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合成并表征了四-[邻(叔丁氧羰甘氨酸)氨基苯基]卟啉H2T(o-BocGly)APP(1)及其锌(Ⅱ)配合物ZnT(o-BocGly)APP(2). 用紫外-可见光谱滴定法测定了配合物2 与6 种咪唑类配体轴向配位反应的平衡常数, 研究了它作为主体分子对咪唑类小分子的识别. 研究结果表明, 各配体的缔合常数按K(Im )> K(2-CH3Im )> K(EMIm )> K(N-CH3Im )> K(2-HOCH2Im )> K(GMZ)的顺序依次减小. 计算了卟啉的侧链取代基R与咪唑取代基R′的排斥作用能. 测定了轴向配位反应的ΔrG○—m , ΔrH○—m 及ΔrS○—m , 发现该反应是放热、熵减小的过程, 该反应体系中存在焓熵补偿关系. 实验发现, R是影响配合物2 对咪唑客体识别能力的主要因素
(O-BocGly) APP (1) and ZnT (o-BocGly) APP (2) were synthesized and characterized. The equilibrium constants of the coordination reaction between the complexes 2 and 6 imidazole ligands were determined by UV-Vis spectrophotometry. The recognition of imidazole small molecules as the main molecule was studied. The results show that the association constants of each ligand are in the order of K (Im)> K (2-CH3Im)> K (EMIm)> K (N-CH3Im)> K (2-HOCH2Im)> K Decrease The repulsion function of the side chain substituent R and the imidazole substituent R ’of porphyrin was calculated. The axial coordination reactions ΔrG ○ -m, ΔrH ○ -m and ΔrS ○ -m were measured and the reaction was found to be exothermic and entropy-reducing. There was an enthalpy-entropy compensation relationship in the reaction system. It was found experimentally that R is the main factor affecting the ability of complex 2 to recognize imidazole