药物类水溶液扩散系数及相关热力学性质的测定与研究
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摘要
氨基酸是重要的生物活性物质，是理论研究中重要的模型化合物。葡萄糖、蔗糖和抗坏血酸是人体发育成长所必需的药物。研究这些药类物质在水溶液中的扩散具有重要的理论和指导意义；研究相关的热力学性质，可以获得对生命系统功能控制的机制，同时可为进一步研究蛋白质大分子的变性行为等提供重要的参考价值。
本文首先对这些药物类水溶液的扩散系数进行了研究：建立了一套激光全息干涉装置，并验证了该装置的可靠性。选择甘氨酸等8种代表性的氨基酸作为研究对象，测量了298.15K下二元水溶液的液相扩散系数。并通过外推方法得到了无限稀释液相扩散系数，结果与由统计力学方法推导出的无限稀释液相扩散系数所得结果吻合很好。
为考察温度对液相扩散系数的影响，用金属膜池法测定了葡萄糖、维生素C和L-苏氨酸三种物质从298.15K到328.15K下的液相扩散系数。并提出了含有温度关联项的估算模型，结果与实验值吻合很好。
其次为系统地研究扩散系数提供基础数据，本文对这些药物类水溶液的相关热力学性质进行了研究：用石英振动管精密密度计和粘度计测定了从293.15K到333.15K不同温度下上述8种氨基酸二元水溶液的密度和粘度，考察了温度对体积和粘度等数据的影响，计算得到了偏摩尔体积和粘度系数等重要的热力学数据。并应用基团贡献法得到了氨基酸中一些相关基团对偏摩尔体积和粘度系数的贡献值。
为研究溶剂对氨基酸热力学性质的影响，本文测定了298.15K下L-苏氨酸和L-精氨酸在不同浓度的葡萄糖、蔗糖和维生素C混合溶剂中的密度和粘度。并相应计算了得到了偏摩尔体积、迁移偏摩尔体积、粘度系数和理论水化数等热力学数据。同时考察了氨基酸侧基对迁移偏摩尔体积的贡献。可为进一步研究蛋白质大分子等相关性质提供重要的参考价值。
Amino acids are useful as models of specific aspects of more complex proteins in aqueous solution. Glucose, sucrose and L-ascorbic acid are necessary to grow in the body. There have been significant interest and value in the investigations on diffusion and thermodynamic property in aqueous solutions.
Firstly, diffusion coefficients of these medicaments were investigated. A set of apparatus of holographic interferometry determining liquid diffusion coefficients was designed and established. The reliability was confirmed with literature data. Liquid diffusion coefficients of aqueous solutions of eight amino acids such as glycine were measured at 298.15K. The influences of molecular structure and polarity on liquid diffusion coefficients were also discussed. At the same time, infinite dilute liquid diffusion coefficients obtained by experimental extrapolation, were good agreement with the results based on the fundamental equation developed from statistical mechanics.
In order to investigate the influence of temperature on liquid diffusion coefficients, liquid diffusion coefficients of aqueous glucose, L-ascorbic acid and L-threonine solutions were determined from 298.15K to 328.15K by metallic diaphragm cell method. A new semi-empirical model for correlating the diffusion coefficients containing temperature was provided with more comprehensive and less experiment compared to the previous model.
Secondly, thermodynamic properties of aqueous some medicaments solutions were investigated. Densities and viscosities of aqueous solutions of eight amino acids such as glycine were measured as a function of amino acid concentration from 293.15K to 333.15K by an oscillating-tube densimeter and a viscositymeter. These data were used to calculate the apparent molar volumes, partial molar volumes and viscosity -coefficients. Using group contribution method the contributions of related groups of amino acids to partial molar volumes and viscosity -coefficients were obtained, the results confirmed this group additivity method had excellent predictive utility.
In order to investigate refluences of solvent on thermodynamic property, densities and viscosities of L-threonine and L-arginine in glucose-water, sucrose-water and L-ascorbic acid-water mixed solvents were measured at 298.15K. Apparent molar volumes, partial molar volumes, numbers of hydration and viscosity
B-coefficients of L-threonine and L-arginine were calculated and correlated. The transfer partial molar volumes from water to sugar-water or L-ascorbic acid-water mixtures and numbers of hydration were also obtained and discussed in terms of the cosphere overlap model. Furtherly, different side chain contributions of amino acids to transfer partial molar volumes were also investigated. Data obtained could provide valuable information that ultimately led to a better understanding of behavior of biological micromolecules or proteins.
