Interactions of Some Amino Acids with Aqueous N,N-Dimethylacetamide Solutions at 298.15 and 308.15 K: A Volumetric Approach

The apparent molar volumes, V _φ , of glycine, L-alanine and L-serine were obtained in aqueous 0 to ∼4 mol⋅kg⁻¹ N,N-dimethylacetamide (DMA) solutions from density measurements at 298.15 and 308.15 K. The standard partial molar volume, V _φ ^o, and standard partial molar volumes of transfer, Δ_tr V _φ ^o, were determined for these amino acids. It has been shown that hydrophilic-hydrophilic interactions between charged groups of the amino acids and the —CON= group of DMA are predominant in the case of glycine and L-serine, but for L-alanine the interactions between its side group (—CH₃) and DMA are predominant. An increase in temperature increases the standard partial molar volumes but decreases the transfer volumes of the amino acids. The results have been interpreted in terms of cosphere overlap model.     

Interactions of Peptides and Lysozyme with Aqueous Tetraethylammonium Bromide at 298.15 K

The apparent molar volumes, V _{ø, 2}, of gly-leu, gly-gly-leu and the partial specific volume ν^° of hen-egg-white lysozyme have been determined in aqueous of TEAB solutions by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes V _2,m ^o for the peptides in aqueous TEAB solutions and the standard partial molar volumes of transfer Δ_tr V _2,m ^o of the peptides from water to aqueous TEAB solutions. The results on Δ_tr V _2,m ^o of peptides from water to aqueous TEAB solutions have been interpreted in terms of ion-ion, ion-polar, hydrophilic-hydrophilic and hydrophobic-hydrophobic group interactions. In order to supplement this information, enthalpies of transfer of aqueous peptides from water to TEAB solution have been determined at 298.15 K using a VP-ITC titration calorimeter. The data on partial molar volumes and enthalpies of transfer have been discussed in light of various interactions operating in the ternary system of peptides, water and TEAB. The partial specific volume of transfer of lysozyme from water to aqueous TEAB solutions also indicates the predominance of hydrophobic interactions.     

Interactions of Some Amino Acids with Aqueous Osmoprotectant Proline at 298.15 K: Volumetric and Calorimetric Studies

Apparent molar volumes of a homologous series of amino acids in aqueous proline solutions have been obtained from densities at 298.15 K, measured with a vibrating-tube digital densimeter. These data have been used to deduce the partial molar volumes of transfer from water to aqueous proline solutions; these partial molar volumes of transfer are found to be positive for glycine, alanine, α-amino-n-butyric acid and valine, whereas they are negative for leucine. The number of water molecules hydrated to the amino acids was estimated from the partial molar volume data. In order to supplement this information, enthalpies of transfer of aqueous amino acids from water to 0.1, 2.25 and 1 mol⋅dm⁻³ aqueous proline have been determined at 298.15 K using a VP-ITC titration calorimeter. The data on the partial molar volumes and enthalpies of transfer are discussed in terms of various interactions operating in the ternary mixtures of amino acids, water and proline.     

Volumetric Properties of Aqueous 2-Chloroethanol Solutions and Volumes of Transfer of Some Amino Acids and Peptides from Water to Aqueous 2-Chloroethanol Solutions

Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V ₂ ^o = 55.05 ± 0.02 cm³-mol^–1, (V ₂ ^o/T)_p = 0.01486 ± 0.00318 cm³-K^–1-mol^–1, and (² V ₂ ^o/T ²)_p = 0.02972 ± 0.00318 cm³-K^–2-mol^–1. Partial molar volumes of transfer from water to 1 mol-dm^–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol.     

Volumetric Properties of Amino Acids and Hen-Egg White Lysozyme in Aqueous Triton X-100 at 298.15 K

The apparent molar volumes, V_,2, of glycine, alanine, -amino-n-butyric acid, valine, leucine, and lysine monohydrochloride have been determined in aqueous solutions of 0.05, 0.1, and 0.4 mol-kg^–1 Triton X-100 (TX-100), and the partial specific volume, v⁰, of hen-egg-white lysozyme in 0.4 mol-kg^–1 TX-100 by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V_2,m⁰, for the amino acids in aqueous TX-100 solutions and the standard partial molar volumes of transfer, _tr V_2,m⁰, of the amino acids from water to the aqueous surfactant solutions. The linear correlation of V_2,m⁰ for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH₃⁺, COO^–), CH₂ group and other alkyl chains of the amino acids to V_2,m⁰. The results on _tr V_2,m⁰, of amino acids from water to aqueous TX-100 solutions have been interpreted in terms of ion–ion, ion–polar, hydrophilic–hydrophilic and hydrophobic–hydrophobic group interactions. For all the six amino acids studied, the values of _tr V_2,m⁰ from water to all the studied concentrations of aqueous TX-100 are small in spite of their different hydrophobic content, indicating an overall balance in interactions of zwitterionic/hydrophilic groups of amino acids with the hydrophilic groups of TX-100, and of hydrophobic and ionic/hydrophilic groups of the amino acids with hydrophobic groups of TX-100. Comparison of the interactions of the amino acids with nonionic, anionic and cationic surfactants has also been made and discussed. The partial specific volume of transfer of lysozyme from water to aqueous TX-100 solutions also indicates a balance of the hydrophobic and hydrophilic interactions in the protein–nonionic surfactant system.     

