Degrees of difficulty of water-consuming reactions in the absence of enzymes

Differences in enzyme proficiency tend to reflect differences between the rates of the uncatalyzed reactions rather than differences between the rates of the enzyme-catalyzed reactions. As a result, enzymes differ greatly from one another in their prowess as catalysts. To shed light on these issues, this review covers water-consuming reactions. Topics discussed include: (1) rates of enzyme reactions, (2) measuring the rates of uncatalyzed reactions in water, (3) rate constants for hydrolysis, (4) hydrolysis of peptides, (5) hydrolysis of urea, carboxylic acid amides and dihydroorotic acid, (6) hydrolytic deamination of cytidine, (7) hydrolysis of phosphoric acid monoesters, (8) hydrolysis of phosphodiesters, (9) hydrolysis of RNA, (10) hydrolysis of carboxylic and phosphoric acid anhydrides, (11) glycoside hydrolysis, (12) hydration reactions of fumarate and 3-chloroacrylate, (13) rate enhnacements produced by hydrolytic and hydrating enzymes, (14) thermodynamic origins of catalysis by hydrolytic and hydrating enzymes and (15) thermodynamic analysis of transition state binding by cytidine deaminase.