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Magic-angle-spinning 31P NMR spectra of solid dihydrogen phosphates. Comparison of ordered and dynamically disordered compounds.

High-resolution 31P NMR spectra are reported for several dihydrogen phosphates in the solid state. Shielding tensor components were retrieved by analysis of the sideband intensities. The results, together with previously published data, can be grouped according to the presence and type of proton exchange occurring in the crystals. Static MH2PO4 samples (M = Na, Li) show a shielding anisotropy delta sigma of approximately 120 ppm. In the case of M = Cs (one static P-OH bond and two oxygens attached to "half" hydrogens on the average) delta sigma is smaller (approximately 75 ppm) and can be understood in terms of the accepted, proton-exchange model. For highly disordered samples (M = K, NH4, Rb), where all four oxygens have nearby hydrogens with 50% occupancy, delta sigma is even smaller (approximately 30 ppm) but not zero. In the last-mentioned cases, 31P NMR information suggests that local PO4 environments may not have the symmetry that could be expected on the basis of the known crystal structures.

Crystallization↗

Characterization of silicon sites in monoclinic zeolite ZSM-5 using 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) and molecular modelling.

An attempt has been made to correlate the experimentally observed 29Si MAS NMR chemical shifts of monoclinic phase of highly siliceous ZSM-5 with their electronic properties. In order to incorporate the influence of next neighbor atoms on the 29Si chemical shielding of central SiO4, a pentameric cluster model (H12Si5O16) has been chosen. Each of the 24 crystallographically distinct Si sites, of ZSM-5 framework has been modelled by such cluster models. Based on semi-empirical quantum chemical calculations, a multiple linear regression analysis of the various electronic properties with the 29Si chemical shifts has been attempted. The relative difference in 29Si chemical shifts for the Si sites in ZSM-5 is reasonably accounted, although quantitative prediction may require non-empirical quantum chemical calculations.

Crystallography↗

Cell signalling: MAGUK magic.

Diverse extracellular signals are coupled at the plasma membrane to intracellular signal transduction pathways and the cytoskeleton. Members of a ubiquitous multidomain family of proteins, the MAGUK proteins, are emerging as common mediators of this coupling.

Actins↗

Magic bullets for protein kinases.

A chemical-genetic method for the generation of target-specific protein kinase inhibitors has been developed recently. This strategy utilizes a functionally silent active-site mutation to sensitize a target kinase to inhibition by a small molecule that does not inhibit wild-type kinases. Tyrosine and serine/threonine kinases are equally amenable to the drug-sensitization approach, which has been used to generate selective inhibitors of mutant Src-family kinases, Abl-family kinases, cyclin-dependent kinases, mitogen-activated kinases, p21-activated kinases and Ca(2+)/calmodulin-dependent kinases. The designed inhibitors are specific for the sensitized kinase in a cellular background where the wild-type kinase has been inactivated. By these means, kinase-sensitization has been used systematically to generate and analyze conditional alleles of several yeast protein kinases in vivo.

Animals↗

The magic of music.

Explore the source record for details and available documents.

Case Management↗

Micro-imaging of articular cartilage: T2, proton density, and the magic angle effect.

RATIONALE AND OBJECTIVES: This study was designed to determine the relative influences of proton density versus collagen fiber orientation (through its influence on T2) in defining the layers of articular cartilage as seen in long-repetition-time magnetic resonance (MR) images. The authors mapped the T2 and proton densities of articular cartilage at 0 degree and 55 degrees with respect to the main magnetic field (B0) to determine the influence of T2 and water content on the normal laminar appearance of hyaline cartilage. MATERIALS AND METHODS: Six patellae of white-tailed deer were imaged at 7 T. T2 and proton densities were calculated from echo time versus signal intensity plots obtained with a multiecho, composite pulse sequence. Regions of interest in the radial and transitional zones were compared with the articular facets at 0 degree and 55 degrees relative to B0. Transmission electron microscopy was performed for correlation. RESULTS: At 0 degree, T2 was longer in the transitional than in the radial zone (29 vs 11 msec). AT 55 degrees, T2 increased in both radial and transitional zones, although the difference between the zones decreased (37 vs 29 msec). There was no difference in proton density between the two layers. CONCLUSION: Collagen fiber orientation, through T2 effects, is the dominant influence on the appearance of layers in hyaline cartilage in long-repetition-time MR images; proton density is not a major factor, and the collagen fiber orientation in the transitional zone is not totally random.

Animals↗