A polarizable empirical force field for molecular dynamics simulation of liquid hydrocarbons

Electronic polarizability is usually treated implicitly in molecular simulations, which may lead to imprecise or even erroneous molecular behavior in spatially electronically inhomogeneous regions of systems such as proteins, membranes, interfaces between compounds, or mixtures of solvents. The majority of available molecular force fields and molecular dynamics simulation software packages does not account explicitly for electronic polarization. Even the simplest charge‐on‐spring (COS) models have only been developed for few types of molecules. In this work, we report a polarizable COS model for cyclohexane, as this molecule is a widely used solvent, and for linear alkanes, which are also used as solvents, and are the precursors of lipids, amino acid side chains, carbohydrates, or nucleic acid backbones. The model is an extension of a nonpolarizable united‐atom model for alkanes that had been calibrated against experimental values of the density, the heat of vaporization and the Gibbs free energy of hydration for each alkane. The latter quantity was used to calibrate the parameters governing the interaction of the polarizable alkanes with water. Subsequently, the model was tested for other structural, thermodynamic, dielectric, and dynamic properties such as trans/gauche ratios, excess free energy, static dielectric permittivity, and self‐diffusion. A good agreement with the experimental data for a large set of properties for each considered system was obtained, resulting in a transferable set of polarizable force‐field parameters for CH₂, CH₃, and CH₄ moieties. © 2014 Wiley Periodicals, Inc.     

纳米α-FeOOH催化剂一段法脱除COS和H2S性能的研究

利用均相沉淀法、氨水滴定法制备纳米α-FeOOH粒子，以该粒子为活性组分制备催化剂，利用微反－色谱联用活性评价技术，在常压、空速10 000 h－1、25 ℃～60 ℃温度范围内考察了纳米α-FeOOH催化剂对COS催化水解的活性。采用热重法对纳米α-FeOOH催化剂脱除H2S的性能进行了研究。结果表明：纳米α-FeOOH催化剂对COS水解在低温度、大空速下具有高的活性，系列Ⅰ和系列Ⅱ催化剂分别在60 ℃和40 ℃～45 ℃时COS转化率达到100%。在60 ℃时各种催化剂吸附H2S的能力最强，最高饱和硫容可达到21.72w%。催化剂表面能量分布不均匀，COS催化水解在低温时存在补偿效应。     

壳寡糖对Hela细胞的增殖抑制与诱导凋亡

为了明确壳寡糖(COS)对Hela细胞的增殖抑制作用及对凋亡的影响,采用3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)法检测增殖抑制作用,Wrights-Giemsa及吖啶橙-溴乙锭(AO-EB)染色观察凋亡细胞的形态,Annexin V-FITC/PI法检测凋亡率,免疫组化法分析Bax,Bcl-2和Survivin表达量变化.结果显示:不同浓度COS处理Hela细胞均能抑制增殖,5.0mg/mL并作用24h对其增殖抑制率为52.15%(P0.01).Wrights-Giemsa染色显示细胞形态趋近圆形,贴壁能力减弱,出现凋亡小体.AO-EB染色时细胞出现早期和晚期凋亡现象.AnnexinV-FITC/PI检测细胞凋亡率为31.75%(P0.05).免疫组化分析细胞内Bax表达量增加,Bcl-2和Survivin表达量降低.表明COS能够抑制Hela细胞增殖并诱导凋亡,其原因与Bax的上调和Bcl-2与Survivin的下调相关.     

Theoretical Study on the Reaction of FeS+(6∑+,4Ф)with COS in the Gas Phase

The possible reaction mechanisms of FeST(6∑+and 4Ф states)with COS in the gas phase have been studied by using density functional theory at the B3LYP/TZVP and B3LYP/6-311+G*levels:the O/S exchange reaction(FeS++COS=FeO++CS2),O-transfer reaction(FeS++COS=FeSO++CS)and S-transfer reaction(FeS++COS=FeS2++CO).The calculation results show that the large barriers(205.7 and 310.1 kJ/mol)and the small probability of forming the preceding intermediate indicate a much lower efficiency of the O/S exchange and the O-transfer reactions and their corresponding products may not be observed experimentally.FeS2+,the product of S-transfer reaction,is predicted to be the main product.But the reactivity of the 6∑+ground state of FeS+toward COS is lower than the earlier transition metal sulfide cations MS+(M=Sc,Ti and V),although it has more reaction channels and different mechanisms.     

