Theoretical Study on Thermodynamic Properties and Hydrophilicity of Polychorinated Phenothiazines （PCPTZs）

The thermodynamic properties of 135 polychlorinated phenothiazines (PCPTZs) in the standard state are calculated using a combination of quantum mechanical computations performed with the Gaussian 03 program at the B3LYP/6-311G** level, and their octanol-water partition coefficients (logKow) are calculated based on group contributions. The chlorine substitution pattern strongly influenced the thermodynamic properties and hydrophilicity of the compounds. The thermodynamic properties of congeners also depend on the chlorine substitution pattern. The effect of chlorine substitution pattern is quantitatively studied by considering the number and position of Cl atom substitution (NPCS). The results show that the NPCS model may be used to predict the thermodynamic properties and hydrophilicity for all 135 PCPTZ congeners.     

多溴吩噻嗪系列化合物的稳定性和热力学性质的密度泛函理论研究

用Gaussian 03程序, 在B3LYP/6-31G*水平上全优化计算了吩噻嗪和135个多溴吩噻嗪系列化合物(PBPTHs)在298.15 K和101.3 kPa状态时的热力学参数. 设计等键反应, 计算了PBPTHs系列化合物的标准生成热( )和标准生成自由能( ). 同时研究了这些参数与溴原子的取代位置及取代数目(NPBS)之间的关系. 结果表明: 多溴吩噻嗪的热能校正值(Eth)、恒容热容( )、标准熵( )、标准焓( )以及标准自由能( )与NPBS之间有很强的相关性(r2≥0.998). 在相关方程中, 溴原子的取代个数对多溴代吩噻嗪热力学数值的大小有很大影响. 根据 的相对大小, 从理论上求得异构体的相对稳定性顺序.     

QSRR Study on the Relationship between the Chromatographic Capacity Factor and Lipophilicity and Structure Parameters of Halogenated Thiophenols

The capacity factors (k') of fourteen types of halogenated thiophenols in different phases of methanol-water eluent were determined by reversed phased high-performance liquid chromatography (RP-HPLC) and the relationships between the logarithm of capacity factor lgK' and methanol ratio ψ were analyzed. A fair linear relationship is found between lgK' and ψ, and the correlation coefficients R2 of the constructed linear equations are all greater than 0.990. Relationship between the chromatographic data lgKw' when extrapolated to pure water and n-octanol/water partition coefficient lgKow obtained by the group contribution method has shown a good linear correlation with R2 = 0.956. The structure parameters of fourteen halogenated thiophenols were calculated by using DFT, and the correlation equation of lgKw' and structure parameters was obtained by using SPSS, lgKw' = -0.409 + 0.039α and R2 = 0.981, meaning that lgKw' is mainly determined by the polarizability α.     

太湖水华过程中微生物群落的动态变化

通过对水华过程的原位观测,运用分子生物学手段对太湖藻类水华过程中微生物的动态变化进行了跟踪测定,PCR-DGGE分析结果显示,水华过程中,水体中细菌的种群结构发生了较大变化,细菌的种类和数量都有明显改变;荧光直接计数水华过程中细菌数量变化表明:在5~10月份水华发生过程中,水体中细菌总量呈逐渐上升趋势(R2=0.836);运用MPN法,对磷分解细菌分析表明,水华发生前期水体中磷分解细菌的数量变化不明显,而在水华后期数量有显著增加趋势.     

大屯孔庄矿副井井筒破裂与底部含水层水文地质条件

本文从水动力和水化学两方面讨论了大屯孔庄矿副井井筒破裂与第四系底部含水层水文地质条件的关系, 详细分析了底部含水层水文地质条件变化可能对底部含水层及其周围岩土体以及井筒受力状态和强度特征产生的影响。首次指出了底部含水层水动力变化在井筒外部受力环境分析中的重要性和水化学作用对井壁混凝土强度的损害性。     

多氯10-氧吩噁噻系列化合物的热力学性质及稳定性的密度泛函理论方法研究

采用Gaussian 03程序中的密度泛函理论(DFT)方法,在BHandHLYP/6-311G**水平上对135个多氯10-氧吩噁噻系列化合物(PCPTO)进行了全优化和振动分析计算,得到了各分子在298.15K,1.013×105Pa标准状态下的热力学参数.设计等键反应,计算了PCPTO系列化合物的标准生成热(△fH)和标准生成自由能(△fG),同时研究了这些参数与氯原子的取代位置及取代数目(NPCS)之间的关系.结果表明:熵(S),△fH,△fG与NPCS之间有很强的相关性(R2≥0.991).根据△fG的相对大小,从理论上求得异构体的相对稳定性.以Gaussian 03程序的输出文件为基础,采用统计热力学程序计算了PCPTO化合物在200至1000K的摩尔恒压热容(Cp,m),并用最小二乘法求得Cp,m与温度之间的相关方程,结果发现Cp,m与T,T-1和T-2之间有着很好的相关性(R2=1.000).