Luminescence properties of the ternary terbium complexes with (ortho and para) aminobenzoic acids and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Ternary complexes of terbium with ortho (and pam) aminobenzoic acid and 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the solid-state samples was studied during the sol-gel aging process by means of emission. excitation spectra, lifetimes and quantum efficiencies.

PROTONIC ACID-DOPING OF POLY-ORTHO-METHYLANILINE

Poly-o-methylaniline (poly-o-toluidine) was doped by some protonic acids. It was found that the acidity, molecular size and oxidizing ability of protonic acids affected the doping level and conductivity of polymer obtained to some extent. The organic acid

SYNTHESIS AND CHARACTERIZATION OF POLY-ORTHO-METHYLANILINE WITH DIFFERENT DEGREES OF OXIDATION

Poly-ortho-methylanilines (POT) in three states fully oxidized, fully reduced and oxidized in varying degrees were synthesized by the reaction of common POT (C-POT) having nearly equal amounts of benzenediamine and quinonediimine units with iodine or phenyl-hydrazine, and the resulting polymers were characterized by IR, C-13-NMR, SEM and elemental analysis. The results showed that the quinonediimine unit in C-POT could be reduced by phenylhydrazine to the benzenediamine unit, forming the polymer with low OD (oxidation degree) or in a fully reduced state and that iodine-oxidation resulted in the increase of quinonediimine unit and decrease of benzenediamine unit. The solubility and flexibility of the formed polymers depend strongly on the amount of quinonediimine unit in it. It is necessary to reduce the content of quinonediimine structure unit in order to improve the solubility of aniline-class polymers.

A STUDY OF ION KINETIC-ENERGY SPECTROMETRY OF ORTHO-DICHLORO, META-DICHLORO AND PARA-DICHLORO BENZENE DOUBLY CHARGED IONS [C6H4CL2]2+ AND [C6H3CL]2+ IN GAS-PHASE

The unimolecular Charge separation reactions of the doubly charged ions [C6H4Cl2]2+, [C6H3Cl]2+ produced in the ion source by electron impact from o-, m-, and p-dichloro benzene have been studied using mass analysed ion kinetic energy spectrometry. The values of kinetic energy releases (T) can be calculated from the energy dispersion of product ions. As T essentially reflects the release of coulombic energy, which can be used to calculate the approximate distances R between the two charges immediately before decomposition of the ions. From these data, some structural information about transiton states could be provided. The ECID and CID processes of above doubly charged ions, have also been studied. We found that the CID reactions of (C6H4Cl2)2+ could be used to distinguish three dichloro benzene isomers.

ON THE IODINE-DOPING OF POLYANILINE AND POLY-ORTHO-METHYLANILINE

The reactions of polyaniline and poly-omicron-methylaniline of different oxidation degrees with I2 were followed by FTIR and electrical conductivity measurements. The results showed that the reaction of common polyanilines with I2 was oxidation in nature whereas that of the fully reduced ones was doping. The latter took place in two steps: oxidation of benzene-diamine units into quinone-diimine units (redox between I2 and the polymer chain) and formation of a conjugated system consisting of four aromatic rings (intramolecular chain redox).

THE INFLUENCE OF PROTONIC ACIDS ON THE CHEMICAL POLYMERIZATION OF ORTHO-METHYLANILINE

The chemical polymerization of ortho-methylaniline (MAn) is performed in aqueous solution of six protonic acids. The MAn polymerization conversion, and the electrical conductivity and doping level as well as molecular chain structure of the polymers obtained depend not only on the acid concentration but also on their acidity and molecular size.

Discovery of Late Cretaceous garnet two-pyroxene granulite in the southern Lhasa terrane, Tibet and its tectonic significances

The Lhasa terrane, located between the Bangonghu-Nujiang suture zone and the Indus-Yalung Tsangpo suture zone in the southern Tibetan Plateau, was considered previously as a Precambrian continental block. Mesozoic and Cenozoic tectonic evolution of the Lhasa terrane is closely related to the subduction of the Tethys ocean and the collision between the Indian and European continents; so it is one of the keys to reveal the formation and evolution of the Tibetan plateau. The garnet two-pyroxene granulite which was found at the Nyingtri rock group of the southeastern Lhasa terrene consists of garnet, clinopyroxene, orthopyroxene, labradorite, Ti-rich amphibolite and biotite, with a chemical composition of mafic rock. The metamorphic conditions were estimated to be at T = 747 similar to 834 degrees C and P = 0.90 similar to 1.35GPa, suggesting a formation depth of 45km. The zircon U-Pb dating for the garnet amphibolite and marble associated with the granulite give a metamorphic age of 85 similar to 90Ma. This granulite-facies metamorphic event together with a contemporaneous magmatism demonstrated that the southern Lhasa terrane has undergone an Andean-type orogeny at Late Mesozoic time.

Acid-base and electrochemical properties of manganese meso(ortho- and meta-N-ethylpyridyl)porphyrins: potentiometric, spectrophotometric and spectroelectrochemical study of protolytic and redox equilibria.

