria present in Chilean winemaking processes using culture-independent analysis.

    PubMed

    Ilabaca, Carolina; Jara, Carla; Romero, Jaime

    2014-01-01

    A polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) analysis of 16S ribosomal RNA (rRNA) genes was developed to identify lactic acid bacteria (LAB) that are commonly present in winemaking processes (Oenococcus, Pediococcus, Lactobacillus, and Leuconostoc). This culture-independent approach revealed the presence of Oenococcus in the spontaneous malolactic fermentation in industrial Chilean wines.

  18. Systematic analysis of reactivities and fragmentation of glutathione and its isomer GluCysGly.

    PubMed

    Feng, Shan; Zheng, Xiaoyan; Wang, Dong; Gong, Yiyi; Wang, Qingtao; Deng, Haiteng

    2014-09-18

    Glutathione (GSH) is the most abundant tripeptide in human cells and plays an important role in protecting cells' integrity against oxidative stress. GSH has an unusual amide linkage formed between the γ-carboxylic group of the glutamic acid in its side-chain and the amine group of cysteine residue. In the present study, we have compared reactivities of GSH to its isomer GluCysGly (ECG), which has a regular amide bond formed between the α-carboxylic group of glutamic acid and the amine group of cysteine residue. The fragmentation pattern of GSH ions in the gas phase is different from that of ECG ions, showing that the loss of H2O is the major dissociation pathway in ECG fragmentation. This is consistent with the dissociation pathway predicted by density functional calculation. Formation of GSSG from oxidation of GSH is faster than that of ECG disulfide, and the gas phase fragmentation pattern of GSSG is different from that of ECG disulfide. GSH and ECG display similar rates in nucleophilic aromatic substitution when reacting with 1-chloro-2,4-dinitrobenzene (CDNB). However, in the presence of glutathione S-transferases (GST), substitution of CDNB by GSH is 10 times faster than that by ECG. GSH and ECG also show differences in clustering patterns in the gas phase. Taken together, our results shed light on understanding effects of unique boding structure in GSH on its stability and reactivities.

  19. Isomer ratio measurements as a probe of the dynamics of breakup and incomplete fusion

    SciTech Connect

    Gasques, L. R.; Dasgupta, M.; Hinde, D. J.; Peatey, T.; Diaz-Torres, A.; Newton, J. O.

    2006-12-15

    The incomplete fusion mechanism following breakup of {sup 6,7}Li and {sup 9}Be projectiles incident on targets of {sup 209}Bi and {sup 208}Pb is investigated through isomer ratio measurements for the {sup 212}At and {sup 211}Po products. The phenomenological analysis presented in this paper indicates that incomplete fusion brings relatively more angular momentum into the system than equivalent reactions with a direct beam of the fused fragment. This is attributed to the trajectories of breakup fragments. Calculations with a 3D classical trajectory model support this. Isomer ratio measurements for incomplete fusion reactions can provide a test of new theoretical models of breakup and fusion.

  20. Foundations of Isomer Physics for Energy Applications

    DTIC Science & Technology

    2008-10-16

    expected to impact the values of detector efficiencies determined from the counts within full-energy peaks. If the goal of the miniball system was to be...This occurs because F(t) is a very steep function . The shortest half-life is expected for decay that reaches the 6* level of the daughter, giving...10-16-2008 2. REPORT TYPE Final Technical Report 3. DATES COVERED (From - To) 9/15/2005 - 5-31-2006 4. TITLE AND SUBTITLE Foundations of Isomer

  1. Differentiation of hydroxyproline isomers and isobars in peptides by tandem mass spectrometry.

    PubMed

    Kassel, D B; Biemann, K

    1990-08-01

    The isomeric 3- and 4-hydroxyprolines are isobaric with the isomers leucine and isoleucine, and all four have, therefore, the same "residue mass" of 113. Secondary fragmentation processes were found that differentiate the hydroxyproline isomers from each other and from the leucines. Variants of synthetic bradykinin containing one or two hydroxyproline moieties were prepared by using manual Edman degradation and/or enzymatic methods. The tandem mass spectra of these peptides were recorded. The C-terminal wn fragment ions allow the differentiation of 4-hydroxyproline from the 3-isomer and isoleucine, while the N-terminal an ions containing 4-hydroxyproline undergo H2O elimination to differentiate this amino acid from the 3-isomer and leucine. Lys-C digestion of a mussel adhesive protein produced a set of decapeptides varying in the degree of hydroxylation of proline and tyrosine. Heterogeneity with respect to 3-hydroxyproline and 4-hydroxyproline at a certain position in these peptides was assessed by tandem mass spectrometry based on the wn ion series in the CID spectra of these Lys-C peptides. Some N-terminal ions further allow for the differentiation of these two isomeric species.

  2. Lactones 42. Stereoselective enzymatic/microbial synthesis of optically active isomers of whisky lactone.

    PubMed

    Boratyński, Filip; Smuga, Małgorzata; Wawrzeńczyk, Czesław

    2013-11-01

    Two different methods, enzyme-mediated reactions and biotrasformations with microorganisms, were applied to obtain optically pure cis- and trans-isomers of whisky lactone 4a and 4b. In the first method, eight alcohol dehydrogenases were investigated as biocatalysts to enantioselective oxidation of racemic erythro- and threo-3-methyloctane-1,4-diols (1a and 1b). Oxidation processes with three of them, alcohol dehydrogenases isolated from horse liver (HLADH) as well as recombinant from Escherichia coli and primary alcohol dehydrogenase (PADH I), were characterized by the highest degree of conversion with moderate enantioselectivity (ee=27-82%) of the reaction. In all enzymatic reactions enantiomerically enriched not naturally occurring isomers of trans-(-)-(4R,5S)-4b or cis-(+)-(4R,5R)-4a were formed preferentially. In the second strategy, based on microbial lactonization of γ-oxoacids, naturally occurring opposite isomers of whisky lactones were obtained. Trans-(+)-(4S,5R)-isomer (ee=99%) of whisky lactone 4b was stereoselectively formed as the only product of biotransformations of 3-methyl-4-oxooctanoic acid (5) catalyzed by Didimospheria igniaria KCH6651, Laetiporus sulphurens AM525, Chaetomium sp.1 KCH6670 and Saccharomyces cerevisiae AM464. Biotransformation of γ-oxoacid 5, in the culture of Beauveria bassiana AM278 and Pycnidiella resinae KCH50 afforded a mixtures of trans-(+)-(4S,5R)-4b with enantiomeric excess ee=99% and cis-(-)-(4S,5S)-4a with enantiomeric excesses ee=77% and ee=45% respectively.

  3. Unprecedented χ isomers of single-side triol-functionalized Anderson polyoxometalates and their proton-controlled isomer transformation.

    PubMed

    Zhang, Jiangwei; Liu, Zhenhua; Huang, Yichao; zhang, Jin; Hao, Jian; Wei, Yongge

    2015-06-04

    The μ2-O atom in Anderson polyoxometalates was regioselectively activated by the introduction of protons, which, upon functionalization with triol ligands, could afford a series of unique χ isomers of the organically-derived Anderson cluster {[RCC(CH2O)3]MMo6O18(OH)3}(3-). Herein proton-controlled isomer transformation between the δ and χ isomer was observed by using the fingerprint region in the IR spectra and (13)C NMR spectra.

  4. The truth about the lower plasma concentration of the (-)-isomer after racemic doxazosin administration in rats: Stereoselective inhibition of the (-)-isomer by the (+)-isomer at CYP3A.

    PubMed

    Kong, Dezhi; Li, Qing; Zhang, Panpan; Zhang, Wei; Zhen, Yaqin; Ren, Leiming

    2015-09-18

    Doxazosin (DOX), a long-lasting α1-adrenoceptor antagonist, is used clinically as a racemate that consists of two optical isomers. In humans and rats, following oral administration of racemic DOX [(±)-DOX], the plasma concentration of the (-)-isomer is lower than that of the (+)-isomer, but the mechanism for this interaction is not known. In this study, a chiral HPLC with fluorescence detection was used to measure the drug concentrations for analysis of the stereoselective metabolism of DOX in in vivo and in vitro experiments. We found that the plasma levels of the (-)-isomer were significantly lower than those of the (+)-enantiomer following i.v. administration of (±)-DOX to the rats and that the depletion rate constant (kdep) of (-)-DOX (0.0107±0.0007L/min) was significantly larger than that of (+)-DOX (kdep 0.0088±0.0005L/min) (p<0.05) when (±)-DOX was incubated with rat liver microsomes (RLMs). However, (-)-DOX was not depleted faster than (+)-DOX following their separate incubation with RLMs. The metabolism of (-)- or (+)-isomer in RLMs was catalysed by CYP3A because the depletion of the compounds was inhibited by ketoconazole (a potent CYP3A-selective inhibitor) similarly. More importantly, the kdep of (+)-DOX in the 1.0/2.0 and 0.5/2.5 (+)-DOX/(-)-DOX mixtures was significantly lower than that of (-)-DOX in the 1.0/2.0 and 0.5/2.5 (-)-DOX/(+)-DOX mixtures (p<0.05). In conclusion, although (-)-DOX is not depleted faster than (+)-DOX when only a single isomer of DOX is incubated with rat liver microsomes, it is depleted much faster than (+)-DOX when a mixture of the two isomers was used, suggesting a prominent and stereoselective inhibition of the (-)-isomer over the (+)-isomer at the CYP3A enzyme.

  5. High excretion of beta-aminoisobutyric acid in patients with ketoacidosis.

    PubMed

    Landaas, S; Solem, E

    1983-02-01

    High concentrations of beta-aminoisobutyric acid (BAIBA) were found to be present in the urine from patients with ketoacidosis. The R-form was always the dominating isomer of BAIBA. The finding is discussed, and it is suggested that the mechanism might be a derangement in the degradation of valine.

  6. Fundamental issues related to the origin of melatonin and melatonin isomers during evolution: relation to their biological functions.

    PubMed

    Tan, Dun-Xian; Zheng, Xiaodong; Kong, Jin; Manchester, Lucien C; Hardeland, Ruediger; Kim, Seok Joong; Xu, Xiaoying; Reiter, Russel J

    2014-09-09

    Melatonin and melatonin isomers exist and/or coexist in living organisms including yeasts, bacteria and plants. The levels of melatonin isomers are significantly higher than that of melatonin in some plants and in several fermented products such as in wine and bread. Currently, there are no reports documenting the presence of melatonin isomers in vertebrates. From an evolutionary point of view, it is unlikely that melatonin isomers do not exist in vertebrates. On the other hand, large quantities of the microbial flora exist in the gut of the vertebrates. These microorganisms frequently exchange materials with the host. Melatonin isomers, which are produced by these organisms inevitably enter the host's system. The origins of melatonin and its isomers can be traced back to photosynthetic bacteria and other primitive unicellular organisms. Since some of these bacteria are believed to be the precursors of mitochondria and chloroplasts these cellular organelles may be the primary sites of melatonin production in animals or in plants, respectively. Phylogenic analysis based on its rate-limiting synthetic enzyme, serotonin N-acetyltransferase (SNAT), indicates its multiple origins during evolution. Therefore, it is likely that melatonin and its isomer are also present in the domain of archaea, which perhaps require these molecules to protect them against hostile environments including extremely high or low temperature. Evidence indicates that the initial and primary function of melatonin and its isomers was to serve as the first-line of defence against oxidative stress and all other functions were acquired during evolution either by the process of adoption or by the extension of its antioxidative capacity.

  7. Fundamental Issues Related to the Origin of Melatonin and Melatonin Isomers during Evolution: Relation to Their Biological Functions

    PubMed Central

    Tan, Dun-Xian; Zheng, Xiaodong; Kong, Jin; Manchester, Lucien C.; Hardeland, Ruediger; Kim, Seok Joong; Xu, Xiaoying; Reiter, Russel J.

    2014-01-01

    Melatonin and melatonin isomers exist and/or coexist in living organisms including yeasts, bacteria and plants. The levels of melatonin isomers are significantly higher than that of melatonin in some plants and in several fermented products such as in wine and bread. Currently, there are no reports documenting the presence of melatonin isomers in vertebrates. From an evolutionary point of view, it is unlikely that melatonin isomers do not exist in vertebrates. On the other hand, large quantities of the microbial flora exist in the gut of the vertebrates. These microorganisms frequently exchange materials with the host. Melatonin isomers, which are produced by these organisms inevitably enter the host’s system. The origins of melatonin and its isomers can be traced back to photosynthetic bacteria and other primitive unicellular organisms. Since some of these bacteria are believed to be the precursors of mitochondria and chloroplasts these cellular organelles may be the primary sites of melatonin production in animals or in plants, respectively. Phylogenic analysis based on its rate-limiting synthetic enzyme, serotonin N-acetyltransferase (SNAT), indicates its multiple origins during evolution. Therefore, it is likely that melatonin and its isomer are also present in the domain of archaea, which perhaps require these molecules to protect them against hostile environments including extremely high or low temperature. Evidence indicates that the initial and primary function of melatonin and its isomers was to serve as the first-line of defence against oxidative stress and all other functions were acquired during evolution either by the process of adoption or by the extension of its antioxidative capacity. PMID:25207599

  8. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  9. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  10. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  11. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  12. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  13. pH dependence of Anabaena sensory rhodopsin: retinal isomer composition, rate of dark adaptation, and photochemistry.

    PubMed

    Rozin, Rinat; Wand, Amir; Jung, Kwang-Hwan; Ruhman, Sanford; Sheves, Mordechai

    2014-07-31

    Microbial rhodopsins are photoactive proteins, and their binding site can accommodate either all-trans or 13-cis retinal chromophore. The pH dependence of isomeric composition, dark-adaptation rate, and primary events of Anabaena sensory rhodopsin (ASR), a microbial rhodopsin discovered a decade ago, are presented. The main findings are: (a) Two pKa values of 6.5 and 4.0 assigned to two different protein residues are observed using spectroscopic titration experiments for both ground-state retinal isomers: all-trans, 15-anti (AT) and 13-cis, 15-syn (13C). The protonation states of these protein residues affect the absorption spectrum of the pigment and most probably the isomerization process of the retinal chromophore. An additional pKa value of 8.5 is observed only for 13C-ASR. (b) The isomeric composition of ASR is determined over a wide pH range and found to be almost pH-independent in the dark (>96% AT isomer) but highly pH-dependent in the light-adapted form. (c) The kinetics of dark adaptation is recorded over a wide pH range, showing that the thermal isomerization from 13C to AT retinal occurs much faster at high pH rather than under acidic conditions. (d) Primary photochemical events of ASR at pH 5 are recorded using VIS hyperspectral pump-probe spectroscopy with <100 fs resolution and compared with the previously recorded results at pH 7.5. For AT-ASR, these are shown to be almost pH-independent. However, photochemistry of 13C-ASR is pH-dependent and slowed down in acidic environments.

  14. Isomer Spectroscopy of the Heaviest Elements

    NASA Astrophysics Data System (ADS)

    Clark, Roderick

    2009-05-01

    A new generation of experiments on the structure and properties of the heaviest elements is being performed in laboratories around the world. These studies are addressing fundamental questions such as the maximum mass and charge that a nucleus can attain. Long-lived high-K isomers are found in the region of prolate-deformed trans-fermium nuclei and by studying their decay one can learn about the single-particle structure, pairing correlations, and excitation modes of the heaviest nuclei. Recent decay spectroscopy experiments using the Berkeley Gas-Filled Separator (BGS) at the 88-Inch Cyclotron of the Lawrence Berkeley National Laboratory have yielded a wealth of detailed new information on many nuclei in the trans-fermium region. I will discuss these new results and their implications.

  15. Nuclear structure and depletion of nuclear isomers using electron linacs

    SciTech Connect

    Carroll, J. J.; Litz, M. S.; Henriquez, S. L.; Burns, D. A.; Netherton, K. A.; Pereira, N. R.; Karamian, S. A.

    2013-04-19

    Long-lived nuclear excited states (isomers) have proven important to understanding nuclear structure. With some isomers having half-lives of decades or longer, and intrinsic energy densities reaching 10{sup 12} J/kg, they have also been suggested for a wide range of applications. The ability to effectively transfer a population of nuclei from an isomer to shorter-lived levels will determine the feasibility of any applications. Here is described a first demonstration of the induced depletion of a population of the 438 year isomer of {sup 108}Ag to its 2.38 min ground state, using 6 MeV bremsstrahlung from a modified medical electron linac. The experiment suggests refinements to be implemented in the future and how a similar approach might be applied to study induced depletion of the 1200 year isomer of {sup 166}Ho.

  16. Inoculation of Pichia kudriavzevii RB1 degrades the organic acids present in raw compost material and accelerates composting.

    PubMed

    Nakasaki, Kiyohiko; Araya, Shogo; Mimoto, Hiroshi

    2013-09-01

    In this study, the yeast strain Pichia kudriavzevii RB1 was used as an inoculum to accelerate organic matter degradation of rabbit food with added organic acids, which was used as a model food waste for composting. The RB1 strain rapidly degraded the organic acids present in the raw compost material, leading to an increase in pH beyond the neutral level, within 2 days. Both mesophilic and thermophilic bacteria proliferated faster in the compost with RB1 inoculation than in that without inoculation. Although the yeast died with the increase in compost temperature, it affected the early stages of composting prior to the thermophilic stage and accelerated the composting process by 2 days by eliminating the initial lag phase seen in the growth of other microorganisms. Moreover, populations of Bacillus thermoamylovorans, Bacillus foraminis, and Bacillus coagulans became dominant during the thermophilic stages of both composting with and without RB1 inoculation.

  17. Failures of fractional crystallization: ordered co-crystals of isomers and near isomers.

    PubMed

    Kelley, Steven P; Fábián, László; Brock, Carolyn Pratt

    2011-02-01

    A list of 270 structures of ordered co-crystals of isomers, near isomers and molecules that are almost the same has been compiled. Searches for structures containing isomers could be automated by the use of IUPAC International Chemical Identifier (InChI™) strings but searches for co-crystals of very similar molecules were more labor intensive. Compounds in which the heteromolecular A···B interactions are clearly better than the average of the homomolecular A···A and B···B interactions were excluded. The two largest structural classes found include co-crystals of configurational diastereomers and of quasienantiomers (or quasiracemates). These two groups overlap. There are 114 co-crystals of diastereomers and the same number of quasiracemates, with 71 structures being counted in both groups; together the groups account for 157 structures or 58% of the total. The large number of quasiracemates is strong evidence for inversion symmetry being very favorable for crystal packing. Co-crystallization of two diastereomers is especially likely if a 1,1 switch of a methyl group and an H atom, or of an inversion of a [2.2.1] or [2.2.2] cage, in one of the diastereomers would make the two molecules enantiomers.

  18. Tailorable PC71 BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High-Performance Polymer Solar Cells.

    PubMed

    Zhan, Xin-Xing; Zhang, Xin; Dai, Si-Min; Li, Shu-Hui; Lu, Xu-Zhai; Deng, Lin-Long; Xie, Su-Yuan; Huang, Rong-Bin; Zheng, Lan-Sun

    2016-12-23

    Despite being widely used as electron acceptor in polymer solar cells, commercially available PC71 BM (phenyl-C71 -butyric acid methyl ester) usually has a "random" composition of mixed regioisomers or stereoisomers. Here PC71 BM has been isolated into three typical isomers, α-, β1 - and β2 -PC71 BM, to establish the isomer-dependent photovoltaic performance on changing the ternary composition of α-, β1 - and β2 -PC71 BM. Mixing the isomers in a ratio of α/β1 /β2 =8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC71 BM as photoactive layer (PTB7=poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl

  19. Experimental and computational investigation of the thermochemistry of the six isomers of dichloroaniline.

    PubMed

    Ribeiro da Silva, Manuel A V; Amaral, Luísa M P F; Gomes, José R B

    2006-07-27

    The standard (p(o) = 0.1 MPa) molar enthalpies of formation of 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dichloroanilines were derived from the standard molar energies of combustion, in oxygen, to yield CO(2)(g), N(2)(g) and HCl.600H(2)O(l), at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of sublimation of the six isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the six isomers of dichloroaniline, in the gaseous phase, at T = 298.15 K. The gas-phase enthalpies of formation were also estimated by G3MP2B3 calculations, which were further extended to the computation of gas-phase acidities, proton affinities, and ionization enthalpies.

  20. Toward the laboratory identification of [O,N,S,S] isomers: Implications for biological NO chemistry

    NASA Astrophysics Data System (ADS)

    Ayari, Tarek; Jaidane, Nejm-Eddine; Al Mogren, Muneerah Mogren; Francisco, Joseph S.; Hochlaf, Majdi

    2016-06-01

    Benchmark ab initio calculations are performed to investigate the stable isomers of [O,N,S,S]. These computations are carried out using coupled cluster (RCCSD(T)) and explicitly correlated coupled cluster methods (RCCSD(T)-F12). In addition to the already known cis isomer of SSNO, nine other stable forms are predicted. The most stable isomer is cis-OSNS. Nine structures are chain bent-bent with relatively large dipole moments which make them detectable, as cis-SSNO, by infrared, far-infrared, and microwave spectroscopies. We found also a C2v isomer (NS2O). Since these species are strongly suggested to play an important role as intermediates during the bioactive reaction products of the NO/H2S interaction, the rotational and vibrational spectroscopic parameters are presented to help aid the in vivo identification and assignment of these spectra. Results from this work show that [O,N,S,S] may play key roles during nitric oxide transport and deliver in biological media, as well as, provide an explanation for the weak characteristic of disulfide bridges within proteins.

  1. Infrared spectroscopy of the acetyl cation and its protonated ketene isomer

    SciTech Connect

    Mosley, J. D.; Young, J. W.; Duncan, M. A.

    2014-07-14

    [C{sub 2},H{sub 3},O]{sup +} ions are generated with a pulsed discharge in a supersonic expansion containing methyl acetate or acetone. These ions are mass selected and their infrared spectra are recorded via laser photodissociation and the method of argon tagging. Computational chemistry is employed to investigate structural isomers and their spectra. The acetyl cation (CH{sub 3}CO{sup +}) is the global minimum and protonated ketene (CH{sub 2}COH{sup +}) is the next lowest energy isomer (+176.2 kJ/mol). When methyl acetate is employed as the precursor, the infrared spectrum reveals that only the acetyl cation is formed. Partially resolved rotational structure reveals rotation about the C{sub 3} axis. When acetone is used as the precursor, acetyl is still the most abundant cation, but there is also a minor component of protonated ketene. Computations reveal a significant barrier to interconversion between the two isomers (+221 kJ/mol), indicating that protonated ketene must be obtained via kinetic trapping. Both isomers may be present in interstellar environments, and their implications for astrochemistry are discussed.

  2. Ultrafast time-resolved absorption spectroscopy of geometric isomers of xanthophylls

    NASA Astrophysics Data System (ADS)

    Niedzwiedzki, Dariusz M.; Enriquez, Miriam M.; LaFountain, Amy M.; Frank, Harry A.

    2010-07-01

    This paper presents an ultrafast optical spectroscopic investigation of the excited state energies, lifetimes and spectra of specific geometric isomers of neoxanthin, violaxanthin, lutein, and zeaxanthin. All- trans- and 15,15'- cis-β-carotene were also examined. The spectroscopy was done on molecules purified by HPLC frozen immediately to inhibit isomerization. The spectra were taken at 77 K to maintain the configurations and to provide better spectral resolution than seen at room temperature. The kinetics reveal that for all of the molecules except neoxanthin, the S 1 state lifetime of the cis isomers is shorter than that of the all- trans isomers. The S 1 excited state energies of all the isomers were determined by recording S 1 → S 2 transient absorption spectra. The results obtained in this manner at cryogenic temperatures provide an unprecedented level of precision in the measurement of the S 1 energies of these xanthophylls, which are critical components in light-harvesting pigment-protein complexes of green plants.

  3. All-trans-retinoic acid metabolites significantly inhibit the proliferation of MCF-7 human breast cancer cells in vitro.

    PubMed Central

    Van heusden, J.; Wouters, W.; Ramaekers, F. C.; Krekels, M. D.; Dillen, L.; Borgers, M.; Smets, G.

    1998-01-01

    All-trans-retinoic acid (ATRA) is well known to inhibit the proliferation of human breast cancer cells. Much less is known about the antiproliferative activity of the naturally occurring metabolites and isomers of ATRA. In the present study, we investigated the antiproliferative activity of ATRA, its physiological catabolites 4-oxo-ATRA and 5,6-epoxy-ATRA and isomers 9-cis-RA and 13-cis-RA in MCF-7 human breast cancer cells by bromodeoxyuridine incorporation. MCF-7 cells were grown in steroid- and retinoid-free medium supplemented with growth factors. Under these culture conditions, ATRA and its naturally occurring catabolites and isomers showed significant antiproliferative activity in MCF-7 cells in a concentration-dependent manner (10[-11] M to 10[-6] M). The antiproliferative activity of ATRA catabolites and isomers was equal to that of the parent compound ATRA at concentrations of 10(-8) M and 10(-7) M. Only at 10(-6) M were the catabolites and the stereoisomer 13-cis-RA less potent. The stereoisomer 9-cis-RA was as potent as ATRA at all concentrations tested (10[-11] M to 10[-6] M). In addition, we show that the catabolites and isomers were formed from ATRA to only a limited extent. Together, our findings suggest that in spite of their high antiproliferative activity the catabolites and isomers of ATRA cannot be responsible for the observed growth inhibition induced by ATRA. PMID:9459142

  4. Vitamin E and cancer: An insight into the anticancer activities of vitamin E isomers and analogs.

    PubMed

    Constantinou, Constantina; Papas, Andreas; Constantinou, Andreas I

    2008-08-15

    Current observations in the literature suggest that vitamin E may be a suitable candidate for the adjuvant treatment of cancer. Even though historically most research focused on alpha-tocopherol, more recent evidence suggests that the other isomers of vitamin E (beta-, gamma- and delta-tocopherols and alpha-, beta-, gamma- and delta-tocotrienols) differ in their proapoptotic potencies. The main focus of this communication is the current understanding of the molecular mechanisms regulated by vitamin E isomers and their analogs during the induction of apoptosis. This review highlights that the mitochondria are the major target for the induction of apoptosis by vitamin E isomers and analogs and that the various signaling pathways regulated by these agents are likely to contribute towards maximizing the intrinsic pathway of apoptosis triggered initially by the mitochondria. Overall, the presentation of recent studies from the literature in this communication allows the drawing of the following important conclusions: (i) no direct link exists between the antioxidant activity of each isomer/derivative and proapoptotic potency, (ii) tocotrienols are more effective proapoptotic agents than tocopherols, (iii) synthetic modifications of the naturally occurring compounds may improve their apoptotic potency and (iv) vitamin E isomers and derivatives regulate caspase-independent pathways of apoptosis. The latter combined with the evidence presented in this review regarding the additive or synergistic anticarcinogenic effects obtained when vitamin E analogs are used in combination with other cancer chemotherapeutic agents, supports further research to design the most promising vitamin E derivatives and clinically test them in adjuvant chemotherapeutic treatments.

  5. Proposed modifications to AOAC 996.06, optimizing the determination of trans fatty acids: presentation of data.

    PubMed

    Rozema, Brent; Mitchell, Barbara; Winters, Doug; Kohn, Andrew; Sullivan, Darryl; Meinholz, Erin

    2008-01-01

    The increased focus on the accuracy of trans fatty acid data generated using current methodologies has resulted in research initiatives to optimize the quality of these assays. In this study, scientists combined the established methodology from AOAC 996.06 and the American Oil Chemists Society method Ce 1h-05, as well as other independent research. As a result, method modifications are proposed that could allow for a more accurate determination of trans fat than the current AOAC 996.06 method. Validation data from this study are presented. The authors encourage peer review and offer to facilitate a collaborative validation to update AOAC 996.06.

  6. Identification/quantification of free and bound phenolic acids in peel and pulp of apples (Malus domestica) using high resolution mass spectrometry (HRMS).

    PubMed

    Lee, Jihyun; Chan, Bronte Lee Shan; Mitchell, Alyson E

    2017-01-15

    Free and bound phenolic acids were measured in the pulp and peel of four varieties of apples using high resolution mass spectrometry. Twenty-five phenolic acids were identified and included: 8 hydroxybenzoic acids, 11 hydroxycinnamic acids, 5 hydroxyphenylacetic acids, and 1 hydoxyphenylpropanoic acid. Several phenolics are tentatively identified for the first time in apples and include: methyl gallate, ethyl gallate, hydroxy phenyl acetic acid, three phenylacetic acid isomers, 3-(4-hydroxyphenyl)propionic acid, and homoveratric acid. With exception of chlorogenic and caffeic acid, most phenolic acids were quantified for the first time in apples. Significant varietal differences (p<0.05) were observed in both peel and pulp. The levels of total phenolic acids were higher in the pulp as compared to apple peel (dry weight) in all varieties. Coumaroylquinic, protocatechuic, 4-hydroxybenzoic, vanillic and t-ferulic acids were present in free forms. With exception of chlorogenic acid, all other phenolic acids were present only as bound forms.

  7. Isomers and Enhanced Stability of Superheavy Elements

    NASA Astrophysics Data System (ADS)

    Kondev, Filip; Anl, Lbnl, Anu, Csnsm, Llnl, Usna, U. Of Edinburgh, U. Of Jyväskylä, U. Of Massachusetts, Lowell Collaboration

    2014-09-01

    There has been continuing activity addressing the complex question of whether excited isomeric states would lead to enhanced stability of superheavy nuclei, given changes in the fission barriers, α-decay probabilities and the effects of nuclear structure (such as K-hindrance). Recently, we have carried out new studies of the 254Rf isotope using the 50Ti + 206Pb reaction at Argonne National Laboratory and Lawrence Berkeley National Laboratory. A digital data acquisition system was deployed in both experiments, which allowed the identification of implant and decay events that were separated by time as short as hundreds of nanoseconds. Two isomeric states were discovered in 254Rf with half-lives of ~4 μs and ~300 μs, the latter being an order of magnitude longer lived than the ground state. In addition, K-isomers in 244Cm and 246Cm were also studied following β- decays of 244Am (Kπ = 6+) and 246Am (Kπ = 7-) mass-separated sources, respectively. The emphasis was on elucidating details of the level schemes, which allowed reliable values for the strength of the K-forbidden transitions to be determined and compared with systematics in other regions of the nuclear chart. There has been continuing activity addressing the complex question of whether excited isomeric states would lead to enhanced stability of superheavy nuclei, given changes in the fission barriers, α-decay probabilities and the effects of nuclear structure (such as K-hindrance). Recently, we have carried out new studies of the 254Rf isotope using the 50Ti + 206Pb reaction at Argonne National Laboratory and Lawrence Berkeley National Laboratory. A digital data acquisition system was deployed in both experiments, which allowed the identification of implant and decay events that were separated by time as short as hundreds of nanoseconds. Two isomeric states were discovered in 254Rf with half-lives of ~4 μs and ~300 μs, the latter being an order of magnitude longer lived than the ground state. In

  8. Detection of Actinides via Nuclear Isomer De-Excitation

    SciTech Connect

    Francy, Christopher J.

    2009-07-01

    This dissertation discusses a data collection experiment within the Actinide Isomer Identification project (AID). The AID project is the investigation of an active interrogation technique that utilizes nuclear isomer production, with the goal of assisting in the interdiction of illicit nuclear materials. In an attempt to find and characterize isomers belonging to 235U and its fission fragments, a 232Th target was bombarded with a monoenergetic 6Li ion beam, operating at 45 MeV.

  9. Profiles of fatty acids and 7-O-acyl okadaic acid esters in bivalves: can bacteria be involved in acyl esterification of okadaic acid?

    PubMed

    Vale, Paulo

    2010-01-01

    The presence of 7-O-acyl okadaic acid (OA) esters was studied by LC-MS in the digestive glands of blue mussel (Mytilus galloprovincialis) and common cockle (Cerastoderma edule) from Albufeira lagoon, located 20km south of Lisbon. The profile of free and total fatty acids (FA) was analysed using a similar LC separation with a reversed phase C8 column and mass spectrometry detection. In mussel the free FA profile was reflected in the FA esterified to OA, being palmitic acid for instance the most abundant in both cases. In cockle, 7-O-acyl esters with palmitic acid were almost absent and esters with a C16:0 isomer were dominant, followed by esters with C15:1 and C15:0. The cockle free FA profile was similar to mussel, and in accordance with literature findings in bivalves. After hydrolysis, a major difference in the FA profile occurred in both species, presenting a high percentage of a C16:0 isomer. The isomer found in general lipids and bound to OA seemed to be related, presenting similar relative retention times (RRT) to C16:0, differing from expected RRT of monomethyl-branched isomers (iso- or anteiso-). A tentative identification was made with the multimethyl-branched isoprenoid, 4,8,12-trimethyltridecanoic acid (TMTD). TMTD is a product of phytol degradation. This was also suspected when the proportion of this compound in relation to palmitic acid was reduced in vivo in mussels fed a chlorophyll-free diet. Extensive esterification of OA by, among others, phytol-degrading bacteria is discussed as a plausible hypothesis in cockle, but not in mussel, due to the relatively high specific proportion of odd-numbered and branched FA.

  10. Quantification of the ratio of positional isomer dilinoleoyl-oleoyl glycerols in vegetable oils.

    PubMed

    Jakab, A; Jablonkai, I; Forgács, E

    2003-01-01

    The distribution of fatty acids in a triacylglycerol is of great importance from nutritional, biochemical, quality and technological points of view. The ratio of triacylglycerol positional isomers containing two linoleic acid (18:2) and one oleic acid (18:1) moieties--namely, 1(3),2-dilinoleoyl-3(1)-oleoyl glycerol (LLO) and 1,3-dilinoleoyl-2-oleoyl glycerol (LOL)--were quantified in grape seed, olive, pumpkin seed, soybean, sunflower and wheat germ oils by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (HPLC/APCI-MS) in selected ion monitoring (SIM) mode. Relative LOL contents (LOL/(LLO+LOL)) of the oils were calculated from the mass abundances of the [LL]+ and [LO]+ diacylglycerol fragment ions ([M+H-RCOOH]+) using a calibration curve. The calibration curve of the relative diacylglycerol mass abundances was measured in SIM mode. The relative LOL contents were found to be relatively consistent for each oil variety. The relative LOL content in grape seed, sunflower, pumpkin seed, soybean and wheat germ oils accounted for 44.2 +/- 2.6, 26.8 +/- 3.2, 16.7 +/- 4.6, 15.9 +/- 2.9 and 13.9 +/- 4.3%, respectively. Only olive oils contained practically 100% of the LLO isomer. These results indicate that the unsaturated fatty acids such as linoleic and oleic acids have 'non-random' distribution patterns in various oils.

  11. Probing ground and low-lying excited states for HIO2 isomers

    NASA Astrophysics Data System (ADS)

    de Souza, Gabriel L. C.; Brown, Alex

    2014-12-01

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10-3).

  12. Probing ground and low-lying excited states for HIO2 isomers.

    PubMed

    de Souza, Gabriel L C; Brown, Alex

    2014-12-21

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10(-3)).

  13. CYANOMETHANIMINE ISOMERS IN COLD INTERSTELLAR CLOUDS: INSIGHTS FROM ELECTRONIC STRUCTURE AND KINETIC CALCULATIONS

    SciTech Connect

    Vazart, Fanny; Latouche, Camille; Skouteris, Dimitrios; Barone, Vincenzo; Balucani, Nadia

    2015-09-10

    New insights into the formation of interstellar cyanomethanimine, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction CN + CH{sub 2} = NH. This reaction is a facile formation route of Z,E-C-cyanomethanimine, even under the extreme conditions of density and temperature typical of cold interstellar clouds. E-C-cyanomethanimine has been recently identified in Sgr B2(N) in the Green Bank Telescope (GBT) PRIMOS survey by P. Zaleski et al. and no efficient formation routes have been envisaged so far. The rate coefficient expression for the reaction channel leading to the observed isomer E-C-cyanomethanimine is 3.15 × 10-10 × (T/300){sup 0.152} × e{sup (−0.0948/T)}. According to the present study, the more stable Z-C-cyanomethanimine isomer is formed with a slightly larger yield (4.59 × 10{sup −10} × (T/300){sup 0.153} × e{sup (−0.0871/T)}. As the detection of E-isomer is favored due to its larger dipole moment, the missing detection of the Z-isomer can be due to the sensitivity limit of the GBT PRIMOS survey and the detection of the Z-isomer should be attempted with more sensitive instrumentation. The CN + CH{sub 2} = NH reaction can also play a role in the chemistry of the upper atmosphere of Titan where the cyanomethanimine products can contribute to the buildup of the observed nitrogen-rich organic aerosols that cover the moon.

  14. Probing ground and low-lying excited states for HIO{sub 2} isomers

    SciTech Connect

    Souza, Gabriel L. C. de; Brown, Alex

    2014-12-21

    We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})

  15. Synthesis and cytotoxic activity of new betulin and betulinic acid esters with conjugated linoleic acid (CLA).

    PubMed

    Tubek, Barbara; Mituła, Paweł; Niezgoda, Natalia; Kempińska, Katarzyna; Wietrzyk, Joanna; Wawrzeńczyk, Czesław

    2013-04-01

    The synthesis of new ester derivatives of betulin (3a-c) and betulinic acid (4) with conjugated linoleic acid isomers (CLA; in a mixture of 43.4% 9c, 11t; 49.5% 10t, 12c; 7.1% other isomers) is presented. Esterification was carried out with N,N'-dicyclohexylcarbodiimide (DCC) as the coupling agent in the presence of 4-dimethylamino-pyridine (DMAP) in dichloromethane (or pyridine). The in vitro cytotoxic effect of betulin (1), betulinic acid (2), a mixture of CLA isomers and their derivatives (3a-c, 4) was examined using the MTT assay against four cancer cell lines (P388, CEM/C2, CCRF/CEM and HL-60) and the SRB assay on the HT-29 cell line. Ester 4 was the most active among the esters synthesized against the CEM/C2 cell line with an ID50 value 16.9 +/- 6.5 microg/mL. Betulin (1), betulinic acid (2) and CLA were the most active agents against the cancer cell lines studied.

  16. Differential adsorption of complex organic molecules isomers at interstellar ice surfaces

    NASA Astrophysics Data System (ADS)

    Lattelais, M.; Bertin, M.; Mokrane, H.; Romanzin, C.; Michaut, X.; Jeseck, P.; Fillion, J.-H.; Chaabouni, H.; Congiu, E.; Dulieu, F.; Baouche, S.; Lemaire, J.-L.; Pauzat, , F.; Pilmé, J.; Minot, C.; Ellinger, Y.