本文首先对这些药物类水溶液的扩散系数进行了研究：建立了一套激光全息干涉装置，并验证了该装置的可靠性。选择甘氨酸等8种代表性的氨基酸作为研究对象，测量了298.15K下二元水溶液的液相扩散系数。并通过外推方法得到了无限稀释液相扩散系数，结果与由统计力学方法推导出的无限稀释液相扩散系数所得结果吻合很好。
为考察温度对液相扩散系数的影响，用金属膜池法测定了葡萄糖、维生素C和L-苏氨酸三种物质从298.15K到328.15K下的液相扩散系数。并提出了含有温度关联项的估算模型，结果与实验值吻合很好。
其次为系统地研究扩散系数提供基础数据，本文对这些药物类水溶液的相关热力学性质进行了研究：用石英振动管精密密度计和粘度计测定了从293.15K到333.15K不同温度下上述8种氨基酸二元水溶液的密度和粘度，考察了温度对体积和粘度等数据的影响，计算得到了偏摩尔体积和粘度系数等重要的热力学数据。并应用基团贡献法得到了氨基酸中一些相关基团对偏摩尔体积和粘度系数的贡献值。
为研究溶剂对氨基酸热力学性质的影响，本文测定了298.15K下L-苏氨酸和L-精氨酸在不同浓度的葡萄糖、蔗糖和维生素C混合溶剂中的密度和粘度。并相应计算了得到了偏摩尔体积、迁移偏摩尔体积、粘度系数和理论水化数等热力学数据。同时考察了氨基酸侧基对迁移偏摩尔体积的贡献。可为进一步研究蛋白质大分子等相关性质提供重要的参考价值。
Amino acids are useful as models of specific aspects of more complex proteins in aqueous solution. Glucose, sucrose and L-ascorbic acid are necessary to grow in the body. There have been significant interest and value in the investigations on diffusion and thermodynamic property in aqueous solutions.
Firstly, diffusion coefficients of these medicaments were investigated. A set of apparatus of holographic interferometry determining liquid diffusion coefficients was designed and established. The reliability was confirmed with literature data. Liquid diffusion coefficients of aqueous solutions of eight amino acids such as glycine were measured at 298.15K. The influences of molecular structure and polarity on liquid diffusion coefficients were also discussed. At the same time, infinite dilute liquid diffusion coefficients obtained by experimental extrapolation, were good agreement with the results based on the fundamental equation developed from statistical mechanics.
In order to investigate the influence of temperature on liquid diffusion coefficients, liquid diffusion coefficients of aqueous glucose, L-ascorbic acid and L-threonine solutions were determined from 298.15K to 328.15K by metallic diaphragm cell method. A new semi-empirical model for correlating the diffusion coefficients containing temperature was provided with more comprehensive and less experiment compared to the previous model.
Secondly, thermodynamic properties of aqueous some medicaments solutions were investigated. Densities and viscosities of aqueous solutions of eight amino acids such as glycine were measured as a function of amino acid concentration from 293.15K to 333.15K by an oscillating-tube densimeter and a viscositymeter. These data were used to calculate the apparent molar volumes, partial molar volumes and viscosity -coefficients. Using group contribution method the contributions of related groups of amino acids to partial molar volumes and viscosity -coefficients were obtained, the results confirmed this group additivity method had excellent predictive utility.
In order to investigate refluences of solvent on thermodynamic property, densities and viscosities of L-threonine and L-arginine in glucose-water, sucrose-water and L-ascorbic acid-water mixed solvents were measured at 298.15K. Apparent molar volumes, partial molar volumes, numbers of hydration and viscosity
B-coefficients of L-threonine and L-arginine were calculated and correlated. The transfer partial molar volumes from water to sugar-water or L-ascorbic acid-water mixtures and numbers of hydration were also obtained and discussed in terms of the cosphere overlap model. Furtherly, different side chain contributions of amino acids to transfer partial molar volumes were also investigated. Data obtained could provide valuable information that ultimately led to a better understanding of behavior of biological micromolecules or proteins.
引文
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