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11.
Based on theoretical thermodynamic principles, the possibility of environmental degradation of polyacrylamide to its starting monomer was investigated. Theoretical electronic structure studies on the geometry and fragmentation energy of acrylamide and N,N‐dimethyl acrylamide tetramer models were carried out using a first principles gradient corrected density functional approach. Thermal degradation to form a radical would require the cleavage of carbon–carbon bonds in the polymer chain; the energy needed for this cleavage was found to depend on the structure of the repeat unit which ranged from low of 72.5 kcal for a rare head‐to‐head construct to 86.2 kcal for a normal head‐to‐tail polymer construct (therefore, for the cleavage of a normal head‐to‐tail repeat unit, temperatures of approximately 450°C would be required). The thermodynamics of the unzipping, disproportionation, and back‐biting reactions in the resulting radical fragments were also investigated; the back‐biting process was found to require the least energy and provided the most stable radical fragment with a low probability for disproportionation or releasing of monomer to occur. The effect of solvation on the hydrogen‐bonding network in the acrylamide tetramer was studied by adding explicit molecules of water to the tetramer models. The addition of water had a significant effect on the stability of the model polymer slightly stabilizing the head‐to‐head polymer, and slightly destabilizing the head to tail polymer. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
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Sem DS Bertolaet B Baker B Chang E Costache AD Coutts S Dong Q Hansen M Hong V Huang X Jack RM Kho R Lang H Ma CT Meininger D Pellecchia M Pierre F Villar H Yu L 《Chemistry & biology》2004,11(2):185-194
Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases. 相似文献
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Determination of capsaicinoids in salsa by liquid chromatography and enzyme immunoassay 总被引:2,自引:0,他引:2
Perkins B Bushway R Guthrie K Fan T Stewart B Prince A Williams M 《Journal of AOAC International》2002,85(1):82-85
Two simple and rapid methods were developed to monitor pungency of salsa in production. Capsaicin (C) and dihydrocapsaicin (DHC) were quantitated in 17 commercially available tomato-based salsas by enzyme immunoassay (EIA) and liquid chromatography (LC) with fluorescent detection. Samples were extracted with methanol and the extracts were subjected to solid-phase extraction (SPE) using polystyrene-divinylbenzene columns. Analysis of SPE eluates showed good correlation (r2 = 0.953) between LC and EIA, with a slightly high bias for EIA. Salsa fortified with C and DHC from 0.118 to 103.2 microg/g resulted in recoveries of 90-112% (C) and 76-97% (DHC). Limits of detection by LC were 0.1 microg/g for each capsaicinoid and 0.1 microg/g by EIA for total capsaicinoids. The LC on-column response was linear from 0.2 to 100 ng for both C and DHC, whereas the working range for EIA was 0.1-2.0 ppm. Pungency varied between different salsa brands labeled mild, medium, and hot. 相似文献
14.
POSTIRRADIATION PROPERTIES OF A UV-SENSITIVE VARIANT OF CHO 总被引:1,自引:0,他引:1
Richard D. Wood Margarita De Veciana Bonnie Presson -Tincknell 《Photochemistry and photobiology》1982,36(2):169-174
Abstract A UV-hypersensitive mutant of Chinese hamster ovary (CHO) cells, termed 43-3B, has been used in a comparative study with the wild type CHO in order to determine the involvement of repair in several postirradiation phenomena. 43-3B has the same growth rate and chromosome number as the wild type CHO-9. It is hypersensitive to UV irradiation (D0 of 0.3 J/m2 as compared to 3.2 J/m2 for the wild type). 43-3B shows only about 17% of the UV-stimulated unscheduled DNA repair synthesis of CHO-9 as measured by autoradiography. When breaks in supercoiled chromatin are measured after UV by the nucleoid sedimentation method, the mutant appears to be capable of carrying out only limited incision. A much reduced ability to recover control rates of semiconservative DNA synthesis after UV irradiation was observed in the repair-deficient 43-3B cell line, suggesting that the removal of UV-induced replication blocks by excision repair is the most important factor in allowing recovery of UV-inhibited DNA synthesis. Recovery of colony-forming ability between fractionated UV exposures was observed in the wild type CHO-9, but little recovery was seen in 43-3B. This indicates that excision repair capability can also be important in split-fluence recovery. 相似文献
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Luís Antônio Dantas Silva Fernanda Vieira Teixeira Raphael Caixeta Serpa Najla Locatelli Esteves Rayane Ramos dos Santos Eliana Martins Lima Marcílio Sérgio Soares da Cunha-Filho Adriano Antunes de Souza Araújo Stephânia Fleury Taveira Ricardo Neves Marreto 《Journal of Thermal Analysis and Calorimetry》2016,123(3):2337-2344
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