Dewar M J, Storch D M
Proc Natl Acad Sci U S A. 1985 Apr;82(8):2225-9. doi: 10.1073/pnas.82.8.2225.
Since adsorption of the substrate in the active site of an enzyme can occur only if all solvent is squeezed out from between them, any reaction between them takes place in the absence of any intervening solvent--i.e., as it would in the gas phase. Recent work has shown that ionic reactions in the gas phase often differ greatly from analogous processes in solution. Therefore, current interpretations of enzyme reactions in terms of solution chemistry are misguided. The large rates and specificity of enzyme reactions may be due simply to elimination of the solvent. The cleavage of peptides by chymotrypsin and carboxypeptidase A can be interpreted satisfactorily in this way.
由于只有当所有溶剂都从酶的活性位点与底物之间被挤出时,底物才能吸附在酶的活性位点上,所以它们之间的任何反应都是在没有任何中间溶剂的情况下发生的——也就是说,就像在气相中发生的那样。最近的研究表明,气相中的离子反应通常与溶液中的类似过程有很大不同。因此,目前用溶液化学来解释酶反应是有误导性的。酶反应的高速度和特异性可能仅仅是由于溶剂的消除。胰凝乳蛋白酶和羧肽酶A对肽的切割可以用这种方式得到令人满意的解释。