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排序方式: 共有138条查询结果,搜索用时 15 毫秒
11.
We study the enzymatic degradation of xenobiotic polymers mathematically. As a mathematical model, we derive a linear second-order hyperbolic partial differential equation which governs the evolution of the weight distribution with respect to the molecular weight. Given an initial weight distribution and a final weight distribution, we formulate a problem to determine a degradation rate. We establish a necessary and sufficient condition for which the problem has a local solution. We also introduce a numerical technique based on our analysis, and present a numerical result that we obtained applying weight distributions before and after enzymatic degradation of polyvinyl alcohol. 相似文献
12.
Tianrong Yu Yang Gao Bo Wang Xing Dai Wanrun Jiang Ruixia Song Prof. Zhanwen Zhang Prof. Mingxing Jin Prof. Yongjian Tang Prof. Zhigang Wang 《Chemphyschem》2015,16(15):3308-3312
The mechanism of depolymerization is one of the most essential issues in chemical engineering and materials science. In this work, we investigate the depolymerization reactions of three typical free‐radical poly(alpha‐methylstyrene) tetramers by using first‐principles density functional theory. The calculated results show that these reactions all need to overcome the energy barriers in the range of 0.58 to 0.77 eV, and that breaking the C?C bond at the chain end leads to the dissociation of alpha‐methylstyrene monomers from the polymers. Electronic‐structure analysis indicates that the reactions occur easily at the CR3 unsaturated end, and that the frontier molecular orbitals that participate in the reactions are mainly localized at the unsaturated ends. Meanwhile, spin population analysis presents the unique net spin‐transfer process in free‐radical depolymerization reactions. We hope the current findings can contribute to understanding the free‐radical depolymerization mechanism and help guide future experiments. 相似文献
13.
Selective Template Removal by Thermal Depolymerization to Obtain Mesostructured Molybdenum Oxycarbide
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Martin Schieder Thomas Lunkenbein Carina Bojer Martin Dulle Julia vom Stein Gudrun Auffermann Tina Löbling Judith Schöbel Holger Schmalz Josef Breu 《无机化学与普通化学杂志》2015,641(10):1829-1834
The carbon content of mesostructured organic‐inorganic hybrid material of a cylindrical block copolymer template of poly(2‐vinylpyridine)‐block‐poly(allyl methacrylate) (P2VP‐b‐PAMA) and ammonium paramolybdate (APM) could be reduced by thermal depolymerization. By calcination in vacuo at 320 °C the PAMA core can be completely removed while the remaining P2VP brush preserves the mesostructure. The P2VP‐APM composite can then be carburized in‐situ to MoOxCy in a second pyrolysis step without any additional carbon source but P2VP. The molybdenum oxycarbide nanotubes obtained, form hierarchically porous non‐woven structures, which were tested as catalyst in the decomposition of NH3. They proved to be catalytically active at temperatures above 450 °C. The activation energy was estimated from an Arrhenius Plot to be 127 kJ · mol–1. 相似文献
14.
Roberts VM Stein V Reiner T Lemonidou A Li X Lercher JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(21):5939-5948
The products of base-catalyzed liquid-phase hydrolysis of lignin depend markedly on the operating conditions. By varying temperature, pressure, catalyst concentration, and residence time, the yield of monomers and oligomers from depolymerized lignin can be adjusted. It is shown that monomers of phenolic derivatives are the only primary products of base-catalyzed hydrolysis and that oligomers form as secondary products. Oligomerization and polymerization of these highly reactive products, however, limit the amount of obtainable product oil containing low-molecular-weight phenolic products. Therefore, inhibition of concurrent oligomerization and polymerization reactions during hydrothermal lignin depolymerization is important to enhance product yields. Applying boric acid as a capping agent to suppress addition and condensation reactions of initially formed products is presented as a successful approach in this direction. Combination of base-catalyzed lignin hydrolysis with addition of boric acid protecting agent shifts the product distribution to lower molecular weight compounds and increases product yields beyond 85%. 相似文献
15.
