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Tight β-turns in peptides. DFT-based study of infrared absorption and vibrational circular dichroism for various conformers including solvent effects

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Abstract

Vibrational circular dichroism (VCD) has had a large impact on configurational studies of organic molecules largely due to the theoretical advances made by Philip Stephens and co-workers. For peptides, the structural issue is not one of the configuration, but of conformation, and the flexibility of the oligomeric structure raises major computational challenges. Turns are a vital aspect of peptide and protein conformation that allow such structures to fold into a compact unit. However, unlike helices and sheets, they are not extended repeating structures, but each residue has a different local conformation. Also, when turns are part of larger peptides their termini are connected to completely different structural elements. We have done extended comparative density functional theory (DFT) computations to characterize the expected spectral contributions of selected turn structures to the amide IR and VCD spectra of peptides. The isolated vacuum results for tri-amide turns (Ac-X-Y-NH2) of a few different sequences are compared with calculations involving correction for solvation effects. In particular, we looked at the sequence variation in spectra and structure between Ala-Ala, Aib-Gly and D-Pro-Gly for the turn-specific X–Y residues. The nature of some turn-associated, amide originating, spectral transitions are developed and tested.

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Authors and Affiliations

  1. Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St. (m/c 111), Chicago, IL, 60607-7061, USA

    Joohyun Kim, Josef Kapitán, Ahmed Lakhani & Timothy A. Keiderling

  2. Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, Prague 6, 16610, Czech Republic

    Petr Bouř

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  1. Joohyun Kim
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  2. Josef Kapitán
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  3. Ahmed Lakhani
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  4. Petr Bouř
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  5. Timothy A. Keiderling
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Correspondence to Timothy A. Keiderling.

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Kim, J., Kapitán, J., Lakhani, A. et al. Tight β-turns in peptides. DFT-based study of infrared absorption and vibrational circular dichroism for various conformers including solvent effects. Theor Chem Account 119, 81–97 (2008). https://doi.org/10.1007/s00214-006-0183-4

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