    2011-08-01

    Context. Over 20 of the ~150 different species detected in the interstellar and circumstellar media have also been identified in icy environments. For most of the species observed so far in the interstellar medium (ISM), the most abundant isomer of a given generic chemical formula is the most stable one (minimum energy principle - MEP) with few exceptions such as, for example, CH3COOH/HCOOCH3 and CH3CH2OH/CH3OCH3, whose formation is thought to occur on the icy mantles of interstellar grains. Aims: We investigate whether differences found in the compositions of molecular ices and the surrounding gas phase could originate from differences between the adsorption of one isomer from that of another at the ice surface. Methods: We performed a coherent and concerted theoretical/experimental study of the adsorption energies of the four molecules mentioned above, i.e. acetic acid (AA)/methyl formate (MF) and ethanol (EtOH)/dimethyl ether (DME) on the surface of water ice at low temperature. The question was first addressed theoretically at LCT using solid state periodic density functional theory (DFT) to represent the organized solid support. The experimental determination of the ice/molecule interaction energies was then carried out independently by two teams at LPMAA and LERMA/LAMAp using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K. Results: For each pair of isomers, theory and experiments both agree that the most stable isomer (AA or EtOH) interacts more efficiently with the water ice than the higher energy isomer (MF or DME). This differential adsorption can be clearly seen in the different desorption temperatures of the isomers. It is not related to their intrinsic stability but instead to both AA and EtOH producing more and stronger hydrogen bonds with the ice surface. Conclusions: We show that hydrogen bonding may play an important role in the release of organic species from grains and propose that, depending on the

  17. Isomer spectroscopy of {sup 127}Cd

    SciTech Connect

    Naqvi, F.; Gorska, M.; Grawe, H.; Beck, T.; Doornenbal, P.; Geissel, H.; Gerl, J.; Kojouharov, I.; Kurz, N.; Montes, F.; Prokopowicz, W.; Schaffner, H.; Tashenov, S.; Wollersheim, H. J.; Caceres, L.; Jungclaus, A.; Pfuetzner, M.; Werner-Malento, E.; Nowacki, F.; Sieja, K.

    2010-09-15

    The spin and configurational structure of excited states of {sup 127}Cd, the two-proton and three-neutron hole neighbor of {sup 132}Sn, has been studied. An isomeric state with a half-life of 17.5(3) {mu}s was populated in the fragmentation of a {sup 136}Xe beam on a {sup 9}Be target at a beam energy of 750 MeV/u. Time distributions of the delayed {gamma} transitions and {gamma}{gamma} coincidence relations were exploited to construct a decay scheme. The observed yrast (19/2){sup +} isomer is proposed to have dominant configurations of {nu}(h{sub 11/2}{sup -3}){pi}(g{sub 9/2}{sup -1},p{sub 1/2}{sup -1}), {nu}(h{sub 11/2}{sup -2}d{sub 3/2}{sup -1}){pi}(g{sub 9/2}{sup -2}), and {nu}(h{sub 11/2}{sup -2},s{sub 1/2}{sup -1}){pi}(g{sub 9/2}{sup -2}) and to decay by two competing stretched M2 and E3 transitions. Experimental results are compared with the isotone {sup 129}Sn. The new information provides input for the proton-neutron interaction and the evolution of neutron hole energies in nuclei around the doubly magic {sup 132}Sn core.

  18. Molecular structure of uranium carbides: isomers of UC3.

    PubMed

    Zalazar, M Fernanda; Rayón, Víctor M; Largo, Antonio

    2013-03-21

    In this article, the most relevant isomers of uranium tricarbide are studied through quantum chemical methods. It is found that the most stable isomer has a fan geometry in which the uranium atom is bonded to a quasilinear C3 unit. Both, a rhombic and a ring CU(C2) structures are found about 104-125 kJ/mol higher in energy. Other possible isomers including linear geometries are located even higher. For each structure, we provide predictions for those molecular properties (vibrational frequencies, IR intensities, dipole moments) that could eventually help in their experimental detection. We also discuss the possible routes for the formation of the different UC3 isomers as well as the bonding situation by means of a topological analysis of the electron density.

  19. Tocopherol isomers in intravenous lipid emulsions and resultant plasma concentrations.

    PubMed

    Gutcher, G R; Lax, A A; Farrell, P M

    1984-01-01

    Conflicting reports exist regarding the relative tocopherol isomer content of Intralipid ranging from 99% as alpha-tocopherol to as much as 90% as gamma-tocopherol. Our direct assay of Intralipid as well as plasma levels measured in premature infants receiving Intralipid confirm the existence of a low alpha, high gamma-tocopherol content and imply the need for alpha-tocopherol supplementation in patients receiving Intralipid, particularly the relatively tocopherol-deficient premature infant. Furthermore, the observation of abnormal erythrocyte hemolysis test values despite "normal" total tocopherol plasma concentrations may be explained by high plasma levels of non-alpha, biologically less active isomers. The quantitation of tocopherol isomers helps explain this discrepancy and suggests the need for future studies of vitamin E status to employ measurements of tocopherol isomers in reporting results.

  20. Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

    NASA Technical Reports Server (NTRS)

    Loo, B. H.; Lee, Y. G.; Frazier, D. O.

    1986-01-01

    Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

  1. Partition function and astronomical observation of interstellar isomers: Is there a link?

    NASA Astrophysics Data System (ADS)

    Etim, Emmanuel E.; Arunan, Elangannan

    2017-02-01

    The unsuccessful astronomical searches for some important astrophysical and astrobiological molecules have been linked to the large partition function of these molecules. This letter reports an extensive investigation of the relationship between partition function and astronomical observation of interstellar isomers using high level quantum chemical calculations. 120 molecules from 30 different isomeric groups have been considered. Partition function and thermodynamic stabilities are determined for each set of isomeric species. From the results, there is no direct correlation between partition function and astronomical observation of the same isomeric species. Though interstellar formations processes are generally controlled by factors like kinetics, thermodynamics, formation and destruction pathways. However, the observation of the isomers seems to correlate well with thermodynamics. For instance, in all the groups considered, the astronomically detected isomers are the thermodynamically most stable molecules in their respective isomeric groups. The implications of these results in accounting for the limited number of known cyclic interstellar molecules, unsuccessful searches for amino acid and the possible molecules for astronomical observations are discussed.

  2. Nonperipheral Tetrakis(dibutylamino)phthalocyanines. New Types of 1,8,15,22-Tetrakis(substituted)phthalocyanine Isomers.

    PubMed

    Chen, Yuxiang; Fang, Wenjuan; Wang, Kang; Liu, Wei; Jiang, Jianzhuang

    2016-09-19

    Cyclic tetramerization of 3-(dibutylamino)phthalonitrile in refluxing n-pentanol in the presence of magnesium pentanoate afforded the four regioisomer-containing nonperipheral 1,8-/11,15-/18,22-/25-tetrakis(dibutylamino)phthalocyaninato magnesium complexes with the 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomer Mg{Pc[α-N(C4H9)2]4-C4} (2). This, in combination with its much superior crystallinity over the remaining three isomers, renders the easy isolation of 2 only through two simple recrystallizations from THF and methanol. Treatment of 2 with trifluoroacetic acid induced the isolation of metal-free 1,8,15,22-tetrakis(dibutylamino)phthalocyanine, H2{Pc[α-N(C4H9)2]4-C4} (1), which further reacted with M(OAc)2·nH2O (M = Ni, Zn) in refluxing n-pentanol, giving the 1,8,15,22-tetrakis(dibutylamino)phthalocyaninato metal complexes M{Pc[α-N(C4H9)2]4-C4} (M = Ni (3), Zn (4)). The full series of four 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric compounds have been characterized by a series of spectroscopic methods and single-crystal X-ray diffraction analyses. Obviously, the present result provides a simple and effective pathway for the synthesis and isolation of novel 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric derivatives, providing one step forward toward completing bis(alkyl)amino-incorporated phthalocyanine species.

  3. Differential degradation of nonylphenol isomers by Sphingomonas xenophaga Bayram.

    PubMed

    Gabriel, Frédéric L P; Giger, Walter; Guenther, Klaus; Kohler, Hans-Peter E

    2005-03-01

    Sphingomonas xenophaga Bayram, isolated from the activated sludge of a municipal wastewater treatment plant, was able to utilize 4-(1-ethyl-1,4-dimethylpentyl)phenol, one of the main isomers of technical nonylphenol mixtures, as a sole carbon and energy source. The isolate degraded 1 mg of 4-(1-ethyl-1,4-dimethylpentyl)phenol/ml in minimal medium within 1 week. Growth experiments with five nonylphenol isomers showed that the three isomers with quaternary benzylic carbon atoms [(1,1,2,4-tetramethylpentyl)phenol, 4-(1-ethyl-1,4-dimethylpentyl)phenol, and 4-(1,1-dimethylheptyl)phenol] served as growth substrates, whereas the isomers containing one or two hydrogen atoms in the benzylic position [4-(1-methyloctyl)phenol and 4-n-nonylphenol] did not. However, when the isomers were incubated as a mixture, all were degraded to a certain degree. Differential degradation was clearly evident, as isomers with more highly branched alkyl side chains were degraded much faster than the others. Furthermore, the C9 alcohols 2,3,5-trimethylhexan-2-ol, 3,6-dimethylheptan-3-ol, and 2-methyloctan-2-ol, derived from the three nonylphenol isomers with quaternary benzylic carbon atoms, were detected in the culture fluid by gas chromatography-mass spectrometry, but no analogous metabolites could be found originating from 4-(1-methyloctyl)phenol and 4-n-nonylphenol. We propose that 4-(1-methyloctyl)phenol and 4-n-nonylphenol were cometabolically transformed in the growth experiments with the mixture but that, unlike the other isomers, they did not participate in the reactions leading to the detachment of the alkyl moiety. This hypothesis was corroborated by the observed accumulation in the culture fluid of an as yet unidentified metabolite derived from 4-(1-methyloctyl)phenol.

  4. Differential Degradation of Nonylphenol Isomers by Sphingomonas xenophaga Bayram

    PubMed Central

    Gabriel, Frédéric L. P.; Giger, Walter; Guenther, Klaus; Kohler, Hans-Peter E.

    2005-01-01

    Sphingomonas xenophaga Bayram, isolated from the activated sludge of a municipal wastewater treatment plant, was able to utilize 4-(1-ethyl-1,4-dimethylpentyl)phenol, one of the main isomers of technical nonylphenol mixtures, as a sole carbon and energy source. The isolate degraded 1 mg of 4-(1-ethyl-1,4-dimethylpentyl)phenol/ml in minimal medium within 1 week. Growth experiments with five nonylphenol isomers showed that the three isomers with quaternary benzylic carbon atoms [(1,1,2,4-tetramethylpentyl)phenol, 4-(1-ethyl-1,4-dimethylpentyl)phenol, and 4-(1,1-dimethylheptyl)phenol] served as growth substrates, whereas the isomers containing one or two hydrogen atoms in the benzylic position [4-(1-methyloctyl)phenol and 4-n-nonylphenol] did not. However, when the isomers were incubated as a mixture, all were degraded to a certain degree. Differential degradation was clearly evident, as isomers with more highly branched alkyl side chains were degraded much faster than the others. Furthermore, the C9 alcohols 2,3,5-trimethylhexan-2-ol, 3,6-dimethylheptan-3-ol, and 2-methyloctan-2-ol, derived from the three nonylphenol isomers with quaternary benzylic carbon atoms, were detected in the culture fluid by gas chromatography-mass spectrometry, but no analogous metabolites could be found originating from 4-(1-methyloctyl)phenol and 4-n-nonylphenol. We propose that 4-(1-methyloctyl)phenol and 4-n-nonylphenol were cometabolically transformed in the growth experiments with the mixture but that, unlike the other isomers, they did not participate in the reactions leading to the detachment of the alkyl moiety. This hypothesis was corroborated by the observed accumulation in the culture fluid of an as yet unidentified metabolite derived from 4-(1-methyloctyl)phenol. PMID:15746308

  5. Rapid survey of four Asp isomers in disease-related proteins by LC-MS combined with commercial enzymes.

    PubMed

    Maeda, Hiroki; Takata, Takumi; Fujii, Norihiko; Sakaue, Hiroaki; Nirasawa, Satoru; Takahashi, Saori; Sasaki, Hiroshi; Fujii, Noriko

    2015-01-06

    Until relatively recently, it was considered that D-amino acids were excluded from living systems except for the cell wall of microorganisms. However, D-aspartate residues have now been detected in long-lived proteins from various tissues of elderly humans. Formation of D-aspartate in proteins induces aggregation and loss of function, leading to age-related disorders such as cataracts and Alzheimer disease. A recent study used LC-MS to analyze isomers of Asp residues in proteins precisely without complex purification of the proteins. However, to identify the four Asp isomers (Lα, Lβ, Dβ, and Dα) on the chromatogram, it was necessary to synthesize reference peptides containing the four different Asp isomers as standards. Here, we describe a method for rapidly and comprehensively identifying Asp isomers in proteins using a combination of LC-MS and commercial enzymes without synthesizing reference peptides. The protein sample is treated with trypsin, trypsin plus Asp-N, trypsin plus PIMT, trypsin plus paenidase, and the resulting peptides are applied to LC-MS. Because Asp-N hydrolyzes peptide bonds on the N-terminus of only Lα-Asp residues, it differentiates peptides containing Lα-Asp from those containing the other three isomers. Similarly, PIMT recognizes only peptides containing Lβ-Asp residues, and paenidase internally cleaves the C-terminus of Dα-Asp residues. This approach was successfully applied to the analysis of all tryptic peptides in aged lens. The comprehensive quantitative data of Asp isomer formation in age-related proteins obtained via this method might be used as biomarkers of age-related disease.

  6. Characteristics of Hepatic Schwannoma Presenting as an Unusual Multi-cystic Mass on Gadoxetic Acid Disodium-enhanced MR Imaging.

    PubMed

    Haradome, Hiroki; Woo, Jun; Nakayama, Hisashi; Watanabe, Haruna N; Ogawa, Masahiro; Moriyama, Mitsuhiko; Sugitani, Masahiko; Takayama, Tadatoshi; Abe, Osamu

    2017-02-13

    Hepatic schwannoma is a very rare hepatic tumor, usually appearing as a hypervascular solid mass with or without various degrees of cystic changes; however, to the best of our knowledge, only the two cases of hepatic schwannoma showing a multi-cystic appearance have previously been reported. We report herein a benign hepatic schwannoma presenting as an unusually large multi-cystic mass. The gadoxetic acid disodium-enhanced magnetic resonance imaging features are described with the histopathologic correlation and briefly review the literature. The solid-like areas showing the early/progressive enhancement, reflecting remnants of the Antoni A/B portion, during the dynamic phases may be helpful imaging features for the differentiation of other multi-cystic hepatic lesions, but pathological evaluation remains essential for diagnosis.

  7. Anaerobic Degradation of Phthalate Isomers by Methanogenic Consortia

    PubMed Central

    Kleerebezem, Robbert; Pol, Look W. Hulshoff; Lettinga, Gatze

    1999-01-01

    Three methanogenic enrichment cultures, grown on ortho-phthalate, iso-phthalate, or terephthalate were obtained from digested sewage sludge or methanogenic granular sludge. Cultures grown on one of the phthalate isomers were not capable of degrading the other phthalate isomers. All three cultures had the ability to degrade benzoate. Maximum specific growth rates (μSmax) and biomass yields (YXtotS) of the mixed cultures were determined by using both the phthalate isomers and benzoate as substrates. Comparable values for these parameters were found for all three cultures. Values for μSmax and YXtotS were higher for growth on benzoate compared to the phthalate isomers. Based on measured and estimated values for the microbial yield of the methanogens in the mixed culture, specific yields for the phthalate and benzoate fermenting organisms were calculated. A kinetic model, involving three microbial species, was developed to predict intermediate acetate and hydrogen accumulation and the final production of methane. Values for the ratio of the concentrations of methanogenic organisms, versus the phthalate isomer and benzoate fermenting organisms, and apparent half-saturation constants (KS) for the methanogens were calculated. By using this combination of measured and estimated parameter values, a reasonable description of intermediate accumulation and methane formation was obtained, with the initial concentration of phthalate fermenting organisms being the only variable. The energetic efficiency for growth of the fermenting organisms on the phthalate isomers was calculated to be significantly smaller than for growth on benzoate. PMID:10049876

  8. Site-specific protein glycosylation analysis with glycan isomer differentiation.

    PubMed

    Hua, Serenus; Nwosu, Charles C; Strum, John S; Seipert, Richard R; An, Hyun Joo; Zivkovic, Angela M; German, J Bruce; Lebrilla, Carlito B

    2012-05-01

    Glycosylation is one of the most common yet diverse post-translational modifications. Information on glycan heterogeneity and glycosite occupancy is increasingly recognized as crucial to understanding glycoprotein structure and function. Yet, no approach currently exists with which to holistically consider both the proteomic and glycomic aspects of a system. Here, we developed a novel method of comprehensive glycosite profiling using nanoflow liquid chromatography/mass spectrometry (nano-LC/MS) that shows glycan isomer-specific differentiation on specific sites. Glycoproteins were digested by controlled non-specific proteolysis in order to produce informative glycopeptides. High-resolution, isomer-sensitive chromatographic separation of the glycopeptides was achieved using microfluidic chip-based capillaries packed with graphitized carbon. Integrated LC/MS/MS not only confirmed glycopeptide composition but also differentiated glycan and peptide isomers and yielded structural information on both the glycan and peptide moieties. Our analysis identified at least 13 distinct glycans (including isomers) corresponding to five compositions at the single N-glycosylation site on bovine ribonuclease B, 59 distinct glycans at five N-glycosylation sites on bovine lactoferrin, 13 distinct glycans at one N-glycosylation site on four subclasses of human immunoglobulin G, and 20 distinct glycans at five O-glycosylation sites on bovine κ-casein. Porous graphitized carbon provided effective separation of glycopeptide isomers. The integration of nano-LC with MS and MS/MS of non-specifically cleaved glycopeptides allows quantitative, isomer-sensitive, and site-specific glycoprotein analysis.

  9. Unraveling the origin of the relative stabilities of group 14 M2N2(2+) (M, N = C, Si, Ge, Sn, and Pb) isomer clusters.

    PubMed

    Díaz-Cervantes, Erik; Poater, Jordi; Robles, Juvencio; Swart, Marcel; Solà, Miquel

    2013-10-10

    We analyze the molecular structure, relative stability, and aromaticity of the lowest-lying isomers of group 14 M2N2(2+) (M and N = C, Si, and Ge) clusters. We use the gradient embedded genetic algorithm to make an exhaustive search for all possible isomers. Group 14 M2N2(2+) clusters are isoelectronic with the previously studied group 13 M2N2(2-) (M and N = B, Al, and Ga) clusters that includes Al4(2-), the archetypal all-metal aromatic molecule. In the two groups of clusters, the cyclic isomers present both σ- and π-aromaticity. However, at variance with group 13 M2N2(2-) clusters, the linear isomer of group 14 M2N2(2+) is the most stable for two of the clusters (C2Si2(2+) and C2Ge2(2+)) , and it is isoenergetic with the cyclic D(4h) isomer in the case of C4(2+). Energy decomposition analyses of the lowest-lying isomers and the calculated magnetic- and electronic-based aromaticity criteria of the cyclic isomers help to understand the nature of the bonding and the origin of the stability of the global minima. Finally, for completeness, we have also analyzed the structure and stability of the heavier Sn and Pb group 14 M2N2(2+) analogues.

  10. Structural Characterization of Monomers and Oligomers of D-Amino Acid-Containing Peptides Using T-Wave Ion Mobility Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Pang, Xueqin; Jia, Chenxi; Chen, Zhengwei; Li, Lingjun

    2017-01-01

    The D-residues are crucial to biological function of D-amino acid containing peptides (DAACPs). Previous ion mobility mass spectrometry (IM-MS) studies revealing oligomerization patterns of amyloid cascade demonstrated conversion from native soluble unstructured assembly to fibril ß-sheet oligomers, which has been implicated in amyloid diseases, such as Alzheimer's disease and type 2 diabetes. Although neuropeptides are typically present at very low concentrations in circulation, their local concentrations could be much higher in large dense core vesicles, forming dimers or oligomers. We studied the oligomerization of protonated and metal-adducted achatin I and dermorphin peptide isomers with IM-MS. Our results suggested that dimerization, oligomerization, and metal adduction augment the structural differences between D/L peptide isomers compared to protonated monomers. Dimers and oligomers enhanced the structural differences between D/L peptide isomers in both aqueous and organic solvent system. Furthermore, some oligomer forms were only observed for either D- or L-isomers, indicating the importance of chiral center in oligomerization process. The oligomerization patterns of D/L isomers appear to be similar. Potassium adducts were detected to enlarge the structural differences between D/L isomers.

  11. 21 CFR 184.1061 - Lactic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Lactic acid. 184.1061 Section 184.1061 Food and... Substances Affirmed as GRAS § 184.1061 Lactic acid. (a) Lactic acid (C3H6O3, CAS Reg. Nos.: dl mixture, 598-82-3; l-isomer, 79-33-4; d-isomer, 10326-41-7), the chemical 2-hydroxypropanoic acid,...

  12. 21 CFR 184.1061 - Lactic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Lactic acid. 184.1061 Section 184.1061 Food and... Substances Affirmed as GRAS § 184.1061 Lactic acid. (a) Lactic acid (C3H6O3, CAS Reg. Nos.: dl mixture, 598-82-3; l-isomer, 79-33-4; d-isomer, 10326-41-7), the chemical 2-hydroxypropanoic acid,...

  13. 21 CFR 184.1061 - Lactic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Lactic acid. 184.1061 Section 184.1061 Food and... Substances Affirmed as GRAS § 184.1061 Lactic acid. (a) Lactic acid (C3H6O3, CAS Reg. Nos.: dl mixture, 598-82-3; l-isomer, 79-33-4; d-isomer, 10326-41-7), the chemical 2-hydroxypropanoic acid,...

  14. 21 CFR 184.1061 - Lactic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Lactic acid. 184.1061 Section 184.1061 Food and....1061 Lactic acid. (a) Lactic acid (C3H6O3, CAS Reg. Nos.: dl mixture, 598-82-3; l-isomer, 79-33-4; d-isomer, 10326-41-7), the chemical 2-hydroxypropanoic acid, occurs naturally in several foods. It...

  15. 21 CFR 184.1061 - Lactic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Lactic acid. 184.1061 Section 184.1061 Food and... Substances Affirmed as GRAS § 184.1061 Lactic acid. (a) Lactic acid (C3H6O3, CAS Reg. Nos.: dl mixture, 598-82-3; l-isomer, 79-33-4; d-isomer, 10326-41-7), the chemical 2-hydroxypropanoic acid,...

  16. 241Am (n,gamma) isomer ratio measurement

    SciTech Connect

    Bond, Evelyn M; Vieira, David J; Moody, Walter A; Slemmons, Alice K

    2011-01-05

    The objective of this project is to improve the accuracy of the {sup 242}Cm/{sup 241}Am radiochemistry ratio. We have performed an activation experiment to measure the {sup 241}Am(n,{gamma}) cross section leading to either the ground state of {sup 242g}Am (t{sub 1/2} = 16 hr) which decays to {sup 242}Cm (t{sub 1/2} = 163 d) or the long-lived isomer {sup 242m}Am (t{sub 1/2} = 141 yr). This experiment will develop a new set of americium cross section evaluations that can be used with a measured {sup 242}Cm/{sup 241}Am radiochemical measurement for nuclear forensic purposes. This measurement is necessary to interpret the {sup 242}Cm/{sup 241}Am ratio because a good measurement of this neutron capture isomer ratio for {sup 241}Am does not exist. The targets were prepared in 2007 from {sup 241}Am purified from LANL stocks. Gold was added to the purified {sup 241}Am as an internal neutron fluence monitor. These targets were placed into a holder, packaged, and shipped to Forschungszentrum Karlsruhe, where they were irradiated at their Van de Graff facility in February 2008. One target was irradiated with {approx}25 keV quasimonoenergetic neutrons produced by the {sup 7}Li(p,n) reaction for 3 days and a second target was also irradiated for 3 days with {approx}500 keV neutrons. Because it will be necessary to separate the {sup 242}Cm from the {sup 241}Am in order to measure the amount of {sup 242}Cm by alpha spectrometry, research into methods for americium/curium separations were conducted concurrently. We found that anion exchange chromatography in methanol/nitric acid solutions produced good separations that could be completed in one day resulting in a sample with no residue. The samples were returned from Germany in July 2009 and were counted by gamma spectrometry. Chemical separations have commenced on the blank sample. Each sample will be spiked with {sup 244}Cm, dissolved and digested in nitric acid solutions. One third of each sample will be processed at a time

  17. Tautomeric conversion, vibrational spectra, and density functional studies on peripheral sulfur derivatives of benzothiazole and benzothiazoline isomers

    NASA Astrophysics Data System (ADS)

    Altun, Ahmet; Kuliyev, Eziz; Aghatabay, Naz M.

    2016-01-01

    The room temperature structural (tautomerism, dimerization, conformational preference, geometry parameters) and vibrational spectral (IR and Raman) analyses have been performed on benzothiazoline (benzothiazoline-2-thione, 3-methyl-benzothiazoline-2-thione) and benzothiazole [2-mercaptobenzothiazole, 2-methylthiobenzothiazole, and bis(benzothiazole-2-ylthio)ethane] derivatives at the B3LYP/6-311++G∗∗ level of theory. Although the keto to enol transition barriers are too high over the most stable benzothiazoline isomers, vibrational spectral analyses reveal some major bands of benzothiazole isomers in the present room temperature experimental FT-IR and FT-Raman specta. Therefore, benzothiazole isomers exist at rare amounts in the powdered samples that are mainly composed of benzothiazoline isomers. The benzothiazole isomers have two stable conformations due to the orientation of their SH and SCH3 moieties. The energetic and vibrational spectral analyses suggest that the benzothiazoline-2-thione molecules can be stabilized further through the NH⋯S intermolecular hydrogen bonds in solid phase. All observed fundamental vibrational bands of the molecules have been assigned based on the calculated mode frequencies and IR/Raman intensities. The mode assignments have been expressed in terms of internal coordinates and their percent potential energy distributions. The effects of substitution at the nitrogen and peripheral sulfur atoms have been analyzed for the geometries and vibrational bands of the molecules.

  18. Tautomeric conversion, vibrational spectra, and density functional studies on peripheral sulfur derivatives of benzothiazole and benzothiazoline isomers.

    PubMed

    Altun, Ahmet; Kuliyev, Eziz; Aghatabay, Naz M

    2016-01-05

    The room temperature structural (tautomerism, dimerization, conformational preference, geometry parameters) and vibrational spectral (IR and Raman) analyses have been performed on benzothiazoline (benzothiazoline-2-thione, 3-methyl-benzothiazoline-2-thione) and benzothiazole [2-mercaptobenzothiazole, 2-methylthiobenzothiazole, and bis(benzothiazole-2-ylthio)ethane] derivatives at the B3LYP/6-311++G(∗∗) level of theory. Although the keto to enol transition barriers are too high over the most stable benzothiazoline isomers, vibrational spectral analyses reveal some major bands of benzothiazole isomers in the present room temperature experimental FT-IR and FT-Raman specta. Therefore, benzothiazole isomers exist at rare amounts in the powdered samples that are mainly composed of benzothiazoline isomers. The benzothiazole isomers have two stable conformations due to the orientation of their SH and SCH3 moieties. The energetic and vibrational spectral analyses suggest that the benzothiazoline-2-thione molecules can be stabilized further through the NH⋯S intermolecular hydrogen bonds in solid phase. All observed fundamental vibrational bands of the molecules have been assigned based on the calculated mode frequencies and IR/Raman intensities. The mode assignments have been expressed in terms of internal coordinates and their percent potential energy distributions. The effects of substitution at the nitrogen and peripheral sulfur atoms have been analyzed for the geometries and vibrational bands of the molecules.

  19. Up- and down-regulation of beta-adrenoreceptors in rat cerebral cortex following exposure to isomers of hexachlorocyclohexane

    SciTech Connect

    Stark, L.; Hollinger, M.; Joy, R.

    1986-03-01

    The authors have shown that the gamma (lindane) and beta isomers of hexachlorocyclohexane (HCH) have opposite effects on the kindling model of epilepsy (gamma facilitates, beta retards kindling acquisition). In the present study the authors determined the effects of these two isomers on ..beta..-adrenoreceptors in rat brain using /sup 3/H-dihydroalprenolol as the ligand following 10 days treatment with 10 mg/kg p.o. of isomers or corn oil. Results showed a statistically significant decrease in the number of ..beta..-adrenoreceptors in cortical tissue taken from lindane treated rats. In contrast, there was a significant increase in the number of ..beta..-adreno receptors in cortical tissue taken from beta-HCH treated rats. Neither treatment caused a significant change in Kd. It is concluded that the ..beta..-adrenoreceptor system in rat brain is differentially affected by the isomers of HCH. Since the kindling model of epilepsy is sensitive to modulation in adrenergic function, this system may be involved in the pro- and anticonvulsant effects of these HCH isomers on kindling acquisition.

  20. PARTICLE-HOLE NATURE OF THE LIGHT HIGH-SPIN TOROIDAL ISOMERS

    SciTech Connect

    Staszczak, A.; Wong, Cheuk-Yin

    2015-01-01

    Nuclei under non-collective rotation with a large angular momentum above some threshold can assume a toroidal shape. In our previous work, we showed by using cranked Skyrme Hartree Fock approach that even even, N = Z, high-K, toroidal isomeric states may have general occurrences for light nuclei with 28 < A < 52. We present here some additional results and systematics on the particle-hole nature of these high-spin toroidal isomers.

  1. High-K isomers in {sup 176}W and mechanisms of K-violation

    SciTech Connect

    Crowell, B.; Janssens, R.V.F.; Blumenthal, D.J.

    1995-08-01

    K-isomers are states in deformed nuclei whose {gamma}-decay is hindered by selection rules involving K, the projection of the angular momentum along the axis of symmetry of the nucleus. Previous work with the Argonne Notre Dame BGO Array delineated the existence of two K-isomers in {sup 176}W, one of which had a very unusual pattern of decay. A short description of this work was published as a letter, and a more complete account is being readied for submission. These results provided evidence that quantum-mechanical fluctuations in the nuclear shape may be responsible for some of the observed K-violating transitions. In addition, hints were present in the data of the existence of another K-isomer with an even higher in. An experiment was performed in September 1994 to observe this isomer, using the reaction {sup 50}Ti({sup 130}Te,4n), and a technique in which recoiling {sup 176}W nuclei were created 17-cm upstream of the center of the array and caught on a Pb catcher foil at the center. Intense ({approximately} 3 pnA) beams of {sup 130}Te were supplied by the ECR source using a new sputtering technique. The recoil-shadow geometry was highly successful at removing the background from non-isomeric decays, allowing the weakly populated K-isomers to be detected cleanly. In addition, the availability of pulsed beams from ATLAS and the timing data from the BGO array provided a second technique for isolating the decays of interest, by selecting events in which a given number of BGO detectors fired between beam pulses. This method was used in the previous experiment, and was also applied in this experiment as a second level of selection. As a result, gamma-ray transitions were detected in the present experiment with intensities as small as {approximately} 0.02 % of the {sup 176}W reaction channel. The existence of the new isomer was confirmed, and a partial level-scheme was constructed.

  2. 227 Views of RNA: Is RNA Unique in Its Chemical Isomer Space?

    PubMed Central

    Meringer, Markus; Goodwin, Jay

    2015-01-01

    Abstract Ribonucleic acid (RNA) is one of the two nucleic acids used by extant biochemistry and plays a central role as the intermediary carrier of genetic information in transcription and translation. If RNA was involved in the origin of life, it should have a facile prebiotic synthesis. A wide variety of such syntheses have been explored. However, to date no one-pot reaction has been shown capable of yielding RNA monomers from likely prebiotically abundant starting materials, though this does not rule out the possibility that simpler, more easily prebiotically accessible nucleic acids may have preceded RNA. Given structural constraints, such as the ability to form complementary base pairs and a linear covalent polymer, a variety of structural isomers of RNA could potentially function as genetic platforms. By using structure-generation software, all the potential structural isomers of the ribosides (BC5H9O4, where B is nucleobase), as well as a set of simpler minimal analogues derived from them, that can potentially serve as monomeric building blocks of nucleic acid–like molecules are enumerated. Molecules are selected based on their likely stability under biochemically relevant conditions (e.g., moderate pH and temperature) and the presence of at least two functional groups allowing the monomers to be incorporated into linear polymers. The resulting structures are then evaluated by using molecular descriptors typically applied in quantitative structure–property relationship (QSPR) studies and predicted physicochemical properties. Several databases have been queried to determine whether any of the computed isomers had been synthesized previously. Very few of the molecules that emerge from this structure set have been previously described. We conclude that ribonucleosides may have competed with a multitude of alternative structures whose potential proto-biochemical roles and abiotic syntheses remain to be explored. Key Words: Evolution—Chemical evolution

  3. Superparamagnetic poly(methyl methacrylate) nanoparticles surface modified with folic acid presenting cell uptake mediated by endocytosis

    NASA Astrophysics Data System (ADS)

    Feuser, Paulo Emilio; Jacques, Amanda Virtuoso; Arévalo, Juan Marcelo Carpio; Rocha, Maria Eliane Merlin; dos Santos-Silva, Maria Claudia; Sayer, Claudia; de Araújo, Pedro H. Hermes

    2016-04-01

    The encapsulation of superparamagnetic nanoparticles (MNPs) in polymeric nanoparticles (NPs) with modified surfaces can improve targeted delivery and induce cell death by hyperthermia. The goals of this study were to synthesize and characterize surface modified superparamagnetic poly(methyl methacrylate) with folic acid (FA) prepared by miniemulsion polymerization (MNPsPMMA-FA) and to evaluate their in vitro cytotoxicity and cellular uptake in non-tumor cells, murine fibroblast (L929) cells and tumor cells that overexpressed folate receptor (FR) β, and chronic myeloid leukemia cells in blast crisis (K562). Lastly, hemolysis assays were performed on human red blood cells. MNPsPMMA-FA presented an average mean diameter of 135 nm and a saturation magnetization (Ms) value of 37 emu/g of iron oxide, as well as superparamagnetic behavior. The MNPsPMMA-FA did not present cytotoxicity in L929 and K562 cells. Cellular uptake assays showed a higher uptake of MNPsPMMA-FA than MNPsPMMA in K562 cells when incubated at 37 °C. On the other hand, MNPsPMMA-FA showed a low uptake when endocytosis mechanisms were blocked at low temperature (4 °C), suggesting that the MNPsPMMA-FA uptake was mediated by endocytosis. High concentrations of MNPsPMMA-FA showed hemocompatibility when incubated for 24 h in human red blood cells. Therefore, our results suggest that these carrier systems can be an excellent alternative in targeted drug delivery via FR.

  4. Cytochromes P450 catalyze both steps of the major pathway of clopidogrel bioactivation, whereas paraoxonase catalyzes the formation of a minor thiol metabolite isomer.

    PubMed

    Dansette, Patrick M; Rosi, Julien; Bertho, Gildas; Mansuy, Daniel

    2012-02-20

    The mechanism generally admitted for the bioactivation of the antithrombotic prodrug, clopidogrel, is its two-step enzymatic conversion into a biologically active thiol metabolite. The first step is a classical cytochrome P450 (P450)-dependent monooxygenation of its thiophene ring leading to 2-oxo-clopidogrel, a thiolactone metabolite. The second step was described as a P450-dependent oxidative opening of the thiolactone ring of 2-oxo-clopidogrel, with intermediate formation of a reactive sulfenic acid metabolite that is eventually reduced to the corresponding thiol 4b. A very recent paper published in Nat. Med. (Bouman et al., (2011) 17, 110) reported that the second step of clopidogrel bioactivation was not catalyzed by P450 enzymes but by paraoxonase-1(PON-1) and that PON-1 was a major determinant of clopidogrel efficacy. The results described in the present article show that there are two metabolic pathways for the opening of the thiolactone ring of 2-oxo-clopidogrel. The major one, that was previously described, results from a P450-dependent redox bioactivation of 2-oxo-clopidogrel and leads to 4b cis, two previously reported thiol diastereomers bearing an exocyclic double bond. The second, minor one, results from a hydrolysis of 2-oxo-clopidogrel, which seems to be dependent on PON-1, and leads to an isomer of 4b cis, 4b "endo", in which the double bond has migrated from an exocyclic to an endocyclic position in the piperidine ring. These results were obtained from a detailed study of the metabolism of 2-oxo-clopidogrel by human liver microsomes and human sera and analysis by HPLC-MS under conditions allowing a complete separation of the thiol metabolite isomers, either as such or after derivatization with 3'-methoxy phenacyl bromide or N-ethyl maleimide (NEM). These results also show that the major bioactive thiol isomer found in the plasma of clopidogrel-treated patients derives from 2-oxo-clopidogrel by the P450-dependent pathway. Finally, chemical

  5. Ab initio molecular orbital studies of low-energy, metastable isomers of the ubiquitous cyclopropenylidene. [in interstellar space

    NASA Technical Reports Server (NTRS)

    Defrees, D. J.; Mclean, A. D.

    1986-01-01

    The discovery of cyclopropenylidene in space suggests that other C3H2 isomers may be present, and a tentative detection of one such isomer, propargylene (HCCCH), has been reported. Ab initio molecular orbital theory has been used to characterize five low-lying, metastable isomers of cyclopropenylidene. Extended calculations including the electron correlation energy, show that the lowest in energy is singlet propadienylidene, followed by propargylene; the singlet and triplet of the latter are too close in energy to allow an assignment of the ground state; triplet propadienylidene is at a significantly higher energy. Rotational frequencies computed to an expected accuracy of + or - 1 -2 percent do not confirm the tentative detection of propargylene in space, although the discrepancy between theory and the observation is not so great as to unequivocally rule out this possibility.

  6. High-K isomers in transactinide nuclei close to N = 162

    SciTech Connect

    Prassa, V. Nikšić, T.; Vretenar, D.; Lu, Bing-Nan; Ackermann, D.

    2015-10-15

    Transactinide nuclei around neutron number N = 162 display axially deformed equilibrium shapes, as shown in our previous analysis [1] of constrained mean-field energy surfaces and collective excitation spectra. In the present study we are particularly interested in the occurrence of high-K isomers in the axially deformed isotopes of Rf (Z = 104), Sg (Z = 106), Hs (Z = 108), and Ds (Z = 110), with neutron number N = 160 − 166 and the effect of the N=162 closure on the structure and distribution of two-quasiparticle (2qp) states. The evolution of high-K isomers is analysed in a self-consistent axially-symmetric relativistic Hartree-Bogoliubov calculation using the blocking approximation with time-reversal symmetry breaking.

  7. Identification of an {alpha}-decaying (9{sup -}) isomer in {sup 216}Fr

    SciTech Connect

    Kurcewicz, J.; Karny, M.; Korgul, A.; Kurcewicz, W.; Kurpeta, J.; Lewandowski, S.; Majorkiewicz, P.; Plochocki, A.; Wojtasiewicz, A.; Czarnacki, W.; Kasztelan, M.; Kisielinski, M.; Penttilae, H.; Roussiere, B.; Steczkiewicz, O.