三种氨基酸在尿素水溶液中的体积性质

精密密度法详细测定甘氨酸、L-丙氨酸、L-丝氨酸在尿素水溶液中的表观摩尔体积,计算了三种氨基酸从水到尿素水溶液的迁移偏摩尔体积,结合前期的氨基酸从水到尿素水溶液的迁移焓,探讨尿素水溶液的结构特点及其对氨基酸与尿素在水溶液中相互作用的影响。结果表明,尿素分子在水溶液中自缔合,引起溶剂结构的变化并削弱其与氨基酸分子的结构相互作用,造成氨基酸从水到尿素水溶液的迁移偏摩尔体积和迁移焓随尿素浓度的增加而出现多个变化点,这一效应随着氨基酸疏水性的增强而增大,表明氨基酸的疏水性越强,其与尿素相互作用引起的去水化作用越明显。     

298.15 K甘氨酰二肽在乙酸钠水溶液中的体积性质

测定了298.15 K三种甘氨酰二肽(甘氨酰甘氨酸、甘氨酰-L-缬氨酸和甘氨酰-L-亮氨酸)在0.5, 1.0, 1.5和2.0 mol•kg－1乙酸钠水溶液中的密度, 计算了这些肽在乙酸钠水溶液中的表观摩尔体积, 标准偏摩尔体积, 标准偏摩尔转移体积, 理论水化数和体积相互作用参数. 结果表明: 甘氨酰二肽的标准偏摩尔体积和标准偏摩尔转移体积均随乙酸钠浓度的增加而增大, 溶液中离子与肽带电基团/甘氨酰基团(CH2CONH)之间的相互作用大于离子与肽的非极性基团间的相互作用, 乙酸钠和甘氨酰二肽之间主要是对相互作用. 利用共球交盖模型对所研究的肽与乙酸钠之间的体积相互作用进行了解释. 利用氨基酸的标准偏摩尔体积值, 对二肽的标准偏摩尔体积进行了估算, 发现计算值与实验值一致.     

氨基酸在木糖醇水溶液中的体积性质

应用精密数字密度计测定了298.15 K时甘氨酸、L-丙氨酸或L-缬氨酸与不同组成的木糖醇-水混合溶剂构成的三元系溶液的密度, 计算了氨基酸的表观摩尔体积、极限偏摩尔体积、迁移偏摩尔体积和水化数. 根据结构水合作用模型讨论了迁移偏摩尔体积和水化数的变化规律. 结果表明, 氨基酸两性离子部分与木糖醇羟基间的相互作用占主导地位, 且随木糖醇浓度的增大而增大. 氨基酸在木糖醇水溶液中的迁移偏摩尔体积为正值, 甘氨酸的迁移偏摩尔体积大于L-丙氨酸和L-缬氨酸的. 氨基酸在木糖醇水溶液中的水化数随溶液中木糖醇浓度的增加而减小.     

Enthalpic Interactions of Amino Acids with Glucose in Aqueous Solutions at 298.15 K

The enthalpies of mixing of aqueous glucose solutions and six kinds of aqueous amino acid solutions (glycine, L-alanine, L-serine, L-valine, L-proline, and L-threonine) and their respective enthalpies of dilution have been determined at 298.15 K using flow microcalorimetry. The experimental data have been analyzed in terms of the McMillan–Mayer model to obtain the heterotactic interaction coefficients. The results have been interpreted from the point of view of solute–solute interactions.     

