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Calculations of one-, two- and three-bond nuclear spin-spin couplings in a model peptide and correlations with experimental data

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Summary

We present ab initio calculations of the Fermi contact term and experimental correlations of six coupling constants, 3JH N H α, 1JC α H α, 2JC′H α, 1JC α N, 2JC α N and 1JC′N, in a peptide as functions of the backbone dihedral angles, ϕ and ψ. Given estimates of experimental uncertainties, we find semiquantitative experimental correlations for 3JH N H α, 1JC α N and 2JC α N, qualitative correlations for 1JC α H α and 2JC′H α, but no experimental correlations of practical utility for 1JC′N, owing to its complex dependence on at least four dihedral angles. Errors in the estimation of dihedral angles from X-ray crystallographic data for proteins, which result from uncertainties in atom-to-atom distances, place substantial limitations on the quantitative reliability of coupling constant calculations fitted to such data. In the accompanying paper [Edison, A.S. et al., J. Biomol. NMR, 4, 543–551] we apply the results of the coupling constant calculations presented here to the estimation of ϕ and ψ angles in staphylococcal nuclease from experimental coupling constants.

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Abbreviations

AO:

atomic orbital

BPTI:

basic pancreatic trypsin inhibitor (bovine)

CI-2:

chymotrypsin inhibitor 2

E.COSY:

exclusive correlation spectroscopy (Griesinger et al., 1986)

nJAB :

single bond (n=1), geminal (n=2), or vicinal (n=3) coupling constant between nuclei A and B

LCAO:

linear combination of atomic orbitals

NBO:

natural bond orbital

n:

lone pair orbitals

σ:

bonding orbitals

σ* :

antibonding orbitals

ψ:

dihedral angle or molecular orbital wave function; r2, correlation coefficient

RHF:

restricted Hartree-Fock; rmsd, root-mean-square deviation

3-21G and 6-31G* :

molecular orbital basis set designations (Hehre et al., 1986)

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Authors and Affiliations

  1. Graduate Biophysics Program, University of Wisconsin at Madison, 53706, WI, U.S.A.

    Arthur S. Edison, John L. Markley & Frank Weinhold

  2. Department of Biochemistry and National Magnetic Resonance Facility at Madison and, University of Wisconsin at Madison, 53706, WI, U.S.A.

    John L. Markley

  3. Theoretical Chemistry Institute and, University of Wisconsin at Madison, 53706, WI, U.S.A.

    Frank Weinhold

  4. Department of Chemistry, University of Wisconsin at Madison, 53706, WI, U.S.A.

    Frank Weinhold

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  1. Arthur S. Edison
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  2. John L. Markley
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Edison, A.S., Markley, J.L. & Weinhold, F. Calculations of one-, two- and three-bond nuclear spin-spin couplings in a model peptide and correlations with experimental data. J Biomol NMR 4, 519–542 (1994). https://doi.org/10.1007/BF00156618

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