Influence of halogen substituents on the catalytic oxidation of 2,4,6-halogenated phenols by Fe(III)-tetrakis(p-hydroxyphenyl) porphyrins and potassium monopersulfate

The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs) by iron(III)-porphyrin/KHSO? catalytic systems was investigated. Iron(III)-5,10,15,20-tetrakis(p-hydroxyphenyl)porphyrin (FeTHP) and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP), Cl (TrCP), Br (TrBP) and I (TrIP) were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III)-porphyrin/KHSO? catalytic systems.     

Multi-Functional Measurement Using a Single FBG Sensor

This paper describes the measurement of average strain, strain distribution and vibration of a cantilever beam made of Carbon Fiber Reinforced Plastics (CFRP), using a single Fibre Bragg Grating (FBG) sensor mounted on the beam surface. Average strain is determined from the displacement of the peak wavelength of reflected spectrum from the FBG sensor. Two unstrained reference FBG sensors were used to compensate for temperature drift. Measured strains agree with those measured by a resistance foil strain gauge attached to the sample. Stress distributions are measured by monitoring the variation in the full width at half maximum (FWHM) values of the reflected spectrum, using a proposed optical analytical model, described in the paper. FWHM values were measured for both the cantilever test beam and for a reference beam, loaded using a four-point bending rig. The trend of the stress distribution for the test beam matches with our analytical model, however with a relatively large noise present in the experimentally determined data. The vibration of a cantilever beam was measured by temporal analysis of the peak reflection wavelength. This technique is very stable as measurements are not affected by variations in the signal amplitude. Finally an application of FBG sensors for damage detection of CFRP plates, by measuring the natural frequency, is demonstrated. With small defects of different sizes applied to the CFRP plate, the natural frequency decreased with damage size.     

Preparation of gold colloid using pyrrole-2-carboxylic acid and characterization of its particle growth

Gold colloid was prepared by reduction of tetrachloroaurate using pyrrole-2-carboxylic acid in the presence of α-methoxy-ω-mercaptoethyl-poly(ethylene glycol). The shape and size of the obtained gold colloids were monitored by absorption spectroscopy and transmission electron microscopy during the reduction reaction. In the early stage of the reducing reaction, large fluffy particles with diameters >100 μm were observed. Some of these large particles had rectangular parallelepiped shapes. However, the mean particle size decreased with increasing time. Eventually, these large, non-round-shaped particles disappeared almost completely, and uniform round-shaped particles with a mean diameter of 10.5 nm became dominant.     

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.     

The Gradient Condition for One-Dimensional Symmetric Exclusion Processes

For every Gibbs measure on the one dimensional lattice Z with translation-invariant potential of finite range, an exchange rate for one-dimensional lattice gas which satisfy both the detailed balance condition relative to the Gibbs measure and the gradient condition is constructed.     

A new class of chiral calix[4]arenes as receptors with planar chirality

The modification of title compounds to chiral receptors and their characterization are reported. The two synthetic methods were developed. The racemates obtained could be resolved to each stable enantiomer by a chiral HPLC column. Chiral calixarenes were designed as the receptors with planar chirality. The (−)-receptor strongly forms 1:1 complex with (R)-(+)--phenylethylammonium picrate.     

Absorption Coefficient Measurements of Strongly Scattering Media Using Time-Resolved Transmittance of a Short Pulse in Near-Infrared (NIR) Wavelength Range

Absorption coefficient measurements of strongly scattering and weakly absorbing media have been performed using time resolved transmittance of a 100 fs pulse through a 30 mm slab containing latex spheres suspended in water and absorbing ink solutions. The scattering and absorption coefficients were selected so that the optical properties of the media were similar to those of biological tissues. Measured curves of time-resolved transmittance of the pulse through the media were used to estimate the optical properties of the media. The experiment was made at two different wavelengths, 784 nm and 810 nm. Estimated absorption coefficients were in good agreement with those measured in a nonscattering case by a spectrophotometer.Presented at the 7th International Workshop on Multiple Scattering Lidar/Light Experiments (MUSCLE7), July 21-23 1994, Chiba, Japan.     

The oldest mid-oceanic carbonate buildup complex: Setting and lithofacies of the Vendian (Late Neoproterozoic) Baratal limestone in the Gorny Altai Mountains,Siberia

The Baratal limestone in the Gorny Altai Mountains, southern Siberia, occurs as large allochthonous blocks within a Cambrian accretionary complex that developed around the Siberia craton. Before the final accretion to Siberia in the Cambrian, the terrigenous clastic-free Baratal limestone was deposited directly upon a basaltic basement with a geochemical signature identical to that of modern oceanic plateau. The Baratal limestone with 598 ± 25 Ma (Early Vendian) Pb-Pb isochron age consists of three distinct facies; 1) massive lime mudstone with ooids and stromatolites, 2) bedded lime mudstone, and 3) limestone conglomerate/breccia dominated by ooid-bearing lime mudstone clasts. The first represents a shallow marine environment on top of an ancient oceanic plateau, while the latter two represent the deeper slope to bottom-of-slope facies of a plateau. The Vendian Baratal limestone provides the oldest example of a reconstructed shallow marine carbonate buildup complex developed on a plateau/seamount in a mid-ocean.