Quadrupole Central Transition 17O NMR Spectroscopy of Biological Macromolecules in Aqueous Solution
journal contributionposted on 02.02.2011, 00:00 authored by Jianfeng Zhu, Gang Wu
We demonstrate a general nuclear magnetic resonance (NMR) spectroscopic approach in obtaining high-resolution 17O (spin-5/2) NMR spectra for biological macromolecules in aqueous solution. This approach, termed quadrupole central transition (QCT) NMR, is based on the multiexponential relaxation properties of half-integer quadrupolar nuclei in molecules undergoing slow isotropic tumbling motion. Under such a circumstance, Redfield’s relaxation theory predicts that the central transition, mI = +1/2 ↔ −1/2, can exhibit relatively long transverse relaxation time constants, thus giving rise to relatively narrow spectral lines. Using three robust protein−ligand complexes of size ranging from 65 to 240 kDa, we have obtained 17O QCT NMR spectra with unprecedented resolution, allowing the chemical environment around the targeted oxygen atoms to be directly probed for the first time. The new QCT approach increases the size limit of molecular systems previously attainable by solution 17O NMR by nearly 3 orders of magnitude (1000-fold). We have also shown that, when both quadrupole and shielding anisotropy interactions are operative, 17O QCT NMR spectra display an analogous transverse relaxation optimized spectroscopy type behavior in that the condition for optimal resolution depends on the applied magnetic field. We conclude that, with the currently available moderate and ultrahigh magnetic fields (14 T and higher), this 17O QCT NMR approach is applicable to a wide variety of biological macromolecules. The new 17O NMR parameters so obtained for biological molecules are complementary to those obtained from 1H, 13C, and 15N NMR studies.
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17 O QCT NMR spectraoxygen atoms13 C17 O QCT NMR spectra display17 Osize limitrelaxation optimized spectroscopy type behaviorsolution 17 O NMR240 kDa15 N NMR studiesmultiexponential relaxation propertiesQuadrupole Central Transition 17 O NMR Spectroscopy3 ordersBiological MacromoleculesAqueous SolutionWechemical environment1 Hspectroscopic approachQCT approach increases17 O NMR parameters17 O QCT NMR approachshielding anisotropy interactionsrelaxation time constants