The rα structure, chemical shift anisotropy, and the abnormal orientation of methyldichlorophosphine from the NMR spectrum

NMR studies of methyldichlorophosphine have been undertaken in the nematic phase of mixed liquid crystals of opposite diamagnetic anisotropies. The rα structure is derived. The proton chemical-shift anisotropy has been determined from the studies without the use of a reference compound and without a change of experimental conditions. It is shown that the molecule orients in the liquid crystal with positive diamagnetic anisotropy in such a way that the C3 symmetry axis of the CH3P moiety is preferentially aligned perpendicular to the direction of the magnetic field, unlike other similar systems. This is interpreted in terms of the formation of a weak solvent-solute molecular complex. The heteronuclear indirect spin-spin coupling constants are determined. The sign of the two-bond JPH is found to be positive.

NMR spectrum of pyridine-N-oxide in a thermotropic nematic phase

Absract is not available.

Nuclear magnetic resonance spectra of oriented bicyclic systems containing heteroatom(s):the spectrum of 2-thiocoumarin

From the proton nmr studies of 2-thiocoumarin and coumarin, it is concluded that the relative interproton distances in the two oxygen heteroatom bicyclic systems are similar. The values for the phenyl ring protons do not deviate significantly from the regular hexagonal geometry, unlike bicyclic systems with nitrogens as the heteroatoms, such as diazanaphthalenes. Larger values of the indirect spin-spin couplings within the protons of the ring containing the oxygen heteroatom, compared to the values between the ortho protons in the phenyl rings in coumarin and 2-thiocoumarin, correspond to the olefinic nature of these protons. This is in contrast to results for the nitrogen heterocycles where both the rings are aromatic.

Side-band intensities in the deuterium magnetic resonance spectra of oriented molecules spinning near the magic angle

The appearance of spinning side bands in the 2H NMR spectra of oriented molecules is investigated. A theoretical interpretation of the side-band intensities is carried out. Information derived on the director orientation and distribution as a function of spinning speedis reported.

Chlorinated Hypoelectronic Dimetallaborane Clusters: Synthesis, Characterization, and Electronic Structures of (eta(5)-C5Me5W)(2)B5HnClm (n=7, m=2 and n=8, m=1)

Pyrolysis of (eta(5)-C5Me5WH3)B4H8, 1, in the presence of excess BHCl2 center dot SMe2 in toluene at 100 degrees C led to the isolation of (eta(5)-C5Me5W)(2)B5H9, 2, and B-Cl inserted (eta(5)-C5Me5W)(2)B5H8Cl, 3, and (eta(5)-C5Me5W)(2)B5H7Cl2, (four isomers). All the Chlorinated tungstaboranes were isolated as red and air and moisture sensitive solids. These new compounds have been characterized in solution by H-1, B-11, C-13 NMR, and the structural types were unequivocally established by crystallographic analysis of compounds 3, 4, and 7. Density functional theory (DFT) calculations were carded out on the model molecules of 3-7 to elucidate the actual electronic structures of these chlorinated species. On grounds of DFT calculations we demonstrated the role of transition metals, bridging hydrogens, and the effect of electrophilic substitution of hydrogens at B-H vertices of metallaborane structures.

Nuclear Magnetic-Resonance Spectra Of Oriented Biologically Important Molecules - The Structure Of And The Internal-Rotation In N,N-Dimethyluracil

From the proton NMR spectra of Nfl-dimethyluracil oriented in two different nematic solvents, the internal rotation of the methyl groups about the N-C bonds is studied. It has been observed that the preferred conformation of the methyl group having one carbonyl in the vicinity is the one where a C-H bond is in the ring plane pointing toward the carbonyl group. The results are not sensitive to the mode of rotation of the other methyl group. These data are interpreted in terms of the bond polarizations.

An NMR study of the interaction of cytosine arabinoside and lysozyme

Abstract is not available.

