Analytical solution to the coupled evolution of multidimensional NMR data.
A substantial time savings in the collection of multidimensional NMR data can be achieved by coupling the evolution of nuclei in the indirect dimensions. In order to save time, the sampling of the indirect dimensions is inherently incomplete. Therefore, many algorithms and samplings schemes have been developed aimed at separating the coevolved frequencies into analyzable data with limited artifacts. This paper extends the use of circulant matrices to describe coupled evolution with convolutions. By understanding the data in terms of convolutions, there is an exact solution to the inversion problem of extracting the orthogonal vectors from the coupled dimensions. Previously, this inversion problem has been solved using peak coordinates extracted from spectra. In contrast, the method described here uses spectra directly. This solution suggests a simple sampling scheme of collecting N orthogonal spectra, and N + 1 projections at specific projection angles, however, the theory developed can be extended generally to arbitrary projection angles. The circulant matrix methodology is demonstrated for simulated and real data. Further, an algorithm for separating overlapped signals in the detected dimension is presented. The algorithm involves the forward calculation of the coupled spectra from the orthogonal spectra, followed by back calculation of the orthogonal spectra from the coupled spectra, thus permitting rigorous cross-validation. This algorithm is shown to be robust in that erroneous solutions give rise to large artifacts.
Mueller
Geoffrey A
GA
National Institute of Environment Health Sciences, 111 T.W. Alexander Drive, MD-MR-01, Research Triangle Park, NC 27709, USA. Mueller3@niehs.nih.gov
D000465:Algorithms; D001426:Bacterial Proteins / Q000737:chemistry; D003198:Computer Simulation; D005583:Fourier Analysis; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods*
D001426:Bacterial Proteins; C106206:NuiA protein, Anabaena