Synthesis of 5-Alkyl- and 5-Phenylamino-Substituted Azothiazole Dyes with Solvatochromic and DNA-Binding Properties

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 (λ_abs=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.     

Effect of hydrothermal aging on NOx reduction performance for Sb–V–CeO2/TiO2 catalyst

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...     

Tractable Partially Ordered Sets Derived from Root Systems and Biased Graphs

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 B _n .) 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 B _n and D _n , we observe curious relationships among the roots of thecharacteristic polynomials of Q, L, and .     

A -deformation of a trivial symmetric group action

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 .

     

Use of complexing reagents as additives to the eluent for optimization of separation selectivity in high-performance chelation ion chromatography

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.     

A Hodge decomposition interpretation for the coefficients of the chromatic polynomial

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 .

     

1,3-Diol synthesis via controlled, radical-mediated C-H functionalization

The invention of a method for the synthesis of 1,3-diols from the corresponding alcohols is described, via controlled, radical-mediated C-H functionalization. The sequence described herein entails near quantitative conversion to the corresponding trifluoroethyl carbamate, followed by a variant of the Hofmann-L?ffler-Freytag reaction, cyclization, and hydrolysis to provide the 1,3-diols. In addition to the 10 examples presented herein, the syntheses of four natural products are facilitated by this directed oxyfunctionalization. This methodology is demonstrated to be orthogonal to other known C-H oxidations. Finally, this sequence is efficient, practical, inexpensive, and scalable.     

Protein-nanoparticle labelling probed by surface enhanced resonance Raman spectroscopy

A benzotriazole dye has been attached to a heme protein via a Michael addition and the unique potential of surface enhanced resonance Raman scattering (SERRS) to provide informative in situ recognition of more than one label on one protein demonstrated.