    2007-11-15

    The {alpha} decay of the trans-lead isotopes {sup 212}At, {sup 216}Fr, and {sup 220}Ac was investigated by using mass-separated sources and analog as well as digital signal processing. By measuring {alpha}-{alpha} time correlations evidence was obtained for the occurrence of an {alpha}-decaying (9{sup -}) isomer in {sup 216}Fr. The {alpha}-decay energy and half-life amount to 9000(5) keV and 850(30) ns, respectively. The excitation energy of the isomer is compared with shell-model predictions for the high-spin members of the {pi}(h{sub 9/2}){nu}(g{sub 9/2}) multiplet, and the relevance of the new data concerning the search for reflection asymmetry is presented.

  8. Sialic acid removal from dendritic cells improves antigen cross-presentation and boosts anti-tumor immune responses

    PubMed Central

    Silva, Mariana; Silva, Zélia; Marques, Graça; Ferro, Tiago; Gonçalves, Márcia; Monteiro, Mauro; van Vliet, Sandra J.; Mohr, Elodie; Lino, Andreia C.; Fernandes, Alexandra R.; Lima, Flávia A.; van Kooyk, Yvette; Matos, Teresa; Tadokoro, Carlos E.; Videira, Paula A.

    2016-01-01

    Dendritic cells (DCs) hold promise for anti-cancer immunotherapy. However, clinically, their efficiency is limited and novel strategies to improve DC-mediated anti-tumor responses are needed. Human DCs display high content of sialic acids, which inhibits their maturation and co-stimulation capacity. Here, we aimed to understand whether exogenous desialylation of DCs improves their anti-tumor immunity. Compared to fully sialylated DCs, desialylated human DCs loaded with tumor-antigens showed enhanced ability to induce autologous T cells to proliferate, to secrete Th1 cytokines, and to specifically induce tumor cell apoptosis. Desialylated DCs showed an increased expression of MHC-I and -II, co-stimulatory molecules and an augmented secretion of IL-12. Desialylated HLA-A*02:01 DCs pulsed with gp100 peptides displayed enhanced peptide presentation through MHC-I, resulting in higher activation ofgp100280–288 specific CD8+ cytotoxic T cells. Desialylated murine DCs also exhibited increased MHC and co-stimulatory molecules and higher antigen cross-presentation via MHC-I. These DCs showed higher ability to activate antigen-specific CD4+ and CD8+ T cells, and to specifically induce tumor cell apoptosis. Collectively, our data demonstrates that desialylation improves DCs' ability to elicit T cell-mediated anti-tumor activity, due to increased MHC-I expression and higher antigen presentation via MHC-I. Sialidase treatment of DCs may represent a technology to improve the efficacy of antigen loaded-DC-based vaccines for anti-cancer immunotherapy. PMID:27203391

  9. Sialic acid removal from dendritic cells improves antigen cross-presentation and boosts anti-tumor immune responses.

    PubMed

    Silva, Mariana; Silva, Zélia; Marques, Graça; Ferro, Tiago; Gonçalves, Márcia; Monteiro, Mauro; van Vliet, Sandra J; Mohr, Elodie; Lino, Andreia C; Fernandes, Alexandra R; Lima, Flávia A; van Kooyk, Yvette; Matos, Teresa; Tadokoro, Carlos E; Videira, Paula A

    2016-07-05

    Dendritic cells (DCs) hold promise for anti-cancer immunotherapy. However, clinically, their efficiency is limited and novel strategies to improve DC-mediated anti-tumor responses are needed. Human DCs display high content of sialic acids, which inhibits their maturation and co-stimulation capacity. Here, we aimed to understand whether exogenous desialylation of DCs improves their anti-tumor immunity. Compared to fully sialylated DCs, desialylated human DCs loaded with tumor-antigens showed enhanced ability to induce autologous T cells to proliferate, to secrete Th1 cytokines, and to specifically induce tumor cell apoptosis. Desialylated DCs showed an increased expression of MHC-I and -II, co-stimulatory molecules and an augmented secretion of IL-12. Desialylated HLA-A*02:01 DCs pulsed with gp100 peptides displayed enhanced peptide presentation through MHC-I, resulting in higher activation ofgp100280-288 specific CD8+ cytotoxic T cells. Desialylated murine DCs also exhibited increased MHC and co-stimulatory molecules and higher antigen cross-presentation via MHC-I. These DCs showed higher ability to activate antigen-specific CD4+ and CD8+ T cells, and to specifically induce tumor cell apoptosis. Collectively, our data demonstrates that desialylation improves DCs' ability to elicit T cell-mediated anti-tumor activity, due to increased MHC-I expression and higher antigen presentation via MHC-I. Sialidase treatment of DCs may represent a technology to improve the efficacy of antigen loaded-DC-based vaccines for anti-cancer immunotherapy.

  10. Quantification of Structural Isomers via Mode-Selective Irmpd

    NASA Astrophysics Data System (ADS)

    Polfer, Nicolas C.

    2016-06-01

    Mixtures of structural isomers can pose a challenge for vibrational ion spectroscopy. In cases where particular structures display diagnostic vibrations, these structures can be selectively "burned away". In ion traps, the ion population can be subjected to multiple laser shots, in order to fully deplete a particular structure, in effect allowing a quantification of this structure. Protonated para-amino benzoic acid (PABA) serves as an illustrative example. PABA is known to preferentially exist in the N-protonated (N-prot) form in solution, but in the gas phase it is energetically favorable in the O-protonated (O-prot) form. As shown in Figure 1, the N-prot structure can be kinetically trapped in the gas phase when sprayed from non-protic solvent, whereas the O-prot structure is obtained when sprayed from protic solvents, analogous to results by others [1,2]. y parking the light source on the diagnostic 3440 wn mode, the percentage of the O-prot structure can be determined, and by default the remainder is assumed to adopt the N-prot structure. It will be shown that the relative percentages of O-prot vs N-prot are highly dependent on the solvent mixture, going from close to 0% O-prot in non-protic solvents, to 99% in protic solvents. Surprisingly, water behaves much more like a non-protic solvent than methanol. It is observed that the capillary temperature, which aids droplet desolvation by black-body radiation in the ESI source, is critical to promote the appearance of O-prot structures. These results are consistent with the picture that a protic bridge mechanism is at play to facilitate proton transfer, and thus allow conversion from N-prot to O-prot, but that this mechanism is subject to appreciable kinetic barriers on the timescale of solvent evaporation. 1. J. Phys. Chem. A 2011, 115, 7625. 2. Anal. Chem. 2012, 84, 7857.

  11. Incorporation mechanisms of a branched nonylphenol isomer in soil-derived organo-clay complexes during a 180-day experiment.

    PubMed

    Riefer, Patrick; Klausmeyer, Timm; Adams, Alina; Schmidt, Burkhard; Schäffer, Andreas; Schwarzbauer, Jan

    2013-07-02

    The incorporation process of a defined (13)C- and (14)C-labeled nonylphenol isomer (4-(3,5-dimethylhept-3-yl)phenol) into soil-derived organo-clay complexes was investigated. Isolated organo-clay complexes were separated into humic subfractions. Noninvasive ((13)C-CP/MAS NMR) and invasive methods (sequential chemical degradation, pyrolysis) were applied to obtain detailed information about the mode of incorporation, chemical structure, and change of the incorporation character of nonextractable residues in course of incubation. (13)C-CP/MAS NMR measurements of humic acids revealed an increasing incorporation of phenolic compounds during the experimental time which was referred to residues of the introduced (13)C-labeled NP isomer. Detailed investigations by means of sequential chemical degradation indicated a predominant incorporation of nonextractable NP isomer residues via reversible ester (amide) bonds. In course of time, the amount of releasable compounds decreased, pointing to altering processes which affected the mode of incorporation. BBr3-treatment, RuO4 oxidation, and thermochemolysis released only low portions of nonextractable radioactivity giving evidence of strongly incorporated residues. With the comprehensive application of complementary methods (e.g., humic matter fractionation, (13)C-CP/MAS NMR, sequential chemical degradation) it was possible to provide a comparatively detailed insight into the incorporation behavior of the applied NP isomer.

  12. A new high-spin isomer in 195Bi

    NASA Astrophysics Data System (ADS)

    Roy, T.; Mukherjee, G.; Madhavan, N.; Rana, T. K.; Bhattacharya, Soumik; Asgar, Md. A.; Bala, I.; Basu, K.; Bhattacharjee, S. S.; Bhattacharya, C.; Bhattacharya, S.; Bhattacharyya, S.; Gehlot, J.; Ghugre, S. S.; Gurjar, R. K.; Jhingan, A.; Kumar, R.; Muralithar, S.; Nath, S.; Pai, H.; Palit, R.; Raut, R.; Singh, R. P.; Sinha, A. K.; Varughese, T.

    2015-11-01

    A new high-spin isomer has been identified in 195Bi at the focal plane of the HYbrid Recoil mass Analyser (HYRA) used in the gas-filled mode. The fusion evaporation reactions 169Tm (30Si, x n) 193, 195Bi were used with the beam energies on targets of 168 and 146MeV for 6n and 4n channels, respectively. The evaporation residues, separated from the fission fragments, and their decays were detected at the focal plane of HYRA using MWPC, Si-Pad and clover HPGe detectors. The half-life of the new isomer in 195Bi has been measured to be 1.6(1)μs. The configuration of the new isomer has been proposed and compared with the other isomers in this region. The Total Routhian Surface (TRS) calculations for the three-quasiparticle configurations corresponding to the new isomer suggest an oblate deformation for this isomeric state. The same calculations for different configurations in 195Bi and for the even-even 194Pb core indicate that the proton i 13/2 orbital has a large shape driving effect towards oblate shape in these nuclei.

  13. A maize death acid, 10-oxo-11-phytoenoic acid, is the predominant cyclopentenone signal present during multiple stress and developmental conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recently we investigated the function of the 9-lipoxygenase (LOX) derived cyclopentenones 10-oxo-11-phytoenoic acid (10-OPEA) and 10-oxo-11-phytodienoic acid (10-OPDA) and identified their C-14 and C-12 derivatives. 10-OPEA accumulation is elicited by fungal and insect attack and acts as a strong in...

  14. Detection of the Rotational Spectrum of Sulfoxylic Acid (hosoh)

    NASA Astrophysics Data System (ADS)

    Crabtree, Kyle N.; Martinez, Oscar, Jr.; Barreau, Lou; McCarthy, Michael C.; Thorwirth, Sven

    2013-06-01

    Sulfoxylic acid (HOSOH) is a chemical intermediate that falls roughly midway in the oxidation states of sulfur, between its highly reduced (H_2S) and oxidixed (H_2SO_4) forms. It is likely formed during atmospheric oxidation of anthropogenic and natural sulfur emissions, and might also be produced by UV processing of circumstellar ices. Despite considerable theoretical work, no gas-phase spectra of sulfoxylic acid or any of its structural isomers have previously been observed. We report the detection of the rotational spectra of the C_2 and C_s rotamers of HOSOH using a combination of Fourier transform microwave spectroscopy and microwave-microwave double resonance techniques, guided by new high-level quantum chemical calculations of their structures. The present work enables radioastronomical searches for these species, and also lays the groundwork for further chemical studies of its gas-phase formation and spectroscopic studies of other H_2SO_2 isomers.

  15. Behavioral and electrophysiological responses of Aedes albopictus to certain acids and alcohols present in human skin emanations.

    PubMed

    Guha, Lopamudra; Seenivasagan, T; Iqbal, S Thanvir; Agrawal, O P; Parashar, B D

    2014-10-01

    Human skin emanations attract hungry female mosquitoes toward their host for blood feeding. In this study, we report the flight orientation and electroantennogram response of Aedes albopictus females to certain unsaturated acids and alcohols found in human skin. In the Y-tube olfactometer, odors of lactic acid and 2-methyl-3-pentanol attracted 54-65% of Ae. albopictus females at all doses in a dose-dependent manner. However, at the highest dose (10(-2) g), the acids repelled 40-45% females. Attractancy (ca. 62-68%) at lower doses and repellency (ca. 30-45%) at higher doses were recorded for 3-methyl-3-pentanol and 1-octen-3-ol, while 5-hexen-1-ol, cis-2-hexen-1-ol, and trans 2-hexen-1-ol odor repelled ca. 55-65% of Ae. albopictus females at all doses. Antenna of female Ae. albopictus exhibited a dose-dependent EAG response up to 10(-3) g of L-lactic acid, trans-2-methyl-2-pentenoic acid, 2-octenoic acid, trans-2-hexen-1-ol and 1-octen-3-ol stimulations; however, the highest dose (10(-2) g) caused a little decline in the EAG response. EAG response of 9-10-fold was elicited by lactic acid, 2-octenoic acid, trans-2-hexenoic acid, and 3-methyl-3-pentanol, while cis-2-hexen-1-ol and trans-2-methyl pentenoic acid elicited 1-5-fold responses compared to solvent control. A blend of attractive compounds could be utilized in odor-baited trap for surveillance and repellent molecules with suitable formulation could be used to reduce the biting menace of mosquitoes.

  16. Differential incorporation of dietary conjugated linolenic and linoleic acids into milk lipids and liver phospholipids in lactating and suckling rats.

    PubMed

    Cao, Ying; Chen, Jingnan; Yang, Lin; Chen, Zhen-Yu

    2009-09-01

    Interest in health benefits of conjugated fatty acids is growing. The present study compared the incorporation pattern of dietary conjugated linolenic acids (CLnA) into milk with that of conjugated linoleic acids (CLA). Lactating Sprague-Dawley rats (Day 1) were divided into five groups fed the control diet (n=4) or one of four experimental diets supplemented with 1-2% CLA or CLnA mixture (n=8 each). Supplementation of 1% and 2% CLA led to enrichment of 4.17% and 8.57% CLA, respectively, while supplementation of 1% and 2% CLnA resulted in enrichment of only 0.98% and 1.71% CLnA in the milk lipids, demonstrating the transfer of CLnA from maternal diet to milk was discriminated. When the lactating rats were given a diet containing a CLnA mixture of 9t,11t,13t-, 9c,11t,13t- and 9c,11t,13c-CLnA isomers, two CLA isomers, namely, 9t,11t (0.59-0.90%) and 9c,11t (1.21-1.96%), were found in the milk, suggesting that three CLnA isomers were Delta-13 saturated. Dietary CLnA at 1-2% had no effect on liver phospholipid (PL) fatty acid composition of both maternal and suckling rats, whereas dietary CLA increased docosahexaenoic acid (4c,7c,10c,13c,16c,19c-22:6) and palmitic acid (16:0) proportionally in the PL of maternal rats, but it suppressed 16:0 in the PL of suckling rats. It is concluded that maternal rats incorporate CLnA isomers into milk differently from that of CLA isomers. Most interesting is that maternal rats can metabolically convert CLnA to CLA.

  17. Low and High Temperature Combustion Chemistry of Butanol Isomers in Premixed Flames and Autoignition Systems

    SciTech Connect

    Sarathy, S M; Pitz, W J; Westbrook, C K; Mehl, M; Yasunaga, K; Curran, H J; Tsujimura, T; Osswald, P; Kohse-Hoinghaus, K

    2010-12-12

    Butanol is a fuel that has been proposed as a bio-derived alternative to conventional petroleum derived fuels. The structural isomer in traditional 'bio-butanol' fuel is n-butanol, but newer conversion technologies produce iso-butanol as a fuel. In order to better understand the combustion chemistry of bio-butanol, this study presents a comprehensive chemical kinetic model for all the four isomers of butanol (e.g., 1-, 2-, iso- and tert-butanol). The proposed model includes detailed high temperature and low temperature reaction pathways. In this study, the primary experimental validation target for the model is premixed flat low-pressure flame species profiles obtained using molecular beam mass spectrometry (MBMS). The model is also validated against previously published data for premixed flame velocity and n-butanol rapid compression machine and shock tube ignition delay. The agreement with these data sets is reasonably good. The dominant reaction pathways at the various pressures and temperatures studied are elucidated. At low temperature conditions, we found that the reaction of alphahydroxybutyl with O{sub 2} was important in controlling the reactivity of the system, and for correctly predicting C{sub 4} aldehyde profiles in low pressure premixed flames. Enol-keto isomerization reactions assisted by HO{sub 2} were also found to be important in converting enols to aldehydes and ketones in the low pressure premixed flames. In the paper, we describe how the structural features of the four different butanol isomers lead to differences in the combustion properties of each isomer.

  18. Optical isomers of a new 2-nitroimidazole nucleoside analog (PR-350 series): Radiosensitization efficiency and toxicity

    SciTech Connect

    Oya, Natsuo; Sasai, Keisuke; Shibata, Toru

    1995-08-30

    A new 2-nitroimidazole nucleoside radiosensitizer, PR-350 (1-[1{prime},3{prime},4{prime}-trihydroxy-2{prime}-butoxy]-methyl-2-nitroimidazole), has been reported to be as efficient as and less toxic than etanidazole. This compound is racemic, and it was recently optically resolved into two isomers, PR-68 (2{prime}R,3{prime}S type) and PR-69 (2{prime}S,3{prime}R type). The other two isomers, PR-28 (2{prime}S,3{prime}S type) and PR-44 (2{prime}R,3{prime}R type), were asymmetrically synthesized. In the present study, we investigated the properties, sensitizing activity, and toxicity of PR-350 and the four optical isomers in comparison with those of other 2-nitroimidazole hypoxic cell radiosensitizers, etanidazole, KU-2285, KIN-804, and RP-170. Because PR-350 and PR-28 can be industrially synthesized, we evaluated whether either of these two drugs are suitable for further investigation. In vivo radiosensitizing activity differed among the four optical isomers, which appeared to be due, at least in part, to differences in lipophilicity. Although PR-28 was the least toxic, its low sensitization efficiency does not warrant clinical trials. Among the PR compounds, PR-68 appears to be most efficient, but optical resolution of PR-68 from PR-350 is expensive, and asymmetrical synthesis of PR-68 is not established. Therefore, PR-350 seems to be most suitable for further investigation among the PR-350 series compounds, considering its higher efficiency compared with PR-28 and PR-44, and established synthesis. 28 refs., 7 figs., 1 tab.

  19. Antioxidant role of N-acetyl cysteine isomers following high dose irradiation.

    PubMed

    Neal, Rachel; Matthews, Richard H; Lutz, Paula; Ercal, Nuran

    2003-03-15

    High dose, acute radiation exposure, as in radiation accidents, induces three clinical syndromes that reflect consequences of oxidative protein, lipid, and DNA damage to tissues such as intestine, lung, and liver. In the present study, we irradiated C57BL/6 mice with 18 Gy whole-body radiation (XRT) and evaluated N-acetyl cysteine (NAC) isomers LNAC and DNAC as potential radioprotectors under conditions that would model the gastrointestinal syndrome. We focused on tissues thought not immediately involved in the gastrointestinal syndrome. Both LNAC and DNAC protected the lung and red blood cells (RBC) from glutathione (GSH) depletion following radiation exposure. However, only LNAC also supplemented the spleen GSH levels following XRT. Protection from increased malondialdehyde (MDA) levels (lung) and increased 8-hydroxy-deoxyguanosine (8-oxo-dG) presence (liver) following XRT was observed with treatment by either isomer of NAC. These results imply that either NAC isomer can act as a radioprotectant against many aspects of oxidative damage; chirality is only important for certain aspects. This pattern would be consistent with direct action of NAC in many radioprotection and repair processes, with a delimited role for NAC in GSH synthesis in some aspects of the problem.

  20. Electronic structure and isomer shifts of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Svane, A.; Petit, L.; Temmerman, W. M.; Szotek, Z.

    2002-08-01

    The electronic structures of αNp metal and 28 Np compounds are calculated with the generalized gradient approximation to density-functional theory, implemented with the full-potential linear-muffin-tin-orbital method. The calculations are compared to experimental isomer shifts providing a calibration of the 237Np isomeric transition with a value of Δ=(-40.1+/-1.3)×10- 3 fm2 for the difference in nuclear radius between the excited isomeric level and the ground state. The isomer shift is primarily determined by the chemical environment. Decreasing the volume, either by external or chemical pressure, causes an f-->s+d charge transfer on Np, which leads to a higher electron contact density. The possible f-electron localization in Np compounds is discussed using self-interaction corrections, and it is concluded that f-electron localization has only a minor influence on the isomer shift.

  1. FY2010 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Miller, Erin A.; Hatarik, R.

    2011-01-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for Special Nuclear Materials (SNM). Future work will include a follow-up measurement scheduled for December 2010 at LBNL. Lessons learned from the July 2010 measurements will be incorporated into these new measurements. Analysis of both the July and December experiments will be completed in a few months. A research paper to be submitted to a peer-reviewed journal will be drafted if the conclusions from the measurements warrant publication.

  2. Investigation of a recently detected 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol isomer: Studies on the degradation of 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol glucuronide.

    PubMed

    Hanisch, Stephanie; Paulke, Alexander; Toennes, Stefan W

    2016-09-10

    An isomer of the tetrahydrocannabinol (THC) metabolite 11-nor-9-carboxy-Δ(9)-THC (THCCOOH) had been detected in blood of cannabis users. The present study was initiated to elucidate whether the labile metabolite THCCOOH-glucuronide could be the precursor. THCCOOH-glucuronide was incubated in human serum and albumin (HSA) solution at various temperatures (-18, 4.5, 22 and 37°C) and pH values (pH 7.4 and 8.3) for seven days in the presence or absence of the esterase inhibitor sodium fluoride. Analysis of incubation samples was performed using LC-MS/MS. Marked degradation of THCCOOH-glucuronide was observed at 37°C. It was found that not only THCCOOH, but also the isomer is a degradation product of THCCOOH-glucuronide and its in-vivo production is assumed. Degradation to THCCOOH and the isomer occurred at alkaline pH, in the presence of fluoride-sensitive esterases and of HSA alone. To inhibit isomer formation during sample storage, refrigeration and controlling of the pH are recommended. However, THCCOOH and the isomer exhibit similar properties during incubations in serum, but differ in their interaction with HSA. The present study confirmed the nature of the isomer as degradation product of the abundant THC metabolite THCCOOH-glucuronide. Serum albumin and esterases are obviously involved. The isomer is formed not only during storage, but also under physiological conditions, suggesting that it can be considered an in-vivo metabolite. However, the chemical structure of the isomer remains unknown and further research is necessary.

  3. Energy spectrum and optical transitions in C80 fullerene isomers

    NASA Astrophysics Data System (ADS)

    Lobanov, B. V.; Murzashev, A. I.

    2013-04-01

    The energy spectra of all isomers of the C80 fullerene have been calculated in terms of the Schubin-Wonsowskii-Hubbard model. On this basis, their optical absorption spectra have also been calculated. The optical absorption spectra calculated for the endohedral Ca@C80, Ba@C80, and Sr@C80 fullerenes with the I h symmetry agree well with the experimental data. This circumstance allows us to conclude that the optical absorption spectra of other isomers (for which experimental data are unavailable) obtained in this work can be used for their identification.

  4. Differentiation of optical isomers through enhanced weak-field interactions

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.

    1980-01-01

    The influence of weak field interaction terms due to the cooperative effects which arise from a macroscopic assemblage of interacting sites is studied. Differential adsorption of optical isomers onto an achiral surface is predicted to occur if the surface was continuous and sufficiently large. However, the quantity of discontinuous crystal surfaces did not enhance the percentage of differentiation and thus the procedure of using large quantities of small particles was not a viable technique for obtaining a detectable differentiation of optical isomers on an achiral surface.

  5. Exotic SiO2H2 Isomers: Theory and Experiment Working in Harmony.

    PubMed

    McCarthy, Michael C; Gauss, Jürgen

    2016-05-19

    Replacing carbon with silicon can result in dramatic and unanticipated changes in isomeric stability, as the well-studied CO2H2 and the essentially unknown SiO2H2 systems illustrate. Guided by coupled-cluster calculations, three SiO2H2 isomers have been detected and spectroscopically characterized in a molecular beam discharge source using rotational spectroscopy. The cis,trans conformer of dihydroxysilylene HOSiOH, the ground-state isomer, and the high-energy, metastable dioxasilirane c-H2SiO2 are abundantly produced in a dilute SiH4/O2 electrical discharge, enabling precise structural determinations of both by a combination of isotopic measurements and calculated vibrational corrections. The isotopic studies also provide insight into their formation route, suggesting that c-H2SiO2 is formed promptly in the expansion but that cis,trans-HOSiOH is likely formed by secondary reactions following formation of the most stable dissociation pair, SiO + H2O. Although less abundant, the rotational spectrum of trans-silanoic acid, the silicon analogue of formic acid, HSi(O)OH, has also been observed.

  6. Characterization of epoxydecenal isomers as potent odorants in black tea (Dimbula) infusion.

    PubMed

    Kumazawa, Kenji; Wada, Yoshiyuki; Masuda, Hideki

    2006-06-28

    In a black tea (Dimbula) infusion, the potent "sweet and/or juicy" odorants were identified as the cis- and trans-4,5-epoxy-(E)-2-decenals by comparison of their gas chromatography retention indices, mass spectra, and odor quality to those of the actual synthetic compounds. Of the two odorants, cis-4,5-epoxy-(E)-2-decenal has been identified for the first time in the black tea. On the basis of the aroma extract dilution analysis on the flavor distillate obtained using the solvent-assisted flavor evaporation technique from the black tea infusion, these isomers showed higher flavor dilution (FD) factors. The FD factors and concentrations of these odorants in the black tea infusion were observed to be much higher than those from Japanese green tea. In addition, the model studies showed that these odorants were generated from linoleic acid and its hydroperoxides by heating, but the generated amounts of these odorants from linoleic acid were much less than those of its hydroperoxides. It can be assumed from these results that the withering and fermentation, which are characteristic processes during the manufacturing of the black tea, which includes the enzymatic reaction such as lipoxygenase, is one of the most important factors for the formation of the epoxydecenal isomers.

  7. Optical isomer separation of potential analgesic drug candidates by using capillary electrophoresis.

    PubMed

    Ferrara, G; Santagati, N A; Aturki, Z; Fanali, S

    1999-09-01

    Using cyclodextrin capillary zone electrophoresis (CD-CZE), baseline separation of synthetic potential analgesic drug diastereoisomer candidates 6,11-dimethyl-1,2,3,4,5,6-hexahydro-3-[(2'-methoxycarbonyl-2'-phenylc yclopropyl)methyl]-2,6-methano-3-benzazocin-8-ol (MPCB) and 6,11-dimethyl-1,2,3,4,5,6-hexahydro-3-[[2'-methoxycarbonyl-2'(4-chloroph enyl)cyclopropyl]methyl]-2,6-methano-3-benzazocin-8-ol (CCB) was achieved. Among the cyclodextrins tested (hydroxypropyl-, carboxymethyl- and sulfobutyl-beta-cyclodextrin (HP-beta-CD, CM-beta-CD and SBE-beta-CD)) SBE-beta-CD was found to be the most effective complexing agent, allowing good optical isomer separation. Resolution was also influenced by the CD concentration, pH of the buffer and presence of organic modifier in the background electrolyte. The optimum experimental conditions for the separation of studied analgesic drugs were found using 25 mM borate buffer at pH 9 containing 40 mM of SBE-beta-CD and 20% v/v of methanol. Using the above-mentioned background electrolyte, it was also possible to separate, in the same run, the enantiomers of normetazocine (NMZ) as well as the optical isomers of (+/-)-cis-2-chloromethyl-1-phenyl cyclopropancarboxylic acid methyl ester (PCE) or (+/-)-cis-2-chloromethyl-1-(4-chlorophenyl)cyclopropancarboxylic acid methyl ester (CPCE) reagents used in the synthesis of the studied analgesic drugs).

  8. The spectroscopy and photochemistry of quinioline structural isomers: (E)- and (Z)-phenylvinylnitrile

    SciTech Connect

    Mehta-Hurt, Deepali N.; Korn, Joseph A.; Navotnaya, Polina; Parobek, Alexander P.; Clayton, Rachel M.; Zwier, Timothy S.

    2015-08-21

    In Titan’s atmosphere, photochemical pathways that lead to nitrogen heteroaromatics may incorporate photoisomerization of their structural isomers as a final step. (E)- and (Z)-phenylvinylnitrile ((E)- and (Z)-PVN, C{sub 6}H{sub 5} —CH=CHCN) are structural isomers of quinoline that themselves possess extensive absorptions in the ultraviolet, and thus may engage in such photoisomerization pathways. The present study explores the vibronic spectroscopy and photo-induced isomerization of gas-phase (E)- and (Z)-PVN in the 33,600-35,850 cm{sup −1} region under jet-cooled conditions. The S{sub 0}-S{sub 1} origins for (E)- and (Z)-PVN have been identified at 33 827 cm{sup −1} and 33 707 cm{sup −1}, respectively. Isomer-specific UV-UV hole-burning and UV depletion spectra reveal sharp vibronic structure that extends over almost 2000 cm{sup −1}, with thresholds for fast non-radiative decay identified by a comparison between hole-burning and UV depletion spectra. Dispersed fluorescence spectra of the two isomers enable the assignment of many low frequency transitions in both molecules, aided by harmonic frequency calculations (B3LYP/6-311++G(d,p)) and a comparison with the established spectroscopy of phenylvinylacetylene, the ethynyl counterpart to PVN. Both isomers are proven to be planar in both the S{sub 0} ground and S{sub 1} electronic excited states. (E)-PVN exhibits extensive Duschinsky mixing involving out-of-plane modes whose frequencies and character change significantly in the ππ{sup ∗} transition, which modulates the degree of single- and double-bond character along the vinylnitrile substituent. This same mixing is much less evident in (Z)-PVN. The spectroscopic characterization of (E)- and (Z)-PVN served as the basis for photoisomerization experiments using ultraviolet hole-filling spectroscopy carried out in a reaction tube affixed to the pulsed valve. Successful interconversion between (E) and (Z)-PVN was demonstrated via ultraviolet hole

  9. SYNTHESIS AND ISOLATION OF TETRAHYDROCANNABINOL ISOMERS.

    DTIC Science & Technology

    In addition to cannabinol, cannabidiol , and trans-1-hydroxy-3-n-amyl-6, 6, 9 trimethyl-6a, 7, 8, 10a-tetrahydro-6-dibenzopyran (tetrahydrocannabinol...only cannabidiolic acid. A second sample of Mexican marijuana furnished only tetrahydrocannabinol A and cannabinol, while a Spanish sample contained an...additional amount of cannabidiol . The structure of tetrahydrocannabinol B was elucidated by chemical and spectral evidence. The partial syntheses of

  10. Effect of acetic acid present in bagasse hydrolysate on the activities of xylose reductase and xylitol dehydrogenase in Candida guilliermondii.

    PubMed

    Lima, Luanne Helena Augusto; das Graças de Almeida Felipe, Maria; Vitolo, Michele; Torres, Fernando Araripe Gonçalves

    2004-11-01

    The first two steps in xylose metabolism are catalyzed by NAD(P)H-dependent xylose reductase (XR) (EC 1.1.1.21) and NAD(P)-dependent xylitol dehydrogenase (XDH) (EC 1.1.1.9), which lead to xylose-->xylitol-->xylulose conversion. Xylitol has high commercial value, due to its sweetening and anticariogenic properties, as well as several clinical applications. The acid hydrolysis of sugarcane bagasse allows the separation of a xylose-rich hemicellulosic fraction that can be used as a substrate for Candida guilliermondii to produce xylitol. However, the hydrolysate contains acetic acid, an inhibitor of microbial metabolism. In this study, the effect of acetic acid on the activities of XR and XDH and on xylitol formation by C. guilliermondii were studied. For this purpose, fermentations were carried out in bagasse hydrolysate and in synthetic medium. The activities of XR and XDH were higher in the medium containing acetic acid than in control medium. Moreover, none of the fermentative parameters were significantly altered during cell culture. It was concluded that acetic acid does not interfere with xylitol formation since the increase in XR activity is proportional to XDH activity, leading to a greater production of xylitol and its subsequent conversion to xylulose.

  11. Health benefits of conjugated linoleic acid (CLA).

    PubMed

    Koba, Kazunori; Yanagita, Teruyoshi

    2014-01-01

    Conjugated linoleic acid (CLA) is a group of positional and geometric (cis or trans) isomers of linoleic acid with a conjugated double bond. The most representative CLA isomers are 9c,11t-18:2 and 10t,12c-18:2. CLA has been shown to exert various potent physiological functions such as anticarcinogenic, antiobese, antidiabetic and antihypertensive properties. This means CLA can be effective to prevent lifestyle diseases or metabolic syndromes. Also, reports suggest that physiological effects of CLA are different between the isomers, for example the 10t,12c isomer is anticarcinogenic, antiobese and antidiabetic, whereas the 9c,11t isomer is mainly anticarcinogenic. We describe here the physiological properties of CLA including the possible mechanism and the possibility to benefit human health.

  12. Characterization of Nα-Fmoc-protected dipeptide isomers by electrospray ionization tandem mass spectrometry (ESI-MS(n)): effect of protecting group on fragmentation of dipeptides.

    PubMed

    Ramesh, M; Raju, B; Srinivas, R; Sureshbabu, V V; Vishwanatha, T M; Hemantha, H P

    2011-07-30

    A series of positional isomeric pairs of Fmoc-protected dipeptides, Fmoc-Gly-Xxx-OY/Fmoc-Xxx-Gly-OY (Xxx=Ala, Val, Leu, Phe) and Fmoc-Ala-Xxx-OY/Fmoc-Xxx-Ala-OY (Xxx=Leu, Phe) (Fmoc=[(9-fluorenylmethyl)oxy]carbonyl) and Y=CH(3)/H), have been characterized and differentiated by both positive and negative ion electrospray ionization ion-trap tandem mass spectrometry (ESI-IT-MS(n)). In contrast to the behavior of reported unprotected dipeptide isomers which mainly produce y(1)(+) and/or a(1)(+) ions, the protonated Fmoc-Xxx-Gly-OY, Fmoc-Ala-Xxx-OY and Fmoc-Xxx-Ala-OY yield significant b(1)(+) ions. These ions are formed, presumably with stable protonated aziridinone structures. However, the peptides with Gly- at the N-terminus do not form b(1)(+) ions. The [M+H](+) ions of all the peptides undergo a McLafferty-type rearrangement followed by loss of CO(2) to form [M+H-Fmoc+H](+). The MS(3) collision-induced dissociation (CID) of these ions helps distinguish the pairs of isomeric dipeptides studied in this work. Further, negative ion MS(3) CID has also been found to be useful for differentiating these isomeric peptide acids. The MS(3) of [M-H-Fmoc+H](-) of isomeric peptide acids produce c(1)(-), z(1)(-) and y(1)(-) ions. Thus the present study of Fmoc-protected peptides provides additional information on mass spectral characterization of the dipeptides and distinguishes the positional isomers.

  13. Characterization and determination of piperine and piperine isomers in eggs.

    PubMed

    Ternes, Waldemar; Krause, Edburga L

    2002-09-01

    A new analytical method for the determination of piperine and its isomers in egg yolk and albumen is described here. All four isomers were separated by HPLC and detected using UV, DAD and electrochemical detection. The absolute detection limit (UV detection, S/ N=3) of a standard solution of piperine was 370 pg piperine. The correlation coefficients for the linear calibration graphs (concentration range: c=100 ng-10 micro g piperine isomer/mL) are generally better than 0.996. The piperine isomers were characterized and identified by spectroscopy (MS, (1)H-NMR, FT-IR). The method was successfully applied to the determination of piperine deposits in eggs (egg yolk and albumen) after feeding hens with piperine-spiked feed. The detection limit for piperine (24.8(+/-0.2) ng/g egg yolk and 37.9(+/-4.9) ng/g albumen) and the recoveries (70.3(+/-7.7)% (egg yolk) and 75.7(+/-1.9)% (albumen)) of piperine were determined.

  14. Short-lived isomers in 192Po and 194Po

    NASA Astrophysics Data System (ADS)

    Andel, B.; Andreyev, A. N.; Antalic, S.; Heßberger, F. P.; Ackermann, D.; Hofmann, S.; Huyse, M.; Kalaninová, Z.; Kindler, B.; Kojouharov, I.; Kuusiniemi, P.; Lommel, B.; Nishio, K.; Page, R. D.; Sulignano, B.; Van Duppen, P.

    2016-06-01

    Isomeric states in 194Po and 192Po were studied at the velocity filter SHIP. The isotopes were produced in the fusion-evaporation reactions 141Pr(56Fe, p 2 n )194Po and 144Sm(51V, p 2 n )192Po . Several new γ -ray transitions were attributed to the isomers and γ -γ coincidences for both isomers were studied for the first time. The 459-keV transition earlier, tentatively proposed as de-exciting the isomeric level in 194Po, was replaced by a new 248-keV transition, and the spin of this isomer was reassigned from (11-) to (10-). The de-excitation of the (11-) isomeric level in 192Po by the 154-keV transition was confirmed and a parallel de-excitation by a 733-keV (E 3 ) transition to (8+) level of the ground-state band was suggested. Moreover, side feeding to the (4+) level of the ground-state band was proposed. The paper also discusses strengths of transitions de-exciting 11- isomers in neighboring Po and Pb isotopes.

  15. Enantioselective separation of defined endocrine-disrupting nonylphenol isomers.

    PubMed

    Acir, Ismail-Hakki; Wüst, Matthias; Guenther, Klaus

    2016-08-01

    Nonylphenol is in the focus of worldwide endocrine-disrupter research and accounted for as a priority hazardous substance of the Water Framework Directive of the European Union. Technical nonylphenol consists of a very complex mixture of isomers and enantiomers. As estrogenic effect and degradation behavior in environmental processes of single nonylphenols are heavily dependent on the structure of the nonyl side chain, it is absolutely necessary to consider the nonylphenol problem from an isomer and enantiomer-specific viewpoint. In this study, an enantiomer-specific separation of eight defined synthesized nonylphenol isomers by five different special chiral cyclodextrin columns was performed underivatized and after methylation, silylation, and acylation. This work demonstrates that three columns out of the investigated five show an excellent separation behavior for the studied different nonylphenol isomers and can be used for the enantiomer-specific determination of nonylphenols in food, other biological matrices, and environmental samples in the future. Graphical abstract Enantiomeric pair of 4-NP170 (4-[1-ethyl-1,3,3-trimethylbutyl]phenol).

  16. High Spin Isomers and Super Heavy Elements (SHE) Synthesis

    SciTech Connect

    Popescu, Domitian G.

    2010-04-30

    To get closer to the SHE-Island the new radioactive beams are proposed for future fusion reaction. We suggest something different: to use the advantage of High Spin Isomer States, by tacking into account the importance of the G (spin-isospin cupling) suggested by Ripka 1.

  17. Flexible metal–organic supramolecular isomers for gas separation

    SciTech Connect

    Motkuri, Radha K.; Tian, Jian; Thallapally, Praveen K.; Fernandez, Carlos A.; Dalgarno, Scott J.; Warren, John E.; McGrail, B. Peter; Atwood, Jerry L.