The difference in electrostatics and reduction potentials between manganese ortho-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP) and manganese meta-tetrakis(N-ethylpyridinium-3-yl)porphyrin (MnTE-3-PyP) is a challenging topic, particularly because of the high likelihood for their clinical development. Hence, a detailed study of the protolytic and electrochemical speciation of Mn(II-IV)TE-2-PyP and Mn(II-IV)TE-3-PyP in a broad pH range has been performed using the combined spectrophotometric and potentiometric methods. The results reveal that in aqueous solutions within the pH range ∼2-13 the following species exist: (H(2)O)Mn(II)TE-m-PyP(4+), (HO)Mn(II)TE-m-PyP(3+), (H(2)O)(2)Mn(III)TE-m-PyP(5+), (HO)(H(2)O)Mn(III)TE-m-PyP(4+), (O)(H(2)O)Mn(III)TE-m-PyP(3+), (O)(H(2)O)Mn(IV)TE-m-PyP(4+) and (O)(HO)Mn(IV)TE-m-PyP(3+) (m = 2, 3). All the protolytic equilibrium constants that include the accessible species as well as the thermodynamic parameters for each particular protolytic equilibrium have been determined. The corresponding formal reduction potentials related to the reduction of the above species and the thermodynamic parameters describing the accessible reduction couples were calculated as well.

YF[MoO4] and YCl[MoO4]: Two halide derivatives of yttrium ortho-oxomolybdate: Syntheses, structures, and luminescence properties

The halide derivatives of yttrium ortho-oxomolybdate YX[MoO4] (X = F, Cl) both crystallize in the monoclinic system with four formula units per unit cell. YF[MoO4] exhibits a primitive cell setting (space group P2(1)/c, a = 519.62(2) pm, b = 1225.14(7) pm, c = 663.30(3) pm, beta = 112.851(4)degrees), whereas the lattice of YCl[MoO4] shows face-centering (space group C2/m; a = 1019.02(5) pm, b = 720.67(4) pm, c = 681.50(3) pm, beta = 107.130(4)degrees). The two compounds each contain crystallographically unique Y3+ cations, which are found to have a coordination environment of six oxide and two halide anions. In the case of YF[MoO4], the coordination environment is seen as square antiprisms, and for YCl[MoO4], trigon-dodecahedra. are found. The discrete tetrahedral [MoO4](2-) units of the fluoride derivative are exclusively bound by six terminal Y3+ cations, while those of the chloride compound show a 5-fold coordination around the tetrahedra with one edge-bridging and four terminal Y3+ cations. The halide anions in each compound exhibit a coordination number of two, building up isolated planar rhombus-shaped units according to [Y2F2](4+) in YF[MoO4] and [Y2Cl2](4+) in YCl[MoO4], respectively. Both compounds were synthesized at high temperatures using Y2O3, MoO3, and the corresponding yttrium trihalide in a molar ratio of 1:3:1. Single crystals of both are insensitive to moist air and are found to be coarse shaped and colorless with optical band gaps situated in the near UV around 3.78 eV for the fluoride and 3.82 eV for the chloride derivative. Furthermore, YF[MoO4] seems to be a suitable material for doping to obtain luminescent materials because the Eu3+-doped compound shows an intense red luminescence, which has been spectroscopically investigated.

Age-dependent increase in ortho-tyrosine and methionine sulfoxide in human skin collagen is not accelerated in diabetes. Evidence against a generalized increase in oxidative stress in diabetes

The glycoxidation products Nepsilon-(carboxymethyl)lysine and pentosidine increase in skin collagen with age and at an accelerated rate in diabetes. Their age-adjusted concentrations in skin collagen are correlated with the severity of diabetic complications. To determine the relative roles of increased glycation and/or oxidation in the accelerated formation of glycoxidation products in diabetes, we measured levels of amino acid oxidation products, distinct from glycoxidative modifications of amino acids, as independent indicators of oxidative stress and damage to collagen in aging and diabetes. We show that ortho-tyrosine and methionine sulfoxide are formed in concert with Nepsilon-(carboxymethyl)lysine and pentosidine during glycoxidation of collagen in vitro, and that they also increase with age in human skin collagen. The age-adjusted levels of these oxidized amino acids in collagen was the same in diabetic and nondiabetic subjects, arguing that diabetes per se does not cause an increase in oxidative stress or damage to extracellular matrix proteins. These results provide evidence for an age-dependent increase in oxidative damage to collagen and support previous conclusions that the increase in glycoxidation products in skin collagen in diabetes can be explained by the increase in glycemia alone, without invoking a generalized, diabetes-dependent increase in oxidative stress.

Removal of ortho-phosphate from aqueous solution by adsorption onto dolomite

An experimental study on the adsorption of phosphate onto cost effective fine dolomite powder is presented. The effect of solution pH, solution ionic strength and adsorption isotherm were examined. The adsorption of phosphate was pH dependent and phosphate adsorption favoured acidic conditions. The adsorption was significantly influenced by solution ionic strength indicating outer-sphere complexation reactions. The experimental data further indicated that the removal of phosphate increased with increase in the ionic strength of solution. The experimental data were modelled with different isotherms: Langmuir, Freundlich and Redlich–Peterson isotherms. It was found that the Redlich–Peterson isotherm depicted the equilibrium data most accurately. The overall kinetic data fitted very well the pseudo-first-order rate model.