J-coupling constants for a trialanine peptide as a function of dihedral angles calculated by density functional theory over the full Ramachandran space

Abstract

We present 13 ³J, seven ²J and four ¹J coupling constants (24 in all) calculated using B3LYP/D95** as a function of the ϕ and ψ Ramachandran dihedral angles of the acetyl(Ala)₃NH₂ capped trialanine peptide over the entire Ramachandran space. With the exception of three of these J couplings, all show significant dependence upon both dihedral angles. For each J coupling considered, a two dimensional grid with respect to ϕ and ψ angles can be used to interpolate the values for any pair of ϕ and ψ values. Such simple interpolation is shown to be very accurate. Most of these calculated J couplings should prove useful for improving the accuracy of the determination of peptide and protein structures from NMR measurements in solution over that provided by the common procedure of treating the J couplings as functions of a single dihedral angle by means of Karplus-type fittings.