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Journal article
Water-Mediated Electronic Structure of Oligopeptides Probed by Their UV Circular Dichroism, Absorption Spectra, and Time-Dependent DFT Calculations
The journal of physical chemistry. B, v 124(13), pp 2579-2590
02 Apr 2020
PMID: 32207305
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
We investigate the UV absorption spectra of a series of cationic G
G peptides (where
denotes a guest residue) in aqueous solution and find that only a subset of these spectra show a strong dependence with temperature. To explore whether or not this observation reflects conformational dependencies, we carry out time-dependent density functional calculations for the polyproline II (pPII) and β-strand conformations in implicit and explicit water. We find that the calculated CD spectra for pPII can qualitatively account for the experimental spectra irrespective of the water model. The β-strand UV-CD spectra, however, require the explicit consideration of water. Contrary to conventional wisdom, we find that both the NV
and NV
band are the envelopes of contributions from multiple transitions that involve more than just the HOMOs and LUMOs of the peptide groups. A natural transition orbital analysis reveals that some of the transitions have a charge-transfer character. The overall manifold of transitions depends on the peptide's backbone conformation, peptide hydration, and side chain of the guest residue. Our results reveal that peptide groups, side chains, and hydration shells must be considered as an entity for a physically valid characterization of UV absorbance and circular dichroism.
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Details
- Title
- Water-Mediated Electronic Structure of Oligopeptides Probed by Their UV Circular Dichroism, Absorption Spectra, and Time-Dependent DFT Calculations
- Creators
- Anshuman Kumar - University of California, RiversideSiobhan E Toal - Rowan UniversityDavid DiGuiseppi - Drexel UniversityReinhard Schweitzer-Stenner - Drexel UniversityBryan M Wong - University of California, Riverside
- Publication Details
- The journal of physical chemistry. B, v 124(13), pp 2579-2590
- Publisher
- American Chemical Society; Washington, DC
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Biochemistry and Molecular Biology; [Retired Faculty]; Chemistry
- Web of Science ID
- WOS:000526866500006
- Scopus ID
- 2-s2.0-85082690140
- Other Identifier
- 991019168097004721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Physical