Dipole-dipole interactions between protons in a glucopyranose derivative have been studied by means of the nuclear Overhauser effect and by spin-lattice relaxation experiments. The Overhauser enhancement measurements utilize a new pulse technique which permits the saturating field to have any specified spectral density function so that finite frequency bands in the NMR spectrum can be irradiated. By this method, the dipolar interactions between the various pairs of protons are evaluated. In contrast, the dipolar relaxation of a chosen proton by all other protons in the sample has been determined by comparing the inversion-recovery rates after selective and nonselective 180· pulses. The relaxation measurements indicate that the relaxation in this molecule is purely dipolar in origin. The Overhauser enhancement measurements of one proton are used to determine the contribution to its relaxation from two neighboring protons and, from these results, information about the geometry of the pyranose ring is evaluated.4466
A group-theoretical analysis of the Raman tensor for helical polymers is given and illustrated for the Pauling α helix which possesses 18 residues in five turns. A detailed determination of the polarized Raman spectra is given for oriented α-helical poly-l-alanine fibers and for four polyribonucleotides in solution. Tentative assignments to A, E1, and E2 symmetry are made on certain Raman bands of poly-l-alanine based on the polarization of the Raman light. A detailed comparison of monomer and polymer bands are given for the four polynucleotides. A theory for the angular dependence of Raman light scattered from helical molecules is given.
A method is described for exciting a nuclear magnetic resonance spectrum with a radio frequency source having any desired frequency spectrum. The frequency spectrum of the source is first specified and then Fourier synthesized to define a function which is used to modulate a radio frequency carrier. The NMR spectrum is obtained by Fourier transforming the response of the spin system to this excitation. The technique is applied to the problem of suppressing a strong solvent line while simultaneously observing all other resonance lines in a spectrum and to homonuclear decoupling while observing a complete spectrum.
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