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51.
Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO2, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO2, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO2 under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO2]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO2), 365.8 K (TCCA-DMF)/NaNO2, and 358 K (TCCA-DMA)/NaNO2. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction. 相似文献
52.
Y. T. Angel Wong Vinicius Martins Dr. Bryan E. G. Lucier Prof. Dr. Yining Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(8):1848-1853
Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development. 相似文献
53.
In this paper, we investigate the evolution of joint invariants under invariant geometric flows using the theory of equivariant moving frames and the induced invariant discrete variational complex. For certain arc length preserving planar curve flows invariant under the special Euclidean group , the special linear group , and the semidirect group , we find that the induced evolution of the discrete curvature satisfies the differential‐difference mKdV, KdV, and Burgers' equations, respectively. These three equations are completely integrable, and we show that a recursion operator can be constructed by precomposing the characteristic operator of the curvature by a certain invariant difference operator. Finally, we derive the constraint for the integrability of the discrete curvature evolution to lift to the evolution of the discrete curve itself. 相似文献
54.
基于单粒子导心运动代码ORBIT,采用测试粒子模拟方法,研究了托卡马克等离子体内部不同径向位置处局域磁场扰动对高能量离子的损失的影响。研究表明,在局域磁扰动主要分布在某磁面附近、其环向具有类似纹波场形式下,可造成一些靠近等离子体中心区域的高能量离子损失,但对靠近等离子边界的离子损失影响相对不大。这些损失的高能量离子均为捕获离子,离子的投掷角越大就越容易损失。此外,造成高能量离子最大损失率的局域场径向位置与这些损失离子的初始径向位置通常存在一定的偏移,而且这个偏移与这些离子的能量密切相关。当局域场出现在某些位置时,能量较低的离子会有一定的损失,能量较高的离子反而不会损失。 相似文献
55.
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57.
为提高计算效率,提出有限体积法离散下的虚拟区域颗粒两相流动直接模拟方法.在控制方程中加入相应的虚拟区域源项,保证了颗粒内部的刚体运动特性.该源项中含有颗粒信息部分及流体信息部分.在每次迭代后,对源项中的流体信息部分进行更新,从而更好地保证颗粒内速度的刚体分布.计算静止颗粒圆柱绕流及单个颗粒的沉降过程,验证了算法的准确性. 相似文献
58.
Khaled Tawfik Alali Dr. Jingyuan Liu Dr. Rongrong Chen Dr. Qi Liu Dr. Hongsen Zhang Jundong Li Jindi Hou Prof. Rumin Li Prof. Jun Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11892-11902
Semiconductor metal oxides (SMO)-based gas-sensing materials suffer from insufficient detection of a specific target gas. Reliable selectivity, high sensitivity, and rapid response–recovery times under various working conditions are the main requirements for optimal gas sensors. Chemical warfare agents (CWA) such as sarin are fatal inhibitors of acetylcholinesterase in the nerve system. So, sensing materials with high sensitivity and selectivity toward CWA are urgently needed. Herein, micro-nano octahedral Co3O4 functionalized with hexafluoroisopropanol (HFIP) were deposited on a layer of reduced graphene oxide (rGO) as a double-layer sensing materials. The Co3O4 micro-nano octahedra were synthesized by direct growth from electrospun fiber templates calcined in ambient air. The double-layer rGO/Co3O4-HFIP sensing materials presented high selectivity toward DMMP (sarin agent simulant, dimethyl methyl phosphonate) versus rGO/Co3O4 and Co3O4 sensors after the exposure to various gases owing to hydrogen bonding between the DMMP molecules and Co3O4-HFIP. The rGO/Co3O4-HFIP sensors showed high stability with a response signal around 11.8 toward 0.5 ppm DMMP at 125 °C, and more than 75 % of the initial response was maintained under a saturated humid environment (85 % relative humidity). These results prove that these double-layer inorganic–organic composite sensing materials are excellent candidates to serve as optimal gas-sensing materials. 相似文献
59.
Samadhan S. Nagane Sachin S. Kuhire Uday A. Jadhav Sushilkumar A. Dhanmane Prakash P. Wadgaonkar 《Journal of polymer science. Part A, Polymer chemistry》2019,57(5):630-640
A bisphenol bearing pendant maleimide group, namely, N‐maleimidoethyl‐3, 3‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrrolidone (PPH‐MA) was synthesized starting from phenolphthalein. Aromatic (co)polyesters bearing pendant maleimide groups were synthesized from PPH‐MA and aromatic diacid chlorides, namely, isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), and 50:50 mol % mixture of IPC and TPC by low temperature solution polycondensation technique. Copolyesters were also synthesized by polycondensation of different molar proportions of PPH‐MA and bisphenol A with IPC. Inherent viscosities and number‐average molecular weights of aromatic (co)polyesters were in the range of 0.52–0.97 dL/g and 20,200–32,800 g/mol, respectively indicating formation of medium to reasonably high‐molecular‐weight polymers. 13C NMR spectral analysis of copolyesters revealed the formation of random copolymers. The 10% weight loss temperature of (co)polyesters was found in the range 470–484 °C, indicating their good thermal stability. A selected aromatic polyester bearing pendant maleimide groups was chemically modified via thiol‐maleimide Michael addition reaction with two representative thiol compounds, namely, 4‐chlorothiophenol and 1‐adamantanethiol to yield post‐modified polymers in a quantitative manner. Additionally, it was demonstrated that polyester containing pendant maleimide groups could be used to form insoluble crosslinked gel in the presence of a multifunctional thiol crosslinker. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 630–640 相似文献
60.
《Physics letters. A》2019,383(22):2594-2603
In this work, we address the systematic biases and random errors stemming from finite step sizes encountered in diffusion simulations. We introduce the Effective Geometry Monte Carlo (EG-MC) simulation algorithm which modifies the geometry of the receiver. We motivate our approach in a 1D toy model and then apply our findings to a spherical absorbing receiver in a 3D unbounded environment. We show that with minimal computational cost the impulse response of this receiver can be precisely simulated using EG-MC. Afterwards, we demonstrate the accuracy of our simulations and give tight constraints on the single free parameter in EG-MC. Finally, we comment on the range of applicability of our results. While we present the EG-MC algorithm for the specific case of molecular diffusion, we believe that analogous methods with effective geometry manipulations can be utilized to approach a variety of problems in other branches of physics such as condensed matter physics and cosmological large scale structure simulations. 相似文献