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71.
The catalytic dechlorination of chlorinated ethylenes by 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin cobalt ((TCPP)Co), a cobalt complex structurally similar to vitamin B12, was studied. It was found to have superior aqueous-phase dechlorination activity on chlorinated ethylenes (CEs) relative to vitamin B12. Bimolecular rate constants for the degradation of CEs by (TCPP)Co of 250, 24, 0.24, and 1.5 M(-1) s(-1) were found for perchloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (cDCE), and trans-dichloroethylene (tDCE), respectively. Through kinetic analysis, the rate laws for PCE and TCE were determined to be first order in substrate and catalyst, and PCE degradation was shown to be sensitive to the concentration of the titanium citrate bulk reductant and pH. The importance of the Co(I) oxidation state on dehalogenation was studied with UV-vis absorbance spectroscopy, a variety of reducing agents, and cyclic voltammetry. Evidence of chlorovinyl complexes as potential catalytic cycle intermediates was obtained through the preparation of (TPP)Co(trans-C2H2Cl) and the observation of (TPP)Co(C2HCl2) and (TCPP)Co(C2HCl2) by mass spectrometry. The X-ray crystal structure of (TPP)Co(trans-C2H2Cl) is reported. 相似文献
72.
2,4-Dichlorobenzoic acid and a suite of models of chlorinated biphenyl carboxylic acids were found to be efficient sensitizers of the reactive oxygen species singlet oxygen (1O2). 相似文献
73.
Willans MJ Feindel KW Ooms KJ Wasylishen RE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):159-168
Lanthanum-139 NMR spectra of stationary samples of several solid La(III) coordination compounds have been obtained at applied magnetic fields of 11.75 and 17.60 T. The breadth and shape of the 139La NMR spectra of the central transition are dominated by the interaction between the 139La nuclear quadrupole moment and the electric field gradient (EFG) at that nucleus; however, the influence of chemical-shift anisotropy on the NMR spectra is non-negligible for the majority of the compounds investigated. Analysis of the experimental NMR spectra reveals that the 139La quadrupolar coupling constants (C(Q)) range from 10.0 to 35.6 MHz, the spans of the chemical-shift tensor (Omega) range from 50 to 260 ppm, and the isotropic chemical shifts (delta(iso)) range from -80 to 178 ppm. In general, there is a correlation between the magnitudes of C(Q) and Omega, and delta(iso) is shown to depend on the La coordination number. Magnetic-shielding tensors, calculated by using relativistic zeroth-order regular approximation density functional theory (ZORA-DFT) and incorporating scalar only or scalar plus spin-orbit relativistic effects, qualitatively reproduce the experimental chemical-shift tensors. In general, the inclusion of spin-orbit coupling yields results that are in better agreement with those from the experiment. The magnetic-shielding calculations and experimentally determined Euler angles can be used to predict the orientation of the chemical-shift and EFG tensors in the molecular frame. This study demonstrates that solid-state 139La NMR spectroscopy is a useful characterization method and can provide insight into the molecular structure of lanthanum coordination compounds. 相似文献
74.
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76.
Kristopher Tapp 《Proceedings of the American Mathematical Society》2008,136(1):295-300
When is a biquotient, we show that there exist vector bundles over with metrics of nonnegative curvature whose normal holonomy groups have arbitrarily large dimension.
77.
Our main result is that every n-dimensional polytope can be described by at most 2n–1 polynomial inequalities and, moreover, these polynomials can explicitly be constructed. For an n-dimensional pointed polyhedral cone we prove the bound 2n–2 and for arbitrary polyhedra we get a constructible representation by 2n polynomial inequalities.Supported by the DFG Research Center Mathematics for key technologies (FZT 86) in Berlin. 相似文献
78.
Krishnan Shankar Kristopher Tapp Wilderich Tuschmann 《Proceedings of the American Mathematical Society》2005,133(8):2449-2459
We derive and study necessary and sufficient conditions for an -bundle to admit an invariant metric of positive or nonnegative sectional curvature. In case the total space has an invariant metric of nonnegative curvature and the base space is odd dimensional, we prove that the total space contains a flat totally geodesic immersed cylinder. We provide several examples, including a connection metric of nonnegative curvature on the trivial bundle that is not a product metric.
79.
Mixing and dispersion phenomena caused by the carrier fluid in an electrophoretic cell is the main subject of this study. In particular, the effects of Joule heating on temperature and velocity profiles for Eyring-model fluids (EMF) are studied. The heat transfer is sequentially coupled with momentum transfer to derive an analytical expression for both the temperature and the velocity profiles. These results are then used to show the hydrodynamic behavior of the fluid in a batch electrophoretic cell. Furthermore, the results obtained are useful to compare with the fluid behavior of other carriers of different rheology, such as Newtonian fluids, power-law fluids, and viscoelastic fluids that obey the CEF model. The results show that EMF are potentially good carriers for relatively high Joule heat generation and therefore good candidates to control mixing inside the electrophoretic cell. 相似文献
80.
Yu Harabuchi Yuriko Ono Satoshi Maeda Tetsuya Taketsugu Kristopher Keipert Mark S. Gordon 《Journal of computational chemistry》2016,37(5):487-493
A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical SN2‐type reaction, NC‐ + CH3X → NC? CH3 + X‐ (X = F, Cl). A nontotally symmetric valley‐ridge inflection (VRI) point was located along the C3v reaction path. For X = F, the minimum energy path (MEP) starting from the transition state (TS) leads to a second‐order saddle point with C3v symmetry, which connects three product minima of Cs symmetry. For X = Cl, four product minima have been observed, of which three belong to Cs symmetry and one to C3v symmetry. The branching path from the VRI point to the lower symmetry minima was determined by a linear interpolation technique. The branching mechanism is discussed based on the reaction path curvature and net atomic charges, and the possibility of a nonotally symmetric n‐furcation is discussed. © 2015 Wiley Periodicals, Inc. 相似文献