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Pasquarello A Petri I Salmon PS Parisel O Car R Toth E Powell DH Fischer HE Helm L Merbach A 《Science (New York, N.Y.)》2001,291(5505):856-859
We determined the structure of the hydrated Cu(II) complex by both neutron diffraction and first-principles molecular dynamics. In contrast with the generally accepted picture, which assumes an octahedrally solvated Cu(II) ion, our experimental and theoretical results favor fivefold coordination. The simulation reveals that the solvated complex undergoes frequent transformations between square pyramidal and trigonal bipyramidal configurations. We argue that this picture is also consistent with experimental data obtained previously by visible near-infrared absorption, x-ray absorption near-edge structure, and nuclear magnetic resonance methods. The preference of the Cu(II) ion for fivefold instead of sixfold coordination, which occurs for other cations of comparable charge and size, results from a Jahn-Teller destabilization of the octahedral complex. 相似文献
84.
Analysis of several well-documented specimens from each of the three volcanic series on Oahu gives the following mean ratios of Sr(87) to Sr(86): the Waianae series, 0.7030 +/- 0.00010 (sigma); the Koolau series, 0.70385+/- 0.00009 (sigma); and the Honolulu series, 0.7029 ++/- 0.00006 ( sigma). The mean ratio of Sr(87) to Sr(86) of the Koolau series specimens is significantly higher than the means of the other two series. With one exception, significant differences in Sr(87)/ Sr(86) within a series were not found, even though some large compositional differences existed. 相似文献
85.
Precipitation of sulfide ores and organic matter: sulfate reactions at pine point, Canada 总被引:1,自引:0,他引:1
Bitumen is a common associate of carbonate-hosted lead-zinc deposits. On the Pine Point lead-zinc property, Northwest Territories, Canada, there are two forms of bitumen. Unaltered bitumens have atomic hydrogen/carbon ratios of about 1.4, sulfur contents of about 7.8 percent, and sulfur isotope ratios ( section sign(34)S) of approximately +4.6 per mil. Altered bitumens occur in proximity to sulfide ore bodies and white sparry dolomite. Their hydrogen/carbon ratios are about 1.02, the sulfur contents average 22 percent, and the section sign(34)S values are about +12.4 per mil. These data indicate that some bitumen has participated in the thermochemical reduction of sulfate to produce hydrogen sulfide required to precipitate the ores. Mass balance considerations show that the amount and degree of alteration of bitumen is more than adequate to account for the reduced sulfur species (lead, zinc, and iron sulfides) deposited at Pine Point. These reactions may provide an important means of generating the large volumes of sulfide necessary to precipitate ore bodies in carbonate rocks. 相似文献
86.
Sulfur difluioride has been identified and characterized from its microwave spectrum. The analysis of rotational transitions for both sulfur difluoride-32 and sulfur difluoride-34 shows that this molecular species has C(2v) symmetry with a bond length of 1.589 angstroms, a bond angle of 98 degrees 16', and a dipole moment of 1.05 Debye. 相似文献
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Wang Z Shen D Parsons DW Bardelli A Sager J Szabo S Ptak J Silliman N Peters BA van der Heijden MS Parmigiani G Yan H Wang TL Riggins G Powell SM Willson JK Markowitz S Kinzler KW Vogelstein B Velculescu VE 《Science (New York, N.Y.)》2004,304(5674):1164-1166
Tyrosine phosphorylation, regulated by protein tyrosine phosphatases (PTPs) and kinases (PTKs), is important in signaling pathways underlying tumorigenesis. A mutational analysis of the tyrosine phosphatase gene superfamily in human cancers identified 83 somatic mutations in six PTPs (PTPRF, PTPRG, PTPRT, PTPN3, PTPN13, PTPN14), affecting 26% of colorectal cancers and a smaller fraction of lung, breast, and gastric cancers. Fifteen mutations were nonsense, frameshift, or splice-site alterations predicted to result in truncated proteins lacking phosphatase activity. Five missense mutations in the most commonly altered PTP (PTPRT) were biochemically examined and found to reduce phosphatase activity. Expression of wild-type but not a mutant PTPRT in human cancer cells inhibited cell growth. These observations suggest that the mutated tyrosine phosphatases are tumor suppressor genes, regulating cellular pathways that may be amenable to therapeutic intervention. 相似文献