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Accurate Measurements of 13C−13C J-Couplings in the Rhodopsin Chromophore by Double-Quantum Solid-State NMR Spectroscopy

A new double-quantum solid-state NMR pulse sequence is presented and used to measure one-bond 13C−13C J-couplings in a set of 13C2-labeled rhodopsin isotopomers. The measured J-couplings reveal a perturbation of the electronic structure at the terminus of the conjugated chain but show no evidence fo...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2006-03, Vol.128 (12), p.3878-3879
Main Authors: Lai, Wai Cheu, McLean, Neville, Gansmüller, Axel, Verhoeven, Michiel A, Antonioli, Gian Carlo, Carravetta, Marina, Duma, Luminita, Bovee-Geurts, Petra H. M, Johannessen, Ole G, de Groot, Huub J. M, Lugtenburg, Johan, Emsley, Lyndon, Brown, Steven P, Brown, Richard C. D, DeGrip, Willem J, Levitt, Malcolm H
Format: Article
Language:English
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Summary:A new double-quantum solid-state NMR pulse sequence is presented and used to measure one-bond 13C−13C J-couplings in a set of 13C2-labeled rhodopsin isotopomers. The measured J-couplings reveal a perturbation of the electronic structure at the terminus of the conjugated chain but show no evidence for protein-induced electronic perturbation near the C11−C12 isomerization site. This work establishes NMR methodology for measuring accurate 1 J CC values in noncrystalline macromolecules and shows that the measured J-couplings may reveal local electronic perturbations of mechanistic significance.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0581604