氨基酸在水/DMF混合溶剂中的焓相互作用

氨基酸是组成蛋白质的基本结构单位。溶质－溶质相互作用是氨基酸溶液热力学性质研究的一个主要方面，氨基酸的稀释焓是与之相应的一个重要热力学性质。目前，研究多集中在水溶液中，研究表明具有非极性侧链氨基酸和具有极性侧链氨基酸的偏摩尔焓是完全不同的，随着氨基酸...     

盐酸在氨基酸水溶液中热力学性质的研究——Ⅰ.甘氨酸+盐酸+水体系

生物体液可看作是由多种离子与氨基酸、蛋白质组成的混合电解质溶液,研究电解质或离子与这些氨基酸、蛋白质间的相互作用对了解生物体液内复杂的作用机理,揭示许多生命现象具有重要意义。1978年以来,Kelley采用有液体接界的电池研究了几种氨基酸或肽与一些碱金属氯化物的相互作用自由能,为研究电解质与氨基酸、蛋白质间的相互作用奠定了基础。研究溶质的迁移热力学性质是了解溶质-溶剂间相互作用以及溶液微观结构的常用手段。以氨基酸水溶液作为含水离子溶剂,用电动势法研究电解质从水到该溶液中的迁移热力学性质,进而研究电解质与氨基酸间的相互作用是可行的,目前这方面的研究工作很少见文献报导。本文通过测定电池:     

葡萄糖与杂环化合物在甲酰胺中的焓相互作用参数

由于糖具有特殊的生物和生理性质 ,在工业生产中已有广泛应用 ,故其溶液热力学性质已成为人们感兴趣的研究课题之一 .糖在水溶液中的热力学性质已见文献报道 [1] ,但在非水体系中的有关数据则较少报道 .研究表明 ,溶剂介质的变化对溶质的溶剂化状态和溶质间相互作用的影响较大 ,选用酰胺为溶剂可以获得模拟蛋白质环境条件下的溶质 -溶剂、溶质 -溶质间相互作用的信息 [2～ 4] .本文利用微量量热法测得了葡萄糖在杂环化合物与甲酰胺的混合溶剂中的溶解焓 .如果把杂环化合物作为 x,葡萄糖作为 y,按照 Mc Millan- Mayer[5 ] 理论 ,1 mol葡萄…     

α-氨基酸在水-乙醇中羟基质子化热力学

α 氨基酸为重要的两性物质 ,其酸碱性质对于维持生物体内的酸碱平衡和蛋白质的生物活性起着十分重要的作用．α 氨基酸在纯水溶剂中的质子化反应热力学性质已进行了广泛的研究［１ -６］,但对球形蛋白来说 ,蛋白亚基间的作用是处在一个大量但不完全由水组成的非水环境中 ,因此 ,研究氨基酸在水 有机物混合溶剂中的质子化热力学性质具有重要意义．但这方面的工作 ,特别是用量热法直接研究溶剂对质子化焓变的影响开展得不多．本文选择乙醇和水组成的混合溶剂模拟蛋白质亚基所处的介质环境 ,利用精密微量流动热量计测定２９８．１５Ｋ时甘氨…     

气相色谱法测定醇在环丁砜＋KCNS混合固定液中的无限稀释活度系数

在有限浓度条件下,含醇多元系的热力学性质由于液态醇的缔合结构而显得复杂。醇浓度无限稀时,为研究排除醇的自身缔合作用时溶质-溶剂相互作用,提供了特殊的条件。许多作者用气液色谱法(GLC)测定了这种条件下溶质在非电解质溶液中的无限稀释热力学参数,而对电解质溶液则很     

丝氨酸在蔗糖水溶液中的稀释焓

利用LKB 2277生物活性检测仪分别测定了298.15 K时丝氨酸在不同组成的蔗糖水溶液中的稀释焓, 利用McMillan-Mayer理论,计算了丝氨酸在不同组成的蔗糖水溶液中的焓对相互作用系数,并与其在葡萄糖水溶液中的焓对相互作用系数h2进行了比较.结果表明,丝氨酸在蔗糖和葡萄糖水溶液中的焓对相互作用系数h2都是负值,并且随着糖浓度的增加,h2系数的绝对值逐渐减少.根据溶质-溶质相互作用和溶质-溶剂相互作用对结果进行了解释.     

肌醇在氯化钠水溶液中的稀释焓和焓对相互作用

应用微量热法测定了298.15K时肌醇在纯水和氯化钠水溶液中的稀释焓,根据McMillan-Mayer理论计算了肌醇在不同浓度的氯化钠溶液中的2到4阶焓相互作用系数.结果表明,肌醇在氯化钠溶液中的焓对相互作用系数h2均为负值,并且随着氯化钠浓度的增大,h2的值呈增大趋势.根据溶质-溶质相互作用和溶质-溶剂相互作用对焓对相互作用系数的变化趋势进行了解释.     

