Temperature-dependent intensity anomalies in amino acid esters: weak hydrogen bonds in protected glycine, alanine and valine

2011 | journal article. A publication with affiliation to the University of Göttingen.

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​Otto KE, Hesse S, Wassermann TN, Rice CA, Suhm MA, Stafforst T, et al. ​Temperature-dependent intensity anomalies in amino acid esters: weak hydrogen bonds in protected glycine, alanine and valine​. ​​Physical Chemistry Chemical Physics. ​2011;​13​(31):​​14119​-14130​. ​doi:10.1039/c1cp20883g. 

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Authors
Otto, Katharina E.; Hesse, Susanne; Wassermann, Tobias N.; Rice, Corey A.; Suhm, Martin A. ; Stafforst, Thorsten; Diederichsen, Ulf 
Abstract
Esters of glycine, alanine and valine are investigated by FTIR and Raman spectroscopy in supersonic jets as gas phase model systems for the neutral peptide N-terminus. The NH-stretching vibrations exhibit very large temperature-and substitution-dependent intensity anomalies which are related to weak, bifurcated intramolecular hydrogen bonds to the carbonyl group. Comparison to theory is only satisfactory at low temperature. Spectral NH aggregation shifts are small or even negligible and the associated IR intensity is remarkably low. In the case of valine, chirality recognition effects are nevertheless detected and rationalized. Comparison to quantum-chemical calculations for dimers shows that dispersion interactions are essential. It also rules out cooperative hydrogen bond topologies and points at deficiencies in standard harmonic treatments with the linear dipole approximation.
Issue Date
2011
Status
published
Publisher
Royal Soc Chemistry
Journal
Physical Chemistry Chemical Physics 
Organization
Institut für Physikalische Chemie 
ISSN
1463-9084; 1463-9076
Sponsor
DFG [Su121/2]; Fonds der Chemischen Industrie

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