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A versatile component-coupling model to account for substituent effects: application to polypeptide phi and chi(1)
1Biosciences Department, University of Kent, Canterbury CT2 7NJ, UK. j.m.schmidt@kent.ac.uk
Abstract:
A model is proposed for collating fundamental and incremental component couplings to account for substituent effects on (3)J arising from, for example, amino-acid type variation. The unique topology patterns encountered in each of the common amino acids were modeled by assigning substituents on a (3)J coupling path to four simple categories comprising only relative positions: central (inner) vs. terminal (outer) and first-sphere vs. second-sphere. Associated increment values then reflect the influences on each (3)J coupling accessible for torsion-angle determination. Facility of use of this model, in comparison with previous ones, owes to its strict limitation to no more than three Karplus coefficients for each specific torsion-angle dependency derived. The model was integrated in the concept of self-consistent (3)J analysis and applied to polypeptide fragments X-N-C(alpha)-Y and X-C(alpha)-C(beta)-Y related to torsions phi and chi(1), respectively, yielding quantitative effects of both first- and second-sphere substituents. Regarding the polypeptide backbone, the model predicts first-sphere substituent effects on phi-related (3)J couplings to be within experimental uncertainty because main-chain topologies are identical in most amino-acid types, except for marginal effects in glycine and proline. However, effects in excess of standard errors in (3)J(phi) measurements are anticipated from second-sphere substituent variation. Regarding amino-acid side chains, first-sphere substituent effects on chi(1)-related (3)J couplings were previously found pivotal to accurate torsion-angle interpretation. Taking additional second-sphere effects on (3)J(chi(1)) into account is here demonstrated further to improve biomolecular structure analysis.
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