Estimation Of Properties Of Rare-Gas Solids From Compression Characteristics Of Closed-Shell Ions

We present a unified approach to repulsion in ionic and van der Waals solids based on a compressible-ion/atom model. Earlier studies have shown that repulsion in ionic crystals can be viewed as arising from the compression energy of ions, described by two parameters per ion. Here we obtain the compression parameters of the rare-gas atoms Ne. Ar. Kr and Xe by interpolation using the known parameters of related equi-electronic ions (e.g. Ar from S2-. Cl-, K- and Ca2-). These parameters fit the experimental zero-temperature interatomic distances and compressibilities of the rare-gas crystals satisfactorily. A hightemperature equation of state based on an Einstein model of thermal motions is used to calculate the thermal expansivities, compressibilities and their temperature derivatives for Ar. Kr and Xe. It is argued that an instability at higher temperatures represents the limit to which the solid can be superheated. beyond which sublimation must occur.

Representation and properties of para-Bose oscillator operators. II. Coherent states and the minimum uncertainty states

The energy, position, and momentum eigenstates of a para-Bose oscillator system were considered in paper I. Here we consider the Bargmann or the analytic function description of the para-Bose system. This brings in, in a natural way, the coherent states ||z;alpha> defined as the eigenstates of the annihilation operator ?. The transformation functions relating this description to the energy, position, and momentum eigenstates are explicitly obtained. Possible resolution of the identity operator using coherent states is examined. A particular resolution contains two integrals, one containing the diagonal basis ||z;alpha><−z;alpha||. We briefly consider the normal and antinormal ordering of the operators and their diagonal and discrete diagonal coherent state approximations. The problem of constructing states with a minimum value of the product of the position and momentum uncertainties and the possible alpha dependence of this minimum value is considered. Journal of Mathematical Physics is copyrighted by The American Institute of Physics.

Ternary metal complexes of anionic and neutral pyridoxine (vitamin B6) with 2,2'-bipyridine. Syntheses and x-ray structures of (pyridoxinato)bis(2,2'-bipyridyl)cobalt(III) perchlorate and chloro(2,2'-bipyridyl)(pyridoxine)copper(II) perchlorate hydrate

Ternary metal complexes involving vitamin B6 with formulas [CO",(PN-H)](anCdI [OC)'(bpy)(PN)Cl]C10(.bpHy 0 = 2,2'-bipyridine, PN = neutral pyridoxine, PN-H = anionic pyridoxine) have been prepared for the first time and characterized by means of magnetic and spectroscopic measurements. The crystal structures of the compounds have also been determined. [CO(PN-H)](CcryIsOta,l)lize s in the space group P2,/c with a = 18.900 (3) A, b = 8.764 (1) A, c = 20.041 (2) A,p = 116.05 (l)', and Z = 4 and [Cu(bpy)(PN)C1]C104-H20in the space group Pi with a = 12.136 (5) A, b = 13.283 (4) A,c = 7.195 (2) A, a = 96.91 (Z)', 0 = 91.25 (3)', y = 71.63 (3)', and Z = 2. The structures were solved by the heavy-atom method and refined by least-squares techniques to R values of 0.080 and 0.042 for 3401 and 2094 independent reflections, respectively. Both structures consist of monomeric units. The geometry around Co(II1) is octahedral and around Cu(I1) is distorted square pyramidal. In [CO(PN-H)]t(wCo IoxOy~ge)n~s ,fro m phenolic and 4-(hydroxymethyl) groups of PN-H and two nitrogens from each of two bpy's form the coordination sphere. In [Cu(bpy)(PN)C1]C104.H20o ne PN and one bpy, with the same donor sites, act as bidentate chelates in the basal plane, with a chloride ion occupying the apical position. In both structures PN and PN-H exist in the tautomeric form wherein pyridine N is protonated and phenolic 0 is deprotonated. However, a novel feature of the cobalt compound is that PN-H is anionic due to the deprotonation of the 4-(hydroxymethyl) group. The packing in both structures is governed by hydrogen bonds, and in the copper compound partial stacking of bpy's at a distance of -3.55 also adds to the stability of the system. Infrared, NMR, and ligand field spectroscopic results and magnetic measurements are interpreted in light of the structures.

