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Solvent‐Enhanced Conformational Flexibility of Cyclic Tetrapeptides
Author(s) -
Berger Nadja,
Wollny Laura J. B.,
Sokkar Pandian,
Mittal Sumit,
MieresPerez Joel,
Stoll Raphael,
Sander Wolfram,
SanchezGarcia Elsa
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201900345
Subject(s) - chemistry , intramolecular force , cyclic peptide , solvent , diastereomer , hydrogen bond , molecular dynamics , atmospheric temperature range , solvent effects , flexibility (engineering) , replica , peptide , computational chemistry , molecule , crystallography , stereochemistry , thermodynamics , organic chemistry , art , biochemistry , physics , statistics , mathematics , visual arts
Solvent and temperature can affect the structural properties of cyclic peptides by controlling their flexibility. Here, we investigate two cyclic peptides, featuring beta turns. Using temperature‐dependent NMR and FT‐IR, we observed a pronounced temperature effect on the conformation of the cyclic peptide D‐1 in CHCl 3 but a much smaller effect in CH 3 CN. Almost no effect was observed for its diastereomer L‐1 within a similar temperature range and using the same solvents. With the aid of Replica Exchange Molecular Dynamics simulations and Quantum Mechanics/Molecular Mechanics calculations, we were able to explain this behavior based on the increased flexibility of D‐1 (in CHCl 3 ) in terms of intramolecular hydrogen bonding. The largest temperature dependence is observed for D ‐ 1 in CHCl 3 , while the temperature effect is less pronounced for L‐1 in CHCl 3 and for both peptides in CH 3 CN. This work provides new insights into the role of the environment and temperature on the conformations of cyclic peptides.