【摘要】 利用精密的流动混合微量热法测定了298.15K时D/L-色氨酸、L-色氨酸、L-组氨酸和L-苯丙氨酸四种天然芳香族氨基酸水溶液的稀释焓,根据所建立的拟等步自堆叠作用的化学模型对实验数据进行了处理,计算得到模型参数KΔHm.该化学作用参数与McMillan-Mayer理论模型中的焓对作用系数具有高度一致性,即hxx=KΔHm.结合文献报道的结果,认为芳核π-π自堆叠作用在本质上是一种特殊的疏水-疏水作用,一般表现为吸热效应;取代基空间位阻、芳核以外部分的静电、氢键和手性选择性作用等对芳核π-π自堆叠作用有更多还原

【Abstract】 Dilution enthalpies of some aromatic amino acids such as D/L-α-tryptophan,L-α-tryptophan,L-α-tyrosine and L-α-phenylalanine in aqueous solutions at 298.15 K were determined by sensitive mixing-flow microcalorimetry. A chemical interaction model for quasi-isodemic self-stacking was proposed and used to process the calorimetric data from which the model parameter KΔHm was calculated. The chemical interaction parameter (KΔHm) agrees well with and provides good insights into the pairwise enthalpic interaction coefficient (hxx) in the McMillan-Mayer approach for the existence of the equation KΔHm=hxx. Combined with results from literature we considered that aromatic π -π self-stacking is essentially a kind of special hydrophobic interaction manifesting commonly as an endothermic effect. Noteworthy effects arising from substituent hindrance,electrostatic interaction,hydrogen bonding and chiral recognition which are directed away from the aromatic core exert on aromatic π-π self-stacking. In nature,the composite parameter KΔHm describes a complex effect between the equilibrium and an enthalpic change of aromatic π-π self-stacking.更多还原