Substituted 1,4-diazepino[5,6,7-kl]acridines as unexpected side products in reaction of 2-(dialkylamino)ethylamine with 1-chloro-7-methyoxy-4-nitro-9-phenoxyacridine

Substituted 1,4-diazepino[5,6,7-kl]acridines were obtained in reaction of 2-(dialkylamino)ethylamine with 1-chloro-7-methoxy-4-nitro-9-phenoxyacridine. The mechanism of their formation was studied. The correct structure of these compounds was established on the basis of their ¹H nmr studies.     

Optimization of sequencing conditions using near-infrared lifetime identification methods in capillary gel electrophoresis

We have investigated the sample preparation and electrophoresis conditions necessary to prepare DNA sequencing samples appropriate for use with near-infrared (IR) fluorescent labels with dye identification accomplished via lifetime techniques. It was found that several sample preparation protocols required attention to maximize the fluorescence yields of the labeling dyes, such as thermal cycling conditions, choice of counter ion used for the ethanol precipitation step and also, dye-primer versus dye-terminator chemistries. In addition, several different sieving matrices were investigated for their effects on both the fluorescence properties of the labeling dyes and electrophoretic resolution. Extended times used for the high temperature denaturing of duplexed DNA fragments during cycle sequencing produced cleavage products, in which the covalently attached dye to the sequencing primer was released through attack by dithiothreitol (DTT). Even under optimized thermal cycling conditions, free dye was generated that masked readable data from the sequencing traces. Ethanol precipitation was necessary to remove this free dye with the proper choice of counter ion (sodium). The results using different sieving matrices indicated that linear polyacrylamides (LPAs) were appropriate for any fluorescence measurement, since they could readily be replaced between runs minimizing deleterious memory effects associated with cross-linked polyacrylamide gels. After investigation of several different sieving LPAs, the commercially available POP6 was found to be particularly attractive, since it produced good electrophoretic resolution, single exponential behavior for the near-IR dye series investigated herein, and also, discernible lifetime differences within the dye set. Finally, dye-terminator chemistry was also found to minimize bleeding in the gel matrix produced by large amounts of unextended dye-primer within the gel lane.     

Conversion of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (mptp) and its 5-methyl analog into pyridinium salts

Monoamine oxidase B metabolizes 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP; 1 ) first to 1-methyl-4-phenyl-2,3-dihydropyridinium salt (MPDP⁺; 5 ), and then to 1-methyl-4-phenylphridinium salt (MPP⁺; 7 ). Chemical synthesis of MPDP⁺ and its 5-methyl analog 6 was accomplished from the N-oxides 3 and 4 of MPTP and its 5-methyl analog, respectively, by a Polonovski reaction. Oxidation of MPDP⁺ to MPPM⁺ was accomplished with air, and greatly accelerated by Pt catalyst. Reduction of MPDP⁺ and MPP⁺ with NaBH₄ afforded MPTP.     

Heteroleptic metal alkoxide "oxoclusters" as molecular models for the sol-gel synthesis of perovskite nanoparticles for bio-imaging applications

Systematic structural study of the molecules, resulting from microhydrolysis of heterometallic beta-diketonate alkoxides of barium and strontium (single-source precursors of perovskite oxide materials), demonstrates that the structures of these products result from a thermodynamically driven self-assembly of metal cations and ligands directed towards the most densely packed cores. The ratio between metal cations, and of the cations to bidentate heteroligands, is easily changed to enable the highest packing density. The key to the application of single-source precursors appears to be the use of stoichiometric or superstoichiometric water amounts together with solvents preventing diffusion of possible homometallic intermediates. Eu-doped BaTiO3 nanoparticles have been successfully obtained and characterized.     

A compact group which is not Valdivia compact

A compact space is Valdivia compact if it can be embedded in a Tikhonov cube in such a way that the intersection is dense in , where is the sigma-product ( the set of points with countably many non-zero coordinates). We show that there exists a compact connected Abelian group of weight which is not Valdivia compact, and deduce that Valdivia compact spaces are not preserved by open maps.

     

Menger algebras of n-place interior operations

Algebraic properties of n-place interior operations on a fixed set are described. Conditions under which a Menger algebra of rank n can be represented by n-place interior operations are found.     

A comparative DFT study of substrates and products of industrial enzyme nitrile hydratase

Nitrile hydratase (NHase) is a metalloenzyme used in industrial biotechnology for a large scale production of common chemicals. NHases convert nitriles to the corresponding amides. Although the structures of some forms of NHases containing nonheme low spin Fe(III) or low spin noncorrinoid Co(III) are known, neither a catalytic mechanism nor the reasons of high selectivity towards aromatic ligands are recognized. Optimized geometries, molecular electrostatic potential maps and infrared spectra of commercially important aromatic substrates of the NHase (nicotinonitrile, o‐, m‐, p‐methylbenzonitrile) and the corresponding products (nicotinamide, o‐, m‐, p‐methylbenzamid) were investigated using the density functional theory method with the B3LYP functional and the 6‐31G(d,p) basis set. Calculated hypothetical intrinsic reaction paths indicate that benzimidic acids may be involved as intermediates. This study elucidates differences in the electronic properties of substrates and products of NHases, provides an insight into the molecular basis of the catalytic reaction and helps to explain varying enzymatic activities of microbial NHases. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Luminescence from γ-irradiated humic acid

This study was conducted to investigate the ultraweak delayed radiochemiluminescence (RCL) spectra, kinetics and spectroscopic properties of humic acids (HAs) after γ-radiation exposure (absorbed doses of 1−10 kGy, Co-60) in model systems.

The kinetics and spectral distribution of RCL (340–650 nm) were measured using the single photon counting (SPC) method and cut-off filters.

The intensity of fluorescence (λ_ex=390, 440, 490 and 540 nm) covering the spectral range 400–580 nm was heavily dependent on the λ_ex and slightly increased with the absorbed dose of γ-radiation.

Absorption spectra (the range 240−800 nm) and color coefficients E_2.6/4 and E_4/6 of irradiated solutions indicated that post-radiative degradation/polymerization processes take place in the HA, changing their macromolecule size or properties.

Comparison of FTIR spectra and elemental analysis proved an increased O and decreased C atoms in irradiated samples. The data indicate on the radiolysis-induced degradation of native HA into fulvic-like acids with higher hydrophilicity and lower molecular size.