Quantitative measurement of transverse and longitudinal cross-correlation between 13C-1H dipolar interaction and 13C chemical shift anisotropy: application to a 13C-labeled DNA duplex.
Measurement of both longitudinal and transverse relaxation interference (cross-correlation) between 13C chemical shift anisotropy and 13C-1H dipolar interactions is described. The ratio of the transverse to longitudinal cross-correlation rates readily yields the ratio of spectral densities J(0)/J(omegaC), independent of any structural attributes such as internuclear distance or chemical shift tensor. The spectral density at zero frequency J(0) is also independent of chemical exchange effects. With limited internal motions, the ratio also enables an accurate evaluation of the correlation time for overall molecular tumbling. Applicability of this approach to investigating dynamics has been demonstrated by measurements made at three temperatures using a DNA decamer duplex with purines randomly enriched to 15% in 13C.
Kojima
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Department of Pharmaceutical Chemistry, University of California, San Francisco, CA, 94143-0446, USA.
Ono
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A
Kainosho
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James
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TL
D016880:Anisotropy; D002247:Carbon Isotopes; D004247:DNA / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D009584:Nitrogen / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D009690:Nucleic Acid Conformation; D013113:Spin Labels; D013696:Temperature; D013997:Time Factors