化学学报 ›› 1982, Vol. 40 ›› Issue (12): 1148-1158. 上一篇    下一篇

论文

螺旋构象的徽环境效应——6.在二甲基亚砜-水混合溶剂体系中糖淀粉包结作用对对硝基苯酚酯水解的催化效应

惠永正, 王淑静, 蒋锡夔   

  1. 中国科学院上海有机化学研究所
  • 投稿日期:1981-11-16 发布日期:2013-06-03
  • 通讯作者: 惠永正

THE MICROENVIRONMENTAL EFFECTS OF THE HELICAL CONFORMATIONS OF AMYLOSE AND ITS DERIVATIVES 6. CATALYTIC HYDROLYSIS OF ESTERS OF p-NITROPHENOL BOUND BY AMYLOSE IN THE DMSO-H2O MIXED-SOLVENT SYSTEM

HUI YONG-ZHENG, WANG SHU-JING, JIANG XI-KUI   

  1. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1981-11-16 Published:2013-06-03

我们研究了在DMSO-H2O混合溶剂内,在糖淀粉存在或不存在的条件下,对硝基苯酚乙酸酯、戊酸酯、辛酸酯、十二酸酯和十六酸酯的水解反应,所用的缓冲液体系为硼酸盐和碳酸盐两种.除乙酸酯外,糖淀粉对其它受物水解的催化都遵循饱和动力学.由动力学实验得出的络合物解离常数Kd和络合物催化效率κc/Kd*;表明:包结络合物的稳定性随受物链长的增长而增大,与以葡萄糖为催化剂的二级反应速度常数κ2相比,糖淀粉对十二酸酯和十六酸酯催化效率分别增加了280和5600倍.催化效率的来源可归因于糖淀粉宿主螺旋内穴提供的微环境效应.在硼酸钠缓冲液体系中,表观速度常数Kobs—糖淀粉浓度曲线在高浓度区域下降而偏离饱和动力学.实验证明,这是由于糖淀粉分子间或分子内烃基与硼酸根离子配位而引起的,并可近似地处理为“硼酸根离子加宿主抑制”机制,从而解出抑制络合物解离常数Kd'.当用碳酸盐缓冲液代替硼酸盐缓冲液时,则得到典型的非抑制性饱和动力学曲线.

Our recent investigations have established that the formation of helical supramolecular complexes of amyloae 1 or its derivatives with long-chain substrates in both aqueous and DMSO=H2O mixed-solvent systems is accompanied by conformational changes of the macromolecules.This paper reports the resalta from an investigation of the hydrolysis of five esters of p-nitrophenol, to wit, the acetate 2,the valerate 3; the caprylate 4, the laurate 6 and the palmitate 6, in the 1:1.V/V DMSO-H2O mixture with amyloae 1 as a catalyat.Two buffers were used, viz.0.01 M sodium borate or sodium bicarbonate; their pH values are 9.5 in pure water.The observed rate constants, kobs, for the hydrolysis of the substrates were determined by monitoring the absorbance at 410 nm.