Glutamine and Asparagine Side Chain Hyperconjugation-Induced Structurally Sensitive Vibrations

David Punihaole, Zhenmin Hong, Ryan S. Jakubek, Elizabeth M. Dahlburg, Steven Geib, Sanford A. Asher

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


We identified vibrational spectral marker bands that sensitively report on the side chain structures of glutamine (Gln) and asparagine (Asn). Density functional theory (DFT) calculations indicate that the Amide IIIP (AmIIIP) vibrations of Gln and Asn depend cosinusoidally on their side chain OCCC dihedral angles (the x3 and x2 angles of Gln and Asn, respectively). We use UV resonance Raman (UVRR) and visible Raman spectroscopy to experimentally correlate the AmIIIP Raman band frequency to the primary amide OCCC dihedral angle. The AmIIIP structural sensitivity derives from the Gln (Asn) Cβ-C (Cα-Cβ) stretching component of the vibration. The Cβ-C (Cα-Cβ) bond length inversely correlates with the AmIIIP band frequency. As the Cβ-C (Cα-Cβ) bond length decreases, its stretching force constant increases, which results in an upshift in the AmIIIP frequency. The Cβ-C (Cα-Cβ) bond length dependence on the x3 (x2) dihedral angle results from hyperconjugation between the CO (CO) ∗ and Cβ-C (Cα-Cβ) orbitals. Using a Protein Data Bank library, we show that the x3 and x2 dihedral angles of Gln and Asn depend on the peptide backbone Ramachandran angles. We demonstrate that the inhomogeneously broadened AmIIIP band line shapes can be used to calculate the x3 and x2 angle distributions of peptides. The spectral correlations determined in this study enable important new insights into protein structure in solution, and in Gln- and Asn-rich amyloid-like fibrils and prions.

Original languageEnglish (US)
Pages (from-to)13039-13051
Number of pages13
JournalJournal of Physical Chemistry B
Issue number41
StatePublished - Oct 15 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.


Dive into the research topics of 'Glutamine and Asparagine Side Chain Hyperconjugation-Induced Structurally Sensitive Vibrations'. Together they form a unique fingerprint.

Cite this