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51.
Stadler C de Lacey AL Montet Y Volbeda A Fontecilla-Camps JC Conesa JC Fernández VM 《Inorganic chemistry》2002,41(17):4424-4434
ZORA relativistic DFT calculations are presented which aim to model the geometric and electronic structure of the active site of NiFe hydrogenases in its EPR-active oxidized states Ni-A (unready state) and Ni-B (ready state). Starting coordinates are taken from the X-ray structure of a mutant of Desulfovibrio fructosovorans hydrogenase refined at 1.81 A resolution. Nine possible candidates for Ni-A and Ni-B are analyzed in terms of their geometric and electronic structure. Comparison of calculated geometric and magnetic resonance parameters with available experimental data indicates that both oxidized states have a micro-hydroxo bridge between the two metal centers. The different electronic structures of both forms can be explained by a modification of a terminal cysteine in Ni-B, best modeled by protonation of the sulfur atom. A possible mechanism for the activation of both oxidized forms is presented. 相似文献
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The effect of toluene solubilization on the size and mobility of Triton X100 (TX100) micelles and TX100/sodium dodecyl sulfate (SDS) mixed micelles was studied by turbidimetry, dynamic light scattering, and capillary electrophoresis. Micelle growth due to toluene solubilization was observed for both surfactant systems; however, two different modes of growth were seen. Mixed micelles in 0.1 M NaCl are spherical (apparent diameter d(app) = 8 nm) and remain so while taking up 3 mM toluene, with a volume increase per micelle of deltaV(m) = 50 nm3. In 0.5 M NaCl, the large d(app) of both nonionic and mixed micelles (14 and 24 nm, respectively) indicate ellipsoidal or rodlike shapes, and their large increases in d(app) upon addition of 3 mM toluene thus correspond to elongational growth, with the same deltaV(m) = 50 nm3. Further addition of toluene to TX100/SDS in 0.5 M NaCl results in a dramatic increase in micelle size followed by an unexpected bimodal size distribution. The addition of excess toluene leads to the formation of ca. 140 nm toluene droplets, stabilized mainly by monomers of the high critical micelle concentration surfactant, SDS. These microemulsions coexist with the smaller (20 nm) swollen mixed micelles. 相似文献
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We study the problem of optimizing nonlinear objective functions over bipartite matchings. While the problem is generally intractable, we provide several efficient algorithms for it, including a deterministic algorithm for maximizing convex objectives, approximative algorithms for norm minimization and maximization, and a randomized algorithm for optimizing arbitrary objectives. 相似文献
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AssumeV is a finite-dimensional vector space over a division ringD having centerF. It is shown that ifT∈ End D (V) is algebraic overF then the double centralizerC(C(T)) ofT is the setF[T] of all polynomials inT with coefficients fromF. Consequently, eachn×n matrix ring overD is an algebraicF-algebra if and only ifC(C(T))=F[T] for allT and all finite-dimensionalV. 相似文献
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OBJECTIVES: (1) To examine attitudes towards termination of pregnancy (TOP) among high-risk and non-high-risk (for cystic fibrosis) Arab-Muslims, and (2) to examine the effect of an intervention, which among other things related explicitly to TOP. METHODS: The study comprised three groups: (1) an intervention group at high risk for CF, which received community genetic counseling; (2) a control group at high risk for CF, and (3) a control group from the general population. The latter two groups were exposed to minimal intervention. Attitudes were measured two or three times during a 1-year period (for the control and intervention groups, respectively). RESULTS: Predictors of an affected fetus being considered a legitimate cause for TOP were religiosity, familiarity with an affected child, and benefits of the test. Predictors of individuals (hypothetically) choosing abortion in the case of an affected fetus were education and age. No change occurred in the attitudes of participants (either experimental or control groups) in the course of 1 year. CONCLUSIONS: Other possible intervention options are discussed, and specifically, the advantages of using opinion leaders such as clergy and medical staff. 相似文献