Nonuniform sampling and maximum entropy reconstruction applied to the accurate measurement of residual dipolar couplings.
Residual dipolar couplings (RDC) provide important global restraints for accurate structure determination by NMR. We show that nonuniform sampling in combination with maximum entropy reconstruction (MaxEnt) is a promising strategy for accelerating and potentially enhancing the acquisition of RDC spectra. Using MaxEnt-processed spectra of nonuniformly sampled data sets that are reduced up to one fifth relative to uniform sampling, accurate 13C'-13Calpha RDCs can be obtained that agree with an RMS of 0.67 Hz with those derived from uniformly sampled, Fourier transformed spectra. While confirming that frequency errors in MaxEnt spectra are very slight, an unexpected class of systematic errors was found to occur in the 6th significant figure of 13C' chemical shifts of doublets obtained by MaxEnt reconstruction. We show that this error stems from slight line shape perturbations and predict it should be encountered in other nonlinear spectral estimation algorithms. In the case of MaxEnt reconstruction, the error can easily be rendered systematic by straightforward optimization of MaxEnt reconstruction parameters and self-cancels in obtaining RDCs from nonuniformly sampled, MaxEnt reconstructed spectra.
Kubat
Jayne A
JA
Bucknell University, Department of Chemistry, Lewisburg, PA 17837, USA.
Chou
James J
JJ
Rovnyak
David
D
D000818:Animals; D002147:Calmodulin / Q000737:chemistry*; D002247:Carbon Isotopes; D019277:Entropy; D005583:Fourier Analysis; D016018:Least-Squares Analysis; D009587:Nitrogen Isotopes; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods*; D012680:Sensitivity and Specificity; D014981:Xenopus
D002147:Calmodulin; D002247:Carbon Isotopes; D009587:Nitrogen Isotopes