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21.
The reactivities of two copper(II)-phenoxyl analogues of the oxidized, active form of the metalloenzyme galactose oxidase, [1tBu2]+ and [2tBu2]+, have been studied using the substrates benzyl alcohol and 9,10-dihydroanthracene, for a total of four reactions. The reaction stoichiometries in all cases show a 2:1 ratio of oxidant to benzaldehyde or anthracene product, indicating that [1tBu2]+ and [2tBu2]+ behave ultimately as only one-electron oxidants, but the reaction kinetics each indicate that only a single copper(II)-phenoxyl complex is involved in the rate-determining step. For each substrate, rate laws indicate that [1tBu2]+ and [2tBu2]+ react by different mechanisms: one proceeds by a simple bimolecular reaction, while the other first enters into a substrate-binding equilibrium before subsequently reacting by an intramolecular reaction. The reactions proceeding by the latter mechanism have faster overall rates, which correlates to a lower entropic barrier for the substrate-binding mechanism. Correlation of the reaction rates with the C-H bond dissociation energies of substrates as well as significant deuterium kinetic isotope effects indicates that the rate-determining steps involve hydrogen atom abstraction from the activated C-H bonds. A variable-temperature study (268-308 K) of the nonclassical KIE of the [1tBu2]+/benzyl alcohol reaction (kH/kD = 15 at 298 K) failed to show evidence for quantum tunneling. The rapid sequence by which a second 1 equiv of copper(II)-phenoxyl oxidant completes the reaction after the rate- and product-determining hydrogen atom abstraction step cannot be probed kinetically. Comparisons are made to the reactivities of other copper(II)-phenoxyl complexes reported in the literature and to galactose oxidase itself.  相似文献   
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A Hilbert transform for Hlder continuous circulant (2 × 2) matrix functions, on the d-summable (or fractal) boundary Γ of a Jordan domain Ω in R2n , has recently been introduced within the framework of Hermitean Clifford analysis. The main goal of the present paper is to estimate the Hlder norm of this Hermitean Hilbert transform. The expression for the upper bound of this norm is given in terms of the Hlder exponents, the diameter of Γ and a specific d-sum (d d) of the Whitney decomposition of Ω. The result is shown to include the case of a more standard Hilbert transform for domains with left Ahlfors-David regular boundary.  相似文献   
24.
In this study, wood production and hydrologic functions of forests were accommodated within a planning procedure for separate working circles (areas dedicated to certain forest functions) that were delineated according to an Ecosystem‐Based Functional Planning approach. Mixed integer goal programming was used as the optimization technique. The timing and scheduling of a maintenance cutting (partial harvest) was the decision variable in the modeling effort, and an original formulation was developed as a multiobjective planning procedure. Four sample planning strategies were developed and model outputs were evaluated according to these strategies. Spatial characteristics of stands were considered, and used to prohibit the regeneration of adjacent stands during the same time period. Because of the positive relationship between qualified water production and standing timber volume in the forest, the model attempts to maximize qualified water production levels by increasing standing volume stocks in the forest through the delay of regeneration activities.  相似文献   
25.
We construct two cohomological invariants associated to pairs of Lagrangian sub-bundles of a symplectic bundle on a compact manifold upon which a compact Lie group is acting. The first invariant, which we call the classical equivariant Maslov H-invariant, provides an obstruction to Lagrangian transversality and lives in the Borel cohomology. The second invariant, which we call the equivariant Maslov U-invariant, generalises the author's results in K-Theory 13 (1998), 347–361 to the equivariant context and provides a necessary and sufficient condition for equivariant Lagrangian transversality, up to homotopic stability, and lives in the U-theory (intermediate between the real complex K-theories). As an application, we show that two Lagrangian sub-bundles of a symplectic bundle on a homogeneous space are always stably transverse.  相似文献   
26.
用三弧Czochralski法和真空电弧熔炼法制备了Ho2Co17-xSix化合物.通过X射线衍射和磁性测量手段研究了化合物的结构与内禀磁性.重点讨论了磁晶各向异性和自旋重取向转变.实验结果表明,Ho2Co17为Th2Ni17型六角结构,在0.5≤x≤3的化合物均为Th2Zn17型菱方结构,能够获得单相2:17型化合物的最大Si含量是x=3.在x≤2的浓度范围,化合物的易磁化方向垂直于c轴.随Si含量增加,化合物的居里温度和Co原子平均磁矩单调减少.根据Ho2Co17-xSix化合物的居里温度和自旋重取向温度,获得了磁相图.根据热磁曲线,确定了温度补偿点.在Ho2Co17化合物中观察到了在1005 K发生自旋重取向转变.  相似文献   
27.
Synthesis of a new fluorescent probe specific for catechols   总被引:1,自引:0,他引:1  
[reaction: see text] The synthesis of a new fluorescent probe, specific for the catechol moiety, has been conducted by preparation of alpha,alpha-dibromomalonamides containing an appropriate fluorophore. N,N'-Bis-anthracen-9-ylmethyl-2,2-dibromomalonamide reacted with various catechols in the presence of cesium carbonate to generate highly fluorescent derivatives.  相似文献   
28.
We use cubic-phase plate imaging to demonstrate an order-of-magnitude improvement in the transverse resolution of three-dimensional objects reconstructed by extended depth-of-field tomography. Our algorithm compensates for the range shear of the cubic-phase approach and uses camera rotation to center the reconstructed volume on a target object point.  相似文献   
29.
One-electron oxidation of two structurally similar CuII-diphenolate complexes, 1 and 2, creates EPR-silent CuII-phenoxyl complexes [1]+ and [2]+ that mimic the oxidized form of the enzyme galactose oxidase (GOase). Both model complexes display novel NIR absorptions assigned to phenolate-phenoxyl charge transfer that resemble a tyrosinate-tyrosyl charge-transfer band observed in the enzymatic system. [1]+ and [2]+ react with benzyl alcohol to form 0.5 equivs of benzaldehyde per complex; biomimetic reduction to CuI-phenol complexes is not observed, but such species may exist transiently. Initial kinetic studies show that [2]+ reacts faster with benzyl alcohol than does [1]+, despite being a significantly weaker oxidant (DeltaE degrees = 370 mV). This acceleration is ascribed to mechanistic differences: [2]+ appears to bind substrate prior to the rate-determining step. Large, nonclassical kinetic isotope effects confirm C-H bond cleavage as the rate-determining step in the reactions of both [1]+ and [2]+ with benzyl alcohol, as is the case for GOase.  相似文献   
30.
Abstract— Ellipsometric angles and reflectivity of black lipid membranes containing either egg lecithin or chloroplast extracts were measured at a wavelength of 6328 Å. Evidence was found for positive uniaxial anisotropy in membranes of lecithin. If the thickness of those films is assumed to be 62 Å, the refractive index normal to the film surface is 1.471 ± 0.004, and the refractive index parallel to the film surface is 1.454 ± 0.003. The results for membranes of chloroplast extracts also indicate a positive anisotropy in the indices of absorption.  相似文献   
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