甘氨酸和L-丝氨酸在LiNO3,NaNO3和KNO3水溶液中的体积性质

用Anton Paar DMA 55精密数字密度计测定了甘氨酸和L-丝氨酸在LiNO3, NaNO3和KNO3水溶液中的密度, 计算了氨基酸的表观摩尔体积、极限偏摩尔体积、迁移偏摩尔体积、理论水化数和体积作用系数. 根据静电相互作用和结构水合作用模型讨论了氨基酸的侧链和阳离子的性质对迁移偏摩尔体积的影响. 结果表明, 甘氨酸和L-丝氨酸在3种硝酸盐水溶液中的迁移体积均为正值, 并且随着盐溶液浓度的增大而增大. 氨基酸两性离子端基和阴阳离子间的静电作用对迁移体积的贡献是主要的, 静电作用削弱了两性离子带电中心对周围水分子的电致收缩效应, 造成氨基酸的理论水化数随盐溶液浓度的增加而减小. L-丝氨酸的侧链与离子之间的亲水-亲水相互作用对迁移体积有小的正贡献, 使得在同一种盐溶液中L-丝氨酸的迁移体积较甘氨酸的大. 同一种氨基酸在NaNO3和KNO3水溶液中的迁移体积较在LiNO3水溶液中的大, 主要是由于Li＋难以去水化. 在低浓度的盐溶液中氨基酸与盐之间的相互作用以1∶1形式为主, 随着溶液浓度的增大, 1∶2形式的相互作用逐渐增大     

298.15 K下氨基酸在D-木糖水溶液中的体积性质

报道了甘氨酸、L-丙氨酸和L-丝氨酸3种典型氨基酸在D-木糖水溶液中的体积性质.     

水溶液中氨基酸与甲脲的焓相互作用

用LKB-2277精密微热量计测定了298.15 K时甘氨酸、L-丙氨酸、L-丝氨酸、L-缬 氨酸、L-苏氨酸和L-脯氨酸六种α-氨基酸分别与甲脲分子在水溶液中的混合过程焓变及 这些溶质分子在水溶液中的稀释焓.实验数据根据McMillan-Mayer理论进行回归分析,得到 各级交叉焓相互作用系数.讨论了不同氨基酸与甲脲分子的相互作用机制.结果表明,氨基酸 的两性离子部分、α-碳上的非极性脂肪侧基、极性的羟基侧基和五元吡咯环结构对交叉焓 对作用系数hxy具有不同贡献.与尿素相比,甲脲分子中-CH3基团的引入明显增强了分子的 疏水性.     

Interactions of D-Maltose and Sucrose with Some Amino Acids in Aqueous Solutions

Calorimetric titrations have been performed at 298.15 K in aqueous solutions to derive the stability constants and thermodynamic parameters of the interactions of D-maltose and sucrose with some amino acids (glycine, DL-alanine, DL-leucine, and L-serine). The apparent molal volumes of the disaccharides in dilute aqueous solutions of the amino acids have been determined from density measurements at 298.15 K. In contrast to D-maltose, sucrose was found to associate with the amino acids and these associated species are preferentially entropy stabilized. These results are interpreted in terms of the influence of the nature of the solutes, their specific conformations, and hydration, on the ability of the disaccharides to form associated complexes with the amino acids.     

Partial Molar Volumes of Some of α-Amino Acids in Binary Aqueous Solutions of MgSO4·7H2O at 298.15 K

The apparent molar volume, V ^o _{φ, 2}, of glycine, alanine, α-amino-n-butyric acid, valine and leucine have been determined in aqueous solutions of 0.25, 0.5 and 1.0 mol⋅dm⁻³ magnesium sulfate, and the partial specific volume from density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volume, V ^o _2,m , group contribution of amino acids and partial molar volume of transfer, Δ_tr V _2,m ^o, from water to aqueous magnesium sulfate solutions. The linear correlation of V _2,m ^o for a homologous series of amino acids has been utilized to calculate the contributions of charged end groups (NH₃ ⁺, COO⁻), CH₂ - groups and other alkyl chains of amino acids to V _2,m ^o. The results for Δ_tr V _2,m ^o of amino acids from water to aqueous magnesium sulfate solutions have been interpreted in terms of ion-ion, ion-polar, hydrophilic-hydrophilic and hydrophobic-hydrophobic group interactions. The values of the standard partial molar volume of transfer for the amino acids with different hydrophobic contents, from water to aqueous MgSO₄ are in general positive, indicating the predominance of the interactions of zwitterionic/hydrophilic groups of amino acids with ions of the salt. The hydration number decreases with increasing concentration of salt. The number of water molecules hydrated to amino acids decreases, further strengthening the predominance of ionic/hydrophilic interactions in this system.     

