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31.
D. Allen Clabo Jr. Hamilton D. Dickson Toby L. Nelson 《Journal of molecular modeling》2000,6(2):341-348
Semiempirical and ab initio theoretical methods have been used to investigate molecular structures of the chalcogen-substituted carboxylic acid isomers RC(=O)XH (chalcogenol acid) and RC(=X)OH (chalcogenon acid). A recent experimental report suggests that the chalcogenon isomers, although less stable at room temperature, predominate at low temperature in polar solvents and that there is only a small barrier to isomerization between the isomers. Theoretical calculations have been used to locate minimum energy structures of chalcogen-substituted carboxylic acid isomers and to calculate energy differences between pairs of isomers. Carboxylic acids are well known to dimerize, especially in the gas phase and in non-polar solvents. We have, therefore, also calculated energies of dimerization of the chalcogen-substituted acids by optimizing the geometries of the symmetric dimers. We note that the PM3 level of theory is only qualitatively correct for sulfur- and selenium-containing species but fails even qualitatively for the tellurium-containing compounds. Ab initio results confirm the experimental observations and provide good estimates of both isomerization and dimerization energies. We conclude that for many functional groups with tautomers RC(=X)YH and RC(=Y)XH, the more acidic tautomer is the one with the acid proton on the smaller, more electronegative atom, although in many cases this may not be the more stable tautomer.Electronic Supplementary Material available. 相似文献
32.
Lawrence Que Jr. 《Journal of biological inorganic chemistry》2004,9(6):684-690
The oxygen activation mechanisms proposed for nonheme iron systems generally follow the heme paradigm in invoking the involvement of iron-peroxo and iron-oxo species in their catalytic cycles. However, the nonheme ligand environments allow for end-on and side-on dioxygen coordination and impart greater flexibility in the modes of dioxygen activation. The currently available evidence for nonheme iron-peroxo and iron-oxo intermediates is summarized and discussed in light of the ongoing discussion on the nature of the oxidant(s) in heme enzymes. 相似文献
33.
MICHIKO WATANABE DONALD R. BERTOLINI J. RANDOLPH SCHNTTMAN ROBERT S. TURNER Jr. 《Differentiation; research in biological diversity》1982,21(1-3):79-85
Sea urchin embryos can be dissociated into a suspension of single cells that reconstitute embryo-like structures. When reconstitution is conducted in stationary cultures the first step is attachment of the cells to the culture plate, which requires calcium and metabolic energy but not protein synthesis. We have found that protease treated cells form cell-cell associations in stationary cultures without attaching to the culture plates, and that cell-plate attachments are unaffected by inhibition of protein synthesis. These data suggest that cell surface proteins are needed for cell-plate attachment and that these proteins are present on freshly dissociated cells. We also demonstrated that butanol extracted cells attach to the plates, but do not form functional cell-cell associations unless the butanol extracted material is restored to them. We conclude that sea urchin embryo cells contain two classes of attachment components. The first class functions in the cell-plate attachments, is protease sensitive, and not extracted by butanol; the second class is necessary for cell-cell associations, is protease insensitive, and extracted by butanol. Since protease treated cells reconstitute embryo-like structures without attaching to the culture plates, only the second class of attachment components is necessary for embryo reconstitution. 相似文献
34.
Charles E. Wenner John C. Cheney L. David Tomei 《Journal of cellular biochemistry》1981,15(2):161-168
The introduction of either PGF2α (10?7 M) or TPA (10?7 M) stimulated, ouabain-sensitive 86Rb+ influx at 30 min in postconfluent 3T3-4 mouse fibroblast cultures by 117% and 124%, respectively. Both TPA and PGF2α at these concentrations stimulated the incorporation of 3H-TdR into DNA. TPA had the greatest stimulatory effect, which was similar to that obtained with 10% fetal calf serum. In accord with the idea that modulation of membrane processes such as Na+/K+ pump activity in fibroblasts may reflect important events related to the initiation of DNA synthesis, it was observed that in both 3T3-4 and C3H-1 0T½ cells there were parallel increases in 3H-TdR incorporation and ouabain-sensitive 86Rb+ influxes with 10?7 M TPA, whereas PGF2α stimulated a significant increase in 3H-TdR incorporation in 3T3-4 but not C3H-10T½ cells and only marginal increases in ouabain-sensitive 86Rb+ influx in both. Therefore, although there appears to be a close correlation between Na+/K+ pump activation and subsequent S-phase entry following TPA stimulation, a similar correlation for PGF2α cannot be confirmed. 相似文献
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36.
S. E. Franklin L. Young D. Watson A. Cigan T. Meyer L. A. Bulla Jr. 《Molecular genetics and genomics : MGG》1997,256(5):517-524
Various subspecies of the gram-positive bacterium Bacillus thuringiensis are known to produce a wide array of insecticidal crystal proteins (ICPs) upon sporulation. These ICPs act primarily on the brush border of midgut epithelial cells of susceptible larvae. Recently, a protein of 210?kDa, isolated from the midgut of Manduca sexta, has been demonstrated to bind the Cry1Ab toxin produced by B. thuringiensis subsp. berliner and is therefore postulated to be involved in mediating the toxicity of Cry1Ab. The cDNA encoding the 210?kDa protein, termed BT-R1 (Bacillus thuringiensis receptor-1), was recently cloned, and shows limited homology to the cadherin superfamily of proteins. Quite naturally, there is a great deal of interest in the characterization of BT-R 1 , the gene encoding the 210?kDa Cry1Ab binding protein. The studies presented here involve the use of various restriction fragments prepared from the cDNA encoding BT-R1 as probes of Southern blots bearing M. sexta genomic DNA cleaved with a variety of restriction endonucleases. These Southern blot data reveal that there are two discrete regions within the M. sexta genome which encode sequences homologous to BT-R1. On the basis of the signal intensities seen on Southern blots, it appears that only one of these genes encodes BT-R1, whereas the other is a closely related homologue. 相似文献
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Summary Osteogenesis imperfecta (OI) is a phenotype with clinical and biochemical heterogeneity. We report here that expression of the OI phenotype extends to the level of dermal fibroblast morphology in vitro. Growth characteristics and morphology of control (n=6) and OI cell strains (n=10, representing the four major OI categories, Sillence classification) were compared by measuring the following: (i) days required in culture to reach confluence after plating at uniform density; (ii) cell density at confluence; (iii) width and length of cells (measured on phase contrast micrographs at 300xmagnification). Our results show that: (i) OI fibroblasts take longer (11–27 days, mean 20 days) than control cells (10–19 days, mean 16 days) to reach stationary phase; (ii) all OI phenotypes achieve a lower cell density (0.87x106 cells/P60, range 0.3–1.6x106) at stationary phase relative to control cells (2.2x106 cells/P60, range 1.7–2.6x106; F4,77=56.1, p<0.01, indicating that OI cells are larger than normal). Cell shape (expressed as the width: length ratio) was also abnormal in OI cells. (F4,730=37.6, p<0.01), types I and II OI cells have significantly increased ratios (p<0.01) relative to control, type III, and type IV cells. Intra-group phenotypic heterogeneity was also apparent in the OI categories and also within the control population. These findings confirm deviant morphologic phenotypes in OI dermal fibroblasts and further demonstrate interindividual heterogeneity in the expression of genes that determine size and shape of dermal fibroblasts in both OI and normal donors.Publication No. 84013 from the Montreal Children's Hospital Research Institute 相似文献