NMR Spectral Information Research Articles

Recent Advances in the Automated Structure Elucidation System, CHEMICS. Utilization of Two-Dimensional NMR Spectral Information and Development of Peripheral Functions for Examination of Candidates

A program for applying two-dimensional NMR spectroscopic data from 1H−13C COSY (one-bond C−H correlations)/1H−1H COSY (three bond H−H correlations) and 2D-INADEQUATE (one-bond C-C correlations) exp...

Combinatorial problems in the treatment of fuzzy 13C NMR spectral information in the process of computer-aided structure elucidation: Estimation of the carbon atom hybridization and α-environment states

The information derived from various 13C nuclear magnetic resonance spectra has in most cases more fuzzy than crisp character. An approach to treat this information by means of the membership function is discussed. The combinatorial problems emerging from such a treatment are critically considered and a structure generation scheme consisting of multiple depth-first procedures is suggested. It permits to constrain the structure generation process through a non-redundant and flexible employment of the spectral information available.

Computer-assisted structure generation from a gross formula. 6. Reducing the structural redundancy by the employment of 2D NMR spectral information

Computer-assisted structure generation from a gross formula. 6. Reducing the structural redundancy by the employment of 2D NMR spectral information

Multivariate data analysis of NMR data

Multivariate methods based on principal components (PCA and PLS) have been used to reduce NMR spectral information, to predict NMR parameters of complicated structures, and to relate shift data sets to dependent descriptors of biological significance. Noise reduction and elimination of instrumental artifacts are easily performed on 2D NMR data. Configurational classification of triterpenes and shift predictions in disubstituted benzenes can be obtained using PCA and PLS analysis. Finally, the shift predictions of tripeptides from descriptors of amino acids open the possibility of automatic analysis of multidimensional data of complex structures.

Fluorescence and 13C NMR determination of side-chain and backbone dynamics of synthetic melittin and melittin analogues in isotropic solvents.

The dynamics in isotopic solvents of selectively 13C labeled synthetic melittin and three analogues have been investigated by using NMR and fluorescence techniques both separately and in combination. In conjunction with the "model-free" approach to interpretation of NMR relaxation data [Lipari, G., & Szabo, A. (1982) J. Am. Chem. Soc. 104, 4546-4570], the availability of steady-state fluorescence anisotropy and lifetime data augment T1, T2, and NOE data to provide quantitative information about fluorophore dynamics in these peptides. A method is presented for using combined fluorescence and NMR data to obtain technique- and model-independent values for parameters describing local motion of 13C-labeled fluorophores in peptides and proteins. The dynamics of melittin and melittin analogues are found to be consistent with structural characteristics inferred from CD, fluorescence, and NMR spectral information presented in the preceding paper (Weaver et al., 1989). In particular, the mobility of the random coil peptide monomers is shown to be quite similar, while side-chain as well as peptide backbone motion in the aggregated or oligomeric species differs markedly among the analogues. For melittin itself, experimentally determined overall rotational correlation times for the monomer and tetramer agree very well with values predicted on the basis of solvent-accessible protein surface area. The local dynamics of selectively 13C-labeled Trp-19 and Gly-12 residues of melittin are also found to be consistent with peptide structure. In random coil melittin monomer, a specific model for the motion indicates that the Trp side chain moves through an approximate angle of +/- 71 degrees about the beta-gamma bond with a correlation time of 159 +/- 24 ps. In melittin tetramer, the indole moiety is spatially more confined with a flip angle of +/- 37 degrees, yet demonstrates an increased rate of motion with a correlation time of 56 +/- 8 ps. The constrained mobility of the Trp-19 side chain is consistent with motional constraints inferred from the X-ray structure of melittin tetramer. These results show that protein side-chain motion, even of moieties as large as indole, can occur on the picosecond time scale and that these motions are reasonably similar to those inferred from molecular dynamics simulations.

Introduction of two-dimensional NMR spectral information to an automated structure elucidation system, CHEMICS. Utilization of 2D-INADEQUATE information

Introduction of two-dimensional NMR spectral information to an automated structure elucidation system, CHEMICS. Utilization of 2D-INADEQUATE information

The lithium aluminium hydride reduction of cyclohexadienylmanganese complexes

Reduction of cyclohexadienyltricarbonylmanganese or its ring-substituted derivatives with lithium aluminium hydride leads to dihydro-derivatives. Preparative and NMR spectral information is presented and interpreted on the basis of the CH-bridged cyclohexenyl structure recently established for these products by Lamanna and Brookhart [3].

Metal cluster chemistry: Structure and stereochemistry in the polynuclear rhodium hydrides H n Rh n [P(OR) 3 ] 2n

Crystallographic analyses of x-ray and neutron diffraction data have provided a definitive structural representation of {HRh[P(O-i-C(3)H(7))(3)](2)}(2) and {HRh[P(OCH(3))(3)](2)}(3). These polynuclear hydrides are generated from square planar H(2)Rh[P(OR)(3)](2) units by edge (hydrogen atom) sharing and by vertex (hydrogen atom) sharing to form the dimeric and trimeric structures, respectively. The square-planar units are held together through four-center and three-center two-electron Rh-H-Rh bonds in the dimer and trimer, respectively. The dimer and trimer molecules each add one molecule of hydrogen to form H[(i-C(3)H(7)O)(3)P](2)RhH(3)Rh [P(O-i-C(3)H(7))(3)](2) and H(5)Rh(3)[P(OCH(3))(3)](6), respectively. NMR spectral information has served to define the stereochemical features of these polyhydrides. The significance of this chemistry in the metal cluster-metal surface analogy is described.