碳羟基磷灰石除废水中铬(Ⅵ)吸附动力学和热力学研究

利用废弃蛋壳合成碳羟基磷灰石(CHAP)对含铬(Ⅵ)离子废水进行吸附实验研究,考查了溶液的pH值、吸附时间和温度对吸附平衡的影响,并探讨了吸附动力学和热力学行为.结果表明:常温下,吸附时间为30min、pH=3.0、5g/L CHAP对50mg/L的铬(Ⅵ)离子的吸附率达到98.3%以上,CHAP对铬(Ⅵ)离子的吸附机理符合Langmuir和Freundlich方程;准二级动力学模型比准一级动力学模型能更好地描述CHAP对含铬(Ⅵ)离子吸附动力学行为;不同温度下的吸附热力学的吉布斯自由能以及熵变和焓变显示该吸附过程为自发吸热反应.     

抗菌素痢菌净与牛血清白蛋白相互作用的光谱研究

用荧光光谱和紫外吸收光谱法研究了抗菌素痢菌净(MEQ)与牛血清白蛋白(BSA)的相互作用。讨论了荧光猝灭机理,结果表明是动态猝灭过程;计算了不同温度下的猝灭常数和热力学参数。MEQ与BSA的相互作用为一个由熵驱动的自发过程,疏水作用力也起重要作用。由FRET能量转移理论计算得出了MEQ与BSA结合位置的距离r=4.5 nm。应用同步荧光和三维荧光研究了BSA在MEQ存在或不存在时的构象变化,结果表明：MEQ对BSA构象的影响不大。     

一种镍的二胺和β-二酮混合配体配合物在不同醇中热致-溶致变色行为的可见光谱研究

用可见光谱法对一种Ni(Ⅱ)的二胺和β-二酮类混合配体配合物([Ni(Ⅱ)(Me4en)(acac)]ClO4)在四种醇类溶剂中所形成的正方半面体和变形八面体物种的平衡过程进行了研究.通过对配合物在醇中的热致-溶致变色光谱曲线的分峰拟合处理,计算出了这一过程的平衡常数,焓变△H和熵变△S等热力学甬数,同时,得到了正方平面体和变形八面体物种各自的光谱吸收曲线.△H数据表明,在醇中形成变形八面体物种是一个放热过程,放热量的大小反映了醇分子与配合物中心离子Ni(Ⅱ)配位能力的强弱.△S的绝对值与中心离子Ni(Ⅱ)配位的或释放的醇分子数相关.计算结果对深化认识Ni(Ⅱ)的二胺和β-二酮类混合配体配合物热致变色的本质有所帮助.     

新型卟啉及其锌配合物的合成与性质研究

设计合成了一种新型的不对称卟啉(5,10,15-三苯基-20-{4-[6′-(4″-o-亚水杨基)-苯亚胺基]己氧基}苯基卟啉)及其锌配合物,并用¹H NMR、质谱及紫外-可见光谱进行表征。采用紫外-可见光谱滴定法,对锌卟啉与4种咪唑类小分子间的轴向配位反应热力学性质的研究表明：反应为放热、熵增加过程,4种咪唑类配体对锌卟啉的配位平衡常数按K^Θ(2-MeIm)>K^Θ(N-MeIm)>K^Θ(2-Et-4-MeIm)>K^Θ(Im)顺序依次减小。运用Z-扫描技术研究了新型卟啉及其锌配合物的非线性光学性质。     

反气相色谱法对八异辛基倍半硅氧烷热力学性质的表征

采用反气相色谱技术,以23种溶剂为探针分子,表征了八异辛基倍半硅氧烷(octaisooctyl-POSS)的热力学性质,包括摩尔溶解焓、分子间相互作用参数、质量活度系数、Hansen溶度参数,并有效判断了溶剂探针分子与共聚物分子间的相互作用以及共聚物在这些溶剂中的溶解性.结果表明,在实验温度范围内(343 ～393 K),烷烃、芳香烃、卤代烃类、乙醚以及乙酸甲酯是octaisooctyl-POSS的良溶剂,乙酸乙酯、乙酸正丙酯、乙酸正丁酯与乙酸正戊酯是中等溶剂,醇类、丙酮以及四氢呋喃是不良溶剂;Hansen溶度参数表明,octaisooctyl-POSS与烷烃分子强烈的色散作用使其在烷烃溶剂中具有优良的溶解性能.     

姜黄素对酪氨酸-过氧化氢-酶催化产物的荧光猝灭机理研究

酪氨酸在辣根过氧化物酶催化下被H2O2氧化为强荧光物质(产物S),姜黄素对其荧光产生猝灭作用,根据Stern-Volmer方程和荧光寿命法研究了姜黄素对产物S的荧光猝灭为静态猝灭.姜黄素与产物S的形成常数K=9.51×108 L/mol(25℃),结合点数n=1.94.探讨了产物S与姜黄素的反应机理,该反应的热力学参数△G=-56.11 kJ\5mol-1,△H=57.37 kJ\5mol-1,△S=365.9 J\5K-1\5mol-1,说明该反应是自发进行的吸热过程.     

Molecular Dynamics Simulations of Thermal Properties of Solid Uranium Dioxide

Molecular dynamics simulations are performed with the recently developed empirical interaction potential by Morelon et al. Thermodynamics properties of solid UO2 that have been assessed include melt point, density, enthalpy, heat capacity, lattice parameter variation with temperature, mean-square-displacement and diffusion coefficients of oxygen ion. The results are compared with the data in literature and it is suggested that the rigid ionic potential provides perfect results below the superionic range. The data showing thermodynamics properties will become unacceptable when the temperature is higher than 2500 K. Compared with the previous empirical potentials, the empirical potential developed by Morelon et al. improves the agreement of these data with the recommend ones.     

Thermodynamic Properties of Higher-Dimensional RN Black Holes

A general calculation formula of the heat capacity for the HRN black holes is derived. The heat capacities for Q, Φ＋ and γ- fixed are obtained. Assuming that the charge-mass ratio of fluctuation modes does not exceed the extremal value, the minimum charge-mass ratio of the black holes for which the heat capacity is positive is determined.     

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.