二元体系C6H5CH3-DMF在293.15 K时的体积性质

利用Anton Paar DMA4500振动管密度计测量了293.15 K时二元体系甲苯-N,N-二甲基甲酰胺(C6H5CH3-DMF)在C6H5CH3(摩尔分数0~1)中的溶液密度, 利用最小二乘法关联了溶液密度与组成的函数关系, 关联精度为±0.005 kg/m3. 通过密度数据分别计算了二元体系中C6H5CH3和DMF的表观摩尔体积, 并利用非线性最小二乘拟合法, 分别拟合得到了优化的C6H5CH3和DMF的表观摩尔体积和摩尔分数的函数关系, 以及C6H5CH3和DMF的表观摩尔体积和质量分数的函数关系. 通过对函数关系的极限运算得到了C6H5CH3和DMF的极限偏摩尔体积、标准偏摩尔体积和摩尔体积. 还计算了不同组分下体系的超额摩尔体积, 数据可用四参数Redlich-Kister方程关联拟合得到方程系数. 计算关联了C6H5CH3和DMF的超额偏摩尔体积与摩尔分数的关系. 由三参数多项式极限法得到组分的极限超额偏摩尔体积值与Redlich-Kister系数法得到的值在误差范围内一致.     

Enthalpic Interaction of Amino Acids with 2-Chloroethanol in Aqueous Solutions at 298.15 K

The enthalpies of mixing have been determined for five kinds of aqueous amino acids solutions (glycine, L-alanine, L-valine, L-serine, and L-proline) with 2-chloroethanol by an LKB-2277 Bio Activity Monitor at 298.15 K. In addition, the enthalpies of dilution at 298.15 K of aqueous solutions containing the five kinds of amino acids and 2-chloroethanol have been obtained. The heterotactic enthalpic pairwise interaction coefficients of the virial expansion of excess enthalpy were evaluated and interpreted from the point of view of solute–solute interactions. In comparison with ethanol, 2-chloroethanol shows a stronger exothermic interaction with amino acids because of its hydrophilic Cl atom and a more acidic –OH group. Using the additivity groups concept by Savage and Wood (SWAG), contributions of each of functional group of the amino acids and ethanol and 2-chloroethanol have been estimated.     

不同温度下水溶液中树胶醛糖与HCl相互作用的体积性质

采用密度法研究了在278.15—318.15 K(间隔10 K)下树胶醛糖+HCl+水三元溶液的密度、树胶醛糖在盐酸(0.2—2.1087 mol/kg)中的表观摩尔体积VΦ,A、标准表观摩尔体积VΦ,A0和树胶醛糖与HCl的体积相互作用参数. 研究结果表明, 树胶醛糖在盐酸中的VΦ,A和VΦ,A0均随HCl浓度的增加而线性增大. 在一定温度下, 树胶醛糖从纯水到盐酸水溶液的标准转移表观摩尔体积均为正值, 且随盐酸浓度的增加而增大. 在所测温度范围内, 树胶醛糖在盐酸中的VΦ,A0随温度T的变化关系可表示为VΦ,A0=b0+b1(T-273.15)0.84. 树胶醛糖与HCl对体积相互作用参数VEN大于零, 但数值很小且对温度变化不甚敏感.     

Physicochemical investigation on interactions of some amino acids with aqueous tetra-butyl ammonium bromide solution at 298.15 K

Apparent molar volumes, viscosity B-coefficients, and apparent molar isentropic compressibilities of glycine, L-alanine, L-valine and L-leucine in 0.062, 0.125 and 0.256 mol kg^?1 aqueous tetra-butyl ammonium bromide (TBAB) solution have been determined at 298.15 K from their experimental density, flow time and sound speed measurements, respectively. The standard partial molar volumes and compressibilities are used to calculate the corresponding volume of transfer at infinite dilution, from water to aqueous TBAB solutions. The linear correlation of partial molar volumes for a homologous series of amino acids has been utilised to calculate the contribution of charged end groups and other alkyl chains of the amino acids to partial molar volumes. The hydration numbers of amino acids have also been determined. Viscosity B-coefficients have been calculated using the Jones–Dole equation. The values of the charged end groups contribution to the viscosity B-coefficients of the amino acids are calculated.     

Volumetric Properties of (Difurylmethane + Alkan-1-ol) Binary Mixtures at 298.15 K

Densities (ρ)of the binary systems of {difurylmethane + (ethanol or propan-1-ol or butan-1-ol or pentan-1-ol or hexan-1-ol)} have been measured with an Anton Paar DMA 4500 vibrating-tube densimeter over the entire composition range at 298.15,K and atmospheric pressure. Excess molar volumes (V _m ^E ) of each binary system were determined and correlated by the Redlich-Kister equation. Limiting (V _i ^E,∞) and excess partial molar volumes (V _i ^E ) of components of each binary system have been calculated to provide insight into the intermolecular interactions present and the packing efficiencies. The results have been discussed in terms of specific intermolecular interactions, dispersive forces and structural effects.