NMR study of the oil build-up in sunflower seeds

THE use of NMR to investigate the quality of the oil as a function of maturity of the seeds is demonstrated for sunflower seeds. The percentages of the saturated and individual unsaturated aids are determined as a function of time after flowering of the seeds. The percentage of saturated fatty acids is found to decrease with maturity of seeds whereas the extent of the unsaturated acids increases.

Steroidogenesis in the desensitized rat corpora-lutea

Earlier workers have observed that in the leydig cell desensitization brings results in addition to down regulation of receptors, in leisons in the steroidogenlc pathway. In the present study immature rats having heavily leutinized ovaries were given 50 iu hCG and the desenasitized CL removed 48h later were used. At that time no change in the 5 3MSD activity and CAMP binding activity(a measure of CAMP dependent protein kinase) was observed.Followlng desensitization however,l)a significent increase in phosphodiestrase activity,ii)a 50% reduction in total mitochondrial cholesterol level, iii)a significant reduction in its ability to utilize cholesterol or hydrolyse its ester and iv)a significant lowering(by 66%)in cholesterol side chain clean age activity(by measuring pregnanalone formed) was observed. Pregnanalone production was restored to normalcy if exogenous cholesterol was added to the mitohondrial preparation. The results suggest that luteal desensitization is due in addition to down regulation of LH receptors, to a marked reduction in available cholesterol pool in the mitochondrial compartment. The increase in phosphodiestrase activity, though probably a secondary effect,might effectively contribute to the overall reduction in the steroid out-put by increasing the catabolism of CAMP.(Aided by grants from ICMR,New Delhi and WHO, Geneva).

A neutron diffraction investigation of the structure of PBO-PBCL2 glasses

Neutron diffraction techniques have been employed to investigate the structure of PbO-PbCl2 glasses as a function of composition in the nominal range PbO.PbCl2 to 9PbO.PbCl2. It is concluded that, whereas the first Pb-O distance is well defined, the distribution of Pb-Cl distances is much broader, in agreement with a previous EXAFS study.

Inhibition of monkey liver serine hydroxymethyltransferase by Cibacron Blue 3G-A

Cibacron Blue 3G-A inhibited monkey liver serine hydroxymethyltransferase competitively with respect to tetrahydrofolate and non-competitively with respect to L-serine. NADH, a positive heterotropic effector, failed to protect the enzymes against inhibition by the dye and was unable to desorb the enzyme from Blue Sepharose CL-6B gel matrix. The binding of the dye to the free enzyme was confirmed by changes in the dye absorption spectrum. The results indicate that the dye probably binds at the tetrahydrofolate-binding domain of the enzyme, rather than at the 'dinucleotide fold'.

Chlorination of silver dosed with potassium and barium in presence of oxygen: An X-ray photoelectron spectroscopy study

XPS studies show that the presence of chemisorbed chlorine stabilizes and also enhances molecular dioxygen species on Ag surfaces dosed with either K or Ba. The surface atomic oxygen is found to become depleted on chlorination. The variation in the nature of surface species with respect to temperature shows chlorine-induced diffusion of atomic oxygen into the subsurface region at 300 K. For coverages of potassium up to 8 × 1014 atoms/cm2, preferential chloridation of Ag occurs while at higher potassium coverages, KCl formation is distinctly observed on the surface. In the case of barium, two types of adsorbed chlorine species, Cl(α) and Cl(β), associated with Ag and Ba, respectively, are clearly seen even at low barium coverages. This is believed to be due to the higher valence occupation of barium compared to potassium. The Cl(α) species associated with Ag is found to occupy a preferred site on both K- and Ba-dosed surfaces, involving chemisorptive replacement of O(α) to the subsurface region.