UV Resonance Raman Elucidation of the Terminal and Internal Peptide Bond Conformations of Crystalline and Solution Oligoglycines.

The Journal of Physical Chemistry Letters
Sergei V Bykov, Sanford A Asher

Abstract

Spectroscopic investigations of macromolecules generally attempt to interpret the measured spectra in terms of the summed contributions of the different molecular fragments. This is the basis of the local mode approximation in vibrational spectroscopy. In the case of resonance Raman spectroscopy independent contributions of molecular fragments require both a local mode-like behavior and the uncoupled electronic transitions. Here we show that the deep UV resonance Raman spectra of aqueous solution phase oligoglycines show independent peptide bond molecular fragment contributions indicating that peptide bonds electronic transitions and vibrational modes are uncoupled. We utilize this result to separately determine the conformational distributions of the internal and penultimate peptide bonds of oligoglycines. Our data indicate that in aqueous solution the oligoglycine terminal residues populate conformations similar to those found in crystals (3(1)-helices and β-strands), but with a broader distribution, while the internal peptide bond conformations are centered around the 3(1)-helix Ramachandran angles.

References

Jul 21, 2006·The Journal of Physical Chemistry. B·Aleksandr V Mikhonin, Sanford A Asher

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Citations

Apr 27, 2010·The Journal of Physical Chemistry. B·Sergei Bykov, Sanford Asher
Mar 8, 2011·The Journal of Physical Chemistry Letters·Sulayman A OladepoSanford A Asher
Feb 18, 2012·Chemical Reviews·Sulayman A OladepoIgor K Lednev
Oct 9, 2012·Journal of the American Chemical Society·Jacob C DeanTimothy S Zwier
Oct 20, 2011·The Journal of Physical Chemistry. B·Hao RenShaul Mukamel
Mar 18, 2011·The Journal of Physical Chemistry. B·Bhavya Sharma, Sanford A Asher

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