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Longer Chains (longer + chain)
Selected AbstractsFatty acid composition abnormalities in atopic disease: evidence explored and role in the disease process examinedCLINICAL & EXPERIMENTAL ALLERGY, Issue 9 2008A. Sala-Vila Summary There is a hypothesis causally linking excess intake of n-6 polyunsaturated fatty acids (PUFAs) to atopic disease. Under most dietary conditions, the main precursor of eicosanoids is the n-6 PUFA arachidonic acid (AA). AA-derived eicosanoids play many roles in sensitization to allergens and in allergic inflammation. Long chain n-3 PUFAs inhibit AA incorporation into cell membranes and inhibit AA metabolism to eicosanoids. It is hypothesized that atopy is associated with a higher n-6 PUFA status and with a low n-3 PUFA status. However, measurements of fatty acid composition do not provide a clear picture that such fatty acid abnormalities exist in atopy with no really clear pattern of altered status of a particular fatty acid or a particular fatty acid family. There are few reports of elevated linoleic acid in atopy. Some studies report lower amounts of the n-6 PUFAs, including AA, and of long chain n-3 PUFAs in atopy, although observations on this are not consistent. Taken together these data clearly do not support the hypothesis that atopy is somehow associated with a high exposure to, and status of, n-6 PUFAs. Intervention studies with n-3 PUFAs in pregnant women, infants and children suggest some clinical benefits, although how long lasting these are remains to be determined. The observation that there may be low AA status in atopy suggests that fish oil intervention, which targets AA status and metabolism, may not be ideal and that a combination of fish oil with some longer chain n-6 PUFAs may be more efficacious. [source] Peptide Nanotubes: Simple Separation Using Size-Exclusion Columns and Use as Templates for Fabricating One-Dimensional Single Chains of Au Nanoparticles,ADVANCED MATERIALS, Issue 14 2005X. Gao Straight single chains of Au nanoparticles have been synthesized using 10,nm diameter peptide nanotubes as templates (see Figure). The 6,nm Au nanoparticles grow in the gaps between the synthetic peptide coating the nanotubes which regulates the size, dispersity, interparticle distance, and crystallinity of the nanoparticles. The use of longer nanotubes results in longer chains. [source] Revisiting the relationship between the bond length alternation and the first hyperpolarizability with range-separated hybrid functionalsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2008Denis Jacquemin Abstract We monitor the influence of the bond length alternation (BLA) modification on the static electronic polarizability and first hyperpolarizability of two polymethineimine oligomers. Four theoretical approaches are compared: HF, PBE0, LC-,PBE, and MP2. For the dodecamer, both HF and PBE0 are unable to foresee even the qualitative evolution of the first hyperpolarizability when varying the BLA. On the contrary, LC-,PBE provides (non)linear optics properties in agreement with MP2 results, especially for the longer chains. This confirms the interest of range-separated hybrids for the computation of the (hyper)polarizabilities of extended ,-conjugated compounds. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008 [source] RAFT polymerization kinetics: How long are the cross-terminating oligomers?JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2009Dominik Konkolewicz Abstract We extend a new model for the kinetics of reversible addition-fragmentation chain transfer (RAFT) polymerization. The essence of this model is that the termination of the radical intermediate formed by the RAFT process occurs only with very short oligomeric radicals. In this work, we consider cross-termination of oligomers up to two monomers and an initiator fragment. This model accounts for the absence of three-armed stars in the molecular weight distribution, which are predicted by other cross-termination models, since the short third arm makes a negligible difference to the polymer's molecular weight. The model is tested against experiments on styrene mediated by cyano-isopropyl dithiobenzoate, and ESR experiments of the intermediate radical concentration. By comparing our model to experiments, we may determine the significance of cross-termination in RAFT kinetics. Our model suggests that to agree with the known data on RAFT kinetics, the majority of cross-terminating chains are dimeric or shorter. If longer chains are considered in cross-termination reactions, then significant discrepancies with the experiments (distinguishable star polymers in the molecular weight distribution) and quantum calculations will result. