Amide I vibrational dynamics of N-methylacetamide in polar solvents: The role of electrostatic interactions

M. F. DeCamp, L. DeFlores, J. M. McCracken, A. Tokmakoff, K. Kwac, Minhaeng Cho

Research output: Contribution to journalArticle

186 Citations (Scopus)

Abstract

The vibrational frequency of the amide I transition of peptides is known to be sensitive to the strength of its hydrogen bonding interactions. In an effort to account for interactions with hydrogen bonding solvents in terms of electrostatics, we study the vibrational dynamics of the amide I coordinate of N-methylacetamide in prototypical polar solvents: D 2O, CDCl 3, and DMSO-d 6. These three solvents have varying hydrogen bonding strengths, and provide three distinct solvent environments for the amide group. The frequency-frequency correlation function, the orientational correlation function, and the vibrational relaxation rate of the amide I vibration in each solvent are retrieved by using three-pulse vibrational photon echoes, two-dimensional infrared spectroscopy, and pump-probe spectroscopy. Direct comparisons are made to molecular dynamics simulations. We find good quantitative agreement between the experimentally retrieved and simulated correlation functions over all time scales when the solute-solvent interactions are determined from the electrostatic potential between the solvent and the atomic sites of the amide group.

Original languageEnglish
Pages (from-to)11016-11026
Number of pages11
JournalJournal of Physical Chemistry B
Volume109
Issue number21
DOIs
Publication statusPublished - 2005 Jun 2

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Coulomb interactions
Amides
amides
electrostatics
interactions
Hydrogen bonds
Electrostatics
hydrogen
Vibrational spectra
molecular relaxation
Dimethyl Sulfoxide
N-methylacetamide
Peptides
peptides
Molecular dynamics
Infrared spectroscopy
echoes
solutes
Photons
infrared spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Amide I vibrational dynamics of N-methylacetamide in polar solvents : The role of electrostatic interactions. / DeCamp, M. F.; DeFlores, L.; McCracken, J. M.; Tokmakoff, A.; Kwac, K.; Cho, Minhaeng.

In: Journal of Physical Chemistry B, Vol. 109, No. 21, 02.06.2005, p. 11016-11026.

Research output: Contribution to journalArticle

DeCamp, M. F. ; DeFlores, L. ; McCracken, J. M. ; Tokmakoff, A. ; Kwac, K. ; Cho, Minhaeng. / Amide I vibrational dynamics of N-methylacetamide in polar solvents : The role of electrostatic interactions. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 21. pp. 11016-11026.
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