General base catalysis, definition

The basics of general acid and general base catalysis are described clearly and in detail in Chapter 8 of Maskill [1]. Acid-base catalysis is termed specific if the rate of the reaction concerned depends only on the acidity (pH, etc.) of the medium. This is the case if the reaction involves the conjugate acid or base of the reactant preformed in a rapid equilibrium process - normal behavior if the reactant is weakly basic or acidic. The conjugate acid or base is then, by definition, a strong... 

The first indication of the importance of proton-transfer reactions in enzyme catalysis come from the observation that the rate of most enzyme-catalysed reactions displays a relatively simply, sigmoidal or bell-shaped pH dependence. Thus enzymatic reactions require a small number of acids in a definite state of ionization. Later mechanistic studies indeed confirmed that in many cases these acids and bases - usually identifiable from the pK values of the pH-rate profile -act as proton donors and proton acceptors in the rate-limiting step of the catalytic process. Since in biological systems enzymatic reactions occur almost invariably near neutrality, where oxonium and hydroxide ion concentrations are at a minimum, it is not surprizing to find that enzymes make extensive use of general acid and general base catalysis. 

Although the concepts of specific acid and specific base catalysis were useful in the analysis of some early kinetic data, it soon became apparent that any species that could effect a proton transfer with the substrate could exert a catalytic influence on the reaction rate. Consequently, it became desirable to employ the more general Br0nsted-Lowry definition of acids and bases and to write the reaction rate constant as... 

Cage, solvent, 134 Cancellation assumption. 447 Catalysis, 263 acid, 453 buffer, 269 definitions of, 263 electrophilic, 265 general acid, 265, 268 general base, 265, 268, 271 intermolecular, 266 intramolecular, 266 nucleophilic, 266, 268, 271... 

General acid catalysis occurs when the rate law includes a concentration term due to added acid (rate = AhaIHA]). Specific acid catalysis involves a rate law with only the oxonium ion (rate = itHlHjOq). Similar definitions apply to general base and specific base catalysis involving base and hydroxide ion respectively. 

As implied above, there is nothing dramatically special about photocatalysis. It is simply another type of catalysis alongside, as it were, redox catalysis, acid-base catalysis, enzyme catalysis, thermal catalysis and others. Consequently, it is worth reemphasising that any description of photocatalysis must correspond to the general definition of catalysis. This said, it could be argued that the broad label photocatalysis simply describes catalysis of a photochemical reaction. 

To discuss acid-base catalysis, it is helpful to recall the definitions of acids and bases. In the Brpnsted-Lowry definition, an acid is a proton donor and a base is a proton acceptor. The concept of general acid-base catalysis depends on donation and acceptance of protons by groups such as the imidazole, hydroxyl, carboxyl, sulfhydryl, amino, and phenolic side chains of amino acids all these functional groups can act as acids or bases. The donation and acceptance of protons gives rise to the bond breaking and re-formation that constitute the enzymatic reaction. 

A second form of acid—base catalysis reflects another, more general definition of acids and bases. In the Lewis formulation, an acid is an electron-pair acceptor, and a base is an electron-pair donor. Metal ions, including such biologically important ones as Mn +, Mg +, and Zn, are Lewis acids. Thus, they can play a role in metal-ion catalysis (also called Lewis acid-base catalysis). The involvement of Zn + in the enzymatic activity of carboxypeptidase A is an example of this type of behavior. This enzyme catalyzes the hydrolysis of... 

Many examples of proximity effects are known. In general, whenever an intramolecular acid or base is invoked in acid-base catalysis, proximity effects can be a factor. Further, when any catalyst holds a substrate near a catalytic group at its active site, or holds two separate substrates next to each other, proximity effects can be relevant. Proximity effects are definitely prevalent in organometallic catalysis, as we will see in Chapter 12. Hence, proximity effects are key to many forms of catalysis. 

In general terms, a solid acid may be understood to be a solid on which the color of a basic indicator changes or a solid on which a base is chemically adsorbed. More strictly, following both the Bronsted and Lewis definitions, a solid acid shows a tendency to donate a proton or to accept an electron pair, whereas a solid base tends to accept a proton or to donate an electron pair. These definitions are adequate for an understanding of the acid-base phenomena shown by various solids, and are convenient for a clear description of solid acid and base catalysis. 

The surface basicity of a solid catalyst can be defined in a way analogous to that applied to conventional bases. Thus, a surface Lewis base site is one that is able to donate an electron pair to an adsorbed molecule. If we take the definition of surface basicity in a more general way, it could be said that the active surface corresponds to sites with relatively high local electron densities. This general definition will include not only Lewis basicity but also single electron donor sites. We emphasize that the literature of heterogeneous catalysis often reports that both single-electron and electron-pair donor sites exist on basic catalysts. 

The catalytic center is formed by residues from both lobes. Sequence comparisons, mutation experiments and biochemical studies indicate an essential fimction in catalysis of phosphate transfer for the conserved amino acids Lys72, Aspl66 and Aspl84 (numbering of PKA). However, the catalytic mechanism of phosphate transfer is not definitely established. It is generally assumed that Aspl66, which is invariant in all protein kinases, serves as a catalytic base for activation of the Ser/Thr hydroxyl and that the reaction takes place by an in-line attack of the Ser-OH at the y-phosphate. 

The present manual is based on the same general principles as those used in the Manual of Symbols and Terminology for Physicochemical Quantities and Units of the Commission on Symbols, Terminology and Units of the Division of Physical Chemistry, Definitions, Terminology and Symbols in Colloid and Surface Chemistry of the Commission on Colloid and Surface Chemistry, Appendix II Part 1 Definitions, Terminology and Symbols in Colloid and Surface Chemistry, Part II Heterogeneous Catalysis, and Recommendations in Reporting Physisorption Data for Gas/Solid Systems [1-3]. 

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