Subangstrom crystallography reveals that short ionic hydrogen bonds, and not a His-Asp low-barrier hydrogen bond, stabilize the transition state in serine protease catalysis

J Am Chem Soc. 2006 Jul 19;128(28):9086-102. doi: 10.1021/ja057721o.

Abstract

To address questions regarding the mechanism of serine protease catalysis, we have solved two X-ray crystal structures of alpha-lytic protease (alphaLP) that mimic aspects of the transition states: alphaLP at pH 5 (0.82 A resolution) and alphaLP bound to the peptidyl boronic acid inhibitor, MeOSuc-Ala-Ala-Pro-boroVal (0.90 A resolution). Based on these structures, there is no evidence of, or requirement for, histidine-flipping during the acylation step of the reaction. Rather, our data suggests that upon protonation of His57, Ser195 undergoes a conformational change that destabilizes the His57-Ser195 hydrogen bond, preventing the back-reaction. In both structures the His57-Asp102 hydrogen bond in the catalytic triad is a normal ionic hydrogen bond, and not a low-barrier hydrogen bond (LBHB) as previously hypothesized. We propose that the enzyme has evolved a network of relatively short hydrogen bonds that collectively stabilize the transition states. In particular, a short ionic hydrogen bond (SIHB) between His57 Nepsilon2 and the substrate's leaving group may promote forward progression of the TI1-to-acylenzyme reaction. We provide experimental evidence that refutes use of either a short donor-acceptor distance or a downfield 1H chemical shift as sole indicators of a LBHB.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Asparagine / chemistry*
  • Catalysis
  • Crystallography
  • Histidine / chemistry*
  • Hydrogen / chemistry
  • Hydrogen Bonding
  • Models, Molecular
  • Protein Conformation
  • Serine / chemistry
  • Serine Endopeptidases / chemistry*
  • Serine Endopeptidases / metabolism*

Substances

  • Serine
  • Histidine
  • Asparagine
  • Hydrogen
  • Serine Endopeptidases