Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet

Vibrational structure in the near-UV circular dichroism (CD) spectra of proteins is an important source of information on protein conformation and can be exploited to study structure and folding. A fully quantitative theory of the relationship between protein conformation and optical spectroscopy wo...

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Main Authors: Li, Zhuo, Hirst, Jonathan D.
Format: Article
Published: Royal Society of Chemistry 2017
Online Access:https://eprints.nottingham.ac.uk/41574/
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author Li, Zhuo
Hirst, Jonathan D.
author_facet Li, Zhuo
Hirst, Jonathan D.
author_sort Li, Zhuo
building Nottingham Research Data Repository
collection Online Access
description Vibrational structure in the near-UV circular dichroism (CD) spectra of proteins is an important source of information on protein conformation and can be exploited to study structure and folding. A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper interpretation and insights into biophysical and simulation studies of protein dynamics and folding. We have developed new models of the aromatic side chain chromophores toluene, p-cresol and 3-methylindole, which incorporate ab initio calculations of the Franck-Condon effect into first principles calculations of CD using an exciton approach. The near-UV CD spectra of 40 proteins are calculated with the new parameter set and the correlation between the computed and the experimental intensity from 270 to 290 nm is much improved. The contribution of individual chromophores to the CD spectra has been calculated for several mutants and in many cases helps rationalize changes in their experimental spectra. Considering conformational flexibility by using families of NMR structures leads to further improvements for some proteins and illustrates an informative level of sensitivity to side chain conformation. In several cases, the near-UV CD calculations can distinguish the native protein structure from a set of computer-generated misfolded decoy structures.
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spelling nottingham-415742020-05-04T18:39:01Z https://eprints.nottingham.ac.uk/41574/ Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet Li, Zhuo Hirst, Jonathan D. Vibrational structure in the near-UV circular dichroism (CD) spectra of proteins is an important source of information on protein conformation and can be exploited to study structure and folding. A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper interpretation and insights into biophysical and simulation studies of protein dynamics and folding. We have developed new models of the aromatic side chain chromophores toluene, p-cresol and 3-methylindole, which incorporate ab initio calculations of the Franck-Condon effect into first principles calculations of CD using an exciton approach. The near-UV CD spectra of 40 proteins are calculated with the new parameter set and the correlation between the computed and the experimental intensity from 270 to 290 nm is much improved. The contribution of individual chromophores to the CD spectra has been calculated for several mutants and in many cases helps rationalize changes in their experimental spectra. Considering conformational flexibility by using families of NMR structures leads to further improvements for some proteins and illustrates an informative level of sensitivity to side chain conformation. In several cases, the near-UV CD calculations can distinguish the native protein structure from a set of computer-generated misfolded decoy structures. Royal Society of Chemistry 2017-03-24 Article PeerReviewed Li, Zhuo and Hirst, Jonathan D. (2017) Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet. Chemical Science . ISSN 2046-2069 doi:10.1039/C7SC00586E doi:10.1039/C7SC00586E
spellingShingle Li, Zhuo
Hirst, Jonathan D.
Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
title Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
title_full Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
title_fullStr Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
title_full_unstemmed Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
title_short Quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
title_sort quantitative first principles calculations of protein circular dichroism in the near-ultraviolet
url https://eprints.nottingham.ac.uk/41574/
https://eprints.nottingham.ac.uk/41574/