A combined theoretical and experimental study of the structure and vibrational absorption, vibrational circular dichroism, Raman and Raman optical activity spectra of the L-histidine zwitterion

Deplazes, E., van Bronswijk, W., Zhu, F., Barron, L. D., Ma, S., Nafie, L. A. and Jalkanen, K. J. (2008) A combined theoretical and experimental study of the structure and vibrational absorption, vibrational circular dichroism, Raman and Raman optical activity spectra of the L-histidine zwitterion. Theoretical Chemistry Accounts, 119(1-3), pp. 155-176. (doi: 10.1007/s00214-007-0276-8)

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Abstract

A combined theoretical and experimental study of the vibrational absorption (VA)/IR, vibrational circular dichroism (VCD), Raman and Raman optical activity (ROA) spectra of L-histidine in aqueous solution has been undertaken to answer the questions (i) what are the species present and (ii) which conformers of the species are present under various experimental conditions. The VA spectra of L-histidine have been measured in aqueous solution and the spectral bands which can be used to identify both species (cation, zwitterion, anion) and conformer of the species have been identified and subsequently used to identify the species (zwitterion) and conformer (gauche minus minus, gauche minus plus for the side chain dihedral angles) present in solution at pH 7.6. The VCD spectral intensities have been used subsequently in combination with further theoretical studies to confirm the conclusions that have been arrived at by only analyzing the VA/IR spectra. Finally a comparison of measured Raman and ROA spectra of L-histidine with Raman and ROA spectral simulations for the conformers and species derived from the combined VA/IR and VCD experimental and theoretical work is presented as a validation of the conclusions arrived at from VA/IR and VCD spectroscopy. The combination of VA/IR and VCD with Raman and ROA is clearly superior and both sets of experiments should be performed.

Item Type:Articles
Keywords:AB-INITIO ABSORPTION ALANYL-L-ALANINE AMINO-ACIDS ANGLE ANION AQUEOUS-SOLUTION CATION CHAIN CIRCULAR-DICHROISM conformational analysis CONFORMERS DENSITY-FUNCTIONAL THEORY DICHROISM DISTAL HISTIDINE EXPLICIT WATER-MOLECULES HORSERADISH-PEROXIDASE hydration IR L-histidine OPTICAL-ACTIVITY PH RAMAN Raman and ROA Raman optical activity ROA SPECTRA SERINE PROTEASES SIMULATION SIMULATIONS SPECTRA SPECTROSCOPY SPECTRUM Structure VALIDATION VCD zwitterion
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Barron, Professor Laurence and Zhu, Dr Fujiang
Authors: Deplazes, E., van Bronswijk, W., Zhu, F., Barron, L. D., Ma, S., Nafie, L. A., and Jalkanen, K. J.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Theoretical Chemistry Accounts
ISSN:1432-881X

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