溶剂效应量子化学研究进展

本文就近年来溶剂效应的量子化学研究状况了综述。介绍了溶剂效应量子化学计算的两种方法－自洽反应场（ＳＣＲＦ）理论计算法和量子力学、分子力学结合模型（ＱＭ－ＭＭ模型）计算法以及它们的应用，并提出了溶剂效应理论研究今后可能发展的方向。     

薄层色谱溶剂系统优化方法进展

介绍了薄层色谱溶剂分类和溶剂强度参数的进展,综述了近年来优化溶剂系统的九种方法,并对它们进行了比较。     

KMgF3∶Ce^3＋,Eu^2＋的溶剂热合成与光谱性质

采用溶剂热法合成了Eu^2＋,Ce^3＋单掺和双掺KMgF3。分析了样品的结构与形貌。结果表明,所合成的样品均为单相,颗粒粒度分布集中。测定了它们的激发和发射光谱,结果显示：在单掺Eu^2＋的KMgF3中,没有观察到位于420nm附近由微量氧色心引起的宽带发射,只发现峰值位于360nm附近的锐峰线发射,说明溶剂热合成的KMgF3∶Eu中氧含量极低;在KMgF3双掺体系中由于Eu^2＋和Ce^3＋竞争吸收激发能,Eu^2＋把能量传递给Ce^3＋,存在Eu^2＋→Ce^3＋能量传递过程,观察到Ce^3＋的较强的发射带和Eu^2＋的较弱的线发射,并讨论了能量传递机理。     

正丁醇在N,N-二甲基甲酰胺+水溶液中的体积性质

测定了２９８。１５Ｋ时正丁醇＋Ｎ，Ｎ－二甲诺甲酰胺（ＤＭＦ）＋水三元系的密度求出正丁醇在ＤＭＦ＋水混合溶剂中的表观摩尔体积。观察２到：⑴Φ＾０．Ｅ～ｆｍ与ＶＤＭＦ＾Ｅ～ｆｍ之间存在相似变化关系，其中Φ２＾０．Ｅ为正丁醇的过量无限稀释表观摩尔体积，ＶＥＭＦ＾Ｅ为ＤＭＦ＋水二元系中ＤＭＦ的过量偏摩尔体积，ｆｍ为混合溶剂中ＤＭＦ的摩尔分数。⑵Ｂ１～ｆｍ与０６２１２＾０．Ｅ～ｆｍ之间存的反向变化关系。Ｂ１     

亚硝基苯与甲醛的反应机理和溶剂效应的理论研究

采用密度泛函理论方法RB3LYP/6-311＋＋G(d,p)研究了亚硝基苯与甲醛在单重态势能面上分别在气相和溶剂中的反应机理. 找到两条反应通道: 协同机理和分步机理, 均生成实验产物N-苯基氧肟酸C6H5NOHCHO. 计算结果表明: 亚硝基苯与甲醛在气相中分步机理为主要通道. 采用导电极化连续介质模型研究了反应体系在水、乙醇、乙腈、二氯甲烷、四氢呋喃、环己烷溶液中反应的溶剂化效应, 这些溶剂可降低反应的活化能, 但反应对溶剂的极性不敏感. 无论在气相还是溶剂中, 亚硝基苯与甲醛的分步机理为优势通道.     

Li＋在PC＋DMF混合溶剂中优先溶剂化的13C NMR研究

利用¹³C NMR光谱技术研究了Li^＋在碳酸丙烯酯(PC)＋N,N-二甲基甲酰胺(DMF)混合溶剂中的优先溶剂化现象. 根据溶剂分子中碳原子的化学位移随锂盐浓度的变化关系, 确定了与Li^＋发生配位的原子. 碳原子的配位位移值随混合溶剂组成的变化关系表明, 在LiClO₄＋PC＋DMF混合物中, DMF分子对Li^＋的溶剂化作用较PC分子强. 定量计算得到, 在n(PC)∶n(DMF)＝1∶1(摩尔比)的混合溶剂中, PC与DMF分子数在Li^＋第一溶剂化层中的比率为0.12, 说明Li^＋优先被DMF分子溶剂化.     

光诱导下卟啉蒽醌化合物分子内电子转移过程的研究（Ⅱ）…

用ＥＳＲ研究了几种新型卟啉蒽醌化合物低温下光诱导产生分子内电子转移产物Ｐ＾＋·－ＡＱ＾－·自由基对。对比研究了不同卟啉配体、金属卟啉、有机碱轴向配位和溶剂对电子转移的影响。     

3-甲基环状乙撑磷酸二酯醇解的反应途径研究

采用密度泛函理论和MP2方法研究了3-甲基环状乙撑磷酸二酯(MEP)与甲醇的反应途径: (I) CH3O－＋MEP; (II) CH3OH＋MEP; (III) CH3O－＋HMEP (MEP的质子化形式); (IV) CH3OH＋HMEP. 在B3LYP/6-31＋＋G(d,p)水平上优化了四条反应途径的反应物、中间体、过渡态及产物的几何构型, 并在同水平上进行了自然电荷分析, 然后在MP2/6-311＋＋G(3df,2p)水平上计算了各驻点的单点能. 采用极化连续介质模型(PCM)研究了各途径在苯、甲醇和水溶液中的溶剂化效应. 计算结果表明, 溶剂效应使途径(I)的自由能垒降低, 而使途径(II)和(IV)的决速步骤的自由能垒升高. 在气相和苯溶剂中途径(IV)是反应的优势途径, 在甲醇和水溶剂中途径(I)则成为最优. 研究结果进一步表明实验条件下途径(II)与(IV)对总醇解反应的贡献相当.     

