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Accepted (AM)Open Access (License Unspecified), Open
Journal article
Decomposition of Vibrational Shifts of Nitriles into Electrostatic and Hydrogen-Bonding Effects
Journal of the American Chemical Society, v 132(37), pp 12811-12813
22 Sep 2010
PMID: 20806897
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Infrared (IR) band shifts of isolated vibrational transitions can serve as quantitative and directional probes of local electrostatic fields, due to the vibrational Stark effect. However, departures from the Stark model can arise when the probe participates in specific, chemical interactions, such as direct hydrogen bonding. We present a method to identify and correct for these departures based on comparison of C-13 NMR chemical shifts and IR frequencies each calibrated in turn by a solvato-chromic model. We demonstrate how the tandem use of these experimental observables can be applied to a thiocyanate-modified protein, ketosteroid isomerase, and show, by comparison to structural models, that changes in electrostatic field can be measured within the complex protein environment even in the background of direct hydrogen bonding to the probe.
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Details
- Title
- Decomposition of Vibrational Shifts of Nitriles into Electrostatic and Hydrogen-Bonding Effects
- Creators
- Aaron T. Fafarman - Stanford UniversityPaul A. Sigala - Stanford UniversityDaniel Herschlag - Stanford UniversitySteven G. Boxer - Stanford University
- Publication Details
- Journal of the American Chemical Society, v 132(37), pp 12811-12813
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 3
- Grant note
- HHMI; Howard Hughes Medical Institute R37GM027738 / NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA; NIH National Institute of General Medical Sciences (NIGMS) GM27738 / NIH; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA MCB-0641393 / NSF; National Science Foundation (NSF) G. Lieberman Predoctoral Fellowship
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemical and Biological Engineering
- Web of Science ID
- WOS:000282013700018
- Scopus ID
- 2-s2.0-77956634583
- Other Identifier
- 991020834713704721
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- Web of Science research areas
- Chemistry, Multidisciplinary