THE REACTION BETWEEN SUPEROXIDE ANION AND HYDROGEN PEROXIDE

Abstract— In order to obtain a better understanding of the kinetics of the Haber-Weiss reaction

often proposed as a source of OH radicals, we have measured the decomposition rate of H₂O₂ in aqueous solutions by y rays and for different pH values. This decomposition proceeds by a chain reaction involving the preceding one as the propagating step.
The rate constant found is to be
     

Astringency Sensitivity to Tannic Acid: Effect of Ageing and Saliva

Astringency is an important sensory characteristic of food and beverages containing polyphenols. However, astringency perception in elderly people has not been previously documented. The aim of the present work was to evaluate sensitivity to astringency as a function of age, salivary flow and protein amount. Fifty-four panellists, including 30 elderly people (age = 75 ± 4.2 years) and 24 young people (age = 29.4 ± 3.8 years), participated in this study. Astringency sensitivity was evaluated by the 2-alternative forced choice (2-AFC) procedure using tannic acid solutions. Whole saliva was collected for 5 min before and after the sensory tests. The results showed that the astringency threshold was significantly higher in the elderly group than the young group. No correlation was observed between the salivary protein amount and threshold value. However, a negative correlation between salivary flow and threshold was observed in the young group only. These results showed a difference in oral astringency perception as a function of age. This difference can be linked to salivary properties that differ as a function of age.     

The determination of organochlorine compounds and petroleum hydrocarbons in a seaweed sample: results of a world-wide intercomparison exercise

A seaweed sample (Fucus sp.) was prepared, homogenised and distributed to laboratories worldwide as the IAEA-140 intercomparison material for the analysis of organochlorine compounds and petroleum hydrocarbons. A total of 80 laboratories from 51 countries reported results for this sample. The data sets reported by laboratories were evaluated statistically and the mean concentration values could be computed with 95% confidence limits for a large number of analytes. The accuracy of the analytical performance of each laboratory has been introduced by using Z-scores. The spread of results reported generally indicates that the accurate determination of many persistent organic pollutants, such as hexachlorobenzene, lindane, Aroclors or fluoranthene, is still difficult for many laboratories. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-140 can now be used as a reference material for quality control in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples.     

trans-cis Photoisomerization of the styrylpyridine Ligand in [Re(CO)3(2,2'-bipyridine)(t-4-styrylpyridine)]+: role of the metal-to-ligand charge-transfer excited states

The trans-cis isomerization of the styrylpyridine carbon-carbon double bond induced by visible light irradiation in fac-[Re(CO)(3)(bpy)(stpy)](+) (bpy = 2,2'-bipyridine; stpy = t-4-styrylpyridine) has been investigated by means of quantum-chemical methods. The structures of the various cis and trans conformers of [Re(CO)(3)(bpy)(stpy)](+) have been optimized at the density functional theory (DFT) level. Three rotational conformers for the most stable trans isomer lie within 2.3 kJ mol(-1) each other. The energy difference between the cis and trans isomers is 27.0 kJ mol(-1). The electronic spectroscopy of the most stable conformers has been investigated by time-dependent DFT (TD-DFT) and complete active space self-consistent field/CAS second order perturbation theory (CASSCF/CASPT2) calculations. The lowest absorption bands are dominated by metal-to-ligand charge-transfer (MLCT, d(Re)-->pi*(bpy)) transitions calculated at about 25,000 cm(-1) and by a strong intraligand (1)IL (pi(stpy)-->pi*(stpy)) transition in the near UV region. On the basis of CASSCF potential energy curves (PECs) calculated as a function of the torsion angle of the C=C bond of the styrylpyridine ligand, it is shown that the role of the low-lying MLCT states is important in the photoisomerization mechanism. In contrast to the free organic ligand, in which the singlet mechanism is operational via the (1)IL (S(1)) and electronic ground (S(0)) states, coordination to the rhenium steers the isomerization to the triplet PEC corresponding to the (3)IL state. From the (3)IL(t) (t = trans) the system evolves to the perpendicular intermediate (3)IL(p) (p = perpendicular) following a 90 degrees rotation around the styrylpyridine C=C bond. The metal center acts as a photosensitizer because of the presence of photoactive MLCT states under visible irradiation. The position of the crossing between the (3)IL and electronic ground state PEC determines the quantum yield of the isomerization process.     

Identification of Apigenin Metabolites in Rat Liver Perfusate by Column Switching High Performance Liquid Chromatography/Electrospray Ionization Mass Spectrometry

Summary.  A selective column switching high performance liquid chromatographic method has been used for the simultaneous determination of apigenin and metabolites in rat liver perfusate. This new method clearly separated apigenin and the metabolites with high resolution. The structures of metabolites were proposed based on selective ion recording and full scan analysis by electrospray ionization mass spectrometry. Corresponding author. E-mail: basly@pharma.unilim.fr Received May 15, 2002; accepted (revised) September 13, 2002     

Mild Synthesis of Amino‐Poly(ethylene glycol)s. Application to Steric Stabilization of Clays

The hydroxyl end groups of poly(ethylene glycol) (PEG) have been transformed easily and quantitatively into amino groups via the Mitsunobu reaction. Phthalimide was alkylated with PEGs and the hydrazinolysis of the resulting phthalimido‐PEGs gave the amino compounds in high yields. Quaternization of the amino groups leads to hydrophilic polymer chains bearing a positive charge on one or two ends, depending on the chosen PEG. Such products can be used to protect sterically, negatively charged particles such as clays.

     

Chiralization in mesogenic 1,3-diacylaminobenzenes

The effect of molecular chirality in thermotropic mesomorphic H-bonded polymeric systems has not really been investigated so far. Therefore, five new chiral mesogenic diamides have been prepared and described. Besides more ordered mesophases, the enantiomers exhibit a chiral nematic polymorphism detected by microcalorimetry and probably corresponding to different modes of chiral coiling to give these singular twisted nematic phases.     

Metal-chelating nanoparticles as selective fluorescent sensor for Cu2+

A fluorescent sensor for Cu(2+) at the nanomolar level in water has been designed by associating a BODIPY fluorophore and a selective ligand (cyclam) in ultrafine polymer nanoparticles.