The Substituent Effects of tert-Butyl Radical Addition to 2-Substituted Allyl Chlorides

The relative rates for the addition reactions of tert-butyl radical to 2-substituted ally chlorides I have een determined. The correlation of log k/k₀, vs. σ_m gives a ρ mvalue of 3.59 with correlation coefficient of 0.930. When the substituent CH₂Cl is excluded, correlation coefficient raises to 0.990 and ρ value becomes 3.39. The large p value and the deviation of relative rate of substituent CH₂C1 are discussed.     

Study of cryostructurization of polymer systems

Summary A possibility of obtaining insoluble gels with the help of freezing-thawing procedures was demonstrated on an example of aqueous solutions of a thiol-containing poly(acryl amide) derivative. The gel formation was proved to occur as a result of oxidation of free SH groups of polymer chains by water-dissolved air oxygen.     

Difference in Conversions Between Dimethyl Sulfide and Methanethiol in a Cold Plasma Environment

This study compared the conversion of two malodorous substances, dimethyl sulfide (CH₃SCH₃, DMS) and methanethiol (CH₃SH) in a cold plasma reactor. The DMS and CH₃SH were successfully destroyed at room temperature. DMS decomposed less than CH₃SH at the same conditions. In oxygen-free condition, CS₂ and hydrocarbons were the major products, while SO₂ and CO_x were main compounds in oxygen-rich environments. The DMS/Ar plasma yielded more hydrocarbons and less CS₂ than that of CH₃SH/Ar plasma. In the CH₃SH/O₂/Ar plasma, rapid formation of SO and CO resulted in the yields much more amounts of SO₂ and CO₂ than those in the DMS/O₂/Ar plasma; and remained only a trace of total hydrocarbons, CH₂O, CH₃OH, CS₂, and OCS. The major differences between the reaction mechanisms of DMS and CH₃SH were also proposed and discussed.     

CH3SH…HOO开壳型氢键复合物的结构及其电子密度拓扑性质

在DFT-B3LYP/6-311++G**水平下求得CH3SH…HOO复合物势能面上的稳定构型. 计算结果表明, 在HOO以其O8—H7作为质子供体与CH3SH分子中的S5原子为质子受体形成的氢键复合物1和2中, O8—H7明显被“拉长”, 且其伸缩振动频率发生显著的红移, 红移值分别为330.1和320.4 cm-1; 在CH3SH分子以其S5—H6作为质子供体与HOO的端基O9原子为质子受体形成的氢键复合物3和4中, 也存在类似的情况, 但S5—H6伸缩振动频率红移不大. 经MP2/6-311++G**水平计算的4种复合物含BSSE校正的相互作用能分别为-20.81, -20.10, -4.46和-4.52 kJ/mol. 自然键轨道理论(NBO)分析表明, 在CH3SH…HOO复合物1和2中, 引起H7—O8键长增加的因素包括两种电荷转移, 即孤对电子n1(S5)→σ*(H7—O8)和孤对电子n2(S5)→σ*(H7—O8), 其中后者为主要作用. 在复合物3和4中也有相似的电荷转移情况, 但轨道间的相互作用要弱一些. AIM理论分析结果表明, 4个复合物中的S5…H7间和O9…H6间都存在键鞍点, 且其Laplacian量▽2ρ(r)都是很小的正值, 说明这种相互作用介于共价键和离子键之间, 偏静电作用为主.     

弹性半空间二维出平面自由波场的一维化时域算法

提出了一种计算出平面SH波斜入射时弹性半空间自由波场时域计算的一维化有限元方法。首先利用Snell定律确定平面波沿水平方向的传播规律,在用有限元法对弹性半空间进行离散化时,竖向单元尺寸根据波动有限元模拟精度要求确定,而水平向有限元网格尺寸根据水平向波的传播规律和采用的离散时间步长确定,使得有限元离散模型中任意节点的运动可以用水平向相邻节点的运动表示,从而将二维有限元节点运动方程组化为一维的形式。求解此一维方程组,可得到弹性半空间中一列节点的运动,再根据行波的传播规律,可确定全空间自由波场。理论分析和数值算例表明,该方法具有较高的精度和良好的稳定性。     

浅埋的圆柱形孔洞对SH波的散射与地震动

研究了浅埋的圆柱形孔洞对以任意方向入射的平面SH波的散射与地震动问题。利用复变函数和多极坐标方法构造了问题的位移解。当入射波的波长与圆孔的半径相比较小时,地震动将受到较大的影响。影响地震动有三个主要参数:(1)SH波的入射角0;(2)入射波波数,即圆柱形孔洞的半径与入射波半波长之比;(3)h/R,即圆柱形孔洞至表面的距离与圆孔半径之比。当较大时,地震动幅值变化激烈,位移幅值可出现跳动和放大的现象。当h/R增大至10～12时,位移幅值变化恢复至半空间的情况,表明圆柱形孔洞的影响可被忽略。     

Design and synthesis of a potential SH2 domain inhibitor bearing a stereodiversified 1,4-cis-enediol scaffold

Synthesis of a potential Src family SH2 domain inhibitor incorporating a 1,4-cis-enediol scaffold is reported. The synthetic route offers straightforward and highly selective access to the enediol and its associated chiral centers. Key steps include stereocontrolled syn-aldol coupling, amide alkynylation, and asymmetric ketone reduction.     

An ab initio-based global potential energy surface for the SH3 system and full-dimensional state-to-state quantum dynamics study for the H2 + HS → H2S + H reaction

An accurate potential energy surface for the ground electronic state of SH₃ system has been constructed with 41,882 high level ab initio energy points and the neural network fitting method. The time-dependent wave packet method has been used to calculate the first state-to-state differential cross sections for the title reaction up to 1.2 eV in full dimensions, based on the reactant–product decoupling scheme. It is found that the majority of H₂S are produced in the ground vibrational state, with a large fraction of available energy for the reaction ending up as product translational motion. The differential cross sections at the threshold energy are dominated by a very narrow peak in the backward direction. With the increase of collision energy, the width of the angular distribution increases considerably, which is a typical feature of a direct reaction via abstract mechanism, similar to the H₂ + OH → H₂O + H reaction. © 2018 Wiley Periodicals, Inc.