Kinetic and thermodynamic control of the relative yield of the deamidation of asparagine and isomerization of aspartic acid residues

J Pept Res. 2000 Dec;56(6):382-7. doi: 10.1034/j.1399-3011.2000.00778.x.

Abstract

Selective deamidation of Asn67 of RNase A to beta-Asp67 and Asp67 residues at neutral pH initially produces greater amounts of the beta-Asp derivative. As the reaction proceeds the relative concentration of [Asp67]-RNase A increases and, at equilibrium, becomes predominant. Such a discrepancy between the kinetic and thermodynamic control on reaction products is discussed in light of information from X-ray three-dimensional analysis and the lower thermodynamic stability of the beta-Asp derivative relative to the parent enzyme.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Asparagine / chemistry*
  • Aspartic Acid / chemistry*
  • Cattle
  • Chromatography, High Pressure Liquid
  • Dose-Response Relationship, Drug
  • Hydrogen-Ion Concentration
  • Isomerism
  • Kinetics
  • Models, Chemical
  • Pancreas / enzymology
  • Ribonuclease, Pancreatic / chemistry
  • Ribonuclease, Pancreatic / metabolism
  • Succinimides / metabolism
  • Temperature
  • Thermodynamics
  • Time Factors

Substances

  • Succinimides
  • succinimide
  • Aspartic Acid
  • Asparagine
  • Ribonuclease, Pancreatic