Details

Autor(en) / Beteiligte

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

Titel

Amide I Vibrational Dynamics of N-Methylacetamide in Polar Solvents:  The Role of Electrostatic Interactions

Ist Teil von

• The journal of physical chemistry. B, 2005-06, Vol.109 (21), p.11016-11026

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2005

Quelle

MEDLINE

Beschreibungen/Notizen

• 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:  D2O, CDCl3, 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.