A series of new 5-mono- and 5,5′-bisamino-substituted azothiazole derivatives was synthesized from the readily available diethyl azothiazole-4,4′-dicarboxylate. This reaction most likely comprises an initial Michael-type addition by the respective primary alkyl and aromatic amines at the carbon atom C5 of the substrate. Subsequently, the resulting intermediates are readily oxidized by molecular oxygen to afford the amino-substituted azothiazole derivatives. The latter exhibit remarkably red-shifted absorption bands (λabs=507–661 nm) with high molar extinction coefficients and show a strong positive solvatochromism. As revealed by spectrometric titrations and circular and linear dichroism studies, the water-soluble, bis-(dimethylaminopropylamino)-substituted azo dye associates with duplex DNA by formation of aggregates along the phosphate backbone at high ligand–DNA ratios (LDR) and by intercalation at low LDR, which also leads to a significant increase of the otherwise low emission intensity at 671 nm. 相似文献
A previously developed model for nonhydrostatic, free surface flow is redesigned to improve computational efficiency without sacrificing accuracy. Both models solve the Reynolds averaged Navier–Stokes equations in a fractional step manner with the pressure split into hydrostatic and nonhydrostatic components. The hydrostatic equations are first solved with an approximate Riemann solver. The hydrostatic solution is then corrected by including the nonhydrostatic pressure and requiring the velocity field to obey the incompressibility constraint. The original model requires the solution of a Riemann problem at every cell face for each vertical layer of cells, which is computationally expensive. The redesigned model instead solves the shallow water (long wave) equations for the hydrostatic solution. Vertical shear is computed by subtracting the shallow water equations from the full three dimensional equations, which removes the hydrostatic thrust terms. Therefore, the required fluxes may be more efficiently computed with velocity based upwind differencing rather than solving a Riemann problem in each vertical layer of cells. This approach is termed mode splitting and has been used in hydrostatic coastal and ocean circulation models, but not surf zone models. Numerical predictions are compared with analytical solutions and experimental data to show that the mode split model is as accurate as the original model, but requires significantly less computational effort especially for large numbers of cell layers. Published 2014. This article is a U.S. Government work and is in the public domain in the USA. 相似文献
Research on Chemical Intermediates - Herein, we investigated the NOx reduction performance of Sb–V–CeO2/TiO2 (SbVCT) catalyst subjected to hydrothermal aging, where 6 vol% of H2O was... 相似文献
We study new posets Q obtained by removing from a geometric lattice L ofa biased graph certain flats indexed by a simplicial complex
. (One example of L is the lattice of flats of thevector matroid of a root system Bn.) We study the structureand compute the characteristic polynomial of Q. With certainchoices of L and
, including ones for which Q is alattice interpolating between those of Bn and Dn, we observe curious relationships among the roots of thecharacteristic polynomials of Q, L, and
. 相似文献
Let be the arrangement of hyperplanes consisting of the reflecting hyperplanes for the root system . Let be the Varchenko matrix for this arrangement with all hyperplane parameters equal to . We show that is the matrix with rows and columns indexed by permutations with entry equal to where is the number of inversions of . Equivalently is the matrix for left multiplication on by
Clearly commutes with the right-regular action of on . A general theorem of Varchenko applied in this special case shows that is singular exactly when is a root of for some between and . In this paper we prove two results which partially solve the problem (originally posed by Varchenko) of describing the -module structure of the nullspace of in the case that is singular. Our first result is that
in the case that where Lie denotes the multilinear part of the free Lie algebra with generators. Our second result gives an elegant formula for the determinant of restricted to the virtual -module with characteristic the power sum symmetric function .
This paper details a study of the selectivity characteristics of high-performance chelation ion chromatography when separating a range of metal ions with a number of complexing eluents. It shows that exploitation of competitive metal complexation between ligands in the eluent and surface bonded chelating groups allows a wide range of control over the retention order and selectivity coefficients of groups of metal ions for specific applications. An indication of the metal separation characteristics found for simple non-complexing eluents on iminodiacetic acid (IDA) silica bonded substrates is given first, followed by an illustration of the selectivity changes that can be achieved by using complexing eluents. Using a novel approach, plots of logbeta(1) of the metal complexes of a chosen eluent ligand against the surface bonded IDA metal complexes were found to be useful indicators of which metals may show unusual selectivity changes during separation. Example chromatograms of metal separations are given for three selected complexing eluent reagents, namely, oxalic acid, picolinic acid, and chloride, either singly or in admixture. For special mention it was found that very specific retention control could be achieved for Cu(II) with picolinic acid, Fe(III) and Fe(II) speciation with oxalic acid, Pb with dipicolinic acid and Cd with chloride. 相似文献
The stoichiometric reduction of N-carbophenoxypyridinium tetraphenylborate (6) by CpRu(P-P)H (Cp = eta(5)-cyclopentadienyl; P-P = dppe, 1,2-bis(diphenylphosphino)ethane, or dppf, 1,1'-bis(diphenylphosphino)ferrocene), and Cp*Ru(P-P)H (Cp* = eta(5)-pentamethylcyclopentadienyl; P-P = dppe) gives mixtures of 1,2- and 1,4-dihydropyridines. The stoichiometric reduction of 6 by Cp*Ru(dppf)H (5) gives only the 1,4-dihydropyridine, and 5 catalyzes the exclusive formation of the 1,4-dihydropyridine from 6, H(2), and 2,2,6,6-tetramethylpiperidine. In the stoichiometric reductions, the ratio of 1,4 to 1,2 product increases as the Ru hydrides become better one-electron reductants, suggesting that the 1,4 product arises from a two-step (e(-)/H(*)) hydride transfer. Calculations at the UB3LYP/6-311++G(3df,3pd)//UB3LYP/6-31G* level support this hypothesis, indicating that the spin density in the N-carbophenoxypyridinium radical (13) resides primarily at C4, while the positive charge in 6 resides primarily at C2 and C6. The isomeric dihydropyridines thus result from the operation of different mechanisms: the 1,2 product from a single-step H(-) transfer and the 1,4 product from a two-step (e(-)/H(*)) transfer. 相似文献
Let be a simple graph with nodes. The coloring complex of , as defined by Steingrimsson, has -faces consisting of all ordered set partitions, in which at least one contains an edge of . Jonsson proved that the homology of the coloring complex is concentrated in the top degree. In addition, Jonsson showed that the dimension of the top homology is one less than the number of acyclic orientations of .
In this paper, we show that the Eulerian idempotents give a decomposition of the top homology of into components . We go on to prove that the dimensions of the Hodge pieces of the homology are equal to the absolute values of the coefficients of the chromatic polynomial of . Specifically, if we write , then .