    2010-01-01

    Here in we report three porous metal-organic supramolecular isomers (PtS, Diamondoid and Lonsdaleite networks) generated from a single building block (tetrakis[4-(carboxyphenyl)oxamethyl]methane, 1), with the differences in solid-state packing, amount of gas uptake and selectivity towards other gases and so on

  18. Electronic Structure Mediated Vibrational Coherence in Methyl Acetophenone Isomers

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Lozovoy, Vadim; Levine, Benjamin; Dantus, Marcos

    2014-05-01

    The role of ground and excited state electronic structures in influencing the vibrational coherences in gas phase polyatomic molecules has been a hot topic for quite some time. Here we explore the time resolved dynamics of acetophenone and its methyl substituted isomer when excited by intense 800nm femtosecond pump and probe pulses. The parent ion yield show 500 fs modulations that die down within 3ps. Similar modulations having the same timescales in the parent ion yield are also observed for the p-methyl isomer. The o-methyl isomer however shows longer 1ps modulations. Interestingly enough no oscillations are observed for the meta isomer. Quantum chemical calculations at the CASSCF/6-311G level of theory predicts that upon excitation the neutral ground state is planar and the energy spacing between the levels is very small. Preliminary calculations also predict torsional motion coupled to electronic modulations on the D0 state and further calculations are being performed to ascertain the involvement of the D1 and D2 states. This could help us better understand the electronic effect of substitution on a benzene ring.

  19. Electronic Structure Mediated Vibrational Coherence in Methyl Acetophenone Isomers

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Levine, Benjamin; Lozovoy, Vadim; Dantus, Marcos

    2014-03-01

    The role of ground and excited state electronic structures in influencing the vibrational coherences in gas phase polyatomic molecules has been a hot topic for quite some time. Here we explore the time resolved dynamics of acetophenone and its methyl substituted isomer when excited by intense 800nm femtosecond pump and probe pulses. The parent ion yield show 500 fs modulations that die down within 3ps. Similar modulations having the same timescales in the parent ion yield are also observed for the p-methyl isomer. The o-methyl isomer however shows longer 1ps modulations. Interestingly enough no oscillations are observed for the meta isomer. Quantum chemical calculations at the CASSCF/6-311G level of theory predicts that upon excitation the neutral ground state is planar and the energy spacing between the levels is very small. Preliminary calculations also predict torsional motion coupled to electronic modulations on the D0 state and further calculations are being performed to ascertain the involvement of the D1 and D2 states. This could help us better understand the electronic effect of substitution on a benzene ring.

  20. Preliminary Results: Release Of Metals From Acid-Mine Drainage Contaminated Streambed Sediments Under Anaerobic Conditions (Presentation)

    EPA Science Inventory

    Many miles of streams in the western U.S. are contaminated with acid-mine drainage (AMD) from abandoned metal mines. Treatment of these streams may include removal of the existing sediments, with subsequent burial (e.g., in a repository). Burial of previously aerobic sediments ma...

  1. FY2011 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Tatishvili, Gocha; Hatarik, R.

    2011-10-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for SNM. This project entails isomer identification and characterization and neutron population studies. This document summarizes activities from its third year - completion of the isomer identification characterization experiments and initialization of the neutron population experiments. The population and decay of the isomeric state in 235U remain elusive, although a number of candidate gamma rays have been identified. In the course of the experiments, a number of fission fragment isomers were populated and measured [Ressler 2010]. The decays from these isomers may also provide a suitable signature for the presence of fissile material. Several measurements were conducted throughout this project. This report focuses on the results of an experiment conducted collaboratively by PNNL, LLNL and LBNL in December 2010 at LBNL. The measurement involved measuring the gamma-rays emitted from an HEU target when bombarded with 11 MeV neutrons. This report discussed the analysis and resulting conclusions from those measurements. There was one strong candidate, at 1204 keV, of an isomeric signature of 235U. The half-life of the state is estimated to be 9.3 {mu}s. The measured time dependence fits the decay time structure very well. Other possible explanations for the 1204-keV state were investigated, but they could not explain the gamma ray. Unfortunately, the relatively limited statistics of the measurement limit, and the lack of understanding of some of the systematic of the experiment, limit

  2. Computational Docking of the Isomers of Nonylphenol to the Ligand Binding Domain of the Estrogen Receptor

    EPA Science Inventory

    Nonylphenols are environmentally persistent endocrine disrupting chemicals. They exist in the environment as complex mixtures containing many nonylphenol isomers. Environmental mixtures of nonylphenols, along with a few single isomers have been tested for their capacity to inte...

  3. Simultaneous extraction and determination of HBCD isomers and TBBPA by ASE and LC-MSMS in fish.

    PubMed

    ten Dam, Guillaume; Pardo, Olga; Traag, Wim; van der Lee, Martijn; Peters, Ruud

    2012-06-01

    Since the EFSA enquired a call for data for TBBPA and HBCD in 2009, the analytical determination of these compounds in food became of regulatory interest. Therefore, a method for the simultaneous determination of TBBPA and the three major HBCD stereoisomers was developed. Conventional techniques like soxhlet, ASE, GPC, sulphuric acid digestion, and acidified silica SPE are generally used in sample pre-treatment while detection is mostly performed by LC-MSMS. A combined analysis of HBCD and TBBPA is problematic due to the hydroxyl groups in the TBBPA molecule. However, using a specific mesh-size sodium sulphate in ASE extraction and an acid silica column combined with a Sep-pack Plus silica cartridge for purification resulted in recoveries between 80% and 110% for all compounds. The accuracy and reproducibility determined using proficiency test samples were 104% and 4% for the sum of the HBCD isomers. Typical limits of detection were 0.01 ng/g product or 0.004 ng on column, while the linear dynamic range is between 0.01 ng and 10 ng on column. Levels of TBBPA and HBCD isomers were determined in eel samples. TBBPA was occasionally detected and only marginally above the quantification limit of 0.05 ng/g, whereas total amounts of HBCD were between 0.2 and 150 ng/g with α-HBCD being the dominant HBCD isomer.

  4. Density functional theory study of the oligomerization of carboxylic acids.

    PubMed

    Di Tommaso, Devis; Watson, Ken L

    2014-11-20

    We present a density functional theory [M06-2X/6-31+G(d,p)] study of the structures and free energies of formation of oligomers of four carboxylic acids (formic acid, acetic acid, tetrolic acid, and benzoic acid) in water, chloroform, and carbon tetrachloride. Solvation effects were treated using the SMD continuum solvation model. The low-lying energy structures of molecular complexes were located by adopting an efficient search procedure to probe the potential energy surfaces of the oligomers of carboxylic acids (CA)n (n = 2-6). The free energies of the isomers of (CA)n in solution were determined as the sum of the electronic energy, vibrational-rotational-translational gas-phase contribution, and solvation free energy. The assessment of the computational protocol adopted in this study with respect to the dimerization of acetic acid, (AA)2, and formic acid, (FA)2, located new isomers of (AA)2 and (FA)2 and gave dimerization constants in good agreement with the experimental values. The calculation of the self-association of acetic acid, tetrolic acid, and benzoic acid shows the following: (i) Classic carboxylic dimers are the most stable isomer of (CA)2 in both the gas phase and solution. (ii) Trimers of carboxylic acid are stable in apolar aprotic solvents. (iii) Molecular clusters consisting of two interacting classic carboxylic dimers (CA)4,(D+D) are the most stable type of tetramers, but their formation from the self-association of classic carboxylic dimers is highly unfavorable. (iv) For acetic acid and tetrolic acid the reactions (CA)2 + 2CA → (CA)4,(D+D) and (CA)3 + CA → (CA)4,(D+D) are exoergonic, but these aggregation pathways go through unstable clusters that could hinder the formation of tetrameric species. (v) For tetrolic acid the prenucleation species that are more likely to form in solution are dimeric and trimeric structures that have encoded structural motifs resembling the α and β solid forms of tetrolic acid. (vi) Stable tetramers of

  5. Low-Lying Isomers of the B9- Boron Cluster: The Planar Molecular Wheel Versus Three-Dimensional Structures

    SciTech Connect

    Pan, Li-Li; Li, Jun; Wang, Lai S.

    2008-07-14

    The B9- cluster was found previously to be an unprecedented molecular wheel containing an octacoordinate planar boron with D8h symmetry in a combined photoelectron spectroscopy (PES) and theoretical study [H. J. Zhai et al., Angew. Chem. Int. Ed. 42, 6004 (2003)]. However, the PES spectra of B9- exhibit minor features that cannot be explained by the global minimum D8h structure, suggesting possible contributions from low-lying isomers at finite temperatures. Here we present Car-Parrinello molecular dynamics with simulated annealing simulations to fully explore the potential energy surface of B9- and search for low-lying isomers that may account for the minor PES features. We performed density functional theory (DFT) calculations with different exchange-correlation functionals and ab initio calculations at various levels of theory with different basis sets. Two three-dimensional low-lying isomers were found, both of Cs symmetry, 6.29 (Cs-2) and 10.23 (Cs-1) kcal/mol higher in energy than the D8h structure at the highest CCSD(T) level of theory. Calculated detachment transitions from the Cs-2 isomer are in excellent agreement with the minor features observed in the PES spectra of B9-. The B9- cluster proves to be a challenge for most DFT methods and the calculated relative energies strongly depend on the exchange-correlation functionals, providing an excellent example for evaluating the accuracies of various DFT methods.

  6. Resonance conditions for Mom93 isomer depletion via nuclear excitation by electron capture in a beam-based scenario

    NASA Astrophysics Data System (ADS)

    Polasik, M.; Słabkowska, K.; Carroll, J. J.; Chiara, C. J.; Syrocki, Ł.; WÈ©der, E.; Rzadkiewicz, J.

    2017-03-01

    We present here a comprehensive analysis to understand the optimal atomic conditions for the first experimental observation of nuclear excitation by electron capture (NEEC) for the 6.85 h Mom93 isomer with spin parity 21 /2+ . The NEEC process would provide an excitation from the long-lived isomer to a depletion level with spin parity 17 /2+ , which lies only 4.85 keV higher in energy, and is itself a shorter-lived isomer that subsequently decays, releasing a substantial amount of stored energy (2429.8 keV). The depletion level decays to a 13 /2+ state through a 267.9-keV transition that offers the opportunity for identification of NEEC because it does not occur in the natural decay of the long-lived isomer. It has been shown that, for the proposed approach, high-precision atomic predictions are essential to understanding the proper physical conditions under which the experimental observation of the NEEC process will be possible using a beam-based scenario.

  7. Unexpected Changes in the Population of Coordination Isomers for the Lanthanide Ion Complexes of DOTMA-Tetraglycinate.

    PubMed

    Kumas, Cemile; Fernando, W Shirangi; Zhao, Piyu; Regueiro-Figueroa, Martín; Kiefer, Garry E; Martins, André F; Platas-Iglesias, Carlos; Sherry, A Dean

    2016-09-19

    Lanthanide complexes with DOTA-tetraglycinate (DOTA-(gly)4) heavily favor the square antiprismatic (SAP) coordination isomer in aqueous solution, a structural feature that has made them useful as water-based paraCEST agents. In an effort to create amide-based paraCEST agents with rapid water exchange rates, we prepared the analogous tetraglycinate complexes with DOTMA, a ligand known to favor the twisted square antiprismatic (TSAP) coordination structures. Unexpectedly, NMR investigations show that the LnDOTMA-(gly)4 complexes, like the LnDOTA-(gly)4 complexes, also favor the SAP isomers in solution. This observation led to density functional theory (DFT) calculations in order to identify the energy terms that favor the SAP structures in lanthanide complexes formed with macrocyclic DOTA- and DOTMA-tetraamide ligands. The DFT calculations revealed that, regardless the nature of the ligand, the TSAP isomers present more negative hydration energies than the SAP counterparts. The extent to which the TSAP isomer is stabilized varies, however, depending on the ligand structure, resulting in different isomeric populations in solution.

  8. 40 CFR 180.1073 - Isomate-M; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Isomate-M; exemption from the... Exemptions From Tolerances § 180.1073 Isomate-M; exemption from the requirement of a tolerance. The oriental fruit moth pheromone (Isomate-M) (Z-8-dodecen-l-yl acetate, E-8-dodecen-l-yl acetate,...

  9. 40 CFR 180.1073 - Isomate-M; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Isomate-M; exemption from the... Exemptions From Tolerances § 180.1073 Isomate-M; exemption from the requirement of a tolerance. The oriental fruit moth pheromone (Isomate-M) (Z-8-dodecen-l-yl acetate, E-8-dodecen-l-yl acetate,...

  10. Isomer selective ionization of chlorinated PAH's: Detection of impurities in technical 9-monochloroanthracene

    SciTech Connect

    Zimmermann, Ralf; Lermer, Christoph; Lenoir, Dieter; Boesl, Ulrich

    1995-04-01

    Two-color RIS of anthracene (A), of all of its monochloroisomers and one dichlorinated (DCA) isomer have been measured. The possibility of isomer selective resonance ionization of the monochloroanthracenes (MCA) is demonstrated. A technical sample of the 9-DCA isomer has been investigated; no impurities of monochroroisomers have been found but significant impurities of non-chlorinated A and 9, 10-DCA.

  11. 40 CFR 721.10564 - Mixed amino diaryl sulfone isomers (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed amino diaryl sulfone isomers... Specific Chemical Substances § 721.10564 Mixed amino diaryl sulfone isomers (generic). (a) Chemical... as mixed amino diaryl sulfone isomers (PMN P-08-39) is subject to reporting under this section...

  12. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Cypermethrin and an isomer zeta... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances for... (±))(cis-trans 3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropanecarboxylate and its inactive R-isomers in...

  13. 40 CFR 721.10564 - Mixed amino diaryl sulfone isomers (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed amino diaryl sulfone isomers... Specific Chemical Substances § 721.10564 Mixed amino diaryl sulfone isomers (generic). (a) Chemical... as mixed amino diaryl sulfone isomers (PMN P-08-39) is subject to reporting under this section...

  14. Isomer-specific biodegradation of nonylphenol in an activated sludge bioreactor and structure-biodegradability relationship.

    PubMed

    Lu, Zhijiang; Reif, Rubén; Gan, Jay

    2015-01-01

    Nonylphenol (NP), one of the priority hazardous substances, is in fact a mixture of numerous isomers. It is inconclusive whether or not biodegradation during wastewater treatment process is isomer-specific, leading to the environmental release of NP in different isomer profiles. In this study, we evaluated the isomer selectivity of 19 NP isomers in a laboratory-scale continuous flow conventional activated sludge bioreactor under various operational conditions. The removal efficiency of NP isomers ranged from 90 to 99%, depending on the operational conditions and isomer structures. Isomer selective biodegradation resulted in the increase of composition of recalcitrant isomers, such as, NP₁₉₃a/b, NP₁₁₀a and NP₁₉₄ in the effluent. Moreover, biodegradability was related to the bulkiness of α-substituents and followed α-dimethyl > α-ethyl-α-methyl > α-methyl-α-n-propyl > α-iso-propyl-α-methyl. Steric effect index, a quantitative descriptor of steric hindrance, was linearly correlated with residues of NP isomers in the effluent (R² = 0.76). Decrease of temperature to 10 °C decreased the overall biodegradability and also enhanced the relative enrichment of recalcitrant isomers. These findings suggest that isomer compositions of NP entering the environment may be different from those in technical mixtures and that isomeric selectivity should be taken into account to better understand the occurrence, fate, and ecological risks of NP.

  15. Effect of storage and cooking on beta-carotene isomers in carrots ( Daucus carota L. cv. 'Stefano').

    PubMed

    Imsic, Michael; Winkler, Sonja; Tomkins, Bruce; Jones, Rod

    2010-04-28

    Carrots are one of the highest dietary sources of beta-carotene and are naturally high in the (all-E)-beta-carotene isomer, which has higher bioavailability, provitamin A activity, and antioxidant capacity compared to Z (cis) isomers. The objectives of the present study were to investigate the effects of storage temperature, time, and cooking (boiling for 15 min) on the levels of carotene isomers in 'Stefano' carrots. Storing carrots at either 4 degrees C to simulate long-term storage or 20 degrees C to simulate marketing practices resulted in increases in (all-E)-beta-carotene of 20.3% after 3 days at 4 degrees C and 34.4% after 14 days at 20 degrees C, respectively. The levels of Z isomers in raw carrots were low with (13Z)-beta-carotene and (9Z)-beta-carotene accounting for less that 1.8% of the total beta-carotene present. Levels of (9Z)-beta-carotene decreased during storage at either temperature, whereas storage at 4 degrees C resulted in a 109% increase in (13Z)-beta-carotene after 56 days. Cooking significantly increased the levels of (13Z)-beta-carotene and (9Z)-beta-carotene and resulted in the production of (15Z)-beta-carotene, which was absent in raw carrots. Storage at 4 degrees C for 15 days or more prior to cooking reduced the susceptibility of (all-E)-beta-carotene to thermal isomerization during cooking, resulting in lower levels of all three Z-beta-carotene isomers being generated, while storage at 20 degrees C for up to 21 days resulted in significantly higher levels of (all-E)-beta-carotene before and after cooking but had no effect on Z-isomer production during cooking. Consequently, we conclude that, for the greatest health benefit, fresh carrots can be stored for up to 21 days at 20 degrees C or at 4 degrees C for up to 56 days without significant reduction in (all-E)-beta-carotene and should be consumed raw or boiled for less than 15 min to limit Z-beta-carotene isomer formation.

  16. Influence of different CLA isomers on insulin resistance and adipocytokines in pre-diabetic, middle-aged men with PPARγ2 Pro12Ala polymorphism.

    PubMed

    Rubin, Diana; Herrmann, Julia; Much, Daniela; Pfeuffer, Maria; Laue, C; Winkler, P; Helwig, Ulf; Bell, Doris; Auinger, Annegret; Darabaneanu, Stephanie; Ruether, Andreas; Schrezenmeir, Jürgen

    2012-10-01

    Conjugated linoleic acids (CLAs) are natural PPARγ ligands, which showed conflicting effects on metabolism in humans. We examined metabolic effects of different isomers of CLA in subjects with PPARγ2 Pro12Ala polymorphisms. A total of 35 men underwent four intervention periods in a crossover study design: subjects with either genotypes received c9, t11 CLA or t10, c12 CLA, a commercially available 1:1 mix of both isomers or reference oil (linoleic acid (LA)). Adipocytokines, insulin, glucose and triglycerides were assessed in the fasting state and after a standardized mixed meal. Across all genotypes, there was a significant (p = 0.025) CLA treatment effect upon postprandial (pp) HOMA-IR values, with c9, t11 CLA and CLA isomer mix improving, but t10, c12 CLA isomer worsening. In Ala12Ala subjects, the t10, c12 isomer caused weight gain (p = 0.03) and tended to increase postprandial insulin levels (p = 0.05). In Pro12Pro subjects, t10, c12 resulted in reduction in waist circumference (p = 0.03). The comparison of the different genotype groups revealed statistically different changes in fasting and postprandial insulin, HOMA-IR and leptin after intervention. c9, t11 CLA and the commercial CLA mix showed beneficial effects on insulin sensitivity compared with LA, while t10, c12 CLA adversely affects body weight and insulin sensitivity in different PPAR genotypes. CLA isomers have different effects on metabolism in Ala and Pro carriers.

  17. Systematic trends in the237neptunium Mössbauer isomer shift: Overlap of IV, V and VI neptunium oxidation states and correlation between isomer shift and crystal structure

    NASA Astrophysics Data System (ADS)

    Jové, J.; Cousson, A.; Abazli, H.; Tabuteau, A.; Thévenin, T.; Pagès, M.

    1988-01-01

    The influence of the neptunium ion environment on the237Np Mössbauer isomer shifts has been studied in various metal coordination complexes: fluorides, oxides, oxide fluorides and polycarboxylates. A linear dependence between the isomer shift and the mean neptunium-ligand distance in a series of hexavalent Np compounds has been evidenced and the feasibility of overlapped isomer shift areas, namely Np(IV), Np(V) and Np(VI) has been established.

  18. Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns.

    PubMed

    Neuer-Etscheidt, K; Orasche, J; Nordsieck, H; Streibel, T; Zimmermann, R; Kettrup, A

    2007-04-01

    In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from

  19. Quadrupole splitting and isomer shifts in Te oxides investigated using nuclear forward scattering

    NASA Astrophysics Data System (ADS)

    Klobes, Benedikt; Barrier, Nicolas; Vertruyen, Benedicte; Martin, Christine; Hermann, Raphaël P.

    2014-04-01

    Nuclear forward scattering by 125Te is a viable alternative to conventional 125Te Mössbauer spectroscopy avoiding all source related issues. Using reference compounds with known hyperfine parameters and Te oxides exhibiting stereochemically active lone pairs, we show that nuclear forward scattering by 125Te can be reliably used to extract quadrupole splitting energy and relative isomer shift. The rough correlation between Te-Ocoordination and quadrupole splitting energy as put forward by Takeda and Greenwood (J. Chem. Soc. Dalton, 2207, 1975), is corroborated by the presented results.

  20. Calculated yield of isomer depletion due to NEEC for {sup 93m}Mo recoils

    SciTech Connect

    Karamian, S. A.; Carroll, J. J.

    2012-11-15

    In the present work, quantitative calculations were carried out for production and depletion of the {sup 93m}Mo isomer in a relatively simple experiment using {sup 91}Zr beam ions. Such studies could be arranged at existing and operating accelerator facilities, e.g. at GSI or in JINR. The {sup 93m}Mo nuclei produced in a He gas target due to the {sup 4}He({sup 91}Zr, 2n) reaction will recoil into a gas stopper with a high velocity, being then depleted due to NEEC in highly-ionized species.

  1. Isomer-specific determination of 4-nonylphenols using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry

    USGS Publications Warehouse

    Eganhouse, R.P.; Pontolillo, J.; Gaines, R.B.; Frysinger, G.S.; Gabriel, F.L.P.; Kohler, H.-P.E.; Giger, W.; Barber, L.B.

    2009-01-01

    Technical nonylphenol (tNP), used for industrial production of nonylphenol polyethoxylate surfactants, is a complex mixture of C3-10-phenols. The major components, 4-nonylphenols, are weak endocrine disruptors whose estrogenicities vary according to the structure of the branched nonyl group. Thus, accurate risk assessment requires isomer-specific determination of 4-NPs. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/ ToFMS) was used to characterize tNP samples obtained from seven commercial suppliers. Under optimal chromatographic conditions, 153-204 alkylphenol peaks, 59-66 of which were identified as 4-NPs, were detected. The 4-NPs comprised ???86-94% of tNP, with 2-NPs and decylphenols making up???2-9%and???2-5%, respectively. The tNP products were analyzed for eight synthetic 4-NP isomers, and results were compared with published data based on GC/ MS analysis. Significant differences were found among the products and between two samples from a single supplier. The enhanced resolution of GC x GC coupled with fast mass spectral data acquisition by ToFMS facilitated identification of all major 4-NP isomers and a number of previously unrecognized components. Analysis of tNP altered by the bacterium, Sphingobium xenophagum Bayram, revealed several persistent 4-NPs whose structures and estrogenicities are presently unknown. The potential of this technology for isomer-specific determination of 4-NP isomers in environmental matrices is demonstrated using samples of wastewatercontaminated groundwater and municipal wastewater. ?? 2009 American Chemical Society.

  2. Cis and Trans Isomers of Cycloalkenes

    ERIC Educational Resources Information Center

    Barrows, Susan E.; Eberlein, Thomas H.

    2005-01-01

    A study investigates the strain in medium-sized cycloalkenes and the geometric and electronic distortions through which alkenes can relieve that strain. Literature data is summarized and results are presented with the aim of providing a concise reference for those interested in addressing the topic in an introductory organic chemistry curriculum.

  3. Population and decay of a Kπ=8– two-quasineutron isomer in Pu244

    DOE PAGES

    Hota, S. S.; Tandel, S. K.; Chowdhury, P.; ...

    2016-08-22

    Here, the decay of a Kπ = 8– isomer in 244Pu and the collective band structures populating the isomer were studied using deep inelastic excitations with 47Ti and 208Pb beams, respectively. Precise measurements of M1/E2 branching ratios in the band confirm a 9/2–[734]νⓍ7/2+[624]ν configuration assignment for the isomer, validating the systematics of Kπ = 8–, two-quasineutron isomers observed in even-Z, N = 150 isotones. These isomers around the deformed shell gap at N = 152 provide critical benchmarks for theoretical predictions of single-particle energies in this gateway region to superheavy nuclei.

  4. Population and decay of a Kπ=8- two-quasineutron isomer in 244Pu

    NASA Astrophysics Data System (ADS)

    Hota, S. S.; Tandel, S. K.; Chowdhury, P.; Ahmad, I.; Carpenter, M. P.; Chiara, C. J.; Greene, J. P.; Hoffman, C. R.; Jackson, E. G.; Janssens, R. V. F.; Kay, B. P.; Khoo, T. L.; Kondev, F. G.; Lakshmi, S.; Lalkovski, S.; Lauritsen, T.; Lister, C. J.; McCutchan, E. A.; Moran, K.; Peterson, D.; Shirwadkar, U.; Seweryniak, D.; Stefanescu, I.; Toh, Y.; Zhu, S.

    2016-08-01

    The decay of a Kπ=8- isomer in 244Pu and the collective band structures populating the isomer were studied using deep inelastic excitations with 47Ti and 208Pb beams, respectively. Precise measurements of M 1 /E 2 branching ratios in the band confirm a 9 /2-[734] ν⊗7 /2+[624] ν configuration assignment for the isomer, validating the systematics of Kπ=8- , two-quasineutron isomers observed in even-Z , N =150 isotones. These isomers around the deformed shell gap at N =152 provide critical benchmarks for theoretical predictions of single-particle energies in this gateway region to superheavy nuclei.

  5. Nalidixic Acid-Resistant Salmonella enterica Serotype Typhi Presenting as a Primary Psoas Abscess: Case Report and Review of the Literature

    PubMed Central

    Shakespeare, William A.; Davie, Daniel; Tonnerre, Claude; Rubin, Michael A.; Strong, Michael; Petti, Cathy A.

    2005-01-01

    We report an unusual case of Salmonella enterica serotype Typhi presenting as a primary psoas abscess. The isolate tested susceptible to ciprofloxacin but resistant to nalidixic acid in vitro, a pattern associated with fluoroquinolone therapeutic failures. We review the literature for serovar Typhi psoas abscess in the absence of bacteremia and discuss the importance of identifying isolates with reduced susceptibility to fluoroquinolones. PMID:15695728

  6. Influence on Levels of Information as Presented by Different Technologies on Students' Understanding of Acid, Base, and pH Concepts.

    ERIC Educational Resources Information Center

    Nakhleh, Mary B.; Krajcik, Joseph S.

    1994-01-01

    Involves secondary students in a study designed to allow investigation into how different levels of information presented by various technologies (chemical indicators, pH meters, and microcomputer-based laboratories-MBLs) affected students' understanding of acid, base, and pH concepts. Results showed that students using MBLs exhibited a greater…

  7. Spectroscopic Studies of the Several Isomers of UO3

    SciTech Connect

    Sweet, Lucas E.; Reilly, Dallas D.; Abrecht, David G.; Buck, Edgar C.; Meier, David E.; Su, Yin-Fong; Brauer, Carolyn S.; Schwantes, Jon M.; Tonkyn, Russell G.; Szecsody, James E.; Blake, Thomas A.; Johnson, Timothy J.

    2013-09-26

    Uranium trioxide is known to adopt seven different structural forms. While these structural forms have been well characterized using x-ray or neutron diffraction techniques, little work has been done to characterize their spectroscopic properties, particularly of the pure phases. Since the structural isomers of UO3 all have similar thermodynamic stabilities and most tend to hydrolyze under open atmospheric conditions, mixtures of UO3 phases and the hydrolysis products are common. Much effort went into isolating pure phases of UO3. Utilizing x-ray diffraction as a sample identification check, UV/Vis/NIR spectroscopic signatures of α-UO3, β-UO3, γ-UO3 and UO2(OH)2 products were obtained. The spectra of the pure phases can now be used to characterize typical samples of UO3, which are often mixtures of isomers.

  8. [Beaded molecule imprinted polymer for stereo isomer separation].

    PubMed

    Meng, Z; Wang, J; Zhou, L; Wang, Q; Zhu, D

    1999-07-01

    Beaded molecule imprinted polymer (MIP) was made by suspension polymerization. Particles with the size of 50-70 microns in diameter were collected and evaluated in HPLC mode to separate stereo isomers. Stereo isomers cinchonine and cinchonidine were successfully discriminated with selectivity factor of 2.89 and resolution factor of 0.76. Stereo selectivity of the MIP was found to come from both the interaction between the analyte and carboxyl group on the MIP and the similarity between the stereo structure of imprinted molecule and the MIP. The thermal analysis results showed that the MIP had high thermal stability with initial thermal decomposition temperature of 320 degrees C. The pore volume of the MIP was 0.1849 mL/g, the specific surface area was 126.84 sqm/g and the average pore diameter was 5.8 nanometer. Scanning electron microscopy showed that MIP had perfect spherical morphology.

  9. Novel bioactive oxazolomycin isomers produced by Streptomyces albus JA3453.

    PubMed

    Kanzaki, H; Wada, K; Nitoda, T; Kawazu, K

    1998-03-01

    Two novel oxazolomycin isomers, oxazolomycins B (2) and C (3), were isolated from the fermentation broth of an oxazolomycin-producing strain, Streptomyces albus JA3453. Both compounds are geometrical isomers of oxazolomycin (1), the configurations of their triene moieties being (4'E, 6'E, 8'E) (2) and (4'Z, 6'E, 8'E) (3) while that of oxazolomycin (1) is (4'Z, 6'Z, 8'E). Compounds 2 and 3 exhibited potent inhibitory activity against crown gall formation with the same MIC (0.8 microgram/disk) as oxazolomycin. Compounds 2 and 3 showed no antibacterial activity against Agrobacterium tumefaciens, in contrast to oxazolomycin which has specific anti-A. tumefaciens activity.

  10. Characterization of geometric isomers of Norbornene end-capped imides

    NASA Technical Reports Server (NTRS)

    Young, P. R.; Chang, A. C.

    1983-01-01

    Three geometric isomers from the thermal isomerization of methylene-4,4' bis(endo-N-phenylbicyclo/2.2.1/hept-2-ene-5,6-di carboximide) (I) were chromatographically separated and isolated in order to investigate the thermal cure of norbornene end-capped imide oligomers, which display considerable promise for use in various aerospace adhesive and composite applications. Endo-endo (I), endo-exo (II), and exo-exo (III) configurations were assigned to each compound based on the results of NMR spectroscopy. Several chromatographic, spectroscopic, and thermal techniques were then used to characterize these three isomers which serve as model compounds for norbornene end-capped polyimides. It was found that each compound thermally isomerized to an equilibrium mixture of all three compounds prior to cure. It is proposed that these compounds react by different mechanisms in air and nitrogen.

  11. A simple, rapid method for HPLC analysis of lycopene isomers.

    PubMed

    Ishida, B K; Ma, J; Chan, B

    2001-01-01

    A rapid method for the extraction, separation and quantification of the geometric isomers of lycopene and beta-carotene from tomato fruit is described. Carotenoids in tomato were separated and eluted using a reversed-phase HPLC with a C30 column and a mobile phase consisting of methyl-t-butyl ether, methanol and ethyl acetate. The system provided sharp resolution of cis- and trans-isomers of lycopene within approximately 23 min in contrast to the longer and more complex gradient procedures required by previously described methods. Experiments indicate that the stability of extracts of fresh tomato may be improved if stored at -20 degrees C, and that the presence of the antioxidant BHA has no apparent effect on stability.

  12. Positional isomer differentiation of synthetic cannabinoid JWH-081 by GC-MS/MS.

    PubMed

    Kusano, Maiko; Zaitsu, Kei; Nakayama, Hiroshi; Nakajima, Junichi; Hisatsune, Kazuaki; Moriyasu, Takako; Matsuta, Shuntaro; Katagi, Munehiro; Tsuchihashi, Hitoshi; Ishii, Akira

    2015-03-01

    Like many new designer drugs of abuse, synthetic cannabinoids (SC) have structural or positional isomers which may or may not all be regulated under law. Differences in acute toxicity may exist between isomers which impose further burden in the fields of forensic toxicology, medicine and legislation. Isomer differentiation therefore becomes crucial from these standpoints as new designer drugs continuously emerge with just minor positional modifications to their preexisting analogs. The aim of this study was to differentiate the positional isomers of JWH-081. Purchased standard compounds of JWH-081 and its positional isomers were analyzed by gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) first in scan mode to investigate those isomers who could be differentiated by EI scan spectra. Isomers with identical or near-identical EI spectra were further subjected to GC-tandem mass spectrometry (MS/MS) analysis with appropriate precursor ions. EI scan was able to distinguish 3 of the 7 isomers: 2-methoxy, 7-methoxy and 8-methoxy. The remaining isomers exhibited near-identical spectra; hence, MS/MS was performed by selecting m/z 185 and 157 as precursor ions. 3-Methoxy and 5-methoxy isomers produced characteristic product ions that enabled the differentiation between them. Product ion spectrum of 6-methoxy isomer resembled that of JWH-081; however, the relative ion intensities were clearly different from one another. The combination of EI scan and MS/MS allowed for the regioisomeric differentiation of the targeted compounds in this study.

  13. Condensations of single DNA molecules induced by heptaplatin and its chiral isomer

    SciTech Connect

    Zhang, Hong-Yan; Liu, Yu-Ru; Li, Wei; Li, Hui; Dou, Shuo-Xing; Xie, Ping; Wang, Wei-Chi; Wang, Peng-Ye

    2014-08-15

    Heptaplatin is a third-generation platinum antitumor drug. It has a chiral isomer. We studied the interactions between the two isomers and DNA by using magnetic tweezers and atomic force microscopy (AFM) to investigate the effect of chiralities of the isomers on the interactions. We found that the extension curves and average condensation rates of DNA molecules incubated with heptaplatin were nearly the same as those incubated with its chiral isomer. In addition, the structures of DNA molecules incubated with heptaplatin were also similar to those incubated with its chiral isomer. These results indicate the difference in chirality of the two isomers does not induce different interactions of the isomers with DNA. Our study may facilitate the understanding of interactions of platinum complexes with DNA and the design of new antitumor platinum complexes.

  14. Condensations of single DNA molecules induced by heptaplatin and its chiral isomer

    NASA Astrophysics Data System (ADS)

    Zhang, Hong-Yan; Liu, Yu-Ru; Li, Wei; Li, Hui; Dou, Shuo-Xing; Xie, Ping; Wang, Wei-Chi; Wang, Peng-Ye

    2014-08-01

    Heptaplatin is a third-generation platinum antitumor drug. It has a chiral isomer. We studied the interactions between the two isomers and DNA by using magnetic tweezers and atomic force microscopy (AFM) to investigate the effect of chiralities of the isomers on the interactions. We found that the extension curves and average condensation rates of DNA molecules incubated with heptaplatin were nearly the same as those incubated with its chiral isomer. In addition, the structures of DNA molecules incubated with heptaplatin were also similar to those incubated with its chiral isomer. These results indicate the difference in chirality of the two isomers does not induce different interactions of the isomers with DNA. Our study may facilitate the understanding of interactions of platinum complexes with DNA and the design of new antitumor platinum complexes.

  15. Determination of aminocresol isomers by high-speed liquid chromatography.

    PubMed

    Sakurai, H; Kito, M

    Aminocresol isomers (4-hydroxy-m-toluidine [II], 3-hydroxy-p-toluidine [II], 2-hydroxy-p-toluidine [III]) and p-aminophenol have been separated and determined by a high-speed liquid Chromatographie method. Since this method is applicable in aqueous media, it was used to investigate the suitability of a haemin-cysteine system as a model for the cytochrome P-450 mono-oxygenase system, by determination of the [I], [II], [III] and p-aminophenol formed.

  16. Flame Propagation of Butanol Isomers/Air Mixtures

    SciTech Connect

    Veloo, Peter S.; Egolfopoulos, Fokion N.

    2011-01-01

    An experimental and computational study was conducted on the propagation of flames of saturated butanol isomers. The experiments were performed in the counterflow configuration under atmospheric pressure, unburned mixture temperature of 343 K, and for a wide range of equivalence ratios. The experiments were simulated using a recent kinetic model for the four isomers of butanol. Results indicate that n-butanol/air flames propagate somewhat faster than both sec-butanol/air and iso-butanol/air flames, and that tert-butanol/air flames propagate notably slower compared to the other three isomers. Reaction path analysis of tert-butanol/air flames revealed that iso-butene is a major intermediate, which subsequently reacts to form the resonantly stable iso-butenyl radical retarding thus the overall reactivity of tert-butanol/air flames relatively to the other three isomers. Through sensitivity analysis, it was determined that the mass burning rates of sec-butanol/air and iso-butanol/air flames are sensitive largely to hydrogen, carbon monoxide, and C{sub 1}–C{sub 2} hydrocarbon kinetics and not to fuel-specific reactions similarly to n-butanol/air flames. However, for tert-butanol/air flames notable sensitivity to fuel-specific reactions exists. While the numerical results predicted closely the experimental data for n-butanol/air and sec-butanol/air flames, they overpredicted and underpredicted the laminar flame speeds for iso-butanol/air and tert-butanol/air flames respectively. It was demonstrated further that the underprediction of the laminar flame speeds of tert-butanol/air flames by the model was most likely due to deficiencies of the C{sub 4}-alkene kinetics.

  17. Preignition and Autoignition Behavior of the Xylene Isomers

    DTIC Science & Technology

    2010-03-01

    for the addition of three additives – a fuel system icing inhibitor, a corrosion inhibitor, and a static dissipater additive. The consequences of...identified were p-tolualdehyde, toluene, and p- cresol . Of note, p- cresol was identified in this experiment but its ortho- and meta- isomers were not...methylbenzaldehyde (p-tolualdehyde) and hydrogen radical. Hydroxyl radical attack on p-tolualdehyde produces p- cresol and formyl radical. Another

  18. Biodegradation of Alpha TNT and Its Production Isomers

    DTIC Science & Technology

    1974-07-01

    1 ^*"* **».-._ BIODEGRADATION OF ALPHA TNT ANT) ITS PRODUCTION ISOMERS Annual Report-U by: Richard W. Traxler University of Rhode Island...associated with the burning process. If these nitrobodies are found to be biodegradable , they could be rendered ecologically safe by biological...molecules are biodegradable by some microbial form whereas the truly recalcitrant molecules are found in broad classes of the synthetic organic compounds

  19. Determination of nonylphenol isomers in landfill leachate and municipal wastewater using steam distillation extraction coupled with comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry

    USGS Publications Warehouse

    Zhang, Caixiang; Eganhouse, Robert P.; Pontolillo, James; Cozzarelli, Isabelle M.; Wang, Yanxin

    2012-01-01

    4-Nonylphenols (4-NPs) are known endocrine disruptors and by-products of the microbial degradation of nonylphenol polyethoxylate surfactants. One of the challenges to understanding the toxic effects of nonylphenols is the large number of isomers that may exist in environmental samples. In order to attribute toxic effects to specific compounds, a method is needed for the separation and quantitation of individual nonylphenol isomers. The pre-concentration methods of solvent sublimation, solid-phase extraction or liquid–liquid extraction prior to chromatographic analysis can be problematic because of co-extraction of thousands of compounds typically found in complex matrices such as municipal wastewater or landfill leachate. In the present study, steam distillation extraction (SDE) was found to be an effective pre-concentration method for extraction of 4-NPs from leachate and wastewater, and comprehensive two-dimensional gas chromatography (GC × GC) coupled with fast mass spectral data acquisition by time-of-flight mass spectrometry (ToFMS) enhanced the resolution and identification of 4-NP isomers. Concentrations of eight 4-NP isomers were determined in leachate from landfill cells of different age and wastewater influent and effluent samples. 4-NP isomers were about 3 times more abundant in leachate from the younger cell than the older one, whereas concentrations in wastewater effluent were either below detection limits or <1% of influent concentrations. 4-NP isomer distribution patterns were found to have been altered following release to the environment. This is believed to reflect isomer-specific degradation and accumulation of 4-NPs in the aquatic environment.

