Exact Solution to the Extended Zwanzig Model for Quasi-Sigmoidal Chemically Induced Denaturation Profiles : Specific Heat and Configurational Entropy

Abstract EN

Temperature and chemically induced denaturation comprise two of the most characteristic mechanisms to achieve the passage from the native state N to any of the unstructured states Dj in the denatured ensemble in proteins and peptides.

In this work we present a full analytical solution for the configurational partition function ?qs of a homopolymer chain poly-X in the extended Zwanzig model (EZM) for a quasisigmoidal denaturation profile.

This solution is built up from an EZM exact solution in the case where the fraction α of native contacts follows exact linear dependence on denaturant’s concentration ζ; thus an analytical solution for ?L in the case of an exact linear denaturation profile is also provided.

A recently established connection between the number ν of potential nonnative conformations per residue and temperature-independent helical propensity ω complements the model in order to identify specific proteinogenic poly-X chains, where X represents any of the twenty naturally occurring aminoacid residues.

From ?qs, equilibrium thermodynamic potentials like entropy ? and average internal energy 〈E〉 and thermodynamic susceptibilities like specific heat C? are calculated for poly-valine (poly-V) and poly-alanine (poly-A) chains.

The influence of the rate at which native contacts denature as function of ζ on thermodynamic stability is also discussed.