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Measurement of Dipolar Couplings for Methylene and Methyl Sites in Weakly Oriented Macromolecules and Their Use in Structure Determination

✍ Scribed by Marcel Ottiger; Frank Delaglio; John L. Marquardt; Nico Tjandra; Ad Bax


Publisher
Elsevier Science
Year
1998
Tongue
English
Weight
153 KB
Volume
134
Category
Article
ISSN
1090-7807

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✦ Synopsis


A simple and effective method is described for simultaneously measuring dipolar couplings for methine, methylene, and methyl groups in weakly oriented macromolecules. The method is a Jmodulated 3D version of the well-known [ 1 H-13 C] CT-HSQC experiment, from which the J and dipolar information are most accurately extracted by using time-domain fitting in the third, constant-time dimension. For CH 2 -sites, the method generally yields only the sum of the two individual 13 C-1 H couplings. Structure calculations are carried out by minimizing the deviation between the measured sum, and the sum predicted for each methylene on the basis of the structure. For rapidly spinning methyl groups the dipolar contribution to the splitting of the outer 13 C quartet components can be used directly to constrain the orientation of the C-CH 3 bond. Measured sidechain dipolar couplings are in good agreement with an ensemble of NMR structures calculated without use of these couplings.