葡萄糖与醇在甲酰0胺溶液中的焓相互作用参数

利用量热法测定了298．15K时葡萄糖在一些醇（甲醇、乙醇、1－丙醇、1－丁醇）与甲酰胺的混合溶剂中的溶解热。采用McMillan-Mayer方法,将溶液热力学过量性质与溶液中粒子的相互作用参数相关联,求得了粒子间的焓对相互作用参数和三分子相互作用参数,并就溶质－溶质间的相互作用及溶剂的影响进行了讨论。     

D-甘露醇与D-山梨醇在纯水和卤化钠水溶液中的稀释焓

应用等温流动微量热技术测定了298.15 K下D-甘露醇和D-山梨醇在纯水和卤化钠水溶液中的稀释焓,利用M cM illan理论计算了D-甘露醇和D-山梨醇在纯水和卤化钠水溶液中焓相互作用系数.结果表明,D-甘露醇和D-山梨醇在纯水和卤化钠水溶液中的二阶焓相互作用系数均为正值,并随着卤离子半径的变化而相应变化;且同种溶剂中,D-甘露醇的二阶焓相互作用系数要大于D-山梨醇的.结合两分子结构的差异,通过溶质-溶质相互作用和溶剂-溶质相互作用对这一结果进行了讨论.     

水溶液中氯化铯与糖(D-葡萄糖、D-果糖和蔗糖)相互作用的热力学参数研究(298.15K)

用钾离子选择性电极为测量电极,氯离子选择性电极为参比电极,设计组成无液接电池,用于氯化铯-糖(葡萄糖、果糖及蔗糖)-水三元体系中组分之间弱相互作用的热力学性质研究.通过测量电池的电动势获得氯化铯在糖水溶液中的活度系数,根据Scatchard理论推测出糖在氯化铯水溶液中的活度系数.通过Mcmillan-Mayer理论将体系的过量热力学函数与溶液中溶质的相互作用参数相关联,获得氯化铯与糖在水溶液中相互作用的吉布斯自由能参数及盐效应常数.运用结构相互作用模型、糖的羟基水化效应及色散能理论,探讨体系中溶质-溶质、溶质-溶剂间的相互作用及糖的立体结构和金属离子体积对热力学参数的影响.     

Molecular dynamics study of hydration in ethanol-water mixtures using a polarizable force field

The abnormal physicochemical characteristics of ethanol solvation in water are commonly attributed to the phenomenon of hydrophobic hydration. To investigate the structural organization of hydrophobic hydration in water-ethanol mixtures, we use molecular dynamics simulations based on detailed atomic models. Induced polarization is incorporated into the potential function on the basis of the classical Drude oscillator model. Water-ethanol mixtures are simulated at 11 ethanol molar fractions, from 0.05 to 0.9. Although the water and ethanol models are parametrized separately to reproduce the vaporization enthalpy, static dielectric constant, and self-diffusion constant of neat liquids at ambient conditions, they also reproduce the energetic and dynamical properties of the mixtures accurately. Furthermore, the calculated dielectric constant for the various water-alcohol mixtures is in excellent agreement with experimental data. The simulations provide a detailed structural characterization of the mixtures. A depletion of water-water hydrogen bonding in the first hydration shell of ethanol is compensated by an enhancement in the second hydration shell. The structuring effect from the second solvation shell gives rise to a net positive hydrogen-bonding excess for ethanol molar fractions up to approximately 0.5. For larger molar fractions, the second hydration shell is not sufficiently populated to overcome the net H-bond depletion from the first shell.     

甘氨酸在DMF/水和乙醇/水混合溶剂中的焓对相互作用

利用LKB2277生物活性检测仪对298.15K时甘;氨酸在纯水,DBF/水和乙醇/水混合溶剂DBF(或乙醇的质量分数为0.05~0.45,以10%递增)中的稀释焓进行了测定,并利用维里展开式法关联得到焓对相互作用系数值.结果表明,焓对相互作用系数h~2与溶剂的结构性质密切相关.在DBF/水混合物溶剂中,h~2随DBF含量的增加而变得更负;而在乙醇/水混合溶剂中,h~2与乙醇含量近似呈抛物线型关系,在乙醇质量分数为0.25时h~2达到一个极小值。     

水-乙醇混合溶剂中过氧化氢酶活性与构象的研究

用微量热法和荧光法分别测定了水-乙醇混合溶剂中过氧化氢酶活性与构象的变化。结果表明,随着乙醇浓度的增大,过氧化氢酶酶促反应的米氏常数K~m有所增大,而反应速率常数k~2及酶的催化活性则明显降低;336nm处的相对荧光强度不断增强,酶分子的构象发生了变化,其结构渐趋松散。乙醇对过氧化氢酶活性的影响乃是乙醇的竞争性抑制和溶剂效应引起的酶构象变化共同作用的结果。     

Thermodynamics of R-(+)-2-(4-Hydroxyphenoxy)propanoic Acid Dissolution in Methanol,Ethanol, and Methanol-Ethanol Mixture

The solubilities of R-(+)-2-(4-hydroxyphenoxy)propanoic acid (D-HPPA) in methanol, ethanol and various methanol-ethanol mixtures are determined in the temperature range from 273.15 to 323.15 K at atmospheric pressure using a laser detecting system. The solubilities of D-HPPA increase with increasing mole fraction of ethanol in the methanol–ethanol mixtures. Experimental data were correlated with Buchowski-Ksiazczak λh equation and modified Apelblat equation; the first one gives better approximation for the experimental results. The enthalpy, entropy and Gibbs free energy of D-HPPA dissolution in methanol, ethanol and methanol-ethanol mixtures were also calculated from the solubility data.     