  20. A Rapid Compression Machine Modelling Study of the Heptane Isomers

    SciTech Connect

    Silke, E J; Curran, H J; Simmie, J M; Pitz, W J; Westbrook, C K

    2005-05-10

    Previously we have reported on the combustion behavior of all nine isomers of heptane in a rapid compression machine (RCM) with stoichiometric fuel and ''air'' mixtures at a compressed gas pressure of 15 atm. The dependence of autoignition delay times on molecular structure was illustrated. Here, we report some additional experimental work that was performed in order to address unusual results regarding significant differences in the ignition delay times recorded at the same fuel and oxygen composition, but with different fractions of nitrogen and argon diluent gases. Moreover, we have begun to simulate these experiments with detailed chemical kinetic mechanisms. These mechanisms are based on previous studies of other alkane molecules, in particular, n-heptane and iso-octane. We have focused our attention on n-heptane in order to systematically redevelop the chemistry and thermochemistry for this C{sub 7} isomer with the intention of extending our greater knowledge gained to the other eight isomers. The addition of new reaction types, that were not included previously, has had a significant impact on the simulations, particularly at low temperatures.

  1. Borromean halo, Tango halo, and halo isomers in atomic nuclei

    NASA Astrophysics Data System (ADS)

    Izosimov, Igor

    2016-01-01

    Structure of the ground and excited states in halo-like nuclei is discussed. Both the Borromean and tango halo types can be observed for n-p configurations of atomic nuclei.Structure of the halo may be different for the different levels and resonances in atomic nuclei. Isobar analog, double isobar analog, configuration, and double configuration states can simultaneously have n-n, n-p, and p-p halo components in their wave functions. When the halo structure of the excited state differs from that of the ground state, or the ground state has non-halo structure, the γ-transition from the excited state to the ground state can be essentially hindered, i.e. the formation of a specific type of isomers (halo isomers) becomes possible. B(Mγ) and B(Eγ) values for γ-transitions in 6,7,8Li, 8,9,10Be, 8,10,11B, 10,11,12,13,14C, 13,14,15,16,17N, 15,16,17,19O, and 17F are analyzed. Special attention is given to nuclei which ground state does not exhibit halo structure but the excited state (halo isomer) may have one.

  2. Three bilindione isomers: synthesis, characterization and reactivity of biliverdin analogs.

    PubMed

    Wang, Jun-Fei; Ma, Fang; Sun, Hao-Ling; Zhang, Jing; Zhang, Jun-Long

    2017-02-07

    Linear tetrapyrrole is the core structure of light-sensitive native cofactors such as phycocyanobilin, phytochromobilin and bile pigments, which attracts increasing attention in biomimetic chemistry, photochemistry and coordination chemistry. To decipher the relationship between structures and functions, in this work, we firstly reported the synthesis, isolation and characterization of three bilindione isomers (ZZZ, syn, syn, syn 1, EZE, syn, syn, anti 2 and EZE, anti, syn, anti 3) bearing meso-pentafluorophenyl groups. The structures were confirmed by X-ray diffraction and 2-D NMR spectroscopes. More importantly, the interconversion between three isomers under heating and light irradiation was investigated, and isomer 3 was found to be transformed to 1 and 2 more easily, which is in line with the results of DFT calculation. This work provides important insights for understanding the relationship between structures and functions and would be important to further construct metal complexes based on linear tetrapyrrole ligands, which are complementary to well-studied the cyclic analogs such as porphyrin and corroles.

  3. Oxidative Transformation of Aminodinitrotoluene Isomers by Multicomponent Dioxygenases

    PubMed Central

    Johnson, Glenn R.; Smets, Barth F.; Spain, Jim C.

    2001-01-01

    The electron-withdrawing nitro substituents of 2,4,6-trinitrotoluene (TNT) make the aromatic ring highly resistant to oxidative transformation. The typical biological transformation of TNT involves reduction of one or more of the nitro groups of the ring to produce the corresponding amine. Reduction of a single nitro substituent of TNT to an amino substituent increases the electron density of the aromatic nucleus considerably. The comparatively electron-dense nuclei of the aminodinitrotoluene (ADNT) isomers would be expected to be more susceptible to oxygenase attack than TNT. The hypothesis was tested by evaluating three nitroarene dioxygenases for the ability to hydroxylate the ADNT isomers. The predominant reaction was dioxygenation of the ring to yield nitrite and the corresponding aminomethylnitrocatechol. A secondary reaction was benzylic monooxygenation to form aminodinitrobenzyl alcohol. The substrate preferences and catalytic specificities of the three enzymes differed considerably. The discovery that the ADNT isomers are substrates for the nitroarene dioxygenases reveals the potential for extensive bacterial transformation of TNT under aerobic conditions. PMID:11722893

  4. Electron attachment and detachment: Electron affinities of isomers of trifluoromethylbenzonitrile

    NASA Astrophysics Data System (ADS)

    Miller, Thomas M.; Viggiano, A. A.; Friedman, Jeffrey F.; Van Doren, Jane M.

    2004-11-01

    Rate constants for electron attachment to the three isomers of trifluoromethylbenzonitrile [(CF3)(CN)C6H4, or TFMBN] were measured over the temperature range of 303-463 K in a 133-Pa He buffer gas, using a flowing-afterglow Langmuir-probe apparatus. At 303 K, the measured attachment rate constants are 9.0×10-8 (o-TFMBN), 5.5×10-8 (m-TFMBN), and 8.9×10-8 cm3 s-1 (p-TFMBN), estimated accurate to ±25%. The attachment process formed only the parent anion in all three cases. Thermal electron detachment was observed for all three anion isomers, and rate constants for this reverse process were also measured. From the attachment and detachment results, the electron affinities of the three isomers of TFMBN were determined to be 0.70(o-TFMBN), 0.67(m-TFMBN), and 0.83 eV (p-TFMBN), all ±0.05 eV. G3(MP2) [Gaussian-3 calculations with reduced Møller-Plesset orders (MP2)] calculations were carried out for the neutrals and anions. Electron affinities derived from these calculations are in good agreement with the experimental values.

  5. Electron attachment and detachment: electron affinities of isomers of trifluoromethylbenzonitrile.

    PubMed

    Miller, Thomas M; Viggiano, A A; Friedman, Jeffrey F; Van Doren, Jane M

    2004-11-22

    Rate constants for electron attachment to the three isomers of trifluoromethylbenzonitrile [(CF(3))(CN)C(6)H(4), or TFMBN] were measured over the temperature range of 303-463 K in a 133-Pa He buffer gas, using a flowing-afterglow Langmuir-probe apparatus. At 303 K, the measured attachment rate constants are 9.0 x 10(-8) (o-TFMBN), 5.5 x 10(-8) (m-TFMBN), and 8.9 x 10(-8) cm(3) s(-1) (p-TFMBN), estimated accurate to +/-25%. The attachment process formed only the parent anion in all three cases. Thermal electron detachment was observed for all three anion isomers, and rate constants for this reverse process were also measured. From the attachment and detachment results, the electron affinities of the three isomers of TFMBN were determined to be 0.70(o-TFMBN), 0.67(m-TFMBN), and 0.83 eV (p-TFMBN), all +/-0.05 eV. G3(MP2) [Gaussian-3 calculations with reduced Møller-Plesset orders (MP2)] calculations were carried out for the neutrals and anions. Electron affinities derived from these calculations are in good agreement with the experimental values.

  6. Isomer-specific biodegradation of methylphenanthrenes by soil bacteria.

    PubMed

    Lamberts, Rasmus F; Christensen, Jan H; Mayer, Philipp; Andersen, Ole; Johnsen, Anders R

    2008-07-01

    It is assumed that bacteria generally degrade 2-methylphenanthrene (2MPhe) in preference to 1-methylphenanthrene (1MPhe), and that environmental biodegradation of methylated PAHs therefore can be described qualitatively by changes in relative concentrations of these isomers. Our objective was to investigate whether microbial phenanthrene degraders (Sphingomonas and Mycobacterium) show such isomer-specific PAH degradation. Eleven out of twenty-nine phenanthrene degraders could grow on methylphenanthrene. The mycobacteria grew only on 2MPhe, the sphingomonads grew mostly on 1MPhe, and one sphingomonad could utilize both substrates. Seven strains were tested in a two-phase system where 1MPhe and 2MPhe were supplied in heptamethylnonane. For these strains, a consistent description of biodegradation based on the 2MPhe/1MPhe diagnostic ratio would not be possible because three Mycobacterium and one Sphingomonas degraded 2MPhe faster than 1MPhe, another Sphingomonas degraded 1MPhe and 2MPhe at almost equal rates, and two Sphingomonas degraded 1MPhe faster than 2MPhe. Thus, environmental biodegradation of phenanthrenes may theoretically proceed with only minor changes in 2MPhe/1MPhe ratios if individual members of the degrader community have different isomer preferences. However, two soil microcosms polluted with bunker oil confirmed the general decline in 2MPhe/1MPhe ratio during oil biodegradation.

  7. Synthesis of lucifensin by native chemical ligation and characteristics of its isomer having different disulfide bridge pattern.

    PubMed

    Stanchev, Stancho; Zawada, Zbigniew; Monincová, Lenka; Bednárová, Lucie; Slaninová, Jiřina; Fučík, Vladimír; Čeřovský, Václav

    2014-09-01

    The antimicrobial 40-amino-acid-peptide lucifensin was synthesized by native chemical ligation (NCL) using N-acylbenzimidazolinone (Nbz) as a linker group. NCL is a method in which a peptide bond between two discreet peptide chains is created. This method has been applied to the synthesis of long peptides and proteins when solid-phase synthesis is imcompatible. Two models of ligation were developed: [15+25] Ala-Cys and [19+21] His-Cys. The [19+21] His-Cys method gives lower yield because of the lower stability of 18-peptide-His-Nbz-CONH2 peptide, as suggested by density functional theory calculation. Acetamidomethyl-deprotection and subsequent oxidation of the ligated linear lucifensin gave a mixture of lucifensin isomers, which differed in the location of their disulfide bridges only. The dominant isomer showed unnatural pairing of cysteines [C1-6], [C3-5], and [C2-4], which limits its ability to form α-helical structure. The activity of isomeric lucifensin toward Bacillus subtilis, Staphylococcus aureus, and Micrococcus luteus was lower than that of the natural lucifensin. The desired product native lucifensin was prepared from this isomer using a one-pot reduction with dithiotreitol and subsequent air oxidation in slightly alkaline medium.

  8. Analysis of the isomer ratios of polymethylated-DOTA complexes and the implications on protein structural studies.

    PubMed

    Opina, Ana Christina L; Strickland, Madeleine; Lee, Yong-Sok; Tjandra, Nico; Andrew Byrd, R; Swenson, Rolf E; Vasalatiy, Olga

    2016-03-21

    A rigidified and symmetrical polymethylated 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) ligand bearing four SSSS methyl groups in both the tetraaza ring and the acetate arms (SSSS-SSSS-M4DOTMA) was prepared. The isomer ratio of SSSS-SSSS-M4DOTMA complexed with a series of lanthanide ions was carefully investigated using RP-HPLC and NMR. A square antiprismatic (SAP) configuration was exclusively observed for the early lanthanides, while the twisted square antiprismatic (TSAP) geometry was preferred as the lanthanide ion size decreases. The late lanthanides preferentially adopted the TSAP geometry. One of the pendant arms was modified with a pyridyl disulfide group (SSSS-SSSS-M8SPy) for cysteine attachment and displayed a similar isomer trend as the parent compound, Ln-SSSS-SSSS-M4DOTMA. Covalent attachment to the ubiquitin S57C mutant showed resonances whose intensities are in agreement with the isomeric population observed by RP-HPLC. Furthermore, the NOE experiments combined with quantum chemical calculations have unequivocally demonstrated that the SAP of Pr-SSSS-SSSS-M4DOTMA and Pr-SSSS-SSSS-M8SPy, as well as the TSAP of Yb-SSSS-SSSS-M8SPy are more stable than their corresponding isomers.

  9. Analysis of the isomer ratios of polymethylated-DOTA complexes and the implications on protein structural studies

    PubMed Central

    Opina, Ana Christina L.; Strickland, Madeleine; Lee, Yong-Sok; Tjandra, Nico; Byrd, R. Andrew; Swenson, Rolf E.; Vasalatiy, Olga

    2016-01-01

    A rigidified and symmetrical polymethylated 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) ligand bearing four SSSS methyl groups in both the tetraaza ring and the acetate arms (SSSS-SSSS-M4DOTMA) was prepared. The isomer ratio of SSSS-SSSS-M4DOTMA complexed with a series of lanthanide ions was carefully investigated using RP-HPLC and NMR. A square antiprismatic (SAP) configuration was exclusively observed for the early lanthanides, while the twisted square antiprismatic (TSAP) geometry was preferred as the lanthanide ion size decreases. The late lanthanides preferentially adopted the TSAP geometry. One of the pendant arms was modified with a pyridyl disulfide group (SSSS-SSSS-M8SPy) for cysteine attachment and displayed a similar isomer trend as the parent compound, Ln-SSSS-SSSS-M4DOTMA. Covalent attachment to the ubiquitin S57C mutant showed resonances whose intensities are in agreement with the isomeric population observed by HPLC. Furthermore, the NOE experiments combined with quantum chemical calculations have unequivocally demonstrated that the SAP of Pr-SSSS-SSSS-M4DOTMA and Pr-SSSS-SSSS-M8SPy, as well as the TSAP of Yb-SSSS-SSSS-M8SPy are more stable than their corresponding isomers. PMID:26857249

  10. Exhaustive Qualitative LC-DAD-MS(n) Analysis of Arabica Green Coffee Beans: Cinnamoyl-glycosides and Cinnamoylshikimic Acids as New Polyphenols in Green Coffee.

    PubMed

    Baeza, Gema; Sarriá, Beatriz; Bravo, Laura; Mateos, Raquel

    2016-12-28

    Coffee is one of the most consumed beverages in the world, due to its unique aroma and stimulant properties. Although its health effects are controversial, moderate intake seems to be beneficial. The present work deals with the characterization and quantification of polyphenols and methylxanthines in four Arabica green coffee beans from different geographical origins. The antioxidant activity was also evaluated. Forty-three polyphenols (cinnamic acid, cinnamoyl-amide, 5 cinammoyl-glycosides, and 36 cinnamate esters) were identified using LC-MS(n). Among these, cinnamate esters of six different chemical groups (including two dimethoxycinnamoylquinic acid isomers, three caffeoyl-feruloylquinic acid isomers, caffeoyl-sinapoylquinic acid, p-coumaroyl-feruloylquinic acid, two caffeoylshikimic acid isomers, and trimethoxycinnamoylshikimic acid) in addition to five isomers of cinnamoyl-glycosides called caffeoyl-2,7-anhydro-3-deoxy-2-octulopyranosic acid (CDOA) are described for the first time in Arabica green coffee beans. Moreover, 38 polyphenols (6-7% w/w) and 2 methylxanthines (1.3% w/w) were quantified by HPLC-DAD. Caffeoylquinic was the most abundant group of compounds (up to 85.5%) followed by dicaffeoylquinic and feruloylquinic acids (up to 8 and 7%, respectively) and the newly identified cinnamoyl-glycosides (CDOA) (up to 2.5%). Caffeine was the main methylxanthine (99.8%), with minimal amounts of theobromine (0.2%). African coffees (from Kenya and Ethiopia) showed higher polyphenolic content than American beans (from Brazil and Colombia), whereas methylxanthine contents varied randomly. Both phenols and methylxanthines contributed to the antioxidant capacity associated with green coffee, with a higher contribution of polyphenols. We conclude that green coffee represents an important source of polyphenols and methylxanthines, with high antioxidant capacity.

  11. Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons

    SciTech Connect

    Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Vereecken, Luc; Leone, Stephen R.

    2008-12-05

    The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

  12. Feeding of the 1 1/2- isomers in stable Ir and Au isotopes

    SciTech Connect

    Fotiadis, Nikolaos; Nelson, Ronald O; Devlin, Matthew; Holloway, Shannon T; Kawano, Toshihiko; Talou, Patrick; Chadwick, Mark B; Becker, John A; Garrett, Paul E

    2008-01-01

    Excited states were studied and absolute partial {gamma}-ray cross sections were measured using the ({eta}, {eta}'{gamma}) reaction in {sup 191}Ir, {sup 193}Ir and {sup 197}Au. A Compton-suppressed germanium-detector array (GEANIE) for {gamma}-ray spectroscopy and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's WNR facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial {gamma}-ray cross sections were measured up to incident neutron energy of 20 MeV for several transitions feeding directly the 1 1/2- isomers and ground states in {sup 191}Ir, {sup 193}Ir and {sup 197}Au. The feeding of the 1 1/2- isomers, which originate from the odd proton occupying the h{sub 1 1/2} orbital, was found for the three targets to be very similar and increasing relative to the feeding of the corresponding ground state with increasing neutron energy up to E{sub n} {approx} 10 MeV. Above this neutron energy the opening of the (n, 2{sub n}) reaction channel strongly affects the population of the isomers and leads to a decrease of their relative population compared to the population of the ground states. The experimental results are compared with theoretical predictions from the GNASH reaction model calculation implementing a version of the spin distribution for the pre-equilibrium reaction piece with either a compound nucleus spin distribution (CN-GNASH) or a Feshbach-Kerman-Koonin (FKK-GNASH) quantum mechanical spin distribution. The effects of the spin cutoff parameter values on the population of states are examined. Evidence is presented that FKK-GNASH provides a description of the experimental data that mitigates the need for adjustment of the level density parameter to fit the data.

  13. Strategies to distinguish new synthetic cannabinoid FUBIMINA (BIM-2201) intake from its isomer THJ-2201: metabolism of FUBIMINA in human hepatocytes.

    PubMed

    Diao, Xingxing; Scheidweiler, Karl B; Wohlfarth, Ariane; Zhu, Mingshe; Pang, Shaokun; Huestis, Marilyn A

    Since 2013, a new drugs-of-abuse trend attempts to bypass drug legislation by marketing isomers of scheduled synthetic cannabinoids (SCs), e.g., FUBIMINA (BIM-2201) and THJ-2201. It is much more challenging to confirm a specific isomer's intake and distinguish it from its structural analog because the isomers and their major metabolites usually have identical molecular weights and display the same product ions. Here, we investigated isomers FUBIMINA and THJ-2201 and propose strategies to distinguish their consumption. THJ-2201 was scheduled in the US, Japan, and Europe; however, FUBIMINA is easily available on the Internet. We previously investigated THJ-2201 metabolism in human hepatocytes, but human FUBIMINA metabolism is unknown. We aim to characterize FUBIMINA metabolism in human hepatocytes, recommend optimal metabolites to confirm its consumption, and propose strategies to distinguish between intakes of FUBIMINA and THJ-2201. FUBIMINA (10 μM) was incubated in human hepatocytes for 3 h, and metabolites were characterized with high-resolution mass spectrometry (HR-MS). We identified 35 metabolites generated by oxidative defluorination, further carboxylation, hydroxylation, dihydrodiol formation, glucuronidation, and their combinations. We recommend 5'-OH-BIM-018 (M34), BIM-018 pentanoic acid (M33), and BIM-018 pentanoic acid dihydrodiol (M7) as FUBIMINA specific metabolites. THJ-2201 produced specific metabolite markers 5'-OH-THJ-018 (F26), THJ-018 pentanoic acid (F25), and hydroxylated THJ-2201 (F13). Optimized chromatographic conditions to achieve different retention times and careful selection of specific product ion spectra enabled differentiation of isomeric metabolites, in this case FUBIMINA from THJ-2201. Our HR-MS approach should be applicable for differentiating future isomeric SCs, which is especially important when different isomers have different legal status.

  14. Influence of Lβ-, Dα- and Dβ-Asp isomers of the Asp-76 residue on the properties of αA-crystallin 70-88 peptide.

    PubMed

    Fujii, Noriko; Fujii, Norihiko; Kida, Masashi; Kinouchi, Tadatoshi

    2010-11-01

    Proteins have been considered to consist exclusively of L-amino acids in living tissues. However, our previous studies showed that two specific aspartyl (Asp) residues in αA- and αB-crystallins from human eye lenses invert to the D-isomers to a high degree during aging. The reaction is also accompanied by isomerization into a form containing β-Asp (isoaspartate) residues. The appearance of D- and β-Asp in a protein potentially induces large changes to the higher order structure of the protein as well as to its function. However, it remains unclear whether the formation of the Asp isomer is the direct trigger of the change to the higher order structure and function. In this study, in order to clarify the effect of the inversion to D-isomers in a protein, we synthesized peptides corresponding to the 70-88 (KFVIFLDVKHFSPEDLTVK) fragment of human αA-crystallin and its corresponding diastereoisomers in which Lα-Asp was replaced with Lβ-Asp, Dα-Asp, and Dβ-Asp at position 76 and compared their biochemical properties with that of normal peptide. The peptides containing abnormal isomers (Lβ-Asp, Dα-Asp, and Dβ-Asp residues, respectively) were more hydrophilic than the normal peptide (containing Lα-Asp), lost β-sheet structure and changed to random structures. The normal peptide promoted the aggregation of insulin while the other three isomers suppressed the aggregation of insulin. This is the first evidence that a single substitution of an Asp isomer in a peptide induces a large change to the properties of the peptide.

  15. Chlorogenic acid compounds from coffee are differentially absorbed and metabolized in humans.

    PubMed

    Monteiro, Mariana; Farah, Adriana; Perrone, Daniel; Trugo, Luiz C; Donangelo, Carmen

    2007-10-01

    Chlorogenic acids (CGA) are abundant phenolic compounds in coffee, with caffeoylquinic (CQA), feruloylquinic (FQA), and dicaffeoylquinic (diCQA) acids being the major subclasses. Despite the potential biopharmacological properties attributed to these compounds, little is known about their bioavailability in humans. In this study, we evaluated the distribution profile of the major CGA isomers and metabolites in plasma and urine of 6 healthy adults for 4 h after brewed coffee consumption. Three CQA isomers and 3 diCQA isomers were identified in the plasma of all subjects after coffee consumption, whereas 2 FQA were identified in only 1 subject. Two plasma concentration peaks were observed, the first at 0.5-1.0 h and the second at 1.5-4.0 h after coffee consumption. The molar ratio CQA:diCQA was 12.2 in the brewed coffee, whereas in plasma it ranged from 0.6-2.9. The molar ratios 5-CQA:3-CQA and 5-CQA:4-CQA were consistently higher in plasma than in the brew. The main CGA metabolites identified in urine after coffee consumption were: dihydrocaffeic, gallic, isoferulic, ferulic, vanillic, caffeic, 5-CQA, sinapic, rho-hydroxybenzoic, and rho-coumaric acids (gallic and dihydrocaffeic acids being the major ones). This study indicates that the major CGA compounds present in coffee are differentially absorbed and/or metabolized in humans, with a large inter-individual variation. Moreover, urine does not appear to be a major excretion pathway of intact CGA compounds in humans.

  16. Clinical vampirism. A presentation of 3 cases and a re-evaluation of Haigh, the 'acid-bath murderer'.

    PubMed

    Hemphill, R E; Zabow, T

    1983-02-19

    Clinical vampirism is named after the mythical vampire, and is a recognizable, although rare, clinical entity characterized by periodic compulsive blood-drinking, affinity with the dead and uncertain identity. It is hypothetically the expression of an inherited archaic myth, the act of taking blood being a ritual that gives temporary relief. From ancient times vampirists have given substance to belief in the existence of supernatural vampires. Four vampirists, including Haigh, the 'acid-bath murderer', are described. From childhood they cut themselves, drank their own, exogenous human or animal blood to relieve a craving, dreamed of blood-shed, associated with the dead, and had a changing identity. They were intelligent, with no family mental or social pathology. Some self-cutters are auto-vampirists; females are not likely to assault others for blood, but males are potentially dangerous. Vampirism may be a cause of unpredictable repeated assault and murder, and should be looked for in violent criminals who are self-mutilators. No specific treatment is known.

  17. Impaired swim bladder inflation in early-life stage fathead minnows exposed to a deiodinase inhibitor, iopanoic acid (presentation)

    EPA Science Inventory

    The present study investigated whether inhibition of deiodinase, the enzyme which converts thyroxine (T4) to the more biologically-active form, 3,5,3'-triiodothyronine (T3), would impact inflation of the posterior and/or anterior chamber of the swim bladder, processes previously ...

  18. Parity nonconservation in the {gamma} decay of polarized 17/2{sup -} isomers in {sup 93}Tc

    SciTech Connect

    Singh, B.S. Nara; Hass, M.; Goldring, G.; Ackermann, D.; Sulignano, B.; Gerl, J.; Hessberger, F.P.; Hofmann, S.; Kojouharov, I.; Kuusiniemi, P.; Schaffner, H.; Brown, B.A.

    2005-08-01

    The determination of the 0 deg. - 180 deg. asymmetry (A{sub {gamma}}), which arises because of the parity nonconserving matrix element, in the 751-keV {gamma} decay of polarized 17/2{sup -} isomers in {sup 93}Tc with respect to the direction of polarization is reported. A combined analysis of the present results together with those from our earlier work yields an effect of two standard deviations.

  19. Conjugated linolenic acids and their bioactivities: a review.

    PubMed

    Yuan, Gao-Feng; Chen, Xiao-E; Li, Duo

    2014-07-25

    Conjugated linolenic acid (CLNA) is a mixture of positional and geometric isomers of octadecatrienoic acid (α-linolenic acid, cis9,cis12,cis15-18:3 n-3) found in plant seeds. Three 8,10,12-18:3 isomers and four 9,11,13-18:3 isomers have been reported to occur naturally. CLNA isomers such as punicic acid, α-eleostearic acid and jacaric acid have been attributed to exhibit several health benefits that are largely based on animal and in vitro studies. This review has summarized and updated the evidence regarding the metabolism and bioactivities of CLNA isomers, and comprehensively discussed the recent studies on the effects of anti-carcinogenic, lipid metabolism regulation, anti-inflammatory, anti-obese and antioxidant activities of CLNA isomers. The available results may provide a potential application for CLNA isomers from natural sources, especially edible plant seeds, as effective functional food ingredients and dietary supplements for the above mentioned disease management. Further research, especially human randomized clinical trials, is warranted to investigate the detailed physiological effects, bioactivity and molecular mechanism of CLNA.

  20. Distribution of perfluorooctane sulfonate isomers and predicted risk of thyroid hormonal perturbation in drinking water.

    PubMed

    Yu, Nanyang; Wang, Xiaoxiang; Zhang, Beibei; Yang, Jingping; Li, Meiying; Li, Jun; Shi, Wei; Wei, Si; Yu, Hongxia

    2015-06-01

    We documented the distribution of seven perfluorooctane sulfonate (PFOS) isomers in drinking water in Jiangsu Province, China. Compared to the 30% proportion of branched PFOS in technical PFOS, the levels of branched PFOS in drinking water increased to 31.8%-44.6% of total PFOS. Because of previous risk assessment without considering the PFOS isomer profile and the toxicity of individual PFOS isomers, here we performed a new health risk assessment of PFOS for thyroid hormonal perturbation in drinking water with the contribution from individual PFOS isomers. The risk quotients (RQs) of individual PFOS isomers indicated that linear PFOS contributed most to the risk among all the target PFOS isomers (83.0%-90.2% of the total PFOS RQ), and that risk from 6m-PFOS (5.2%-11.9% of the total PFOS RQ) was higher than that from other branched PFOS isomers. We found that the risks associated with PFOS in drinking water would be overestimated by 10.0%-91.7% if contributions from individual PFOS isomers were not considered. The results revealed that the PFOS isomer profile and the toxicity of individual PFOS isomers were important factors in health risk assessment of PFOS and should be considered in the future risk assessments.

  1. Infrared detection of (H2O)20 isomers of exceptional stability: A drop-like and a face-sharing pentagonal prism cluster

    DOE PAGES

    Pradzynski, Christoph C.; Dierking, Christoph W.; Zurheide, Florian; ...

    2014-09-01

    Water clusters containing fully coordinated water molecules are model systems that mimic the local environment of the condensed phase. Present knowledge about the water cluster size regime in which the transition from the allsurface to the fully solvated water molecules occurs is mainly based on theoretical predictions in lieu of the absence of precisely size resolved experimental measurements. Here, we report size and isomer selective infrared (IR) spectra of (H2O)20 clusters tagged with a sodium atom by employing IR excitation modulated photoionization spectroscopy. The observed absorption patterns in the OH stretching ”fingerprint” region are consistent with the theoretically predicted spectramore » of two structurally distinct isomers: A drop-like cluster with a fully coordinated (interior) water and an edge-sharing pentagonal prism cluster in which all atoms are on the surface. The observed isomers show exceptional stability and are predicted to be nearly isoenergetic.« less

  2. Performance of some DFT functionals with dispersion on modeling of the translational isomers of a solvent-switchable [2]rotaxane

    NASA Astrophysics Data System (ADS)

    Ivanov, Petko

    2016-03-01

    presented qualitatively correct behavior for the relative stability of the two translational isomers, namely, slight preference of station II for the isolated molecule and higher relative energy of the same isomer with the model solvent DMSO. The electrostatic interactions in 2 have the decisive contribution both when the macroring is positioned at the dipeptide residue for the neutral form, and at the N-benzylalanine fragment after protonation, and the observed behavior of the [2]rotaxane is correctly reproduced by the methods used.

  3. Accurate thermochemistry and spectroscopy of the oxygen-protonated sulfur dioxide isomers.

    PubMed

    Puzzarini, Cristina

    2011-12-28

    Despite the promising relevance of protonated sulfur dioxide in astrophysical and atmospheric fields, its thermochemical and spectroscopic characterization is very limited. High-level quantum-chemical calculations have shown that the most stable isomer is the cis oxygen-protonated sulfur dioxide, HOSO(+), while the trans form is about 2 kcal mol(-1) less stable; even less stable (by about 42 kcal mol(-1)) is the S-protonated isomer [V. Lattanzi et al., J. Chem. Phys., 2010, 133, 194305]. The enthalpy of formation for the cis- and trans-HOSO(+) is presented, based on the well tested HEAT protocol [A. Tajti et al., J. Chem. Phys., 2004, 121, 11599]. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled cluster theory, including up to single, double, triple and quadruple excitations, have been corrected for core-electron correlation, anharmonic zero-point vibrational energy, diagonal Born-Oppenheimer and scalar relativistic effects. As a byproduct, proton affinity of sulfur dioxide and atomization energies have also been obtained at the same levels of theory. Vibrational and rotational spectroscopic properties have been investigated by means of composite schemes that allow us to account for truncation of basis set as well as core correlation. Where available, for both thermochemistry and spectroscopy, very good agreement with experimental data has been observed.

  4. The association of matrix Gla protein isomers with calcification in capsules surrounding silicone breast implants.

    PubMed

    Hunter, Larry W; Lieske, John C; Tran, Nho V; Miller, Virginia M

    2011-11-01

    Implanted silicone medical prostheses induce a dynamic sequence of histologic events in adjacent tissue resulting in the formation of a fibrotic peri-prosthetic capsule. In some cases, capsular calcification occurs, requiring surgical intervention. In this study we investigated capsules from silicone gel-filled breast prostheses to test the hypothesis that this calcification might be regulated by the small vitamin K-dependent protein, matrix Gla protein (MGP), a potent inhibitor of arterial calcification, or by Fetuin-A, a hepatocyte-derived glycoprotein also implicated as a regulator of pathologic calcification. Immunolocalization studies of explanted capsular tissue, using conformation-specific antibodies, identified the mineralization-protective γ-carboxylated MGP isomer (cMGP) within cells of uncalcified capsules, whereas the non-functional undercarboxylated isomer (uMGP) was typically absent. Both were upregulated in calcific capsules and co-localized with mineral plaque and adjacent fibers. Synovial-like metaplasia was present in one uncalcified capsule in which MGP species were differentially localized within the pseudosynovium. Fetuin-A was localized to cells within uncalcified capsules and to mineral deposits within calcific capsules. The osteoinductive cytokine bone morphogenic protein-2 localized to collagen fibers in uncalcified capsules. These findings demonstrate that MGP, in its vitamin K-activated conformer, may represent a pharmacological target to sustain the health of the peri-prosthetic tissue which encapsulates silicone breast implants as well as other implanted silicone medical devices.

  5. The CH3CHOO 'Criegee intermediate' and its anion: Isomers, infrared spectra, and W3-F12 energetics

    NASA Astrophysics Data System (ADS)

    Kettner, M.; Karton, A.; McKinley, A. J.; Wild, D. A.

    2015-02-01

    For the CH3CHOO Criegee intermediates (ethanal-oxide) and analogous anions, we obtain heats of formations and electron affinities at CCSDT(Q)/CBS level of theory by means of the high-level W3-F12 thermochemical protocol. The electron affinities amount to 0.20 eV and 0.35 eV for the cis and trans isomer, respectively. Neutral cis and trans isomers are separated by 14.1 kJ/mol, the anions are almost isoenergetic (0.4 kJ/mol separation). Harmonic vibrational frequencies are presented at CCSD(T)/aug'-cc-pVTZ level of theory. Since the synthesis of these species in gas-phase experiments might be possible in the near future, we include a predicted photoelectron spectrum.

  6. Formation of melatonin and its isomer during bread dough fermentation and effect of baking.

    PubMed

    Yılmaz, Cemile; Kocadağlı, Tolgahan; Gökmen, Vural

    2014-04-02

    Melatonin is produced mainly by the pineal gland in vertebrates. Also, melatonin and its isomer are found in foods. Investigating the formation of melatonin and its isomer is of importance during bread dough fermentation and its degradation during baking since bread is widely consumed in high amounts. Formation of melatonin was not significant during dough fermentation. The melatonin isomer content of nonfermented dough was found to be 4.02 ng/g and increased up to 16.71 ng/g during fermentation. Lower amounts of isomer in crumb and crust than dough showed that the thermal process caused a remarkable degree of degradation in melatonin isomer. At the end of the 180 min fermentation Trp decreased by 58%. The results revealed for the first time the formation of a melatonin isomer in bread dough during yeast fermentation.

  7. Relationship between Menthiafolic Acid and Wine Lactone in Wine.

    PubMed

    Giaccio, Joanne; Curtin, Chris D; Sefton, Mark A; Taylor, Dennis K

    2015-09-23

    Menthiafolic acid (6-hydroxy-2,6-dimethylocta-2,7-dienoic acid, 2a) was quantified by GC-MS in 28 white wines, 4 Shiraz wines, and for the first time in 6 white grape juice samples. Menthiafolic acid was detected in all but one of the wine samples at concentrations ranging from 26 to 342 μg/L and in the juice samples from 16 to 236 μg/L. Various model fermentation experiments showed that some menthiafolic acid in wine could be generated from the grape-derived menthiafolic acid glucose ester (2b) during alcoholic and malolactic fermentation. Samples containing high concentrations of menthiafolic acid were also analyzed by enantioselective GC-MS and were shown to contain this compound in predominantly the (S)-configuration. Enantioselective analysis of wine lactone (1) in one of these samples, a four-year-old Chardonnay wine showed, for the first time, the presence of the 3R,3aR,7aS isomer of wine lactone (1b), which is the enantiomer of the form previously reported as the sole isomer present in young wine samples. The weakly odorous 3R,3aR,7aS 1b form comprised 69% of the total wine lactone in the sample. On the basis of the enantioselectivity of the hydrolytic conversion of menthiafolic acid to wine lactone at pH 3.0 determined previously and the relative proportions of (R)- and (S)-menthiafolic acid in the Chardonnay wine, the predicted ratio of wine lactone enantiomers that would be formed from hydrolysis at ambient temperature of the menthiafolic acid present in this wine was close to the ratio measured, which was consistent with menthiafolic acid being the major or sole precursor to wine lactone in this sample.

  8. Isomers of broparoestrol and antiestrogen action: comparison with tamoxifen.

    PubMed

    Edery, M; Barnova, A; Drosdowsky, M; Guggiari, M; Vives, C; Rudali, G

    1985-01-01

    This study compares the relative biological potencies of a known antiestrogen tamoxifen to two triarylethylene compounds which have been shown previously to be potent inhibitors of rodent mammary tumorigenesis. Based on a) uterotrophic and anti-uterotrophic tests, b) indexes of cellularity, and c) protein content, these studies indicate that the trans, as well as the cis, isomers of bromotriphenylethylene are partial estrogen antagonists with no estrogenic effects in rat uteri and partial agonists in mouse uteri, whereas tamoxifen shows partial antiestrogenic/estrogenic effects in rats and is fully estrogenic in mice.

  9. Isomerism in the "south-east" of 132Sn and a predicted neutron-decaying isomer in 129Pd

    NASA Astrophysics Data System (ADS)

    Yuan, Cenxi; Liu, Zhong; Xu, Furong; Walker, P. M.; Podolyák, Zs.; Xu, C.; Ren, Z. Z.; Ding, B.; Liu, M. L.; Liu, X. Y.; Xu, H. S.; Zhang, Y. H.; Zhou, X. H.; Zuo, W.

    2016-11-01

    Excited states in neutron-rich nuclei located south-east of 132Sn are investigated by shell-model calculations. A new shell-model Hamiltonian is constructed for the present study. The proton-proton and neutron-neutron interactions of the Hamiltonian are obtained through the existing CD-Bonn G matrix results, while the proton-neutron interaction across two major shells is derived from the monopole based universal interaction plus the M3Y spin-orbit force. The present Hamiltonian can reproduce well the experimental data available in this region, including one-neutron separation energies, level energies and the experimental B (E 2) values of isomers in 134,136,138Sn, 130Cd, and 128Pd. New isomers are predicted in this region, e.g. in 135Sn, 131Cd, 129Pd, 132,134In and 130Ag, in which almost no excited states are known experimentally yet. In the odd-odd 132,134In and 130Ag, the predicted very long E2 life-times of the low-lying 5- states are discussed, demanding more information on the related proton-neutron interaction. The low-lying states of 132In are discussed in connection with the recently observed γ rays. The predicted 19 /2- isomer in 129Pd could decay by both electromagnetic transitions and neutron emission with comparable partial life-times, making it a good candidate for neutron radioactivity, a decay mode which is yet to be discovered.

