Intramolecular Reactions and the Relevance of Models

  • Richard D. Gandour


In the past few years, there has been a growing interest in chemical models of enzyme action. In this large body of research, two distinct types of models emerge. The first type is mimetic models; i.e., the reactions model specific enzymes. This area will not be covered in this chapter, but the reader is referred to an excellent review by Fife(1) which covers this approach for three enzymic reactions. The second type is nonmimetic models; i.e., the reactions or interactions model a specific feature of the general process of enzyme catalysis. Among nonmimetic models are two further subdivisions. One subdivision encompasses catalysis by complexation, thus modeling the binding of the substrate to the protein. This subdivision includes reactions catalyzed by micelles, cyclodextrins, hydrophobic interactions in aqueous solution, chargetransfer complexes, and polar associations in apolar solvents. The other subdivision encompasses catalysis by functional groups, thus modeling catalysis by functional groups on side chains of the peptide backbone in the enzyme—substrate complex. This topic is our major concern in this chapter.


Isotope Effect Rate Enhancement Rate Acceleration Ester Hydrolysis Entropy Loss 
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© Springer Science+Business Media New York 1978

Authors and Affiliations

  • Richard D. Gandour
    • 1
  1. 1.Department of ChemistryLouisiana State UniversityBaton RougeUSA

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