Peroxyoxalate chemiluminescence detection of condensates of malondialdehyde with thiobarbituric acids using a flow system.

The peroxyoxalate chemiluminescence(CL) detection method for the evaluation of the CL intensity of malondialdehyde(MDA) condensates with seven 2-thiobarbituric acid derivatives is described. The method consists of a flow injection technique together with a CL detection system using bis(2,4,6-trichlorophenyl) oxalate(TCPO) and hydrogen peroxide as chemiluminogenic reagents. Linear correlations between CL intensity and concentration are obtained for pmol levels of condensates. Among the condensates, 1,3-diethyl-2-thiobarbituric acid(DETBA)-MDA shows the largest CL intensity. High performance liquid chromatography (HPLC)/CL detection of DETBA-MDA and 1,3-diphenyl-2-thiobarbituric acid(DPTBA)-MDA using a mixture of TCPO and hydrogen peroxide in acetonitrile as a postcolumn reagent solution is also described. The detection limits for DETBA-MDA and DPTBA-MDA are 20 and 200 fmol, respectively, per 20 microL injection at a signal-to-noise ratio of 2. This HPLC/CL detection system was applied to the determination of MDA in rat brains by using DETBA as a fluorescent derivatizing reagent.     

An approach to numerical solution of multipoint boundary-value problems

An approach is proposed to solving multipoint boundary-value problems for linear differential equation of w-th order, based on reduction to two-point boundary-value problems. The two-point problems are solved by the stable discrete orthogonalization method. Some numerical examples are considered.Translated from Vychislitel'naya i Prikladnaya Matematika, No. 58, pp. 36–45, 1986.     

Fluorides of ruthenium and chromium: Theoretical studies

The electronic and structural characteristics of CrF₅, CrF₄, RuF₅ and RuF₄ were studied. Ab initio (SCF-CI) calculations were performed with different structures and spin states for each complex. The favored conformation always corresponds to the highest multiplicity: doublet for CrF₅ in D_3h, triplet for CrF₄ in T_d, quadruplet for RuF₅ in C_4v and quintuplet for RuF₄ in D_4h symmetry.     

The Almost Sure Limit Theorem for Sums of Random Vectors

We establish a sufficient condition for an almost sure limit theorem for sums of independent random vectors under minimal moment conditions and assumptions on normalizing sequences. We provide an example showing that our condition is close to the optimal one, as well as a related sufficient condition due to Berkes and Dehling. Bibliography: 5 titles.     

Transport of gases in aromatic polyesters: Correlation with WAXD studies

Polymer packing density can be conveniently measured by either density-based measurements (direct or estimated free volume) or wide-angle X-ray diffraction (WAXD) spectra. Previously reported diffusivity and permeability values for various polyarylates and polyimides are examined on the basis of the packing density measured by these different techniques. It is shown that in these rigid glassy polymers, the mean intersegmental distance, the d-spacing, obtained from WAXD provides a better measure of the effect of polymer packing on diffusivity than either direct density measurements or estimated free volumes. It has been possible to correlate previously reported diffusivity and sorption data for various polyarylates and polycarbonate on the basis of the WAXD investigation, using the d-spacing and the amorphous peak width, respectively. The effect of polyarylate structure on d-spacing has been studied. A series of polyarylates have been synthesized with different substituents on the bridge carbon. In this series the d-spacing remains constant while the carbonyl group density and the glass transition temperatures are varied. However, small substituents on the aromatic ring cause significant changes in the d-spacing. These results can be used to tailor polyarylates with desired intersegmental distances and chain flexibility.     

Study of the reciprocal space image of the biaxial nematic phase in the plane of the amphiphilic bilayer

High resolution synchrotron X-ray measurements have been performed on the uniaxial and biaxial phases of the lyotropic mixture potassuim laurate, decanol and water. An elegant magnetic orientational procedure allows us to obtain the cut of the reciprocal space image of the biaxial phase at the plane perpendicular to the amphiphilic bilayer. The analysis of densitometric profiles of the diffracted bands indicate an anisotropic micellar correlation in the plane of the amphiphilic bilayer. It is suggested that an anisotropic distribution of decanol and potassium laurate in this plane could be responsible for this effect.     

Kinetics and mechanism of oxidation of indigo carmine by hypohalites

Kinetics of oxidation of indigo carmine (IC) by sodium hypohalites, NaOX (X ? Cl or Br), in alkaline buffer of pH 9–11 has been studied spectrophotometrically at λ = 610 nm. The experimental rate law obtained is ?d[IC]/dt = k[OX^?][IC][OH^?]^x where x <1. Variation of ionic strength or dielectric constant of the medium had no effect on the reaction rate while the addition of halide ions slightly retarded the rate. A most plausible mechanism proposed on the basis of experimental results involves the formation of isatin sulphonate which undergoes further oxidation to anthranilate. Activation parameters have been evaluated.     

Spectroscopic imaging display and analysis.

A system for display of magnetic resonance (MR) spectroscopic imaging (SI) data is described which provides for efficient review and analysis of the multidimensional spectroscopic and spatial data format of this technique. Features include the rapid display of spectra from selected image voxels, formation of spectroscopic images, spectral and image data processing operations, methods for correlating spectroscopic image data with high resolution 1H MR images, and hardcopy facilities. Examples are shown for 31P and 1H spectroscopic imaging studies obtained in human and rat brain.     

Inertia-preserving secant updates

Corrections to the last two equations of Ref. 1 are given.