Evaluation of antioxidant activity and electronic structure of aspirin and paracetamol

We present a study of electronic structure, chemical bonding, and antioxidant activity of phenolic antioxidants (aspirin and paracetamol). X-ray photoelectron and emission spectra of the antioxidants have been simulated by deMon density functional theory (DFT) calculations of the molecules. The chemical bonding of aspirin is characterized by the formation of oxygen ‘lone-pair’ π-orbitals which can neutralize free radicals and thus be related to antioxidant properties of the drug. In the case of paracetamol the additional nitrogen ‘lone pair’ is formed which can explain toxicity of the drug. We propose an evaluation method of antioxidant activity based on the relationship between experimental half-wave oxidation potential (E_p/2) and calculated ionization potentials (I_P) by the DFT calculations, and can conclude that paracetamol has the higher antioxidant activity than aspirin.     

Langmuir monolayers of a cholesterol-armed cyclen complex that can control enantioselectivity of amino acid recognition by surface pressure

The cholesterol-armed cyclen Na(+) complex formed stable Langmuir monolayers at the air-water interface. The π-A isotherm displayed a reasonable limiting molecular area of ～1.57 nm(2) and the areas expanded when amino acids were dissolved in water, indicating the efficient accommodation in the monolayers. Brewster angle microscopy (BAM) images exhibited almost no defects of the compressed Langmuir monolayers regardless of the presence of amino acids. Based on the idea that the increase in the limiting molecular areas corresponds to the amount of the adsorbed amino acid, the binding constants of three enantiomeric amino acids, namely valine (Val), leucine (Leu), and phenylalanine (Phe), were calculated at different surface pressures. Remarkably, a surface pressure dependent enantioselectivity of amino acid recognition was observed. Upon compression of the monolayers, the binding constants of amino acids increased accompanying an inversion of chiral selectivity from the D- to L-form in the case of Val and, conversely, from L- to D-form in the case of Phe.     

Single microdroplet/water extraction and in situ microanalysis by microcapillary injection and differential pulse voltammetry.

A redox species was extracted from water (50 x 10(-6) dm3) into a single micro-oil-droplet (30 x 10(-12) dm3) in contact with a microelectrode using microcapillary injection and manipulation techniques. Further, an in situ microanalysis of the solute in a single oil droplet was demonstrated by differential pulse voltammetry. The redox species of 10(-16) mol concentrated in the droplet could be quantitatively analyzed independently of the distribution coefficient of the solute between the oil and water phases. The potential of this technique was considered in terms of the preconcentration and separation as well as a microanalysis and an ultratrace analysis.     

Permeation flux of organic molecules through silica-surfactant nanochannels in a porous alumina membrane.

The permeation fluxes of phenol, benzene sulfonate (BS) and benzene disulfonate (BDS) through a porous anodic alumina membrane with the perpendicularly oriented silica-surfactant nanochannel assembly membrane (NAM) were measured in water-ethanol mixture media. The permeation flux depended on solute charges and on solvent composition. As the ethanol ratio increased, the fluxes of BS and BDS increased and the flux of phenol decreased. The results of extraction/elution experiments also depended on the solute charges and the solvent composition. Chromatographic experiments in n-hexane showed that dipole and hydrophobic interactions affect the retention of solutes. Permeation of the solute across the NAM in water-ethanol mixture is likely to be determined by various factors such as dipole interaction, hydrophobic interaction, solvation, and anion-exchange efficiencies.     

Characterization of rankings generated by linear discriminant analysis

Pairwise linear discriminant analysis can be regarded as a process to generate rankings of the populations. But in general, not all rankings are generated. We give a characterization of generated rankings. We also derive some basic properties of this model.     

Classification of non‐well‐founded sets and an application

A complete list of Finsler, Scott and Boffa sets whose transitive closures contain 1, 2 and 3 elements is given. An algorithm for deciding the identity of hereditarily finite Scott sets is presented. Anti‐well‐founded (awf) sets, i. e., non‐well‐founded sets whose all maximal ∈‐paths are circular, are studied. For example they form transitive inner models of ZFC minus foundation and empty set, and they include uncountably many hereditarily finite awf sets. A complete list of Finsler and Boffa awf sets with 2 and 3 elements in their transitive closure is given. Next the existence of infinite descending ∈‐sequences in Aczel universes is shown. Finally a theorem of Ballard and Hrbá?ek concerning nonstandard Boffa universes of sets is considerably extended.     

Micro flow injection analysis combined with a separation technique for the urinary glucose assay.

A urinary glucose assay has been investigated, employing a micro flow injection analysis (microFIA) combined with a separation technique of glucose from the analyte. The adsorption part using activated alumina for the glucose in the analyte can be successively integrated onto a microFI chip. The selective adsorption-desorption of glucose in the artificial urine can progress on the adsorption part. Along with this selective preconcentration of glucose, the typical FI peak of glucose can be obtained just by feeding the sample and deionized water as an elutant sandwiched with the reagent on the carrier stream. The glucose concentration in artificial urine can be quantitatively determined with the present microFIA system, while the interference of other components coexisting in urine occurs in the case of the conventional FIA system without any separation part. The described method serves as a template for improving the selectivity for the analyte in the multi-component system.     

Sensitive derivatizatton reagents for the resolution of carboxylic acid enantiomers by high-performance liquid chromatography

Two highly sensitive, chiral derivatization reagents, D- and L-1-aminoethyl-4-dimethyl-aminonaphthalene, were synthesized from 1-dimethylaminonaphthalene. Condensation of carboxylic acids with the chiral reagent was readily effected in the presence of a watersoluble carbodiimide. The diastereoisomeric amides formed from N-acetylamino acid and α-arylpropionic acid enantiomers were efficiently resolved by normal phase chromatography (μPorasil column) -with hexane/ethyl acetate or hexane/tetrahydrofuran as a mobile phase. With a fluorescence detector (excitation 320 nm, emission 395 nm), the detection limit was 0.1 ng.     

A dielectric rod waveguide coupled with metal rectangular waveguide

Measurements have been done in the millimeter wave region on a composite waveguide which comprises a dielectric rod waveguide connecting two metal rectangular waveguides. Such a waveguide has been used by us in a Josephson harmonic mixer installed in a small metal cryostat, to prevent the thermal invasion from outside environment and to transmit both signal and LO waves with small losses. The measured transmission loss, that is caused mainly by the coupling loss between metal rectangular waveguides (TE₁₀ mode) and a dielectric rod waveguide (HE₁₁ mode), has been less than 2dB in the frequency range of 52–104 GHz.