用最优化方法选择磺胺类药物的薄层色谱溶剂系统

薄层色谱是药学工作者最常用的分离分析手段,而溶剂系统的选择则是薄层色谱中最重要的问题。但目前在此问题上,人们往往只凭借经验而无比较实用的系统化方法可循,若实验者的经验较少,则会在溶剂系统选择上浪费大量时间或选出的溶剂系统不够合理。因此,笔者等曾提出一种比较实用的系统化方法:即利用均匀设计试验法选择溶剂系统组分,再利用单纯形优化法选择溶剂系统配比。本文通过对磺胺类药物的成功分离,进一步验证了该方法的可行性。     

溶剂性质对星形聚电解质构象的影响

采用分子动力学方法模拟仿真溶剂对星形聚电解质构象的影响.选择的溶剂是从良溶剂到不良溶剂.研究了溶剂性质对单体的密度曲线、均方末端距、均方旋转半径、均方位移和系统渗透压的影响,结果表明星形聚电解质的构象随着溶剂参数β的增加而逐渐收缩,另外随着溶剂参数β的不断变大,系统中反离子的扩散能力不断下降,反离子凝聚能力增强,系统的...     

溶剂对SBS溶液浇铸膜形态结构及性能影响

聚苯乙烯 聚丁二烯 聚苯乙烯 (ＳＢＳ)嵌段共聚物所兼具的高弹性与热塑性来源于其独特的微观相分离结构 ,其形态结构与性能的关系长期以来一直倍受人们的关注 .对于这种微相分离体系 ,除了传统意义上的良溶剂 (对两种嵌段均具有良好的溶解性 ,又称非选择性溶剂 )与不良溶剂外 ,还存在着对两种嵌段中的一种溶解性较好 ,对另一种溶解性较差的选择性溶剂[1,2 ].在溶液浇铸成膜过程中 ,不同溶剂与组成共聚物的两种嵌段的相互作用参数的差异将导致溶液中大分子构象的差异以及微观相分离过程的差异 ,从而影响浇铸膜的形态以及性能[3].本文首先利用…     

Enthalpy of solution of 1,4-naphthoquinone in CO2 + n-pentane in the critical region of the binary mixture: mechanism of solubility enhancement

The enthalpy of solution (Delta(solv)H(m)) and solubility of 1,4-naphthoquinone in CO(2) + n-pentane were measured at 308.15 K in the critical region of the binary fluid. In order to study the effect of phase behavior of the mixed solvent on Delta(solv)H(m), the experiments were carried out in the supercritical (SC) and subcritical region of the binary solvent. The density of the mixed solvent in different conditions was determined. The isothermal compressibility (K(T)) of the mixed solvent, and the partial molar volume (V(n-pentane)) of n-pentane in the solution were calculated. It was demonstrated that the Delta(solv)H(m) was negative in all conditions. Delta(solv)H(m) is nearly independent of pressure or density in all the solvents in a high-density region, in which compressibility of the solvent is very small; this indicates that the intermolecular interaction between the solvent and the solute is similar to that for liquid solutions. It is very interesting that Delta(solv)H(m) in the mixed SC fluid differs from the Delta(solv)H(m) in mixed subcritical fluids. The absolute value of Delta(solv)H(m) in the mixed SC fluid is close to that in pure SC CO(2) in the high-density region, and is much lower than that in pure SC CO(2) in the low-density region. In the mixed subcritical fluids, the Delta(solv)H(m) is also close to that in the pure CO(2) in the high-density region. However, at the same density, the absolute value of Delta(solv)H(m) in the binary subcritical fluid is larger than that in pure CO(2) in the high-compressible region of the mixed solvent. The main reason for this is that the degree of clustering in the SC solutions is small at the density in which the degree of clustering is large in the subcritical solutions. It can be concluded that solubility enhancement by n-pentane in the mixed SC fluid is entropy driven. In contrast, the solubility enhancement by n-pentane in subcritical fluids is enthalpy driven. The intermolecular interaction in the SC solutions and subcritical solutions can be significantly different even if their densities are the same.     

