Selection of Suitable Combination of Nonfunctional Micellar Catalyst and Heteroaromatic Nitrogen Base as Promoter for Chromic Acid Oxidation of Ethanol to Acetaldehyde in Aqueous Medium at Room Temperature

The effect of the promoter and micellar catalyst on chromic acid on the oxidation of ethanol in aqueous acid media has been studied. Picolinic acid (PA), 1,10‐phenanthroline (phen), and 2,2′‐bipyridine (bipy) are used as promoters. Sodium dodecyl sulfate (SDS), cetyl pyridinium chloride (CPC), and Triton‐X‐100 (TX‐100) are tested as micellar catalysts. Hexavelent chromium is an active species in the absence of the promoter. In the presence of the heteroaromatic nitrogen bases used as the promoter, Cr(VI)–PA, Cr(VI)–bipy, and Cr(VI)–phen complexes have been proposed as the active oxidants. The time taken for completion of the reaction using different combinations of promoter and micellar catalysts are different. Although the rate is highest (12.5 times) in TX‐100 in the absence of the promoter, it is observed that the rate is almost 737 times faster for the combination of SDS and bipy compared to the unpromoted and uncatalyzed path. CPC inhibits the oxidation process. The observed acceleration and retardation of the rate of oxidation process has been explained on the basis of partitioning of the reactants in the micellar and aqueous phase. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 175–186, 2013     

Arylsulfimide Polymers. V. Polysaccharins of the A-B Type

6-Aminosaccharin and related monomers were subjected to polymerization as melts and in solvents. The products from these studies passed through soluble, hemipolymer stages corresponding to polyamide structures before being cyclized at higher temperatures to the final, insoluble, thermally stable polymers. Melt polymerization of 6-aminosaccharin as the triethylamine salt was the preferred procedure and yielded products of highest intrinsic viscosity (0.431 dl/g in N,N-dimethylacetamide).     

Generation of amplitude death and rhythmogenesis in coupled hidden attractor system with experimental demonstration

Nonlinear Dynamics - Third-order nonlinear dynamical systems with attractors (one with no fixed point and the other with a stable fixed point) are conjugately coupled. It is observed that the...     

Singly and doubly excited states of butadiene, acrolein, and glyoxal: Geometries and electronic spectra

Excited-state geometries and electronic spectra of butadiene, acrolein, and glyoxal have been investigated by the symmetry adapted cluster configuration interaction (SAC-CI) method in their s-trans conformation. Valence and Rydberg states below the ionization threshold have been precisely calculated with sufficiently flexible basis sets. Vertical and adiabatic excitation energies were well reproduced and the detailed assignments were given taking account of the second moments. The deviations of the vertical excitation energies from the experiment were less than 0.3 eV for all cases. The SAC-CI geometry optimization has been applied to some valence and Rydberg excited states of these molecules in the planar structure. The optimized ground- and excited-state geometries agree well with the available experimental values; deviations lie within 0.03 A and 0.7 degrees for the bond lengths and angles, respectively. The force acting on the nuclei caused by the excitations has been discussed in detail by calculating the SAC-CI electron density difference between the ground and excited states; the geometry relaxation was well interpreted with the electrostatic force theory. In Rydberg excitations, geometry changes were also noticed. Doubly excited states (so-called 2 (1)A(g) states) were investigated by the SAC-CI general-R method considering up to quadruple excitations. The characteristic geometrical changes and large energetic relaxations were predicted for these states.     

Sorption of atrazine on conventional and surface modified activated carbons

The sorption of atrazine from water has been studied using a conventional activated carbon, F400, an annealed carbon sample, F400AN, and an aminated carbon sample, F400NH(2). Characterisation of the carbon samples showed that sample F400NH(2) had the highest proportion of micropores, but had the lowest values of point of zero charge (PZC) and iso-electric point (IEP). This was attributed to the existence of a high proportion of oxygen containing functional groups. Sorption data showed that sample F400AN was superior in the sorption of atrazine to samples F400 and F400NH(2). It was noted that pore size distribution alone was not the only contributing factor for the uptake of atrazine onto the activated carbons. The sorption data were fitted well using the Freundlich isotherm. The free energy change showed that sorption of atrazine on activated carbons is a spontaneous process. A pseudo-second order kinetic model was used for analysing the kinetic data, and it was concluded that adsorption of atrazine was controlled by a film diffusion mechanism.     

