15N and 13C NMR study of the effects of hydrogen bonding and protonation in linear schiff bases: Models for structural studies of rhodopsin and bacteriorhodopsin†

The effects of protonation and hydrogen bonding in linear Schiff bases obtained from n-butylamine with butyraldehyde, crotonaldehyde, sorbaldehyde and all-trans-retinal were studied by means of 15N and 13C NMR. The protonation-induced chemical shifts (Δδ) are an order of magnitude larger for 15N than for 13C. For 15N, this effect was found to increase with the extent of conjugation, culminating in the retinylideneimine (Δδ = −146 ppm), which constitutes a model for the study of the structure of the Schiff base linkage in visual pigments and related systems. Theoretical calculations of protonation-induced Δδ values based on MINDO/ 3 are in agreement with experimental results.