Linear free energy relationship of the energy of the CTTS transition of Halide ions with the solvatochromic parameter α

A linear free energy relationship was found betweenv _max, the energy of the absorption maximum of chloride, bromide, or iodide ion in various solvents, and the solvatochromic parameter which is a measure of the hydrogen bond donor ability of the solvent. The relationships are: for chloride,v _max=6.99+50.16 kK; for bromide,v _max=5.52+45.20 kK; for iodide,v _max=5.02+40.33 kK. The correlation ofv _max for iodide ion with gave a larger correlation coefficient and smaller standard deviation than a correlation with the E _T (30) parameter of Dimroth. From the values ofv _max for iodide ion and the solvated electron in liquid ammonia at 25°C, these correlations indicate a preliminary value of 0.00 for the parameter of liquid ammonia. This had not been reported before and is lower than expected from a general knowledge of the physical and chemical properties of liquid ammonia but is consistent with a more detailed consideration and recent gas phase measurements of hydrogen bond donor strength.     

Strategies to model the near-solute solvent molecular density/polarization

The solvent molecular distribution significantly affects the behavior of the solute molecules and is thus important in studying many biological phenomena. It can be described by the solvent molecular density distribution, g, and the solvent electric dipole distribution, p. The g and p can be computed directly by counting the number of solvent molecules/dipoles in a microscopic volume centered at r during a simulation or indirectly from the mean force F and electrostatic field E acting on the solvent molecule at r, respectively. However, it is not clear how the g and p derived from simulations depend on the solvent molecular center or the solute charge and if the g(F) and p(E) computed from the mean force and electric field acting on the solvent molecule, respectively, could reproduce the corresponding g and p obtained by direct counting. Hence, we have computed g, p, g(F), and p(E) using different water centers from simulations of a solute atom of varying charge solvated in TIP3P water. The results show that g(F) and p(E) can reproduce the g and p obtained using a given count center. This implies that rather than solving the coordinates of each water molecule by MD simulations, the distribution of water molecules could be indirectly obtained from analytical formulas for the mean force F and electrostatic field E acting on the solvent molecule at r. Furthermore, the dependence of the g and p distributions on the solute charge revealed provides an estimate of the change in g and p surrounding a biomolecule upon a change in its conformation.     

The effects of solvent chemistry on the impedance of aged gels

Sols were prepared in the system TMOS:H₂O:SOLV:HCl with molar ratios of 1:4:3:0.0005 for SOLV = MEOH and DMF. The sols were cast into cuvettes and covered with parafilm during gelation and aging. The bulk resistance of aged samples was determined by impedance spectroscopy at room temperature. The use of different solvents in the synthesis of silica gels leads to considerable variation in bulk resistance. The results of solvent exchange were found to depend greatly upon the nature of the solvent.     

高分子的良溶剂和不良溶剂的两种定义辩析

介绍了目前国际学术界存在的对高分子溶液体系的溶剂优劣性的两种判断标准 ,即相互作用参数χ=1 /2和χ=0 ,前者基于混合自由能 ,后者基于混合热。作者阐明了其倾向于采用后者的观点 ,而后者在目前国内所有高分子物理学教科书中均未被介绍。     

Development of Abraham model correlations for describing the transfer of molecular solutes into propanenitrile and butanenitrile from water and from the gas phase

Experimental solubilities were measured for 20 crystalline organic solutes dissolved in propanenitrile and for 13 crystalline organic solutes dissolved in butanenitrile at 298.15 K. Infinite dilution activity coefficient data for solutes dissolved in propanenitrile and butanenitrile have been compiled from the published chemical and engineering literature and converted into gas-to-liquid partition coefficients and water-to-organic solvent partition coefficients through standard thermodynamic relationships. Abraham model correlations were developed for describing solute transfer into both propanenitrile and butanenitrile by combining our measured solubility data with the partition coefficients that we calculated from the published activity coefficient data. The derived Abraham model correlations were found to back-calculate the observed partition coefficients and molar solubility data to within 0.14 log units.     

用分子动力学模拟方法研究磺酰脲化合物在溶液中构象的变化

农药化合物通常在溶液中起作用 ,由于溶剂的作用 ,其结构与在固体状态下有很大不同 ,因此研究农药化合物分子在溶液中结构的变化 ,对于了解农药作用机理以及与受体的相互作用是非常有意义的 .磺酰脲是一种超高效低毒 ,有着重要用途的除草剂 ,因而得到了广泛的应用与研究 .我们曾对其结构与性能的关系进行了系统的研究 ,并在此基础上建立了一个能解释若干实验规律的初级作用模型 [1] .但是以往有关结构的研究都是针对晶体和真空中的自由构象进行的 .由于在实际溶液中的结构情况会有所不同 ,因此 ,研究分子在不同溶液中的行为具有十分重要的意…     

溶剂气浮分离技术研究现状与发展方向

溶剂气浮技术是一种较为简捷有效的水中微量、痕量组分分离与富集方法, 也可用于水中有机污染物的去除, 它在许多方面优于传统的萃取方法。本文比较全面地综述了溶剂气浮技术的装置、影响因素、机理及其应用, 并指出了溶剂气浮技术的发展方向。