  10. Production of the 178m2Hf isomer using a 4.5-GeV electron accelerator

    NASA Astrophysics Data System (ADS)

    Karamian, S. A.; Carroll, J. J.; Adam, J.; Demekhina, N. A.

    2004-09-01

    High-productivity methods are required for the accumulation of long-lived isomers in amounts that are sufficient for the creation of experimental targets. A tantalum sample was activated with the Yerevan synchrotron using 4.5-GeV bremsstrahlung and the presence of 178m2Hf was detected with good statistical accuracy by γ-activity measurements. The integrated and mean cross-section values were deduced from the experiment. The isomer-to-ground-state ratio was then estimated and compared with that known for the p+ Ta reaction studied at 660 MeV. In the present experiment, both converter and target were relatively thin for better definition of the experimental conditions. However, an assembly designed for high-productivity irradiations should be thick and then the converter can also serve as the target sample when irradiated with a high-energy electron beam. The optimization of the isomer production was solved analytically and the largest estimated yield was determined as calibrated to the experimental yield. The maximum yield of 178m2Hf was found to be of about 3×109 nuclei/s using an electron beam current of 100 μA. This is lower than the yield achieved with proton beams, although for a practical comparison the total cost and radiation safety conditions should be considered. The present results provide a basis for numerical estimations.

  11. A kinetic study on the isomerization of hop alpha-acids.

    PubMed

    Jaskula, Barbara; Kafarski, Pawel; Aerts, Guido; De Cooman, Luc

    2008-08-13

    In this article, a detailed study on hop alpha-acid isomerization kinetics is presented. Because of the complex wort matrix and interfering interactions occurring during real wort boiling (i.e., trub formation and alpha-acids/iso-alpha-acids complexation), this investigation on alpha-acid isomerization kinetics was performed in aqueous buffer solution as a function of time (0-90 min) and heating temperature (80-100 degrees C). Rate constants and activation energies for the formation of individual iso-alpha-acids were determined. It was found that iso-alpha-acid formation follows first-order kinetics and Arrhenius behavior. Differences in activation energies for the formation of trans- and cis-isomers were noticed, the activation energy for the formation of trans-iso-alpha-acids being approximately 9 kJmol (-1) lower.

  12. System-pH-dependent supramolecular isomers of puckered three-dimensional layered hydrogen-bonded networks: Syntheses, characterization and fluorescent properties

    NASA Astrophysics Data System (ADS)

    Chen, Pang-Kuan; Che, Yun-Xia; Li, Yu-Mei; Zheng, Ji-Min

    2006-08-01

    Two true supramolecular isomers ( 1 and 2) formulated as [Zn(bipy)(H 2btc) 2] n (bipy=2,2'-bipyridine, H 3btc=benzene-1,3,5-tricarboxylic acid) have been hydrothermally prepared through systematically changing the pH value of reaction mixture, and characterized by single-crystal X-ray diffraction, element analysis, infrared spectra (IR), and differential scanning calorimetry (DSC). Isomer 1 crystallizes in triclinic space group P-1, tetrahedral Zn(ΙΙ) ions possess four-coordinated environment, while isomer 2 crystallizes in monoclinic space group C2/ c and the distorted octahedral Zn(II) ions adopt six-coordinated fashion. 1 and 2 can be regarded as supramolecular structural isomers, the formation of which should be undoubtedly attributed to the preference for pH-dependent crystallization leading to multiple connectivity (monodentate and chelating bidentate) of organic ligand despite the same stoichiometry employed. The supramolecular chemistry, which organizes the coordination complexes into three-dimensional (3D) layered open structure, is driven by a combination of hydrogen-bond and π- π interactions. Moreover, 1 emits fluorescence at 350.1 nm ( λ=310.0 nm) and 2 exhibits fluorescent property at about 351.4 nm ( λ=302.0 nm).

  13. A family of single-isomer, dicationic cyclodextrin chiral selectors for capillary electrophoresis: mono-6(A)-ammonium-6(C)-butylimidazolium-β-cyclodextrin chlorides.

    PubMed

    Dai, Yun; Wang, Shuye; Zhou, Jie; Tang, Jian; Tang, Weihua

    2013-03-01

    The first member of the single-isomer, dicationic cyclodextrin (CD) family, 6(A)-ammonium-6(C)-butylimidazolium-β-cyclodextrin chlorides (AMBIMCD), has been synthesized, analytically characterized, and used to separate a variety of acidic enantiomers and amino acids by CE. Starting from mono-6(A)-azido-β-cyclodextrin, the cationic imidazolium and ammonium moieties were subsequently introduced onto primary ring of β-cyclodextrin via nucleophilic addition and Staudinger reaction. The analytically pure AC regio-isomer CD was further obtained via column chromatography. This dicationic CD exhibited excellent enantioselectivities for selected analytes at concentration as low as 0.5 mM, which were even better than those of its mono-imidazolium or ammonium-substitued counterpart CDs at 10 equivalent concentrations. The effective mobilities of all studied analytes were found to decrease with the concentration of AMBIMCD. Inclusion complexation in combination with eletrostatic interactions seemed to account for the enhanced chiral discrimination process.

  14. The absolute configurations of hydroxy fatty acids from the royal jelly of honeybees (Apis mellifera).

    PubMed

    Kodai, Tetsuya; Nakatani, Takafumi; Noda, Naoki

    2011-03-01

    9-Hydroxy-2E-decenoic acid (9-HDA) is a precursor of the queen-produced substance, 9-oxo-2E-decenoic acid (9-ODA), which has various important functions and roles for caste maintenance in honeybee colonies (Apis mellifera). 9-HDA in royal jelly is considered to be a metabolite of 9-ODA produced by worker bees, and it is fed back to the queen who then transforms it into 9-ODA. Recently we found that 9-HDA is present in royal jelly as a mixture of optical isomers (R:S, 2:1). The finding leads us to suspect that chiral fatty acids in royal jelly are precursors of semiochemicals. Rather than looking for semiochemicals in the mandibular glands of the queen bee, this study involves the search for precursors of pheromones from large quantities of royal jelly. Seven chiral hydroxy fatty acids, 9,10-dihydroxy-2E-decenoic, 4,10-dihydroxy-2E-decenoic, 4,9-dihydroxy-2E-decenoic, 3-hydroxydecanoic, 3,9-dihydroxydecanoic, 3,11-dihydroxydodecanoic, and 3,10-dihydroxydecanoic acids were isolated. The absolute configurations of these acids were determined using the modified Mosher's method, and it was revealed that, similar to 9-HDA, five acids are present in royal jelly as mixtures of optical isomers.

  15. Isomer-Specific Binding Affinity of Perfluorooctanesulfonate (PFOS) and Perfluorooctanoate (PFOA) to Serum Proteins.

    PubMed

    Beesoon, Sanjay; Martin, Jonathan W

    2015-05-05

    Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are among the most prominent contaminants in human serum, and these were historically manufactured as technical mixtures of linear and branched isomers. The isomers display unique pharmacokinetics in humans and in animal models, but molecular mechanisms underlying isomer-specific PFOS and PFOA disposition have not previously been studied. Here, ultrafiltration devices were used to examine (i) the dissociation constants (Kd) of individual PFOS and PFOA isomers with human serum albumin (HSA) and (ii) relative binding affinity of isomers in technical mixtures spiked to whole calf serum and human serum. Measurement of HSA Kd's demonstrated that linear PFOS (Kd=8(±4)×10(-8) M) was much more tightly bound than branched PFOS isomers (Kd range from 8(±1)×10(-5) M to 4(±2)×10(-4) M). Similarly, linear PFOA (Kd=1(±0.9)×10(-4) M) was more strongly bound to HSA compared to branched PFOA isomers (Kd range from 4(±2)×10(-4) M to 3(±2)×10(-4) M). The higher binding affinities of linear PFOS and PFOA to total serum protein were confirmed when both calf serum and human serum were spiked with technical mixtures. Overall, these data provide a mechanistic explanation for the longer biological half-life of PFOS in humans, compared to PFOA, and for the higher transplacental transfer efficiencies and renal clearance of branched PFOS and PFOA isomers, compared to the respective linear isomer.

  16. A bidirectional approach to the synthesis of polypropionates: synthesis of C1-C13 fragment of zincophorin and related isomers.

    PubMed

    Mochirian, Philippe; Godin, François; Katsoulis, Ioannis; Fontaine, Isabelle; Brazeau, Jean-François; Guindon, Yvan

    2011-10-07

    The structure-activity study of a bioactive natural product containing polypropionate subunits requires that its stereoisomers also be evaluated. Therefore, a general approach to synthesize these motifs is necessary. We describe herein the synthesis of the C1-C13 polypropionate subunit of zincophorin and isomers thereof using a two-reaction sequence: an aldol reaction using a mixture of tetrasubstituted enoxysilanes and a hydrogen-transfer reaction, both under Lewis acid control. Selection of the appropriate Lewis acid dictates the stereochemical outcome of these reactions. From a tactical standpoint, this study shows how a polypropionate sequence can be read and constructed in two directions, either the east-west or the west-east approaches. The choice of the optimal route is influenced by the number of complexation sites that can interfere in the aldol step under bidentate Lewis acid control.

  17. Role of Tyrosine Isomers in Acute and Chronic Diseases Leading to Oxidative Stress - A Review

    PubMed Central

    Molnár, Gergő A.; Kun, Szilárd; Sélley, Eszter; Kertész, Melinda; Szélig, Lívia; Csontos, Csaba; Böddi, Katalin; Bogár, Lajos; Miseta, Attila; Wittmann, István

    2016-01-01

    Oxidative stress plays a major role in the pathogenesis of a variety of acute and chronic diseases. Measurement of the oxidative stress-related end products may be performed, e.g. that of structural isomers of the physiological para-tyrosine, namely meta- and ortho-tyrosine, that are oxidized derivatives of phenylalanine. Recent data suggest that in sepsis, serum level of meta-tyrosine increases, which peaks on the 2nd and 3rd days (p<0.05 vs. controls), and the kinetics follows the intensity of the systemic inflammation correlating with serum procalcitonin levels. In a similar study subset, urinary meta-tyrosine excretion correlated with both need of daily insulin dose and the insulin-glucose product in non-diabetic septic cases (p<0.01 for both). Using linear regression model, meta-tyrosine excretion, urinary meta-tyrosine/para-tyrosine, urinary ortho-tyrosine/para-tyrosine and urinary (meta- + ortho-tyrosine)/para-tyrosine proved to be markers of carbohydrate homeostasis. In a chronic rodent model, we tried to compensate the abnormal tyrosine isomers using para-tyrosine, the physiological amino acid. Rats were fed a standard high cholesterol-diet, and were given para-tyrosine or vehicle orally. High-cholesterol feeding lead to a significant increase in aortic wall meta-tyrosine content and a decreased vasorelaxation of the aorta to insulin and the glucagon-like peptide-1 analogue, liraglutide, that both could be prevented by administration of para-tyrosine. Concluding, these data suggest that meta- and ortho-tyrosine are potential markers of oxidative stress in acute diseases related to oxidative stress, and may also interfere with insulin action in septic humans. Competition of meta- and ortho-tyrosine by supplementation of para-tyrosine may exert a protective role in oxidative stress-related diseases. PMID:26785996

  18. A strategy for the separation of diterpenoid isomers from the root of Aralia continentalis by countercurrent chromatography: The distribution ratio as a substitute for the partition coefficient and a three-phase solvent system.

    PubMed

    Lee, Kyoung Jin; Song, Kwang Ho; Choi, Wonmin; Kim, Yeong Shik

    2015-08-07

    Aralia continentalis (Araliaceae) is widely used as a medicinal plant in East Asia. Previous studies have indicated that diterpenoid isomers (kaurenoic acid, continentalic acid, and ent-continentalic acid) are the major bioactive compounds of this plant. A new strategy was developed to alleviate difficulties in the separation of these isomers from this plant. A three-phase solvent system was applied to separate the isomers, and furthermore, the distribution ratio (Kc) was introduced as a substitute for the partition coefficient (KD). For compounds exhibiting a single equilibrium, their distributions in two immiscible phases were only affected by the partition coefficient of each solute. However, compounds that have a dissociating functional group (e.g., -COOH) are involved in two types of equilibrium in the two-phase system. In this case, the partitioning behaviors of the solutes are greatly affected by the pH of the solution. A mathematical prediction was applied for adjusting the solutions to the proper pH values. To prevent non-used phase (medium phase) waste, both the stationary phase (upper phase) and mobile phase (lower phase) were prepared on-demand without pre-saturation with the application of (1)H NMR. Each fraction obtained was collected and dried, yielding the following diterpenoid isomers from the 50mg injected sample: kaurenoic acid (19.7mg, yield: 39%) and ent-continentalic acid (21.3mg, yield: 42%).

  19. Individual CLA Isomers, c9t11 and t10c12, Prevent Excess Liver Glycogen Storage and Inhibit Lipogenic Genes Expression Induced by High-Fructose Diet in Rats.

    PubMed

    Maslak, Edyta; Buczek, Elzbieta; Szumny, Antoni; Szczepnski, Wojciech; Franczyk-Zarow, Magdalena; Kopec, Aneta; Chlopicki, Stefan; Leszczynska, Teresa; Kostogrys, Renata B

    2015-01-01

    This study assessed the effects of individual conjugated linoleic acid isomers, c9t11-CLA and t10c12-CLA, on nonalcoholic fatty liver disease (NAFLD) and systemic endothelial dysfunction in rats fed for four weeks with control or high-fructose diet. The high-fructose diet hampered body weight gain (without influencing food intake), increased liver weight and glycogen storage in hepatocytes, upregulated expression of fatty acid synthase (FAS) and stearoyl-CoA desaturase-1 (SCD-1), and increased saturated fatty acid (SFA) content in the liver. Both CLA isomers prevented excessive accumulation of glycogen in the liver. Specifically, t10c12-CLA decreased concentration of serum triacylglycerols and LDL + VLDL cholesterol, increased HDL cholesterol, and affected liver lipid content and fatty acid composition by downregulation of liver SCD-1 and FAS expression. In turn, the c9t11-CLA decreased LDL+VLDL cholesterol in the control group and downregulated liver expression of FAS without significant effects on liver weight, lipid content, and fatty acid composition. In summary, feeding rats with a high-fructose diet resulted in increased liver glycogen storage, indicating the induction of gluconeogenesis despite simultaneous upregulation of genes involved in de novo lipogenesis. Although both CLA isomers (c9t11 and t10c12) display hepatoprotective activity, the hypolipemic action of the t10c12-CLA isomer proved to be more pronounced than that of c9t11-CLA.

  20. Synthesis of deuterated [D32 ]oleic acid and its phospholipid derivative [D64 ]dioleoyl-sn-glycero-3-phosphocholine.

    PubMed

    Darwish, Tamim A; Luks, Emily; Moraes, Greta; Yepuri, Nageshwar R; Holden, Peter J; James, Michael

    2013-01-01

    Oleic acid and its phospholipid derivatives are fundamental to the structure and function of cellular membranes. As a result, there has been increasing interest in the availability of their deuterated forms for many nuclear magnetic resonance, infrared, mass spectroscopy and neutron scattering studies. Here, we present for the first time a straightforward, large-scale (gram quantities) synthesis of highly deuterated [D32 ]oleic acid by using multiple, yet simple and high yielding reactions. The precursors for the synthesis of [D32 ]oleic acid are [D14 ]azelaic acid and [D17 ]nonanoic acid, which were obtained by complete deuteration (>98% D) of their (1) H forms by using metal catalysed hydrothermal H/D exchange reactions. The oleic acid was produced with ca. 94% D isotopic purity and with no contamination by the trans-isomer (elaidic acid). The subsequent synthesis of [D64 ]dioleoyl-sn-glycero-3-phosphocholine from [D32 ]oleic acid is also described.

  1. The acetyl bromide method is faster, simpler and presents best recovery of lignin in different herbaceous tissues than Klason and thioglycolic acid methods.

    PubMed

    Moreira-Vilar, Flavia Carolina; Siqueira-Soares, Rita de Cássia; Finger-Teixeira, Aline; de Oliveira, Dyoni Matias; Ferro, Ana Paula; da Rocha, George Jackson; Ferrarese, Maria de Lourdes L; dos Santos, Wanderley Dantas; Ferrarese-Filho, Osvaldo

    2014-01-01

    We compared the amount of lignin as determined by the three most traditional methods for lignin measurement in three tissues (sugarcane bagasse, soybean roots and soybean seed coat) contrasting for lignin amount and composition. Although all methods presented high reproducibility, major inconsistencies among them were found. The amount of lignin determined by thioglycolic acid method was severely lower than that provided by the other methods (up to 95%) in all tissues analyzed. Klason method was quite similar to acetyl bromide in tissues containing higher amounts of lignin, but presented lower recovery of lignin in the less lignified tissue. To investigate the causes of the inconsistencies observed, we determined the monomer composition of all plant materials, but found no correlation. We found that the low recovery of lignin presented by the thioglycolic acid method were due losses of lignin in the residues disposed throughout the procedures. The production of furfurals by acetyl bromide method does not explain the differences observed. The acetyl bromide method is the simplest and fastest among the methods evaluated presenting similar or best recovery of lignin in all the tissues assessed.

  2. The prenucleosome, a stable conformational isomer of the nucleosome.

    PubMed

    Fei, Jia; Torigoe, Sharon E; Brown, Christopher R; Khuong, Mai T; Kassavetis, George A; Boeger, Hinrich; Kadonaga, James T

    2015-12-15

    Chromatin comprises nucleosomes as well as nonnucleosomal histone-DNA particles. Prenucleosomes are rapidly formed histone-DNA particles that can be converted into canonical nucleosomes by a motor protein such as ACF. Here we show that the prenucleosome is a stable conformational isomer of the nucleosome. It consists of a histone octamer associated with ∼ 80 base pair (bp) of DNA, which is located at a position that corresponds to the central 80 bp of a nucleosome core particle. Monomeric prenucleosomes with free flanking DNA do not spontaneously fold into nucleosomes but can be converted into canonical nucleosomes by an ATP-driven motor protein such as ACF or Chd1. In addition, histone H3K56, which is located at the DNA entry and exit points of a canonical nucleosome, is specifically acetylated by p300 in prenucleosomes relative to nucleosomes. Prenucleosomes assembled in vitro exhibit properties that are strikingly similar to those of nonnucleosomal histone-DNA particles in the upstream region of active promoters in vivo. These findings suggest that the prenucleosome, the only known stable conformational isomer of the nucleosome, is related to nonnucleosomal histone-DNA species in the cell.

  3. Calculations of long-lived isomer production in neutron reactions

    SciTech Connect

    Chadwick, M.B.; Young, P.G.

    1991-01-01

    We have carried out theoretical calculations for the production of the long-lived isomers {sup 93m}Nb({1/2}{sup {minus}}, 16y), {sup 121m}Sn(11/2{minus}, 55 yr), {sup 166m}Ho(7-, 1200 yr), {sup 184m}Re(8+, 165 d), {sup 186m}Re(8+, 2{times}10{sup 5} yr), {sup 178m}Hf(16+, 31 yr), {sup 179m}Hf(25/2-, 25 d), {sup 192m}Ir(9+, 241 yr), all of which pose potential radiation activation problems in nuclear fusion reactors. We consider (n, 2n), (n,n{prime}), and (n, {gamma}) production modes and compare our results both with experimental data (where available) and systematic. We also investigate the dependence of the isomeric cross section ratio on incident neutron energy for the isomers under consideration. The statistical Hauser-Feshbach plus preequilibrium code GNASH was used for the calculations. Where discrete state experimental information was lacking, rotational band members above the isomeric state, which can be justified theoretically but have not been experimentally resolved, were reconstructed. 16 refs., 8 figs.

  4. Estrogenic effects of nonylphenol and octylphenol isomers in vitro by recombinant yeast assay (RYA) and in vivo with early life stages of zebrafish.

    PubMed

    Puy-Azurmendi, E; Olivares, A; Vallejo, A; Ortiz-Zarragoitia, M; Piña, B; Zuloaga, O; Cajaraville, M P

    2014-01-01

    Commercial OP and NP are complex isomer mixtures that can be individually present in the environment, showing different estrogenic potencies. The aims of this study were to establish the estrogenic potency of some AP isomers in comparison to the commercial NP (cNP) mixture in vitro and to investigate in vivo their possible effects during the embryo and larval development of zebrafish. An in vitro estrogen receptor-based recombinant yeast assay was used to test the estrogenicity of specific AP isomers (22-OP, 33-OP, 22-NP, 33-NP and 363-NP) and cNP. The EC₅₀ was in the range of 0.6-7.7 mg/L. Both OP isomers and 363-NP exhibited higher estrogenic activity than cNP. For in vivo experiments, one-day postfertilisation (dpf) embryos were exposed to cNP (50, 250 and 500 μg/L), 363-NP and 33-OP (50 μg/L), 17β-estradiol (100 ng/L) and DMSO (0.01% v/v) for 4weeks. After exposure fish were maintained for 2 weeks in clean water in order to evaluate a possible recovery. Fish of groups exposed to cNP and 363-NP were the last to hatch. Histological alterations were not observed after 7, 28 or 42 dpf. Exposure to 33-OP increased transcriptional levels of erα, vtg and cyp19a1b genes. However, transcriptional response in E2 exposure was observed at later stages and with higher fold induction levels. Exposure to cNP decreased levels of erα whereas increased levels of rxrγ and cyp19a1b. Exposure to 363-NP did not cause changes in transcriptional levels of studied genes. The differences in response of the OP isomer compared to the NP isomer in zebrafish could be related to the rapid decay in concentration of the latter.

  5. The role of core excitations in the structure and decay of the 16+ spin-gap isomer in 96Cd

    NASA Astrophysics Data System (ADS)

    Davies, P. J.; Grawe, H.; Moschner, K.; Blazhev, A.; Wadsworth, R.; Boutachkov, P.; Ameil, F.; Yagi, A.; Baba, H.; Bäck, T.; Dewald, M.; Doornenbal, P.; Faestermann, T.; Gengelbach, A.; Gerl, J.; Gernhäeuser, R.; Go, S.; Górska, M.; Gregor, E.; Isobe, T.; Jenkins, D. G.; Hotaka, H.; Jolie, J.; Kojouharov, I.; Kurz, N.; Lewitowicz, M.; Lorusso, G.; Maier, L.; Merchan, E.; Naqvi, F.; Nishibata, H.; Nishimura, D.; Nishimura, S.; Nowacki, F.; Pietralla, N.; Schaffner, H.; Söderström, P.-A.; Jung, H. S.; Steiger, K.; Sumikama, T.; Taprogge, J.; Thöle, P.; Warr, N.; Watanabe, H.; Werner, V.; Xu, Z. Y.; Yoshinaga, K.; Zhu, Y.

    2017-04-01

    The first evidence for β-delayed proton emission from the 16+ spin gap isomer in 96Cd is presented. The data were obtained from the Rare Isotope Beam Factory, at the RIKEN Nishina Center, using the BigRIPS spectrometer and the EURICA decay station. βp branching ratios for the ground state and 16+ isomer have been extracted along with more precise lifetimes for these states and the lifetime for the ground state decay of 95Cd. Large scale shell model (LSSM) calculations have been performed and WKB estimates made for ℓ = 0 , 2 , 4 proton emission from three resonance-like states in 96Ag, that are populated by the β decay of the isomer, and the results compared to the new data. The calculations suggest that ℓ = 2 proton emission from the resonance states, which reside ∼ 5 MeV above the proton separation energy, dominates the proton decay. The results highlight the importance of core-excited wavefunction components for the 16+ state.

  6. Effects of ionic liquid as additive and the pH of the mobile phase on the retention factors of amino benzoic acids in RP-HPLC.

    PubMed

    Zheng, J; Polyakova, Y; Row, K H

    2007-01-01

    As an organic salt, ionic liquids are widely used as new solvent media. In this paper, three positional isomers, such as o-amino benzoic acid, m-amino benzoic acid, and p-amino benzoic acid are separated with four different ionic liquids as additives to the mobile phase using reversed-phase (RP) high-performance liquid chromatography (HPLC). Amino benzoic acids are biologically active substances; the p-isomer is present in a group of water-soluble vitamins and is widely known as a sunscreen agent. The ionic liquids used are 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium methylsulfate, and 1-octyl-3-methylimidazolium methylsulfate. The effects of the length of the alkyl group on the imidazolium ring and its counterion, the concentrations of the ionic liquid, and the effect of the pH of the mobile phase on the retention factor of the amino benzoic acid isomers are studied. Separation with the ionic liquid in the eluent was better than the separation without the ionic liquid. The pH mainly affected the retention and elution order of the solutes in RP-HPLC.

  7. Effect of phospholipid-based formulations of Boswellia serrata extract on the solubility, permeability, and absorption of the individual boswellic acid constituents present.

    PubMed

    Hüsch, Jan; Gerbeth, Kathleen; Fricker, Gert; Setzer, Constanze; Zirkel, Jürgen; Rebmann, Herbert; Schubert-Zsilavecz, Manfred; Abdel-Tawab, Mona

    2012-10-26

    Boswellia serrata gum resin extracts are used widely for the treatment of inflammatory diseases. However, very low concentrations in the plasma and brain were observed for the boswellic acids (1-6, the active constituents of B. serrata). The present study investigated the effect of phospholipids alone and in combination with common co-surfactants (e.g., Tween 80, vitamin E-TPGS, pluronic f127) on the solubility of 1-6 in physiologically relevant media and on the permeability in the Caco-2 cell model. Because of the high lipophilicity of 1-6, the permeability experiments were adapted to physiological conditions using modified fasted state simulated intestinal fluid as apical (donor) medium and 4% bovine serum albumin in the basolateral (receiver) compartment. A formulation composed of extract/phospholipid/pluronic f127 (1:1:1 w/w/w) increased the solubility of 1-6 up to 54 times compared with the nonformulated extract and exhibited the highest mass net flux in the permeability tests. The oral administration of this formulation to rats (240 mg/kg) resulted in 26 and 14 times higher plasma levels for 11-keto-β-boswellic acid (1) and acetyl-11-keto-β-boswellic acid (2), respectively. In the brain, five times higher levels for 2 compared to the nonformulated extract were determined 8 h after oral administration.

  8. Determination of unsaturation grade and trans isomers generated during thermal oxidation of edible oils and fats by FTIR

    NASA Astrophysics Data System (ADS)

    Moya Moreno, M. C. M.; Mendoza Olivares, D.; Amézquita López, F. J.; Gimeno Adelantado, J. V.; Bosch Reig, F.

    1999-05-01

    The oxidative deterioration of culinary oils and fats during episodes of heating associated with normal usage (80°C-300°C, 20-40 min) was monitored by FTIR spectroscopy. The thermal oxidation of polyunsaturated fatty acids during heating was studied by the determination of unsaturation percentage and trans isomers at various temperatures and heating times. Oils frequently used in food frying such as olive oil, sunflower oil, corn oil and seeds oil (sunflower, safflower and canola seed), and lard were studied. The Absorbance Correction Method is proposed to correct the spectral interference and allows the analytic use of signal which would not be initially valid for quantitative analysis. The results show that there is a decrease in unsaturation and an increase in trans isomers starting at 150°C and becomes more pronounced at temperatures around 250°C. This variation in unsaturation grade and conformation provides evidence of the transformation of essential polyunsaturated fatty acids and subsequent decrease in the oils' nutritional value.

  9. Sources and Bioactive Properties of Conjugated Dietary Fatty Acids.

    PubMed

    Hennessy, Alan A; Ross, Paul R; Fitzgerald, Gerald F; Stanton, Catherine

    2016-04-01

    The group of conjugated fatty acids known as conjugated linoleic acid (CLA) isomers have been extensively studied with regard to their bioactive potential in treating some of the most prominent human health malignancies. However, CLA isomers are not the only group of potentially bioactive conjugated fatty acids currently undergoing study. In this regard, isomers of conjugated α-linolenic acid, conjugated nonadecadienoic acid and conjugated eicosapentaenoic acid, to name but a few, have undergone experimental assessment. These studies have indicated many of these conjugated fatty acid isomers commonly possess anti-carcinogenic, anti-adipogenic, anti-inflammatory and immune modulating properties, a number of which will be discussed in this review. The mechanisms through which these bioactivities are mediated have not yet been fully elucidated. However, existing evidence indicates that these fatty acids may play a role in modulating the expression of several oncogenes, cell cycle regulators, and genes associated with energy metabolism. Despite such bioactive potential, interest in these conjugated fatty acids has remained low relative to the CLA isomers. This may be partly attributed to the relatively recent emergence of these fatty acids as bioactives, but also due to a lack of awareness regarding sources from which they can be produced. In this review, we will also highlight the common sources of these conjugated fatty acids, including plants, algae, microbes and chemosynthesis.

  10. Synthesis of β- and γ-hydroxy α-amino acids via enzymatic kinetic resolution and cyanate-to-isocyanate rearrangement.

    PubMed

    Szcześniak, Piotr; Październiok-Holewa, Agnieszka; Klimczak, Urszula; Stecko, Sebastian

    2014-12-05

    A new strategy for stereoselective preparation of all four isomers of β- and γ-hydroxy α-amino acids is presented. The developed procedure is based on enzymatic kinetic resolution and cyanate-to-isocyanate rearrangement as key steps. Stereocontrol is achieved by proper choice of the starting hydroxyacid, the course of kinetic resolution, and the stereospecific sigmatropic rearrangement step, which proceeds with full chirality transfer.

  11. Keto-acids in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, G.; Chang, P. M.; Dugas, A.; Byrd, A.; Chang, P. M.; Washington, N.

    2005-01-01

    The Murchison and Murray meteorites are the best-characterized carbonaceous meteorites with respect to organic chemistry and are generally used as references for organic compounds in extraterrestrial material. Among the classes of organic compounds found in these meteorites are amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds, important in contemporary biochemistry, are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in early life and/or the origin of life. Absent among (today's) critically important biological compounds reported in carbonaceous meteorites are keto acids, i.e., pyruvic acid, acetoacetic acid, and higher homologs. These compounds are key intermediates in such critical processes as glycolysis and the citric acid cycle. In this study several individual meteoritic keto acids were identified by gas chromatography-mass spectrometry (GC-MS) (see figure below). All compounds were identified as their trimethylsilyl (TMS), isopropyl ester (ISP), and tert-butyldimethylsilyl (tBDMS) derivatives. In general, the compounds follow the abiotic synthesis pattern of other known meteorite classes of organic compounds [1,2]: a general decrease in abundance with increasing carbon number within a class of compounds and many, if not all, possible isomers present at a given carbon number. The majority of the shown compounds was positively identified by comparison of their mass spectra to commercially available standards or synthesized standards.

  12. Disulfide isomers of alpha-neurotoxins from King cobra (Ophiophagus hannah) venom.

    PubMed

    Lin, S R; Chang, L S; Chang, C C

    1999-01-08

    Two novel alpha-neurotoxins, Oh-6A and Oh-6B, isolated from the king cobra (Ophiophagus hannah) venom, consist of 70 amino acid residues with 10 cysteine residues and share the same amino acid sequences as determined by Edman degradation on the peptide fragments generated from the proteolytic hydrolysates. Their sequences share 46-53% homology with Oh-4, Oh-5, Toxin a, and Toxin b from the same venom. The finding that Oh-6A and Oh-6B had different retention times in the reversed-phase column suggested that the two toxin molecules should not have the same conformation. Selective reduction on the disulfide bond, Cys26--Cys30, at the tip of their loop II structures resulted in the production of the partially reduced derivatives eluted at the same position. Under redox conditions, the partially reduced Oh-6A and 6B exclusively converted into native Oh-6A as evidenced by HPLC analyses. This suggests that Oh-6A and Oh-6B are disulfide isomers which probably arise from cis-trans isomerization of the Cys26--Cys30 disulfide bond. Alternatively, the two toxins exhibited binding activity toward nAChR and lethal toxicity equally. It reflects that the diversity around the extra loop at the loop II structure does not exert a significant effect on the manifestation of the neurotoxicity of Oh-6A and Oh-6B.

  13. Studies on the production of conjugated linoleic acid from linoleic and vaccenic acids by mixed rumen protozoa.

    PubMed

    Or-Rashid, Mamun M; AlZahal, Ousama; McBride, Brian W

    2008-12-01

    The present study was designed to investigate the capability of mixed rumen protozoa to synthesize conjugated linoleic acid (CLA) from linoleic (LA) and vaccenic acids (VA). Rumen contents were collected from fistulated cows. The protozoal fraction was separated and washed several times with MB9 buffer and then resuspended in autoclaved rumen fluid. The suspensions were anaerobically incubated up to 18 h at 38.5 degrees C with substrates in the presence (P-AB) or the absence of antibacterial-agents (P-No-AB). Neither P-AB nor P-No-AB suspensions were capable of producing CLA from VA (11t-18:1). Linoleic acid was catabolized by P-No-AB to a greater extent than P-AB. Different isomers of CLA were synthesized by P-AB from LA. The 9c11t-CLA was predominant. Thirty seven percent of the maximum accumulated 9c11t-CLA was found in the P-AB suspension as early as 0.1 h into the incubation period. Accumulation of 10t12c-CLA in P-AB suspension was approximately 10.0 times lower than that of 9c11t-CLA. There were no significant productions of VA, 10t-18:1, and 18:0 in P-AB compared with the control, indicating that rumen protozoa have no ability to biohydrogenate CLA isomers. On the other hand, the concentrations of 10t-18:1, VA, and 18:0 in P-No-AB were greater (P < 0.05) compared with those in P-AB, indicating the role of symbiotic bacteria associated with P-No-AB in biohydrogenating CLA isomers. We concluded that mixed rumen protozoa are capable of synthesizing CLA from LA through isomerization reactions. However, they are incapable of metabolizing CLA further. They are also incapable of vaccenic acid biohydrogenation and/or desaturation.

  14. A Highly Sensitive Diketopyrrolopyrrole-Based Ambipolar Transistor for Selective Detection and Discrimination of Xylene Isomers.

    PubMed

    Wang, Bin; Huynh, Tan-Phat; Wu, Weiwei; Hayek, Naseem; Do, Thu Trang; Cancilla, John C; Torrecilla, Jose S; Nahid, Masrur Morshed; Colwell, John M; Gazit, Oz M; Puniredd, Sreenivasa Reddy; McNeill, Christopher R; Sonar, Prashant; Haick, Hossam

    2016-06-01

    An ambipolar poly(diketopyrrolopyrrole-terthiophene)-based field-effect transistor (FET) sensitively detects xylene isomers at low ppm levels with multiple sensing features. Combined with pattern-recognition algorithms, a sole ambipolar FET sensor, rather than arrays of sensors, can discriminate highly similar xylene structural isomers from one another.

  15. Theoretical Prediction of the Structures and Energies of Olympicene and its Isomers

    NASA Astrophysics Data System (ADS)

    Valentine, Andrew J. S.; Mazziotti, David A.

    2013-10-01

    Pentacene, a linear five-ringed polyaromatic hydrocarbon, has recently been used as an organic semiconductor in field-effect transistors. The recently synthesized olympicene molecule, so named because of its resemblance to the olympic rings, is a more compact five-ringed structure. This paper offers the first theoretical study of the kinetic stability of olympicene and its isomers. We use the parametric two-electron reduced density matrix (2-RDM) method, which takes the 2-RDM as the basic variable in lieu of the traditional wave function in calculations [ Mazziotti, D. A. Phys. Rev. Lett. 2008, 101, 253002 ]. Our calculations demonstrate that olympicene-s isomers may be separated into aromatic and diradical isomers, the latter of which require accurate treatment of strong electron correlation to detect multireference character. Albeit formally a single-reference method, the parametric 2-RDM captures the multireference correlation of the diradical isomers; relative to olympicene, the 2-RDM predicts five diradical isomers that are 16-22 kcal/mol lower in energy than those from coupled cluster with single and double excitations-a significant change that causes these isomers to be stable to dissociation by 2-20 kcal/mol. We characterize the transition states between olympicene-s isomers, observe differences in aromaticity among the different isomers, and compare the electronic properties of olympicene to those of pentacene. The olympicene molecule has the potential to complement pentacene as an organic semiconductor.

  16. Comparison of some specific polychlorinated biphenyl isomers in human and monkey milk

    SciTech Connect

    Mes, J.; Marchand, L.

    1987-11-01

    The presence and levels of polychlorinated biphenyls (PCBs) in monkey milk have been reported earlier as part of studies which investigated the overall toxicity of PCBs in commercial Aroclors. Some of this information has served as a basis for an estimation of the potential health hazard of PCB contaminated breast milk to human infants. To further support such extrapolation from one primate situation to another, it would be desirable to know not only the levels of PCBs in the milk of these primates, but also the isomeric distribution in order to better evaluate the contribution of each isomer to the overall toxicity. A large concentration in breast milk of an isomer of relatively low toxicity may have the same effect on an infant as a smaller concentration of a highly toxic isomer. This paper compares the relative amounts of 29 selected PCB isomers in human milk and monkey milk samples. The selection of isomers was based on the most prevalent PCB isomers in human milk and represented approximately 80% of all reported isomers. In addition, Aroclor 1254, whose toxicity in monkeys has been investigated recently by several investigators, was analyzed for the same 29 selected PCB isomers.

  17. Synthesis of the optical isomers of a new anticholinergic drug, penehyclidine hydrochloride (8018).

    PubMed

    Han, Xiang-Yu; Liu, He; Liu, Chun-He; Wu, Bo; Chen, Lan-Fu; Zhong, Bo-Hua; Liu, Ke-Liang

    2005-04-15

    A practical diastereoselective synthetic method for 8018 enantiopure isomers is described. The intramolecular asymmetric epoxidation of mono-sulfonate 4 was applied for the execution of the synthesis of the key chiral building block for the first time. The isomers were obtained with 70-76% yields in 99-100% ee.

  18. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues. 180.418 Section 180.418 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances...

  19. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues. 180.418 Section 180.418 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances...

  20. Red cell membrane and plasma linoleic acid nitration products: synthesis, clinical identification, and quantitation.

    PubMed

    Baker, Paul R S; Schopfer, Francisco J; Sweeney, Scott; Freeman, Bruce A

    2004-08-10

    Nitric oxide (*NO) and its reactive metabolites mediate the oxidation, nitration, and nitrosation of DNA bases, amino acids, and lipids. Here, we report the structural characterization and quantitation of two allylic nitro derivatives of linoleic acid (LNO(2)), present as both free and esterified species in human red cell membranes and plasma lipids. The LNO(2) isomers 10-nitro-9-cis, 12-cis-octadecadienoic acid and 12-nitro-9-cis, 12-cis-octadecadienoic acid were synthesized and compared with red cell and plasma LNO(2) species based on chromatographic elution and mass spectral properties. Collision-induced dissociation fragmentation patterns from synthetic LNO(2) isomers were identical to those of the two most prevalent LNO(2) positional isomers found in red cells and plasma. By using [(13)C]LNO(2) as an internal standard, red cell free and esterified LNO(2) content was 50 +/- 17 and 249 +/- 104 nM, respectively. The free and esterified LNO(2) content of plasma was 79 +/- 35 and 550 +/- 275 nM, respectively. Nitrated fatty acids, thus, represent the single largest pool of bioactive oxides of nitrogen in the vasculature, with a net LNO(2) concentration of 477 +/- 128 nM, excluding buffy coat cells. These observations affirm that basal oxidative and nitrating conditions occur in healthy humans to an extent that is sufficient to induce abundant membrane and lipoprotein-fatty acid nitration. Given that LNO(2) is capable of mediating cGMP and non-cGMP-dependent signaling reactions, fatty acid nitration products are species representing the convergence of ()NO and oxygenated lipid cell-signaling pathways.

