UV Raman demonstrates that alpha-helical polyalanine peptides melt to polyproline II conformations

Journal of the American Chemical Society
Sanford A AsherSergei V Bykov

Abstract

We examined the 204-nm UV Raman spectra of the peptide XAO, which was previously found by Shi et al.'s NMR study to occur in aqueous solution in a polyproline II (PPII) conformation. The UV Raman spectra of XAO are essentially identical to the spectra of small peptides such as ala(5) and to the large 21-residue predominantly Ala peptide, AP. We conclude that the non-alpha-helical conformations of these peptides are dominantly PPII. Thus, AP, which is highly alpha-helical at room temperature, melts to a PPII conformation. There is no indication of any population of intermediate disordered conformations. We continued our development of methods to relate the Ramachandran Psi-angle to the amide III band frequency. We describe a new method to estimate the Ramachandran Psi-angular distributions from amide III band line shapes measured in 204-nm UV Raman spectra. We used this method to compare the Psi-distributions in XAO, ala(5), the non-alpha-helical state of AP, and acid-denatured apomyoglobin. In addition, we estimated the Psi-angle distributions of peptide bonds which occur in non-alpha-helix and non-beta-sheet conformations in a small library of proteins.

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Citations

Dec 31, 2004·Analytical and Bioanalytical Chemistry·Igor K LednevMing Xu
Oct 23, 2009·Biochemistry·Kan XiongSanford A Asher
Feb 18, 2012·Chemical Reviews·Sulayman A OladepoIgor K Lednev
Oct 4, 2007·Journal of the American Chemical Society·Gurusamy BalakrishnanThomas G Spiro
Dec 20, 2011·Journal of the American Chemical Society·Liu HeNeville R Kallenbach
Apr 22, 2010·Journal of the American Chemical Society·Ludmila A PopovaIgor K Lednev
Oct 19, 2007·The Journal of Physical Chemistry. a·Zhenyu Li, Shaul Mukamel
Mar 18, 2011·The Journal of Physical Chemistry. B·Bhavya Sharma, Sanford A Asher
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May 23, 2012·The Journal of Physical Chemistry. B·Kan Xiong, Sanford A Asher
Aug 21, 2008·The Journal of Physical Chemistry. B·Bhavya SharmaSanford A Asher
May 11, 2010·Biochemistry and Cell Biology = Biochimie Et Biologie Cellulaire·Lisa D MuiznieksFred W Keeley
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