COS Activation by Zr~＋ in the Gas Phase：A Case of Two-state Reactivity Process

To elucidate the mechanisms of Zr + reacting with COS,both the quartet and doublet potential energy surfaces (PESs) for reactions of Zr + (4 F,2 D) with COS in the gas phase have been investigated in detail by means of density functional method (B3LYP).To obtain more accurate results,the coupled cluster single-point calculations (CCSD(T)) using B3LYP optimized geometries were performed.For the C-O bond activation,the calculated results indicate that both the quartet and doublet states proceed via an insertion-elimination mechanism.For the C-S bond activation,the quartet reaction has an insertion-elimination mechanism,but the doublet reaction is a direct abstraction of the sulfur atom by Zr +.The C-S bond activation is found to be energetically more favorable than the C-O bond activation.It is found that the reaction of the 4 F gound state of Zr + to yield ZrO + is spin-forbidden (Zr + (4 F) + COS (1 Σ) → ZrO + (2) + CS (1 Σ)) and the crossing points were approximately determined.All the results have been compared with the existing experimental and theoretical data.     

双接口智能卡COS软件的设计与实现

文章首先分析了双接口智能卡的特点，然后详细介绍了双接口智能卡COS软件的设计与实现，特别对COS软件的传输管理、文件管理、安全管理以及命令解释等进行了详细描述，并介绍了实现方法。     

CS2和COS在y-A12O3表面吸附的密度泛函理论研究

煤气中的有机含硫化合物CS2和COS对环境及后续的反应带来很大的危害,常用Al2O3进行脱硫处理。小分子在固体表面的吸附是研究气固反应的基础。采用量子化学密度泛函理论方法研究了CS2和COS在y-Al2O3（110）表面的吸附,结果表明CS2最稳定的构型为C82的3个原子分别与表面的Al0一Al键中的3个原子作用,形成了（COS2）。一物种,此构型的吸附能为107．98kJ／mol;COS以SC键-9表面的1个Al-O键作用时最稳定,吸附能为99．99kJ／mol。通过分波态密度和小分子吸附前后净电荷的变化可知,在这两个构型中,小分子与表面有很强的相互作用。     

预测[C,O,S]体系的稳定异构体

采用 DFT, QCISD及CCSD(T)方法对单重态和三重态的COS分子体系势能面进行了理论计算, 在 QCISD/6-311G(d) 水平上得到4个过渡态连接的6个稳定构型. 经动力学及热力学分析发现只有一个单重态线性的分子11(O—C—S) 能够稳定存在.     

低温条件下二氧化碳存在时羰基硫催化水解本征动力学

在自行设计和安装的一套微反-色谱联用装置上，以TGH为催化剂，进行了二氧化碳对羰基硫催化水解本征动力学影响的研究，得出了在低温50 ℃～70 ℃、高水汽摩尔比(H2O/COS=60～550)，分别对原料气中有无存在CO2的条件下,采用非线性Marquart法对实验数据进行回归，所建立的本征动力学方程式为：     

氧化铝基COS、CS_2水解催化剂表面碱性和催化作用

进行了３种氧化铝基催化剂上ＣＯ２的ＴＰＤ和ＣＯＳ、ＣＳ２的水解活性研究．结果表明，催化剂表面碱性中心类型、强度和数目是不相同的；Ｋ２Ｏ和Ｐｔ的负载能提高弱碱性中心的数目和强度，同时能显著提高ＣＯＳ、ＣＳ２的水解转化率．关联第一类ＣＯ２脱附活化能和峰面积与ＣＯＳ水解反应活化能和速率常数，发现呈线性关系，说明弱碱性中心是ＣＯＳ催化水解的活性中心．关联第一、二两类ＣＯ２脱附峰面积与ＣＳ２水解速率常数，指出弱、次弱两类碱性中心均参与了ＣＳ２催化水解．催化剂表面上能量的分布是不均匀的．