Comparison of the performance of round and rectangular wire in small solenoids for high-field NMR

This paper considers the effects of conductor geometry on the performance of small solenoidal coils for high-field NMR. First, a simple analytical model is presented for investigating the effects of conductor geometry on the current distribution in such coils. The model was used to derive optimum parameters for coils constructed from wire with either rectangular or circular cross-sections as a function of the length-to-diameter ratio. Second, a commercial software package utilizing full three-dimensional finite-element solutions to Maxwell's equations was used to confirm the basic findings of the simple analytical model, and also to compare simulated S/N estimations with experimental NMR spectra acquired with 2.5 mm and 1.0 mm-diameter solenoid coils: reasonable agreement was found. Third, as a demonstration of the usefulness of such coils for mass-limited samples, multidimensional experiments were performed at 750 MHz on approximately 4.7 nmol (41 microg) of PF1061, a protein from Pyrococcus furiosus.     

Electrophoretic mobility of linear and star-branched DNA in semidilute polymer solutions

Electrophoresis of large linear T2 (162 kbp) and 3-arm star-branched (N(Arm) = 48.5 kbp) DNA in linear polyacrylamide (LPA) solutions above the overlap concentration c* has been investigated using a fluorescence visualization technique that allows both the conformation and mobility mu of the DNA to be determined. LPA solutions of moderate polydispersity index (PI approximately 1.7-2.1) and variable polymer molecular weight Mw (0.59-2.05 MDa) are used as the sieving media. In unentangled semidilute solutions (c* < c < c(e)), we find that the conformational dynamics of linear and star-branched DNA in electric fields are strikingly different; the former migrating in predominantly U- or I-shaped conformations, depending on electric field strength E, and the latter migrating in a squid-like profile with the star-arms outstretched in the direction opposite to E and dragging the branch point through the sieving medium. Despite these visual differences, mu for linear and star-branched DNA of comparable size are found to be nearly identical in semidilute, unentangled LPA solutions. For LPA concentrations above the entanglement threshold (c > c(e)), the conformation of migrating linear and star-shaped DNA manifest only subtle changes from their unentangled solution features, but mu for the stars decreases strongly with increasing LPA concentration and molecular weight, while mu for linear DNA becomes nearly independent of c and Mw. These findings are discussed in the context of current theories for electrophoresis of large polyelectrolytes.     

Adenine tautomers: relative stabilities, ionization energies, and mismatch with cytosine

In this study, we have investigated 12 tautomers of the DNA base adenine at the BP86/TZ2P and BP86/QZ4P levels of density functional theory. The vertical and adiabatic ionization energies of all tautomers were determined as the difference in energy between the radical cation and the corresponding neutral system. Furthermore, an evaluation is made for the eigenvalue spectra calculated with the SAOP functional, which is shown to lead to substantial improvements for orbital energies compared to BP86. We have also explored the correlations between the Kohn-Sham orbitals of the different tautomers at the BP86/QZ4P and SAOP/QZ4P levels. Finally, we discuss implications of the existence of the tautomeric forms of adenine for the DNA replication.     

Method for homogeneous spotting of antibodies on membranes: application to the sensitive detection of ochratoxin A

Membrane-based dot immunoassays are now widely used in almost every branch of biology and medicine. However, the quality of the immobilized antigen or antibody spots on the membranes was found to be highly operator-dependent and spotting by conventional methods often leads to heterogeneous spot morphologies and deposition inconsistencies. To circumvent these problems, a spotting method has been developed which is based on focussed absorption of an applied antibody solution through an aqueous network of capillary channels formed between the membrane and a wetted absorbent body. The method does not require any equipment for creating vacuum and according to assay requirements highly homogeneous spots of uniform size, in the range of 0.8- to 9-mm diameter, can be obtained by varying the volume of the applied antibody solution. Spot intensities were sufficiently high even at high antibody dilutions. Immobilization of anti-ochratoxin A (anti-OA) antibody by this method gave 2-fold increased sensitivity in a competitive assay of the toxin compared to conventional spotting methods. The calculated CV of the colour intensity for spots of different sizes (0.8 to 9 mm) was between 4.5 and 1%. Application of this spotting technique has been demonstrated for detection of OA in wine and coffee samples with the elimination of matrix interferences in the same immunoassay system. This was achieved by selective removal of nonspecific interfering substances from the sample extract during the assay. The detection limit of OA in wine (1 μg L⁻¹) and coffee (2.5 μg kg⁻¹) obtained by the present new method is superior to values reported recently. Thus, the present new method will be highly useful for improved performance of membrane-based immunoassays in almost every branch of biology and medicine.