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3455,3466, 2009 [source] Growth and pectate-lyase activity of the ruminal bacterium Lachnospira multiparus in the presence of short-chain organic acidsLETTERS IN APPLIED MICROBIOLOGY, Issue 5 2005R.A. Paggi Abstract Aims:, Acetic, propionic, butyric and lactic acids are end products of feed fermentation by rumen microbes. The effects of these short chain acids on growth and pectate-lyase (PL) activity of Lachnospira multiparus were studied. Methods and Results:, The bacterial strain used was L. multiparus D32. Acids were tested between 50 and 300 mmol l,1. Growth and PL activity were measured by the increase in total protein content and by the increase in absorbance at 235 nm in the reaction medium respectively. With the exception of lactic acid, all acids decreased bacterial growth rates; generally, these effects were more pronounced at higher concentrations and with acids of longer chains. PL activity was inhibited by all the acids except by butyric acid at 50 and 100 mmol l,1. Enzyme inhibition increased with the concentrations of the acids and lactic acid was the most inhibitory. Conclusions:, High concentrations of short chain acids can differentially inhibit the growth rate and the PL activity of L. multiparus. Significance and Impact of the Study:, Products of fermentation generated by the ruminal microbiota could modify the degradation of pectic substances by this bacterium. [source] Influence of solvent quality on successive solution fractionation (SSF) efficiency of high-density polyethylenePOLYMER INTERNATIONAL, Issue 4 2009Vincent Stéphenne Abstract BACKGROUND: Preparative successive solution fractionation (SSF) is a powerful technique for obtaining narrow-dispersity fractions on a multi-gram scale of high-density polyethylene (HDPE). In a previous paper, the operative separation mechanisms during SSF of a broad HDPE in cyclohexanone were studied. Two mechanisms, and not only one as expected from the literature, contribute to the separation of HDPE molecules according to their molar mass (MM). The very low MM chains are separated by a solid,liquid (S,L) mechanism, while the longer chains are isolated by a liquid,liquid (L,L) phase separation. In the present paper, the influence of a poorer solvent, diphenyl ether, is reported. RESULTS: It is shown that the relative importance of the S,L mechanism with respect to the L,L one is altered by the use of this solvent. The L,L temperature range is increased in diphenyl ether while the S,L transition temperature remains unchanged. Consequently, the SSF efficiency is improved. Large amounts (on a gram scale) of narrow-dispersity fractions are isolated, mainly by the L,L mechanism. Polydispersities are about 1.5 (compared to 2.0 for cyclohexanone) and a broader MM range of closer molar mass distribution fractions is available. CONCLUSION: This work demonstrates that the use of diphenyl ether, a poorer solvent than cyclohexanone (always used as SSF solvent for polyethylene in the literature), leads to an improvement of SSF efficiency for an essentially linear HDPE. The differences of behaviour during the separation with cyclohexanone or diphenyl ether are explained by the establishment of a phase diagram. Copyright © 2009 Society of Chemical Industry [source] Diastereo- and Enantioselective Intramolecular [2+2],Photocycloaddition Reactions of 3-(,,-Alkenyl)- and 3-(,,-Alkenyloxy)-Substituted 5,6-Dihydro-1H -pyridin-2-onesCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2010Dominik Albrecht Dr. Abstract 3-(,,-Alkenyl)-substituted 5,6-dihydro-1H -pyridin-2-ones 2,4 were prepared as photocycloaddition precursors either by cross-coupling from 3-iodo-5,6-dihydro-1H -pyridin-2-one (8) or,more favorably,from the corresponding ,-(,,-alkenyl)-substituted ,-valerolactams 9,11 by a selenylation/elimination sequence (56,62,% overall yield). 3-(,,-Alkenyloxy)-substituted 5,6-dihydro-1H -pyridin-2-ones 5 and 6 were accessible in 43 and 37,% overall yield from 3-diazopiperidin-2-one (15) by an ,,,-chloroselenylation reaction at the 3-position followed by nucleophilic displacement of a chloride ion with an ,-alkenolate and oxidative elimination of selenoxide. Upon irradiation at ,=254,nm, the precursor compounds underwent a clean intramolecular [2+2] photocycloaddition reaction. Substrates 2 and 5, tethered by a two-atom chain, exclusively delivered the respective crossed products 19 and 20, and substrates 3, 5, and 6, tethered by longer chains, gave the straight products 21,23. The completely regio- and diastereoselective photocycloaddition reactions proceeded in 63,83,% yield. Irradiation in the presence of the chiral templates (,)- 1 and (+)- 31 at ,75,°C in toluene rendered the reactions enantioselective with selectivities varying between 40 and 85,%,ee. Truncated template rac - 31 was prepared as a noranalogue of the well-established template 1 in eight steps and 56,% yield from the Kemp triacid (24). Subsequent resolution delivered the enantiomerically pure templates (,)- 31 and (+)- 31. The outcome of the reactions is compared to the results achieved with 4-substituted 5,6-dihydro-1H -pyridin-2-ones and quinolones. 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