Analysis of the factors that influence the C=N stretching frequency of polyene Schiff bases. Implications for bacteriorhodopsin and rhodopsin

Biophys J. 1988 Feb;53(2):261-9. doi: 10.1016/S0006-3495(88)83087-X.

Abstract

In this study quantum mechanical calculations of force constants and normal mode analysis are used to elucidate the factors that influence the C=C and C=N stretching frequencies in polyenes and in protonated Schiff bases. The C=N stretching frequency is found to depend on both the C=N stretching force constant and the C=N-H bending force constant. Due to the contributions of these two modes, the C=N stretching frequency is particularly sensitive to the magnitude of the Schiff base counterion interactions and to the hydrogen bonding environment of the Schiff base nitrogen. Models for chromophore-protein interactions in the retinal binding site and for the photochemical transformations of bacteriorhodopsin and rhodopsin are evaluated in light of these results.

Publication types

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

MeSH terms

  • Bacteriorhodopsins*
  • Binding Sites
  • Hydrogen Bonding
  • Protein Binding
  • Protein Conformation
  • Retinal Pigments*
  • Retinaldehyde
  • Rhodopsin*
  • Schiff Bases
  • Spectrum Analysis, Raman

Substances

  • Retinal Pigments
  • Schiff Bases
  • Bacteriorhodopsins
  • Rhodopsin
  • Retinaldehyde