  1. Manifesting Subtle Differences of Neutral Hydrophilic Guest Isomers in a Molecular Container by Phase Transfer.

    PubMed

    Lee, Hyun Hee L; Lee, Jong Wha; Jang, Yoonjung; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I

    2016-07-11

    Achieving strong host-guest interactions between synthetic hosts and hydrophilic guests in solution is challenging because solvation effects overwhelm other effects. To resolve this issue, we transferred complexes of cucurbit[7]uril (CB[7]) and monosaccharides to the gas phase and report here their intrinsic host-guest chemistry in the absence of solvation effects. It was observed that effective host-guest interactions in the gas phase mediated by ammonium cations allow the differentiation of the monosaccharide isomers in complex with CB[7] upon vibrational excitation. The potential of the unique observation was extended to a quantitative supramolecular analytical method for the monosaccharide guests. The combination of host-guest chemistry and phase transfer presented in this study is an effective approach to overcome current limitations in supramolecular chemistry.

  2. Uncovering biologically significant lipid isomers with liquid chromatography, ion mobility spectrometry and mass spectrometry

    SciTech Connect

    Kyle, Jennifer E.; Zhang, Xing; Weitz, Karl K.; Monroe, Matthew E.; Ibrahim, Yehia M.; Moore, Ronald J.; Cha, Jeeyeon; Sun, Xiaofei; Lovelace, Erica S.; Wagoner, Jessica; Polyak, Stephen J.; Metz, Thomas O.; Dey, Sudhansu K.; Smith, Richard D.; Burnum-Johnson, Kristin E.; Baker, Erin S.

    2016-01-01

    Understanding how biological molecules are generated, metabolized and eliminated in living systems is important for interpreting processes such as immune response and disease pathology. While genomic and proteomic studies have provided vast amounts of information over the last several decades, interest in lipidomics has also grown due to improved analytical technologies revealing altered lipid metabolism in type 2 diabetes, cancer, and lipid storage disease. Liquid chromatography and mass spectrometry (LC-MS) measurements are currently the dominant approach for characterizing the lipidome by providing detailed information on the spatial and temporal composition of lipids. However, interpreting lipids’ biological roles is challenging due to the existence of numerous structural and stereoisomers (i.e. distinct acyl chain and double-bond positions), which are unresolvable using present LC-MS approaches. Here we show that combining structurally-based ion mobility spectrometry (IMS) with LC-MS measurements distinguishes lipid isomers and allows insight into biological and disease processes.

  3. Uncovering Biologically Significant Lipid Isomers with Liquid Chromatography, Ion Mobility Spectrometry and Mass Spectrometry

    PubMed Central

    Kyle, Jennifer E.; Zhang, Xing; Weitz, Karl K.; Monroe, Matthew E.; Ibrahim, Yehia M.; Moore, Ronald J.; Cha, Jeeyeon; Sun, Xiaofei; Lovelace, Erica S.; Wagoner, Jessica; Polyak, Stephen J.; Metz, Thomas O.; Dey, Sudhansu K.; Smith, Richard D.; Burnum-Johnson, Kristin E.; Baker, Erin S.

    2016-01-01

    Understanding how biological molecules are generated, metabolized and eliminated in living systems is important for interpreting processes such as immune response and disease pathology. While genomic and proteomic studies have provided vast amounts of information over the last several decades, interest in lipidomics has also grown due to improved analytical technologies revealing altered lipid metabolism in type 2 diabetes, cancer, and lipid storage disease. Mass spectrometry (MS) measurements are currently the dominant approach for characterizing the lipidome by providing detailed information on the spatial and temporal composition of lipids. However, interpreting lipids’ biological roles is challenging due to the existence of numerous structural and stereoisomers (i.e. distinct acyl chain and double-bond positions), which are often unresolvable using present approaches. Here we show that combining liquid chromatography (LC) and structurally-based ion mobility spectrometry (IMS) measurement with MS analyses distinguishes lipid isomers and allows insight into biological and disease processes. PMID:26734689

  4. The Effect of Ursolic Acid on Leishmania (Leishmania) amazonensis Is Related to Programed Cell Death and Presents Therapeutic Potential in Experimental Cutaneous Leishmaniasis

    PubMed Central

    Yamamoto, Eduardo S.; Campos, Bruno L. S.; Jesus, Jéssica A.; Laurenti, Márcia D.; Ribeiro, Susan P.; Kallás, Esper G.; Rafael-Fernandes, Mariana; Santos-Gomes, Gabriela; Silva, Marcelo S.; Sessa, Deborah P.; Lago, João H. G.; Levy, Débora; Passero, Luiz F. D.

    2015-01-01

    Among neglected tropical diseases, leishmaniasis is one of the most important ones, affecting more than 12 million people worldwide. The available treatments are not well tolerated, and present diverse side effects, justifying the search for new therapeutic compounds. In the present study, the activity of ursolic acid (UA) and oleanolic acid (OA) were assayed in experimental cutaneous leishmaniasis (in vitro and in vivo). Promastigote forms of L. amazonensis were incubated with OA and UA for 24h, and effective concentration 50% (EC50) was estimated. Ultraestructural alterations in Leishmania amazonensis promastigotes after UA treatment were evaluated by transmission electron microscopy, and the possible mode of action was assayed through Annexin V and propidium iodide staining, caspase 3/7 activity, DNA fragmentation and transmembrane mitochondrial potential. The UA potential was evaluated in intracellular amastigotes, and its therapeutic potential was evaluated in L. amazonensis infected BALB/c mice. UA eliminated L. amazonensis promastigotes with an EC50 of 6.4 μg/mL, comparable with miltefosine, while OA presented only a marginal effect on promastigote forms at 100 μg/mL. The possible mechanism by which promastigotes were eliminated by UA was programmed cell death, independent of caspase 3/7, but it was highly dependent on mitochondria activity. UA was not toxic for peritoneal macrophages from BALB/c mice, and it was able to eliminate intracellular amastigotes, associated with nitric oxide (NO) production. OA did not eliminate amastigotes nor trigger NO. L. amazonensis infected BALB/c mice submitted to UA treatment presented lesser lesion size and parasitism compared to control. This study showed, for the first time, that UA eliminate promastigote forms through a mechanism associated with programed cell death, and importantly, was effective in vivo. Therefore, UA can be considered an interesting candidate for future tests as a prototype drug for the treatment

  5. Disruption of HLA class II antigen presentation in Burkitt lymphoma: implication of a 47,000 MW acid labile protein in CD4+ T-cell recognition.

    PubMed

    God, Jason M; Zhao, Dan; Cameron, Christine A; Amria, Shereen; Bethard, Jennifer R; Haque, Azizul

    2014-07-01

    While Burkitt lymphoma (BL) has a well-known defect in HLA class I-mediated antigen presentation, the exact role of BL-associated HLA class II in generating a poor CD4(+) T-cell response remains unresolved. Here, we found that BL cells are deficient in their ability to optimally stimulate CD4(+) T cells via the HLA class II pathway. This defect in CD4(+) T-cell recognition was not associated with low levels of co-stimulatory molecules on BL cells, as addition of external co-stimulation failed to elicit CD4(+) T-cell activation by BL. Further, the defect was not caused by faulty antigen/class II interaction, because antigenic peptides bound with measurable affinity to BL-associated class II molecules. Interestingly, functional class II-peptide complexes were formed at acidic pH 5·5, which restored immune recognition. Acidic buffer (pH 5·5) eluate from BL cells contained molecules that impaired class II-mediated antigen presentation and CD4(+) T-cell recognition. Biochemical analysis showed that these molecules were greater than 30,000 molecular weight in size, and proteinaceous in nature. In addition, BL was found to have decreased expression of a 47,000 molecular weight enolase-like molecule that enhances class II-mediated antigen presentation in B cells, macrophages and dendritic cells, but not in BL cells. These findings demonstrate that BL likely has multiple defects in HLA class II-mediated antigen presentation and immune recognition, which may be exploited for future immunotherapies.

  6. Enantiomers of a nonylphenol isomer: absolute configurations and estrogenic potencies.

    PubMed

    Zhang, Haifeng; Oppel, Iris M; Spiteller, Michael; Guenther, Klaus; Boehmler, Gabriele; Zuehlke, Sebastian

    2009-02-01

    Enantiomers of 4-(1,1,2-trimethylhexyl)phenol, a chiral isomer of the endocrine disrupting chemical nonylphenol, have been resolved and isolated by preparative chiral HPLC. The absolute configurations of the enantiomers were then determined by an X-ray crystallographic study of the (-)-camphanoyl derivative of the first eluted enantiomer NP(35)E1. The first enantiomer (NP(35)E1) and the second enantiomer (NP(35)E2) eluted were found to have the S and R absolute configurations, respectively. The estrogenic potencies of the S and R enantiomers were tested by the E-screen assay. A slight difference was observed in the relative proliferative effect between the S enantiomer and R enantiomer in the E-screen assay.

  7. Social isomers of picolines in a small space.

    PubMed

    Ajami, Dariush; Theodorakopoulos, Giannoula; Petsalakis, Ioannis D; Rebek, Julius

    2013-12-09

    Encapsulation complexes permit the observation of molecules under conditions of limited motion. Inside capsules, molecular encounters are prolonged, prearranged, and protected from the medium, in contrast to the short-lived and random encounters that occur in bulk solution. Herein, the interaction of α-, β-, and γ-picolines in a cylindrical capsule is described. Two picolines were taken up, and NMR spectra indicated dynamic combinations of various social isomers. The stabilities of the complexes are interpreted through computational methods. The shape of the space in the capsule allowed the alignment of molecules and revealed delicate, atom-to-atom interactions and attractive forces that elude observation in dilute solution. These weak forces were amplified in the isolated small space of the capsule.

  8. Theoretical study of structural patterns in CH₂OP₂ isomers.

    PubMed

    Septelean, Raluca; Petrar, Petronela Maria; Gabriela, Nemes; Escudié, Jean; Silaghi-Dumitrescu, Ioan

    2011-07-01

    DFT calculations have been performed on the derivatives of formula CH₂OP₂ to determine their total energy, the relative energy between the isomers and their geometry. Among compounds with a P-C-P linkage, the most stable one is the 2-hydroxy-1,2-diphosphirene II.1, a three-membered heterocycle with a P=C unsaturation. The phosphavinylidene(oxo)phosphorane HP=C=P(O)H IV.5 (which has the same skeleton as the experimentally obtained Mes*P=C=P(O)Mes*) lies 36.30 kcal mol⁻¹ above it. The least stable compounds are carbenes; the singlet carbenes are more stable than the triplet ones.

  9. Communication: "Position" does matter: The photofragmentation of the nitroimidazole isomers

    NASA Astrophysics Data System (ADS)

    Bolognesi, P.; Casavola, A. R.; Cartoni, A.; Richter, R.; Markus, P.; Borocci, S.; Chiarinelli, J.; Tošić, S.; Sa'adeh, H.; Masič, M.; Marinković, B. P.; Prince, K. C.; Avaldi, L.

    2016-11-01

    A combined experimental and theoretical approach has been used to disentangle the fundamental mechanisms of the fragmentation of the three isomers of nitroimidazole induced by vacuum ultra-violet (VUV) radiation, namely, 4-, 5-, and 2-nitroimidazole. The results of mass spectrometry as well as photoelectron-photoion coincidence spectroscopy display striking differences in the radiation-induced decomposition of the different nitroimidazole radical cations. Based on density functional theory (DFT) calculations, a model is proposed which fully explains such differences, and reveals the subtle fragmentation mechanisms leading to the release of neutral species like NO, CO, and HCN. Such species have a profound impact in biological media and may play a fundamental role in radiosensitising mechanisms during radiotherapy.

  10. Lifetime Measurement of the 229Th nuclear isomer

    NASA Astrophysics Data System (ADS)

    Seiferle, Benedict; von der Wense, Lars; Thirolf, Peter G.

    2017-01-01

    The first excited isomeric state of 229Th possesses the lowest energy among all known excited nuclear states. The expected energy is accessible with today's laser technology and in principle allows for a direct optical laser excitation of the nucleus. The isomer decays via three channels to its ground state (internal conversion, γ decay, and bound internal conversion), whose strengths depend on the charge state of Thm229 . We report on the measurement of the internal-conversion decay half-life of neutral Thm229 . A half-life of 7 ±1 μ s has been measured, which is in the range of theoretical predictions and, based on the theoretically expected lifetime of ≈1 04 s of the photonic decay channel, gives further support for an internal conversion coefficient of ≈1 09, thus constraining the strength of a radiative branch in the presence of internal conversion.

  11. Structures of cage, prism, and book isomers of water hexamer from broadband rotational spectroscopy.

    PubMed

    Pérez, Cristóbal; Muckle, Matt T; Zaleski, Daniel P; Seifert, Nathan A; Temelso, Berhane; Shields, George C; Kisiel, Zbigniew; Pate, Brooks H

    2012-05-18

    Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18-substituted water (H(2)(18)O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified.

  12. An inconvenient influence of iridium(III) isomer on OLED efficiency.

    PubMed

    Baranoff, Etienne; Bolink, Henk J; De Angelis, Filippo; Fantacci, Simona; Di Censo, Davide; Djellab, Karim; Grätzel, Michael; Nazeeruddin, Md Khaja

    2010-10-14

    The recently reported heteroleptic cyclometallated iridium(III) complex [Ir(2-phenylpyridine)(2)(2-carboxy-4-dimethylaminopyridine)] N984 and its isomer N984b have been studied more in detail. While photo- and electrochemical properties are very similar, DFT/TDDFT calculations show that the two isomers have different HOMO orbital characteristics. As a consequence, solution processed OLEDs made using a mixture of N984 and isomer N984b similar to vacuum processed devices show that the isomer has a dramatic detrimental effect on the performances of the device. In addition, commonly used thermogravimetric analysis is not suitable for showing the isomerization process. The isomer could impact performances of vacuum processed OLEDs using heteroleptic cyclometallated iridium(III) complexes as dopant.

  13. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    SciTech Connect

    Wojcik, Roza; Webb, Ian; Deng, Liulin; Garimella, Sandilya; Prost, Spencer; Ibrahim, Yehia; Baker, Erin; Smith, Richard

    2017-01-01

    Understanding the biological mechanisms related to lipids and glycolipids is challenging due to the vast number of possible isomers. Mass spectrometry (MS) measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid structures. However, difficulties in distinguishing many structural isomers (e.g. distinct acyl chain positions, double bond locations, as well as glycan isomers) inhibit the understanding of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS) separations based upon the use of traveling waves in a serpentine long path length multi-pass Structures for Lossless Manipulations (SLIM) to enhance isomer resolution. The multi-pass arrangement allowed separations ranging from ~16 m (1 pass) to ~470 m (32 passes) to be investigated for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer specific biological and disease processes.

  14. Odd tensor electric transitions in high-spin Sn-isomers and generalized seniority

    NASA Astrophysics Data System (ADS)

    Maheshwari, Bhoomika; Jain, Ashok Kumar

    2016-02-01

    The similar behavior of the B (E 1) values of the recently observed 13- odd tensor E1 isomers and the B (E 2) values of the 10+ and 15- even tensor E2 isomers in the Sn-isotopes has been understood in terms of the generalized seniority for multi-j orbits by using the quasi-spin scheme. This simple approach proves to be quite successful in explaining the measured transition probabilities and the corresponding half-lives in the high-spin isomers of the semi-magic Sn-isotopes. Hence, we show for the first time the occurrence of seniority isomers in the 13- Sn-isomers, which decay by odd-tensor E1 transitions to the same seniority states.

  15. Table of superdeformed nuclear bands and fission isomers

    SciTech Connect

    Firestone, R.B.; Singh, B.

    1994-06-01

    A minimum in the second potential well of deformed nuclei was predicted and the associated shell gaps are illustrated in the harmonic oscillator potential shell energy surface calculations shown in this report. A strong superdeformed minimum in {sup 152}Dy was predicted for {beta}{sub 2}-0.65. Subsequently, a discrete set of {gamma}-ray transitions in {sup 152}DY was observed and, assigned to the predicted superdeformed band. Extensive research at several laboratories has since focused on searching for other mass regions of large deformation. A new generation of {gamma}-ray detector arrays is already producing a wealth of information about the mechanisms for feeding and deexciting superdeformed bands. These bands have been found in three distinct regions near A=l30, 150, and 190. This research extends upon previous work in the actinide region near A=240 where fission isomers were identified and also associated with the second potential well. Quadrupole moment measurements for selected cases in each mass region are consistent with assigning the bands to excitations in the second local minimum. As part of our committment to maintain nuclear structure data as current as possible in the Evaluated Nuclear Structure Reference File (ENSDF) and the Table of Isotopes, we have updated the information on superdeformed nuclear bands. As of April 1994, we have complied data from 86 superdeformed bands and 46 fission isomers identified in 73 nuclides for this report. For each nuclide there is a complete level table listing both normal and superdeformed band assignments; level energy, spin, parity, half-life, magneto moments, decay branchings; and the energies, final levels, relative intensities, multipolarities, and mixing ratios for transitions deexciting each level. Mass excess, decay energies, and proton and neutron separation energies are also provided from the evaluation of Audi and Wapstra.

  16. Beef, chicken and lamb fatty acid analysis--a simplified direct bimethylation procedure using freeze-dried material.

    PubMed

    Lee, M R F; Tweed, J K S; Kim, E J; Scollan, N D

    2012-12-01

    When fractionation of meat lipids is not required, procedures such as saponification can be used to extract total fatty acids, reducing reliance on toxic organic compounds. However, saponification of muscle fatty acids is laborious, and requires extended heating times, and a second methylation step to convert the extracted fatty acids to fatty acid methyl esters prior to gas chromatography. Therefore the development of a more rapid direct methylation procedure would be of merit. The use of freeze-dried material for analysis is common and allows for greater homogenisation of the sample. The present study investigated the potential of using freeze-dried muscle samples and a direct bimethylation to analyse total fatty acids of meat (beef, chicken and lamb) in comparison with a saponification procedure followed by bimethylation. Both methods compared favourably for all major fatty acids measured. There was a minor difference in relation to the C18:1 trans 10 isomer with a greater (P<0.05) recovery with saponification. However, numerically the difference was small and likely as a result of approaching the limits of isomer identification by single column gas chromatography. Differences (P<0.001) between species were found for all fatty acids measured with no interaction effects. The described technique offers a simplified, quick and reliable alternative to saponification to analyse total fatty acids from muscle samples.

  17. Examination of isomer specific bioaccumulation parameters and potential in vivo hepatic metabolites of syn- and anti-Dechlorane Plus isomers in juvenile rainbow trout (Oncorhynchus mykiss).

    PubMed

    Tomy, Gregg T; Thomas, Caden R; Zidane, Thane M; Murison, Kathryn E; Pleskach, Kerri; Hare, Jonathon; Arsenault, Gilles; Marvin, Chris H; Sverko, Ed

    2008-08-01

    Juvenile rainbow trout (Oncorhynchus mykiss) were exposed in the laboratory to elevated doses of syn- and anti-isomers of Dechlorane Plus (DP) via their diet for 49 days (uptake phase), followed by 112 days of untreated food (depuration phase) to examine bioaccumulation parameters and possible metabolic products. Three groups of 60 fish were used in the study. Two groups were exposed separately to food fortified with known concentrations of syn- (0.79 +/- 0.03 microg/g, lipid weight) and anti-DP (1.17 +/- 0.12 microg/g, lipid weight) while a third control group was fed unfortified food. Neither isomer reached steady-state after 49 days of exposure. Only the syn-isomer accumulated linearly in the fish (whole-body minus liver) during the dosing phase with a calculated uptake rate constant of 0.045 +/- 0.005 (arithmetic mean +/- 1 x standard error) nmoles per day. A similar uptake rate was also observed for this isomer in the liver. The elimination of both isomers from the whole fish (minus liver) obeyed first order depuration kinetics (syn-: r2 = 0.6427, p < 0.001, anti-: r2 = 0.5350, p < 0.005) with calculated half-lives (t1/2) of 53.3 +/- 13.1 (syn-) and 30.4 +/- 5.7 (anti-) days. Elimination of the isomers from the liver was difficult to interpret because of suspected enterohepatic circulation and redistribution of the isomers in the liver during clearance from other tissues. The biomagnification factor (BMF, determined in whole fish minus liver) of the syn-isomer (5.2) was greater than the anti-isomer (1.9) suggesting that the former isomer is more bioavailable. A suite of metabolites were screened for in the liver including dechlorinated, hydroxylated, methoxylated and methyl sulfone degradates. Even with the purposely high dose used in the uptake phase, none of these degradates could be detected in the extracts. This suggests that if metabolites of DP are detected in fish from aquatic food webs their presence is likely not from in vivo biotransformation of the

  18. Lycopene from heat-induced cis-isomer-rich tomato sauce is more bioavailable than from all-trans-rich tomato sauce in human subjects.

    PubMed

    Unlu, Nuray Z; Bohn, Torsten; Francis, David M; Nagaraja, Haikady N; Clinton, Steven K; Schwartz, Steven J

    2007-07-01

    Lycopene is present mainly as cis-isomers in human serum and tissues whereas all-trans-lycopene predominates in tomato products, suggesting that all-trans-lycopene is isomerised in the body or is less bioavailable. The objectives of the present study were to develop processing conditions for tomatoes to obtain products with different cis-trans-lycopene isomer distribution and to assess their bioavailability. Healthy adult subjects (n 12) were recruited for this randomised cross-over trial. Each intervention was preceded by a 2-week washout period. Two tomato sauces, one rich in all-trans-lycopene (32.5 mg total lycopene/100 g sauce; 5 % cis-isomers), the other high in cis-lycopene (26.4 mg total lycopene/100 g sauce; 45 % cis-isomers), were produced by different heat-processing techniques. Each sauce (150 g) was served in a standardised meal at 08.00 hours after overnight fasting. Plasma TAG-rich lipoprotein fractions over 9.5 h following test-meal consumption as a measure of lycopene absorption were obtained and expressed as baseline-corrected area under the concentration v. time curves (AUC), using HPLC-electrochemical detection. AUC values adjusted for the amount lycopene consumed showed that total, total cis-, and all-trans-lycopene responses were significantly higher from the cis-isomer-rich sauce, compared with the all-trans-rich sauce, being 7.30 (sem 1.45) v. 4.74 (sem 1.08) nmol x h/l (P = 0.002), 3.80 (sem 0.76) v. 1.98 (sem 0.37) nmol x h/l (P = 0.0005) and 3.50 (sem 0.76) v. 2.76 (sem 0.76) nmol x h/l (P = 0.01), respectively. The present study demonstrates significant lycopene bioavailability from cis-lycopene-rich tomato sauce and highlights the importance of considering isomer-distribution for lycopene bioavailability. Furthermore, processing parameters can be controlled to alter isomer patterns of tomato products and influence lycopene bioavailability.

  19. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Excitation of nuclear isomers by X rays from laser plasma

    NASA Astrophysics Data System (ADS)

    Andreev, Aleksandr A.; Platonov, Konstantin Yu; Rozhdestvenskii, Yu V.; Karpeshin, F.; Trzhaskovskaya, M. B.

    2010-06-01

    The possibility of obtaining isomer nuclei is studied by the example of the molybdenum isomer 93Mo upon irradiation of a niobium 93Nb target by ~50-J, 100-fs laser pulses. It is shown that the modern laser technique allows production of isomer nuclei by accelerated protons and radiative de-excitation of isomer nuclear states by thermal or line X-rays from laser plasma.

  20. Combined experimental and computational investigation of the absorption spectra of E- and Z-cinnamic acids in solution: The peculiarity of Z-cinnamics.

    PubMed

    Salum, María L; Arroyo Mañez, Pau; Luque, F Javier; Erra-Balsells, Rosa

    2015-07-01

    Cinnamic acids are present in all kinds of plant tissues and hence in herbs and derived medicines, cosmetics and foods. The interest in their role in plants and their therapeutic applications has grown exponentially. Because of their molecular structure they can exist in E- and Z-forms, which are both found in plants. However, since only the E-forms are commercially available, very few in vitro and in vivo studies of the Z-form have been reported. In this work the physico-chemical properties of Z-cinnamic acids in solution have been examined by means of UV-absorption spectroscopy and high-level quantum mechanical computations. For each isomer similar absorption spectra were obtained in methanol and acetonitrile. However, distinct trends were found for Z- and E forms of cinnamic acids in water, where a higher hypsochromic shift of the Z-isomer relative to the E-form was observed. In general the wavelength of maximal absorption of the Z-form is dramatically blue shifted (-30 to -40 nm) to λ<280 nm, while a slightly blue shift of the absorption maxima for the corresponding E-form (+3 to -4 nm) was observed. This difference is associated with the non-planar, largely distorted, Z-structure and to the almost complete flat structure of the E-form. The results provide a basis for the study of functional and biotechnological roles of cinnamic acids and for the analysis of samples containing mixture of both geometric isomers.

  1. Mind-body interface: the role of n-3 fatty acids in psychoneuroimmunology, somatic presentation, and medical illness comorbidity of depression.

    PubMed

    Su, Kuan-Pin

    2008-01-01

    With the unsatisfaction of monoamine-based pharmacotherapy and the high comorbidity of other medical illness in depression, the serotonin hypothesis seems to fail in approaching the aetiology of depression. Based upon the evidence from epidemiological data, case-control studies of phospholipid polyunsaturated fatty acids (PUFAs) levels in human tissues, and antidepressant effect in clinical trials, PUFAs have shed a light to discover the unsolved of depression and connect the mind and body. Briefly, the deficit of n-3 PUFAs has been reported to be associated with neurological, cardiovascular, cerebrovascular, autoimmune, metabolic diseases and cancers. Recent studies revealed that the deficit of n-3 PUFAs is also associated with depression. For example, societies that consume a small amount of omega-3 PUFAs appear to have a higher prevalence of major depressive disorder. In addition, depressive patients had showed a lower level of omega-3 PUFAs; and the antidepressant effect of PUFAs had been reported in a number of clinical trials. The PUFAs are classified into n-3 (or omega-3) and n-6 (or omega-6) groups. Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), the major bioactive components of n-3 PUFAs, are not synthesized in human body and can only be obtained directly from the diet, particularly by consuming fish. DHA deficit is associated with dysfunctions of neuronal membrane stability and transmission of serotonin, norepinephrine and dopamine, which might connect to the aetiology of mood and cognitive dysfunction of depression. On the other hand, EPA is important in balancing the immune function and physical healthy by reducing arachidonic acid (AA, an n-6 PUFA) level on cell membrane and prostaglandin E2 (PGE2) synthesis. Interestingly, animals fed with high AA diet or treated with PGE2 were observed to present sickness behaviours of anorexia, low activity, change in sleep pattern and attention, which are similar to somatic symptoms of depression in

  2. β-N-methylamino-l-alanine (BMAA) and isomers: Distribution in different food web compartments of Thau lagoon, French Mediterranean Sea.

    PubMed

    Réveillon, Damien; Abadie, Eric; Séchet, Véronique; Masseret, Estelle; Hess, Philipp; Amzil, Zouher

    2015-09-01

    The neurotoxin BMAA (β-N-methylamino-l-alanine) and its isomer DAB (2,4-diaminobutyric acid) have been detected in seafood worldwide, including in Thau lagoon (French Mediterranean Sea). A cluster of amyotrophic lateral sclerosis (ALS), a neurodegenerative disease associated with BMAA, has also been observed in this region. Mussels, periphyton (i.e. biofilms attached to mussels) and plankton were sampled between July 2013 and October 2014, and analyzed using HILIC-MS/MS. BMAA, DAB and AEG (N-(2-aminoethyl)glycine) were found in almost all the samples of the lagoon. BMAA and DAB were present at 0.58 and 0.83, 2.6 and 3.3, 4.0 and 7.2 μg g(-1) dry weight in plankton collected with nets, periphyton and mussels, respectively. Synechococcus sp., Ostreococcus tauri, Alexandrium catenella and eight species of diatoms were cultured and screened for BMAA and analogs. While Synechococcus sp., O. tauri and A. catenella did not produce BMAA under our culture conditions, four diatoms species contained both BMAA and DAB. Hence, diatoms may be a source of BMAA for mussels. Unlike other toxins produced by microalgae, BMAA and DAB were detected in significant amounts in tissues other than digestive glands in mussels.

  3. Matrix Isolation and Computational Study of [2C, 2N, x] (X=S, Se) Isomers

    NASA Astrophysics Data System (ADS)

    Voros, Tamas; Tarczay, Gyorgy

    2015-06-01

    The [2C, 2N, S] and the [2C, 2N, Se] systems were investigated by quantum chemical computations and matrix isolation IR spectroscopy. For both systems nine isomers were computationally investigated, for which harmonic and anharmonic vibrational wavenumbers and infrared (IR) intensities were calculated using the CCSD(T)/aug-cc-pVTZ level of theory. The results show that each of the isomers have two or more detectable bands in the mid IR region, which have one or two orders of magnitude larger intensity compared to the IR intensity of the most intense bands of the most stable NCSCN and NCSeCN isomers'. It follows that if the most stable isomers can be detected, then the other previously unobserved isomers generated from NCSCN or NCSeCN should also be detectable with IR spectroscopy. UV spectra were also computed for each isomer at the TD-DFT B3LYP/aug-cc-pVTZ level of theory. These computations showed that the most stable isomers (NCSCN and NCSeCN) can absorb the UV radiation around 250 nm, and the irradiation may promote photoisomerization. This means that if the initial isomers are irradiated by narrow-band UV radiation, new isomers may be generated, which likely decompose by irradiating broad-band UV radiation. The two most stable isomers, sulphur dicyanide (NCSCN) and selenium dicyanide (NCSeCN), were prepared following literature methods. The matrix isolation IR spectra of these molecules in Ar and Kr were measured for the first time. As a result of a selective 254 nm-irradiation of the deposited matrices some new bands appeared in the IR spectra, while the intensity of the bands of NCSCN or NCSeCN were decreased at the same time. Irradiation of the matrices with broad-band UV light decreased the intensity of the bands corresponding to the deposited isomers and some of the bands appeared on the 254 nm-irradiation. On the basis of the analysis of the formation rates of the different bands upon 254 nm photolysis and by comparison with the results of the quantum

  4. Determination of Lutein and Zeaxanthin Esters and Their Geometric Isomers in Carotenoid Ester Concentrates Used as Ingredients in Nutritional Supplements: Validation of a Combined Spectrophotometric-HPLC Method.

    PubMed

    Lombeida, Wagner O; Rubio, Fernando; Levy, Luis W

    2016-11-01

    A combined spectrophotometric-LC method is described for the determination of total lutein and zeaxanthin ester content in carotenoid ester concentrates, including their main geometrical isomers. The concept of composite-specific absorbance is introduced for this purpose. The method is applicable to carotenoid ester concentrates used as ingredients in oil suspensions and dosage forms. The sample is dissolved in a hexane-2-propanol mixture (95 + 5, v/v) for spectrophotometric measurement at a maximum absorption of ~445 nm. Subsequently, in parallel, a sample is saponified and chromatographed on a normal-phase HPLC column to determine the relative percentage profile of the main geometrical isomers of both carotenoid esters. This, in turn, is used to calculate the composite-specific absorbance of the sample for the final calculation of results. The method, which solely uses reference standards to validate chromatographic conditions, avoids the common error of applying the specific absorbance of only the trans isomer for the calculation of total carotenoid content when cis isomers are present.

  5. Rare Form of Erdheim-Chester Disease Presenting with Isolated Central Skeletal Lesions Treated with a Combination of Alfa-Interferon and Zoledronic Acid

    PubMed Central

    Bulycheva, E. N.; Baykov, V. V.; Zaraĭskiĭ, M. I.; Salogub, G. N.

    2015-01-01

    Erdheim-Chester disease (ECD) represents a clonal non-Langerhans histiocytosis, which manifests under an extensive variety of clinical symptoms. This creates a challenge for the physician, who is required to recognize and diagnose the disease in the early stages. Despite this considerable challenge, in the last decade there has been a dramatic increase in ECD diagnoses, in most part due to an increasing awareness of this rare disorder. Involvement of the axial skeleton is exclusively uncommon with no official recommendations for the treatment of the bone lesions. Here, we present a case report of a young male patient with isolated lesions of the spine, ribs, and pelvis, who was successfully treated with a combination therapy of alfa-interferon and zoledronic acid. PMID:25949835

  6. 40 CFR 180.157 - Methyl 3-[(dimethoxyphos-phinyl) oxy]butenoate, alpha and beta isomers; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... isomers; tolerances for residues. 180.157 Section 180.157 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.157 Methyl 3- butenoate, alpha and beta isomers; tolerances for residues... and beta isomers, in or on the following raw agricultural commodities: Commodity Parts per...

  7. 40 CFR 180.157 - Methyl 3-[(dimethoxyphos-phinyl) oxy]butenoate, alpha and beta isomers; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... isomers; tolerances for residues. 180.157 Section 180.157 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.157 Methyl 3- butenoate, alpha and beta isomers; tolerances for residues... and beta isomers, in or on the following raw agricultural commodities: Commodity Parts per...

  8. 40 CFR 180.449 - Avermectin B1 and its delta-8,9-isomer; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Avermectin B1 and its delta-8,9-isomer... Tolerances § 180.449 Avermectin B1 and its delta-8,9-isomer; tolerances for residues. (a) General. Tolerances... delta-8,9-isomer in or on the following commodities: Commodity Parts per million Almond, hulls...

  9. A rapid, comprehensive liquid chromatography-mass spectrometry (LC-MS)-based survey of the Asp isomers in crystallins from human cataract lenses.

    PubMed

    Fujii, Norihiko; Sakaue, Hiroaki; Sasaki, Hiroshi; Fujii, Noriko

    2012-11-16

    Cataracts are caused by clouding of the eye lens and may lead to partial or total loss of vision. The mechanism of cataract development, however, is not well understood. It is thought that abnormal aggregates of lens proteins form with age, causing loss of lens clarity and development of the cataract. Lens proteins are composed of soluble α-, β-, and γ-crystallins, and as long lived proteins, they undergo post-translational modifications including isomerization, deamidation, and oxidation, which induce insolubilization, aggregation, and loss of function that may lead to cataracts. Therefore, analysis of post-translational modifications of individual amino acid residues in proteins is important. However, detection of the optical isomers of amino acids formed in these proteins is difficult because optical resolution is only achieved using complex methodology. In this study, we describe a new method for the analysis of isomerization of individual Asp residues in proteins using LC-MS and the corresponding synthetic peptides containing the Asp isomers. This makes it possible to analyze isomers of Asp residues in proteins precisely and quickly. We demonstrate that Asp-58, -76, -84, and -151 of αA-crystallin and Asp-62 and -96 of αB-crystallin are highly converted to lβ-, dβ-, and dα-isomers. The amount of isomerization of Asp is greater in the insoluble fraction at all Asp sites in lens proteins, therefore indicating that isomerization of these Asp residues affects the higher order structure of the proteins and contributes to the increase in aggregation, insolubilization, and disruption of function of proteins in the lens, leading to the cataract.

  10. The Development of a Specific and Sensitive LC-MS-Based Method for the Detection and Quantification of Hydroperoxy- and Hydroxydocosahexaenoic Acids as a Tool for Lipidomic Analysis

    PubMed Central

    Derogis, Priscilla B. M. C.; Freitas, Florêncio P.; Marques, Anna S. F.; Cunha, Daniela; Appolinário, Patricia P.; de Paula, Fernando; Lourenço, Tiago C.; Murgu, Michael; Di Mascio, Paolo; Medeiros, Marisa H. G.; Miyamoto, Sayuri

    2013-01-01

    Docosahexaenoic acid (DHA) is an n-3 polyunsaturated fatty acid that is highly enriched in the brain, and the oxidation products of DHA are present or increased during neurodegenerative disease progression. The characterization of the oxidation products of DHA is critical to understanding the roles that these products play in the development of such diseases. In this study, we developed a sensitive and specific analytical tool for the detection and quantification of twelve major DHA hydroperoxide (HpDoHE) and hydroxide (HDoHE) isomers (isomers at positions 4, 5, 7, 8, 10, 11, 13, 14, 16, 17, 19 and 20) in biological systems. In this study, HpDoHE were synthesized by photooxidation, and the corresponding hydroxides were obtained by reduction with NaBH4. The isolated isomers were characterized by LC-MS/MS, and unique and specific fragment ions were chosen to construct a selected reaction monitoring (SRM) method for the targeted quantitative analysis of each HpDoHE and HDoHE isomer. The detection limits for the LC-MS/MS-SRM assay were 1−670 pg for HpDoHE and 0.5−8.5 pg for HDoHE injected onto a column. Using this method, it was possible to detect the basal levels of HDoHE isomers in both rat plasma and brain samples. Therefore, the developed LC-MS/MS-SRM can be used as an important tool to identify and quantify the hydro(pero)xy derivatives of DHA in biological system and may be helpful for the oxidative lipidomic studies. PMID:24204871

  11. Impact of restricted amoxicillin/clavulanic acid use on Escherichia coli resistance--antibiotic DU90% profiles with bacterial resistance rates: a visual presentation.

    PubMed

    Mimica Matanovic, Suzana; Bergman, Ulf; Vukovic, Dubravka; Wettermark, Björn; Vlahovic-Palcevski, Vera

    2010-10-01

    High use of amoxicillin/clavulanic acid (AMC) at the University Hospital Osijek (Croatia) contributed to high rates of resistance in Enterobacteriaceae, in particular Escherichia coli (50%). Thus, in order to decrease bacterial resistance, AMC use was restricted. We present results of the restriction on resistance amongst antibiotics accounting for 90% of antibiotic use [drug utilisation 90% (DU90%)]. Data were analysed on antibiotic use and microbiological susceptibility of E. coli during two 9-month periods, before and after the restriction of AMC use. Drug use was presented as numbers of defined daily doses (DDDs) and DDDs/100 bed-days. Resistance of E. coli to antibiotics was presented as percentages of isolated strains in the DU90% segment. Use of AMC was 16 DDDs/100 bed-days or 30% of all antibiotics before the intervention. Use of AMC fell to 2 DDDs/100 bed-days or 4% after the intervention, and resistance of E. coli fell from 37% to 11%. In conclusion, restricted use of AMC resulted in a significant decrease of E. coli resistance. DU90% resistance profiles are simple and useful tools in highlighting problems in antibiotic use and resistance but may also be useful in long-term follow-up of antibiotic policy.