Investigation and radiometric determination of saturated and unsaturated aliphatic dicarboxylic acids

Radiometric determination of saturated and unsaturated aliphatic dicarboxylic acids has been developed using a precipitation reaction. The influence of the conditions of precipitation, the composition of the calcium salts of the acids, thepH, and the composition of solvent mixtures were investigated. The solubility of the calcium salts diminished with an increase of the ethanol content in weakly alkaline medium. Linear relations were found between the solubilities of the calcium salts and the dielectric constants of the solvent mixtures. The calcium salts have poor solubilities atpH 9 in 20% aqueous ethanol containing ammonia. The radiometric titrations were carried out in 0.05M solutions, using 0.05M ⁴⁵Ca-labelled CaCl₂ solution in 20% aqueous ethanol. The titrations were done in an apparatus suitable for the detection of soft β-emitting isotopes.     

Densities and Volumetric Properties of Binary and Ternary Mixtures of Diisopropyl Ether, Fluorobenzene, α,α,α-Trifluorotoluene, and Ethanol at Temperature 298.15 K and Pressure 101 kPa

Excess molar volumes of binary mixtures of (fluorobenzene + ethanol), (fluorobenzene + diisopropyl ether), (α,α,α-trifluorotoluene + ethanol), (diisopropyl ether + ethanol), (α,α,α-trifluorotoluene + diisopropyl ether), and the ternary mixtures of (fluorobenzene + diisopropyl ether + ethanol), and (α,α,α-trifluorotoluene + diisopropyl ether + ethanol) were evaluated from density data. The densities were measured with a vibrating-tube densimeter at the temperature 298.15 K and the pressure 101 kPa.The values of the mixing volumes of the ternary systems were predicted in terms of empirical equations using binary solution data alone. The extent of chemical associations among the molecules forming the mixtures is discussed.     

水/乙醇混合溶剂中氨基酸离解的取代基效应

用LKB-2277BioActivityMonitor测定了298.15K时甘氨酸,丙氨酸和丝氨酸在水/乙醇混合溶剂中的离解焓,计算了相应的离解熵。根据三个氨基酸分别与某一参考酸之间的质子交换反应,重点讨论了溶剂结构变化对取代基效应焓,熵变化的影响。实验结果表明在水/乙醇混合溶剂的最大结构化区域,取代基效应最为显著。认为在混合溶剂的富水区大块的似冰山结构的水分子簇的寿命大大延长。     

Peculiar properties of sodium lodide in alcohols,acetone, and alcohol-water mixtures at lower temperatures

The enthalpies of solution of sodium iodide in methanol, ethanol and acetone and in mixtures of methanol and ethanol with water were measured over wide ranges of electrolyte concentration and temperature. Standard enthalpies of solution, transfer enthalpies of NaI from alcohols to alcohol-water mixtures, and temperature coefficients of enthalpies of solution have been calculated. Thermodyanmic characteristics of solution and solvation of the Na⁺ and I^– ions in acetone and ethanol were determined at 243–298 K. It is noted that at lower temperatures the disruption of solvent structure by ions is a local effect. The presence of negative solvation of the Na⁺ and I^– ions in alcohol-water mixtures at lower temperatures is demonstrated.     

Measurements and predictions of density and carbon dioxide solubility in binary mixtures of ethanol and n-decane

The solubility of carbon dioxide (CO₂) in binary mixtures of ethanol and n-decane has been measured using an in-house developed pressure-volume-temperature (PVT) apparatus at pressures up to 6 MPa and two different temperatures (303.2 and 323.2 K). Three different binary mixtures of ethanol and n-decane were prepared, and the densities of the prepared mixtures were measured over the studied pressure and temperature ranges. The experimental data of CO₂ solubility in the prepared mixtures and their saturated liquid densities were then reported at each temperature and pressure. The solubility data indicated that the gas solubility reduced as the ethanol mole fraction in the liquid mixture increased. The dissolution of CO₂ in the liquid mixtures resulted in the increase in the saturated liquid densities. The impact of gas dissolution on the saturated liquid densities was more pronounced at the lower temperature and lower ethanol compositions. The experimental solubility and density data were compared with the results of two cubic equations of state (EOSs), Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR). The modeling results demonstrated that both EOSs could predict the solubility data well, while the saturated liquid densities calculated with the PR EOS were much better than those predicted with the SRK EOS.