Liang Ma Ryan Baumgartner Yanfeng Zhang Ziyuan Song Kaimin Cai Jianjun Cheng 《Journal of polymer science. Part A, Polymer chemistry》2015,53(9):1161-1168
A UV‐responsive polymer was prepared via condensation polymerization of 2‐nitrobenzyl(4‐(1,2‐dihydroxyethyl)phenyl)carbamate and azalaic acid dichloride. When the polymer was irradiated with UV light, the nitrobenzyl urethane protecting group was removed and the deprotected aniline underwent spontaneous 1,6‐elimination reactions, resulting in degradation of the polymer. Nanoparticles with encapsulated Nile Red were formulated with the degradable polymer and triggered burst release of Nile Red was observed when the nanoparticles were irradiated by UV light. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1161–1168 相似文献
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布朗动力学理论模拟动态肌动蛋白纤维的增长 总被引:1,自引:0,他引:1
肌动蛋白的聚合耦合三磷酸腺酐(ATP)分子水解成二磷酸腺苷(ADP)分子和磷酸(Pi)的释放两个过程. 因此, 肌动蛋白纤维上的原聚体存在三种不同状态, 即分别结合ATP, ADP/Pi和ADP分子. 原聚体的不同状态导致纤维具有不同的空间图谱, 这些状态的空间分布将影响纤维的各种行为. 为此,建立了相应的分子模型,在布朗动力学模拟中实现了遵循时间演化的连续马尔可夫随机过程的解聚和水解反应; 重点阐述了如何实现纤维两端的聚合和解聚达到化学平衡的方法, 并系统研究了纤维在结合ATP分子的肌动蛋白单体溶液中的增长行为. 相似文献
18.
Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic,Green, and Sustainable Sources 下载免费PDF全文
Richard M. Laine Joseph C. Furgal Phi Doan David Pan Vera Popova Xingwen Zhang 《Angewandte Chemie (International ed. in English)》2016,55(3):1065-1069
The direct depolymerization of SiO2 to distillable alkoxysilanes has been explored repeatedly without success for 85 years as an alternative to carbothermal reduction (1900 °C) to Simet, followed by treatment with ROH. We report herein the base‐catalyzed depolymerization of SiO2 with diols to form distillable spirocyclic alkoxysilanes and Si(OEt)4. Thus, 2‐methyl‐2,4‐pentanediol, 2,2,4‐trimethyl‐1,3‐pentanediol, or ethylene glycol (EGH2) react with silica sources, such as rice hull ash, in the presence of NaOH (10 %) to form H2O and distillable spirocyclic alkoxysilanes [bis(2‐methyl‐2,4‐pentanediolato) silicate, bis(2,2,4‐trimethyl‐1,3‐pentanediolato) silicate or Si(eg)2 polymer with 5–98 % conversion, as governed by surface area/crystallinity. Si(eg)2 or bis(2‐methyl‐2,4‐pentanediolato) silicate reacted with EtOH and catalytic acid to give Si(OEt)4 in 60 % yield, thus providing inexpensive routes to high‐purity precipitated or fumed silica and compounds with single Si?C bonds. 相似文献
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20.
Condensed tannins take an important part in the sensory quality of food and beverage. Sensory analyses are usually carried out with various tannin fractions isolated from food or beverage, and their interpretation are limited by the lack of knowledge in the fine and accurate molecular composition of the tannin fractions. Besides, the studies of the chemical reactivity conducted in model solutions with ‘simple’ flavanols allow a better understanding of their evolution pathways, but they cannot take into account their reactivity as polymers, specifically regarding oxidation. In particular, competition between intramolecular and intermolecular reactions may strongly impact on the tannin structures (size, branching and conformation) and consequently on their properties. An ultra‐performance liquid chromatography‐mass spectrometry electrospray ionization mass spectrometer analytical method was thus developed in order to identify oxidized tannins generated by autoxidation. Given the difficulties to separate and detect tannins with high DP, samples were depolymerized by chemical depolymerization prior to analysis. Since the linkages created by oxidation are not cleavable in the usual depolymerization conditions (contrarily to the original interflavanic linkages), specific oxidation residues are released from tannins structures after their autoxidation. Oxidation markers of both intermolecular and intramolecular mechanisms have been identified; these are mainly dimers and trimers, more or less oxidized, and some contain additional hydroxyl groups. Furthermore, the nature of the subunits (extension vs terminal) making up these dimers and trimers was clearly established. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献