  12. Optimization to eliminate the interference of migration isomers for measuring 1-O-beta-acyl glucuronide without extensive chromatographic separation.

    PubMed

    Xue, Y-J; Akinsanya, J Billy; Raghavan, Nirmala; Zhang, Donglu

    2008-01-01

    A highly selected reaction monitoring (SRM) method has been investigated for the determination of muraglitazar 1-O-beta-acyl glucuronide in animal and human plasma without chromatographic separation of this naturally formed acyl glucuronide from its migration isomers. In the ion source or the collision cell, glucuronides are often prone to lose the dehydrated glucuronic acid (176 Da) and convert back into the parent drug (aglycone). The extent of loss of the glucuronide moiety can differ among glucuronides. For the naturally occurring muraglitazar 1-O-beta-acyl glucuronide, or its synthetic anomer 1-O-alpha-glucuronide, the loss of the glucuronide moiety was a major fragment ion. The loss of the glucuronide moiety was greater for the 1-O-beta-acyl glucuronide than the 1-O-alpha-anomer. In addition, the loss of the glucuronide moiety was insignificant (less than 0.01%) with the other glucuronide isomers (2-, 3- or 4-O, alpha or beta). Given the fact that the 1-O-alpha-anomer was a minor impurity in the muraglitazar 1-O-beta-acyl glucuronide reference standard, and not either a conversion product of 1-O-beta-acyl glucuronide or endogenously formed, the SRM transition corresponding to the loss of the glucuronide moiety was very specific for 1-O-beta-acyl glucuronide, and practically free from interference of the other isomers under optimized collision-cell conditions. As a result, extensive chromatographic separation of 1-O-beta-acyl glucuronide from its migration isomers was not required. The use of this specific SRM transition effectively reduced the separation time from 12.0 min of a long-column high-performance liquid chromatography (HPLC) method to 2.5 min by use of a shorter column. The standard curve performance and analysis results of 1-O-beta-acyl glucuronide incubation samples showed that the short-column method could produce equivalent results to the long-column method but with a 4.5-fold improvement in sample throughput. This approach may be useful for

  13. Structural-based differences in ecotoxicity of benzoquinoline isomers to the zebra mussel (Dreissena polymorpha)

    SciTech Connect

    Kraak, M.H.S.; Wijnands, P.; Govers, H.A.J.; Admiraal, W.; Voogt, P. de

    1997-10-01

    Effects of four benzoquinoline isomers on the filtration rate of the zebra mussel (Dreissena polymorpha) were analyzed, to study the effect of minor differences in chemical structure on adverse biological effects. Filtration rates were measured after 48 h of exposure to different concentrations of acridine, phenanthridine, benzo[f]quinoline, and benzo[h]quinoline in the water. The 50% effective concentration (EC50) values for filtration rate of the four isomers differed significantly. Effects increased in the order benzo[f], -[h], -[b], and -[c]quinoline, and the difference between the most toxic isomer and the least toxic isomer amounted to a factor of 30. Attempts were made to relate these differences in toxicity to the structure of the isomers. Size- or topology-related molecular descriptors provided insufficient resolution to distinguish between the benzoquinoline isomers, and none of the electronic descriptors separately provided a significant correlation with the observed effects. In an alternative approach, molecular shape, accessibility, and minimum agent-macromolecule distance were used to represent repulsive and attractive forces between the benzoquinoline isomers and biological membranes. This approach could tentatively explain the observed effects and is supported by a high correlation between the EC50 data and the reversed-phase C18-HPLC behavior of the benzoquinolines (k{sub 0}), which is likely to be governed by similar processes.

  14. Decay and Fission Hindrance of Two- and Four-Quasiparticle K Isomers in 254Rf

    NASA Astrophysics Data System (ADS)

    David, H. M.; Chen, J.; Seweryniak, D.; Kondev, F. G.; Gates, J. M.; Gregorich, K. E.; Ahmad, I.; Albers, M.; Alcorta, M.; Back, B. B.; Baartman, B.; Bertone, P. F.; Bernstein, L. A.; Campbell, C. M.; Carpenter, M. P.; Chiara, C. J.; Clark, R. M.; Cromaz, M.; Doherty, D. T.; Dracoulis, G. D.; Esker, N. E.; Fallon, P.; Gothe, O. R.; Greene, J. P.; Greenlees, P. T.; Hartley, D. J.; Hauschild, K.; Hoffman, C. R.; Hota, S. S.; Janssens, R. V. F.; Khoo, T. L.; Konki, J.; Kwarsick, J. T.; Lauritsen, T.; Macchiavelli, A. O.; Mudder, P. R.; Nair, C.; Qiu, Y.; Rissanen, J.; Rogers, A. M.; Ruotsalainen, P.; Savard, G.; Stolze, S.; Wiens, A.; Zhu, S.

    2015-09-01

    Two isomers decaying by electromagnetic transitions with half-lives of 4.7(1.1) and 247 (73 ) μ s have been discovered in the heavy 254Rf nucleus. The observation of the shorter-lived isomer was made possible by a novel application of a digital data acquisition system. The isomers were interpreted as the Kπ=8- , ν2(7 /2+[624 ],9 /2-[734 ]) two-quasineutron and the Kπ=1 6+, 8-ν2(7 /2+[624 ],9 /2-[734 ])⊗8-π2(7 /2-[514 ],9 /2+[624 ]) four-quasiparticle configurations, respectively. Surprisingly, the lifetime of the two-quasiparticle isomer is more than 4 orders of magnitude shorter than what has been observed for analogous isomers in the lighter N =150 isotones. The four-quasiparticle isomer is longer lived than the 254Rf ground state that decays exclusively by spontaneous fission with a half-life of 23.2 (1.1 ) μ s . The absence of sizable fission branches from either of the isomers implies unprecedented fission hindrance relative to the ground state.

  15. Gas-phase Ion Isomer Analysis Reveals the Mechanism of Peptide Sequence Scrambling

    PubMed Central

    Jia, Chenxi; Wu, Zhe; Lietz, Christopher B.; Liang, Zhidan; Cui, Qiang; Li, Lingjun

    2014-01-01

    Peptide sequence scrambling during mass spectrometry-based gas-phase fragmentation analysis causes misidentification of peptides and proteins. Thus, there is a need to develop an efficient approach to probing the gas-phase fragment ion isomers related to sequence scrambling and the underlying fragmentation mechanism, which will facilitate the development of bioinformatics algorithm for proteomics research. Herein, we report on the first use of electron transfer dissociation (ETD)-produced diagnostic fragment ions to probe the components of gas-phase peptide fragment ion isomers. In combination with ion mobility spectrometry (IMS) and formaldehyde labeling, this novel strategy enables qualitative and quantitative analysis of b-type fragment ion isomers. ETD fragmentation produced diagnostic fragment ions indicative of the precursor ion isomer components, and subsequent IMS analysis of b ion isomers provided their quantitative and structural information. The isomer components of three representative b ions (b9, b10, and b33 from three different peptides) were accurately profiled by this method. IMS analysis of the b9 ion isomers exhibited dynamic conversion among these structures. Furthermore, molecular dynamics simulation predicted theoretical drift time values which were in good agreement with experimentally measured values. Our results strongly support the mechanism of peptide sequence scrambling via b ion cyclization, and provide the first experimental evidence to support that the conversion from molecular precursor ion to cyclic b ion (M→cb) pathway is less energetically (or kinetically) favored. PMID:24313304

  16. Gas-phase ion isomer analysis reveals the mechanism of peptide sequence scrambling.

    PubMed

    Jia, Chenxi; Wu, Zhe; Lietz, Christopher B; Liang, Zhidan; Cui, Qiang; Li, Lingjun

    2014-03-18

    Peptide sequence scrambling during mass spectrometry-based gas-phase fragmentation analysis causes misidentification of peptides and proteins. Thus, there is a need to develop an efficient approach to probing the gas-phase fragment ion isomers related to sequence scrambling and the underlying fragmentation mechanism, which will facilitate the development of bioinformatics algorithm for proteomics research. Herein, we report on the first use of electron transfer dissociation (ETD)-produced diagnostic fragment ions to probe the components of gas-phase peptide fragment ion isomers. In combination with ion mobility spectrometry (IMS) and formaldehyde labeling, this novel strategy enables qualitative and quantitative analysis of b-type fragment ion isomers. ETD fragmentation produced diagnostic fragment ions indicative of the precursor ion isomer components, and subsequent IMS analysis of b ion isomers provided their quantitative and structural information. The isomer components of three representative b ions (b9, b10, and b33 from three different peptides) were accurately profiled by this method. IMS analysis of the b9 ion isomers exhibited dynamic conversion among these structures. Furthermore, molecular dynamics simulation predicted theoretical drift time values, which were in good agreement with experimentally measured values. Our results strongly support the mechanism of peptide sequence scrambling via b ion cyclization, and provide the first experimental evidence to support that the conversion from molecular precursor ion to cyclic b ion (M → (c)b) pathway is less energetically (or kinetically) favored.

  17. Search for a 2-quasiparticle high-K isomer in {sup 256}Rf

    SciTech Connect

    Robinson, A. P.; Jenkins, D. G.; Marley, P.; Khoo, T. L.; Seweryniak, D.; Ahmad, I.; Back, B. B.; Carpenter, M. P.; Davids, C. N.; Greene, J.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Lister, C. J.; McCutchan, E.; Peterson, D.; Stefanescu, I.; Zhu, S.; Asai, M.; Chowdhury, P.

    2011-06-15

    The energies of 2-quasiparticle (2-qp) states in heavy shell-stabilized nuclei provide information on the single-particle states that are responsible for the stability of superheavy nuclei. We have calculated the energies of 2-qp states in {sup 256}Rf, which suggest that a long-lived, low-energy 8{sup -} isomer should exist. A search was conducted for this isomer through a calorimetric conversion electron signal, sandwiched in time between implantation of a {sup 256}Rf nucleus and its fission decay, all within the same pixel of a double-sided Si strip detector. A 17(5)-{mu}s isomer was identified. However, its low population, {approx}5(2)% that of the ground state instead of the expected {approx}30%, suggests that it is more likely a 4-qp isomer. Possible reasons for the absence of an electromagnetic signature of a 2-qp isomer decay are discussed. These include the favored possibility that the isomer decays by fission, with a half-life indistinguishably close to that of the ground state. Another possibility, that there is no 2-qp isomer at all, would imply an abrupt termination of axially symmetric deformed shapes at Z=104, which describes nuclei with Z=92-103 very well.

  18. Search for a 2-quasiparticle high-K isomer in {sup 256}Rf.

    SciTech Connect

    Robinson, A. P.; Khoo, T. L.; Seweryniak, D.; Ahmad, I.; Asai, M.; Back, B. B.; Carpenter, M. P.; Davids, C. N.; Greene, J.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Lister, C. J.; McCutchan, E.; Peterson, D.; Zhu, S.

    2011-06-13

    The energies of 2-quasiparticle (2-qp) states in heavy shell-stabilized nuclei provide information on the single-particle states that are responsible for the stability of superheavy nuclei. We have calculated the energies of 2-qp states in {sup 256}Rf, which suggest that a long-lived, low-energy 8{sup -} isomer should exist. A search was conducted for this isomer through a calorimetric conversion electron signal, sandwiched in time between implantation of a {sup 256}Rf nucleus and its fission decay, all within the same pixel of a double-sided Si strip detector. A 17(5)-{micro}s isomer was identified. However, its low population, {approx}5(2)% that of the ground state instead of the expected {approx}30%, suggests that it is more likely a 4-qp isomer. Possible reasons for the absence of an electromagnetic signature of a 2-qp isomer decay are discussed. These include the favored possibility that the isomer decays by fission, with a half-life indistinguishably close to that of the ground state. Another possibility, that there is no 2-qp isomer at all, would imply an abrupt termination of axially symmetric deformed shapes at Z = 104, which describes nuclei with Z = 92-103 very well.

  19. Isomer-specific investigation of PCDD/F mobility and other fate processes in deep soil cores.

    PubMed

    Grant, Sharon; Stevenson, Gavin; Malcolm, Don; Zennegg, Markus; Gaus, Caroline

    2015-10-01

    Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are highly hydrophobic compounds with low migration potential in soil-water. Nevertheless, they have been occasionally reported in subsurface soils hypothesised as the result of facilitated transport processes with colloids or surfactants, or yet unidentified in-situ formation processes. To date, however, the prevalence of deep soil contamination, involved processes and their kinetics remain poorly understood. This study investigated PCDD/F concentrations and isomer profiles through deep soil cores (to 20 m) from agricultural, industrial and urban sites in Queensland, Australia. Based on isomer profiles, a unique source common to all core soils (regardless of depth) was identified, dominated by octachlorodibenzo-p-dioxin (OCDD). The source was consistent with contamination resulting from pesticide impurities. Elevated PCDD concentrations (μg/kg range) to depths up to ∼4-17 m and a continuous increase of peri-chlorinated (1,4,6,9-substituted) isomers through the cores suggested that vertical transport and lateral dechlorination were key post-depositional processes at these sites. The mobility of PCDDs in the present study is far greater than previously reported in soils in general. High estimated mass transport rates for OCDD in four agricultural cores (3.0-6.2% year(-1)) likely reflect significant levels of facilitating species, including surfactants, and intensive rainfall at these sites. The implications of such extensive subsurface transport of PCDD/Fs for groundwater contamination and load estimates may be significant. If the cores of the present study are assumed representative of the region, a total PCDD/F load in the order of 800 tonnes (1.6 tonnes TEQ) could be present in subsurface Queensland coastal soils.

  20. Photoelectron spectroscopy of the [glycine.(H2O)1,2]- clusters: Sequential hydration shifts and observation of isomers

    NASA Astrophysics Data System (ADS)

    Diken, Eric G.; Headrick, Jeffrey M.; Johnson, Mark A.

    2005-06-01

    The electron binding energies of the small hydrated amino acid anions, [glycine•(H2O)1,2]-, are determined using photoelectron spectroscopy. The vertical electron detachment energies (VDEs) are found to increase by approximately 0.12 eV with each additional water molecule such that the higher electron binding isomer of the dihydrate is rather robust, with a VDE value of 0.33 eV. A weak binding isomer of the dihydrate is also recovered, however, with a VDE value (0.14 eV) lower than that of the monohydrate. Unlike the situation in the smaller (n⩽13) water cluster anions, the [Gly•(H2O)n⩾6]- clusters are observed to photodissociate via water monomer evaporation upon photoexcitation in the O-H stretching region. We discuss this observation in the context of the mechanism responsible for the previously observed [S. Xu, M. Nilles, and K. H. Bowen, Jr., J. Chem. Phys. 119, 10696 (2003)] sudden onset in the cluster formation at [Gly•(H2O)5]-.

  1. Rearrangement of vinyl allene oxide geometric isomers to cyclopentenones. Further computational insights with biologically relevant model systems.

    PubMed

    González-Pérez, Adán B; Grechkin, Alexander; de Lera, Ángel R

    2017-03-28

    Pathways for the rearrangement of the E and Z isomers of allyl- and methyl-substituted vinyl allene oxides to stereodefined cyclopentenones have been studied by DFT computations. Regardless of the reactant geometry, cis-configured cyclopentenones are found to be formed in a stepwise cascade comprising as key steps the ring opening of the oxirane to give an oxidopentadienyl diradical, its isomerization, and electrocyclization. An allyl substituent at the Csp(3) atom of the starting vinyl allene oxide induces opposite effects on the activation energies for ring opening: a decrease owing to assistance by homoconjugation for the out motion and an increase due to the stereoelectronic stabilization of the reactant. As a result, allyl- and methyl-substituted vinyl allene oxides exhibit comparable activation energies. Only model systems with crotyl substituents afford lower activation energies than the methyl counterparts due to the additional stabilization of the forming charge deficiency at a secondary carbon by homoconjugation. Moreover, upon homoconjugative interaction reactants of Z geometry are predicted to undergo cyclization more readily than the E isomers. The results with Z-crotyl substituent are congruent with the spontaneous rearrangement of natural vinyl allene oxide derived from α-linolenic acid to a racemic cis-cyclopentenone (12-oxo-PDA).

  2. Detailed Chemical Kinetic Reaction Mechanisms for Autoignition of Isomers of Heptane Under Rapid Compression

    SciTech Connect

    Westbrook, C K; Pitz, W J; Boercker, J E; Curran, H J; Griffiths, J F; Mohamed, C; Ribaucour, M

    2001-12-17

    Detailed chemical kinetic reaction mechanisms are developed for combustion of all nine isomers of heptane (C{sub 7}H{sub 16}), and these mechanisms are tested by simulating autoignition of each isomer under rapid compression machine conditions. The reaction mechanisms focus on the manner in which the molecular structure of each isomer determines the rates and product distributions of possible classes of reactions. The reaction pathways emphasize the importance of alkylperoxy radical isomerizations and addition reactions of molecular oxygen to alkyl and hydroperoxyalkyl radicals. A new reaction group has been added to past models, in which hydroperoxyalkyl radicals that originated with abstraction of an H atom from a tertiary site in the parent heptane molecule are assigned new reaction sequences involving additional internal H atom abstractions not previously allowed. This process accelerates autoignition in fuels with tertiary C-H bonds in the parent fuel. In addition, the rates of hydroperoxyalkylperoxy radical isomerization reactions have all been reduced so that they are now equal to rates of analogous alkylperoxy radical isomerizations, significantly improving agreement between computed and experimental ignition delay times in the rapid compression machine. Computed ignition delay times agree well with experimental results in the few cases where experiments have been carried out for specific heptane isomers, and predictive model calculations are reported for the remaining isomers. The computed results fall into three general groups; the first consists of the most reactive isomers, including n-heptane, 2-methyl hexane and 3-methyl hexane. The second group consists of the least reactive isomers, including 2,2-dimethyl pentane, 3,3-dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentane and 2,2,3-trimethyl butane. The remaining isomer, 3-ethyl pentane, was observed computationally to have an intermediate level of reactivity. These observations are generally

  3. Isomer Shift and Magnetic Moment of the Long-Lived 1 /2+ Isomer in 30,79Zn49: Signature of Shape Coexistence near 78Ni

    NASA Astrophysics Data System (ADS)

    Yang, X. F.; Wraith, C.; Xie, L.; Babcock, C.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Flanagan, K. T.; Garcia Ruiz, R. F.; Gins, W.; Gorges, C.; Grob, L. K.; Heylen, H.; Kaufmann, S.; Kowalska, M.; Kraemer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Papuga, J.; Sánchez, R.; Yordanov, D. T.

    2016-05-01

    Collinear laser spectroscopy is performed on the 30,79Zn49 isotope at ISOLDE-CERN. The existence of a long-lived isomer with a few hundred milliseconds half-life is confirmed, and the nuclear spins and moments of the ground and isomeric states in 79Zn as well as the isomer shift are measured. From the observed hyperfine structures, spins I =9 /2 and I =1 /2 are firmly assigned to the ground and isomeric states. The magnetic moment μ (79Zn)=-1.1866 (10 )μN , confirms the spin-parity 9 /2+ with a ν g9/2 -1 shell-model configuration, in excellent agreement with the prediction from large scale shell-model theories. The magnetic moment μ (Znm79)=-1.0180 (12 )μN supports a positive parity for the isomer, with a wave function dominated by a 2 h -1 p neutron excitation across the N =50 shell gap. The large isomer shift reveals an increase of the intruder isomer mean square charge radius with respect to that of the ground state, δ ⟨rc2⟩79 ,79 m=+0.204 (6 ) fm2 , providing first evidence of shape coexistence.

  4. Isolation and spectral characterization of thermally generated multi-Z-isomers of lycopene and the theoretically preferred pathway to di-Z-isomers.

    PubMed

    Honda, Masaki; Kudo, Tatsuya; Kuwa, Takahiro; Higashiura, Takuma; Fukaya, Tetsuya; Inoue, Yoshinori; Kitamura, Chitoshi; Takehara, Munenori

    2017-02-01

    Lycopene has a large number of geometric isomers caused by E/Z isomerization at arbitrary sites within the 11 conjugated double bonds, offering varying characteristics related to features such as antioxidant capacity and bioavailability. However, the geometric structures of only a few lycopene Z-isomers have been thoroughly identified from natural sources. In this study, seven multi-Z-isomers of lycopene, (9Z,13'Z)-, (5Z,13Z,9'Z)-, (9Z,9'Z)-, (5Z,13'Z)-, (5Z,9'Z)-, (5Z,9Z,5'Z)-, and (5Z,9Z)-lycopene, were obtained from tomato samples by thermal isomerization, and then isolated by elaborate chromatography, and fully assigned using proton nuclear magnetic resonance. Moreover, the theoretically preferred pathway from (all-E)-lycopene to di-Z-isomers was examined with a computational approach using a Gaussian program. Fine-tuning of the HPLC separation conditions led to the discovery of novel multi-Z-isomers, and whose formation was supported by advanced theoretical calculations.

  5. Isomer Shift and Magnetic Moment of the Long-Lived 1/2^{+} Isomer in _{30}^{79}Zn_{49}: Signature of Shape Coexistence near ^{78}Ni.

    PubMed

    Yang, X F; Wraith, C; Xie, L; Babcock, C; Billowes, J; Bissell, M L; Blaum, K; Cheal, B; Flanagan, K T; Garcia Ruiz, R F; Gins, W; Gorges, C; Grob, L K; Heylen, H; Kaufmann, S; Kowalska, M; Kraemer, J; Malbrunot-Ettenauer, S; Neugart, R; Neyens, G; Nörtershäuser, W; Papuga, J; Sánchez, R; Yordanov, D T

    2016-05-06

    Collinear laser spectroscopy is performed on the _{30}^{79}Zn_{49} isotope at ISOLDE-CERN. The existence of a long-lived isomer with a few hundred milliseconds half-life is confirmed, and the nuclear spins and moments of the ground and isomeric states in ^{79}Zn as well as the isomer shift are measured. From the observed hyperfine structures, spins I=9/2 and I=1/2 are firmly assigned to the ground and isomeric states. The magnetic moment μ (^{79}Zn)=-1.1866(10)μ_{N}, confirms the spin-parity 9/2^{+} with a νg_{9/2}^{-1} shell-model configuration, in excellent agreement with the prediction from large scale shell-model theories. The magnetic moment μ (^{79m}Zn)=-1.0180(12)μ_{N} supports a positive parity for the isomer, with a wave function dominated by a 2h-1p neutron excitation across the N=50 shell gap. The large isomer shift reveals an increase of the intruder isomer mean square charge radius with respect to that of the ground state, δ⟨r_{c}^{2}⟩^{79,79m}=+0.204(6)  fm^{2}, providing first evidence of shape coexistence.

  6. Physical chemistry and membrane properties of two phosphatidylinositol bisphosphate isomers.

    PubMed

    Slochower, David R; Wang, Yu-Hsiu; Radhakrishnan, Ravi; Janmey, Paul A

    2015-05-21

    The most highly charged phospholipids, polyphosphoinositides, are often involved in signaling pathways that originate at cell-cell and cell-matrix contacts, and different isomers of polyphosphoinositides have distinct biological functions that cannot be explained by separate highly specific protein ligand binding sites [Lemmon, Nat. Rev. Mol. Cell Biol., 2008, 9, 99-111]. PtdIns(3,5)P2 is a low abundance phosphoinositide localized to cytoplasmic-facing membrane surfaces, with relatively few known ligands, yet PtdIns(3,5)P2 plays a key role in controlling membrane trafficking events and cellular stress responses that cannot be duplicated by other phosphoinositides [Dove et al., Nature, 1997, 390, 187-192; Michell, FEBS J., 2013, 280, 6281-6294]. Here we show that PtdIns(3,5)P2 is structurally distinct from PtdIns(4,5)P2 and other more common phospholipids, with unique physical chemistry. Using multiscale molecular dynamics techniques on the quantum level, single molecule, and in bilayer settings, we found that the negative charge of PtdIns(3,5)P2 is spread over a larger area, compared to PtdIns(4,5)P2, leading to a decreased ability to bind divalent ions. Additionally, our results match well with experimental data characterizing the cluster forming potential of these isomers in the presence of Ca(2+) [Wang et al., J. Am. Chem. Soc., 2012, 134, 3387-3395; van den Bogaart et al., Nature, 2011, 479, 552-555]. Our results demonstrate that the different cellular roles of PtdIns(4,5)P2 and PtdIns(3,5)P2in vivo are not simply determined by their localization by enzymes that produce or degrade them, but also by their molecular size, ability to chelate ions, and the partial dehydration of those ions, which might affect the ability of PtdIns(3,5)P2 and PtdIns(4,5)P2 to form phosphoinositide-rich clusters in vitro and in vivo.

  7. Enantioselective Total Synthesis of Mandelalide A and Isomandelalide A: Discovery of a Cytotoxic Ring-Expanded Isomer.

    PubMed

    Veerasamy, Nagarathanam; Ghosh, Ankan; Li, Jinming; Watanabe, Kazuhiro; Serrill, Jeffrey D; Ishmael, Jane E; McPhail, Kerry L; Carter, Rich G

    2016-01-27

    The total synthesis of mandelalide A and its ring-expanded macrolide isomer isomandelalide A has been achieved. Unexpected high levels of cytotoxicity were observed with the ring-expanded isomandelalide A with a rank order of potency: mandelalide A > isomandelalide A > mandelalide B. Key aspects of the synthesis include Ag-catalyzed cyclizations (AgCC's) to construct both the THF and THP rings present in the macrocycle, diastereoselective Sharpless dihydroylation of a cis-enyne, and lithium acetylide coupling with a chiral epoxide.

  8. Ab initio quantum chemical investigation of several isomers of anionic Si 6

    NASA Astrophysics Data System (ADS)

    Takahashi, Masae; Kawazoe, Yoshiyuki

    2006-02-01

    Eight isomers (planar hexagon, benzvalene, Dewar benzene, triangular prismane, bicyclopropenyl, octahedron, chair form, and twist boat form) of Si 6, Si62-, Si64-, and Si66-, have been searched for by the MP2 and B3LYP electronic structure calculations. Totally 14 isomers were found: two Si 6, six Si62-, five Si64-, and one Si66-. Two of them are different from the eight isomers: deformed triangle Si62-; pentagonal pyramidal Si64-. We discovered that the predicted stable shapes of Si62-, Si64-, and Si66- are octahedral, pentagonal pyramidal, and hexagonal, respectively, which agrees well with Wade rule.

  9. Controlling the Excited-State Dynamics of Nuclear Spin Isomers Using the Dynamic Stark Effect.

    PubMed

    Waldl, Maria; Oppel, Markus; González, Leticia

    2016-07-14

    Stark control of chemical reactions uses intense laser pulses to distort the potential energy surfaces of a molecule, thus opening new chemical pathways. We use the concept of Stark shifts to convert a local minimum into a local maximum of the potential energy surface, triggering constructive and destructive wave-packet interferences, which then induce different dynamics on nuclear spin isomers in the electronically excited state of a quinodimethane derivative. Model quantum-dynamical simulations on reduced dimensionality using optimized ultrashort laser pulses demonstrate a difference of the excited-state dynamics of two sets of nuclear spin isomers, which ultimately can be used to discriminate between these isomers.

  10. Theoretical studies of possible toroidal high-spin isomers in the light-mass region

    DOE PAGES

    Staszczak, A.; Wong, Cheuk-Yin

    2016-05-11

    We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28≤A≤52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in 56Ni with I=114ℏ and 140ℏ, which follow the same (multi-particle) (multi-hole) systematics as other toroidal high-spin isomers. We examine the production of these exotic nuclei by fusion of various projectiles on 20Ne or 28Si as an active target in time-projection-chamber (TPC) experiments.

  11. Identification of a new isomer from a reversible isomerization of ceftriaxone in aqueous solution.

    PubMed

    Tian, Ye; Lu, Li; Chang, Yan; Zhang, Dou-sheng; Li, Jin; Feng, Yan-Chun; Hu, Chang-Qin

    2015-01-01

    A reversible isomerization of ceftriaxone in aqueous solution was observed, and the structure of the isomer was determined by mass spectrometry and various 1D and 2D NMR techniques. The mechanism of isomerization was also discussed. Finally, molecular docking simulations were performed and the antimicrobial activities of the isomers were measured. This showed that the biological activity of ceftriaxone was stronger than that of its isomer. The results reported in this article may be important to quality control requirements and to the stability of ceftriaxone products.

  12. Theoretical studies of possible toroidal high-spin isomers in the light-mass region

    SciTech Connect

    Staszczak, A.; Wong, Cheuk-Yin

    2016-05-11

    We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28≤A≤52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in 56Ni with I=114ℏ and 140ℏ, which follow the same (multi-particle) (multi-hole) systematics as other toroidal high-spin isomers. We examine the production of these exotic nuclei by fusion of various projectiles on 20Ne or 28Si as an active target in time-projection-chamber (TPC) experiments.

  13. Stereocontrolled synthesis of the four 16-hydroxymethyl-19-nortestosterone isomers and their antiproliferative activities.

    PubMed

    Schneider, Gyula; Kiss, Anita; Mernyák, Erzsébet; Benke, Zsanett; Wölfling, János; Frank, Éva; Bózsity, Noémi; Gyovai, András; Minorics, Renáta; Zupkó, István

    2016-01-01

    Novel 16-hydroxymethyl-19-nortestosterone diastereomers were prepared by Birch reduction from the corresponding 3-methoxy-16-hydroxymethylestra-1,3,5(10)-trien-17-ol isomers with known configurations. The synthesized compounds are 16α- and 16β-hydroxymethyl-substituted 19-nortestosterone and their 17α-epimers. To prepare 17α-19-nortestosterone, the Mitsunobu inversion reaction of 19-nortestosterone with different alkyl and aryl carboxylic acids was chosen. Deacylation of the new compounds by the Zemplén method yielded the required 17α-19-nortestosterone. The antiproliferative activities of the structurally related compounds were determined in vitro through microculture tetrazolium assays on a panel of human adherent cervical (HeLa, SiHa and C33A), breast (MCF-7, MDA-MB-231, MDA-MB-361 and T47D) and ovarian (A2780) cell lines. The 17α epimer of 19-nortestosterone demonstrated considerable activity, selectively for HeLa cells, with a calculated IC50 of 0.65 μM. The reference compound, cisplatin, displayed an order of magnitude higher IC50 (12.4 μM). The cancer selectivity of 17α-19-nortestosterone was tested by MTT assay performed with noncancerous human fibroblast cell line MRC-5. The results indicated that 17α-19-nortestosterone selectively disturbs the viability of HeLa cells without greatly affecting other cancer cell types and intact fibroblasts.

  14. Laboratory detection of the D3h isomer of carbon trioxide (CO3): Potential intermediate in the CO2 + O reaction in atmospheres

    NASA Astrophysics Data System (ADS)

    Jamieson, C.; Mebel, A.; Kaiser, R.

    Radiation induced degradation of oxygen-bearing molecules like ozone or carbon dioxide can liberate oxygen atoms that are electronically excited 1 D state and or superthermal high kinetic energy and may subsequently react with carbon dioxide in the atmospheres of Venus Mars or the Earth In this reaction the carbon trioxide CO 3 intermediate was found to form and has been subsequently included in many reaction models to explain the heavy isotope enrichment of stratospheric carbon dioxide on Earth and the regeneration of carbon dioxide on Mars both in the upper atmosphere and catalyzed in solid CO 2 surfaces Studies of the O 1 D CO 2 reaction show a nearly statistical rate of isotope exchange suggesting that the CO 3 intermediate may possess a high degree of symmetry From theoretical calculations and matrix isolation studies we know that the lowest energy CO 3 isomer has C 2v symmetry however the D 3h isomer lies only 0 1 kcal mol -1 higher in energy than the C 2v structure with an isomerization barrier of 4 4 kcal mol -1 thus interconversion of these two structures should readily occur To date the C 2v structure has been the only isomer that has been experimentally detected and therefore inclusion of the symmetric D 3h isomer in the isotope exchange models is only theoretical Here we present the first experimental detection of the D 3h isomer of carbon trioxide which was identified by two fundamental vibrational frequencies nu 1 and nu 5 using infrared

  15. Collision-induced dissociation of fatty acid [M - 2H + Na]- ions: charge-directed fragmentation and assignment of double bond position.

    PubMed

    Thomas, Michael C; Altvater, Jens; Gallagher, Thomas J; Nette, Geoffrey W

    2014-11-01

    The collision-induced dissociation (CID) of cationic fatty acid-metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid-sodium ion complexes, referred to as [M - 2H + Na] (-) ions. In the current manuscript, the CID behavior of these [M - 2H + Na] (-) ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the α-carbon in the formation of fatty acid [M - H + NaF](-) ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M - 2H + Na](-) ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon-carbon double bonds. In addition, CID of [M - 2H + Na](-) ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ∆(9,12,15)18:3, ∆(6,9,12)18:3, and ∆(5,8,11)18:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the α-carbon.

  16. Electron and Positron Scattering from C3H6 Isomers

    NASA Astrophysics Data System (ADS)

    Makochekanwa, Casten; Sueoka, Osamu; Kimura, Mineo; Hoshino, Masamitsu; Tanaka, Takahiro; Kitajima, Masashi; Tanaka, Hiroshi

    2004-09-01

    Hydrocarbons play an important role in high temperature plasmas in Tokamak fusion devices in plasma processing and many other fields [1]. In this paper we report experiments for 0.4-1000 eV electron and 0.2-1000 eV positron total cross sections (TCS) measured using a linear time-of-flight apparatus [2], and electron differential cross sections (DCS) for elastic, vibrational and electronic excitations covering the ranges 1.5 to 100 eV and 15 deg to 130 deg, measured using the crossed beam and relative flow method [3]. The continuum multiple scattering (CMS) [4] calculations have also been performed for the theoretical analysis of the observed features in our cross sections. We observe the isomer effect in both electron and positron TCSs and DCSs. The presence of a dipole moment in propene molecules shows up in enhanced forward scattering in DCSs, leading to larger TCSs and integral cross sections compared to cyclopropane at energies less than 20 eV. However, both electron and positron TCSs for these two molecules nearly equal each other above 100 eV, i.e. the molecular size effect. [1] W. L. Moragn, Adv. At. Mol. Opt. Phys. 43, 79 (2000). [2] O. Sueoka, S. Mori and A. Hamada, J. Phys. B 27, 1453 (1994). [3] H. Tanaka, L. Boesten, D. Matsunaga and T. Kudo, J. Phys. B 21, 1255 (1988). [4] M. Kimura and H. Sato, Comments At. Mol. Phys. 26, 333 (1991).

  17. Search for superradiant emission states in nuclear isomer crystals

    SciTech Connect

    Rundberg, R.S.; Wilhelmy, J.B.; Taylor, R.D.; Solem, J.C.; Fowler, M.M.; Miller, G.G.; Baldwin, G.

    1998-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The objective was to verify the stimulated emission of gamma rays from {sup 125m}Te, as claimed by Russian scientists. The reported cross section for stimulated emission was sufficiently large to allow gain in a single-pass gamma-ray laser. The stimulated emission of gamma rays from a nuclear isomer is expected to result in collinear photons and, therefore, should be observable as a sum peak in the gamma-ray spectrum. Skorobogatov and Dzevitskii reported an increase of an order of magnitude in the sum peak (218.56 keV) when a sample of beryllium telluride containing {sup 125m}Te was cooled from room temperature to near-liquid-helium temperatures. The authors have repeated their experiment and have observed no increase in the sum peak above accidental summing. The upper limit for the stimulated-emission cross section based on the three-standard-deviation statistical error is 6.8 x 10 {sup {minus}21} cm{sup 2}. This result is one order of magnitude lower than the cross section reported by Skorobogatov and Dzevitskii. The cross section would not allow gain in a single-pass gamma-ray laser. Their results support the position of Baldwin and Solem rather than that of Kamenov.

  18. Chemical profiling of the cytotoxic triterpenoid-concentrating fraction and characterization of ergostane stereo-isomer ingredients from Antrodia camphorata.

    PubMed

    Du, Ying-Chi; Wu, Tung-Ying; Chang, Fang-Rong; Lin, Wan-Yu; Hsu, Yu-Ming; Cheng, Fu-Ting; Lu, Chi-Yu; Yen, Ming-Hong; Tsui, Ya-Ting; Chen, Hsuan-Lun; Hou, Ming-Feng; Lu, Mei-Chin; Wu, Yang-Chang

    2012-01-25

    Antrodia camphorata (AC), also known as Antrodia cinnamomea, an endemic species in Taiwan, is one of the treasured medicinal mushrooms. AC is traditionally used for its chemopreventive biofunctions. In this investigation, we report a convenient method for concentrating the antiproliferative active triterpenoid-rich fraction (FEA), from ethanolic extract of AC (EEAC). A series of stereo-isomers of zhankuic acids (1-8) from the FEA was purified by HPLC using an efficient acidic solvent system. The structures of compounds 1-8 were elucidated based on spectroscopic data analysis, and the absolute configuration of α-chiral carboxylic acid at C-25 in the structures was assigned based on reaction with (R)- and (S)-1-(9-anthryl)-2,2,2-trifluoroethanol. Major ingredients of FEA (eight ergostanes 1-8 and two lanostanes 9-10) were further characterised by high-performance liquid chromatography-photodiode array detection/mass spectrometry (HPLC-PDA/MS). Compounds 1-8 and their pair mixture forms (antcin K, antcin C, zhankuic acid C, and zhankuic acid A) were subjected to anti-proliferative assay against three human leukemia cell lines. Among them, the derivatives with carbonyl group at C-3 showed cytotoxicity with IC(50) values ranging from 16.44 to 77.04 μg/ml.

  19. Identification of geranic acid, a tyrosinase inhibitor in lemongrass (Cymbopogon citratus).

    PubMed

    Masuda, Toshiya; Odaka, Yuka; Ogawa, Natsuko; Nakamoto, Katsuo; Kuninaga, Hideki

    2008-01-23

    Lemongrass is a popular Asian herb having a lemon-like flavor. Very recently, potent tyrosinase inhibitory activity has been found in lemongrass in addition to various biological activities reported in the literature. The aim of the present study is to identify the active compounds in the lemongrass. An assay-guided purification revealed that one of the active substances was geranic acid. Geranic acid has two stereoisomers, which are responsible for the trans and cis geometry on the conjugated double bond. Both isomers are present in the active ethyl acetate-soluble extract of the lemongrass, and their IC50 values were calculated to be 0.14 and 2.3 mM, respectively. The structure requirement of geranic acid for the potent tyrosinase inhibitory activity was investigated using geranic acid-related compounds.

  20. AN ISOMER PREDICTION MODEL FOR PCNS, PCDD/FS, AND PCBS FROM MUNICIPAL WASTE INCINERATORS

    EPA Science Inventory

    Isomer patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated biphenyls (PCBs) from municipal waste incinerators (MWIs) were predicted by a model based on dechlorination kinetics from the most-chlorinated species. Successfu...