Side-chain and backbone ordering in Homopolymers

Physics – Condensed Matter – Statistical Mechanics

Scientific paper

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12 pages,11 figures

Scientific paper

In order to study the relation between backbone and side chain ordering in proteins, we have performed multicanonical simulations of deka-peptide chains with various side groups. Glu10, Gln10, Asp10, Asn10, and Lys10 were selected to cover a wide variety of possible interactions between the side chains of the monomers. All homopolymers undergo helix-coil transitions. We found that peptides with long side chains that are capable of hydrogen bonding, i.e. Glu10, and Gln10, exhibit a second transition at lower temperatures connected with side chain ordering. This occurs in gas phase as well as in solvent, although the character of the side chain structure is different in each case. However, in polymers with short side chains capable of hydrogen bonding, i.e. Asp10 and Asn10, side chain ordering takes place over a wide temperature range and exhibits no phase transition like character. Moreover, non-backbone hydrogen bonds show enhanced formation and fluctuations already at the helix-coil transition temperature, indicating competition between side chain and backbone hydrogen bond formation. Again, these results are qualitatively independent of the environment. Side chain ordering in Lys10, whose side groups are long and polar, also takes place over a wide temperature range and exhibits no phase transition like character in both environments. Reasons for the observed chain length threshold and consequences from these results for protein folding are discussed.

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