Electric field gradients in (111)In-doped (Hf/Zr)(3)Al(2) and (Hf/Zr)(4)Al(3) mixed compounds: ab initio calculations, perturbed angular correlation measurements and site preference

The quadrupolar hyperfine interactions of in-diffused (111)In -> (111)Cd probes in polycrystalline isostructural Zr(4)Al(3) and Hf(4)Al(3) samples containing small admixtures of the phases (Zr/Hf)(3)Al(2) were investigated. A strong preference of (111)In solutes for the contaminant (Zr/Hf)(3)Al(2) minority phases was observed. Detailed calculations of the electric field gradient (EFG) at the Cd nucleus using the full-potential augmented plane wave + local orbital formalism allowed us to assign the observed EFG fractions to the various lattice sites in the (Zr/Hf)(3)Al(2) compounds and to understand the preferential site occupation of the minority phases by the (111)In atoms. The effects of the size of the supercell and relaxation around the oversized In and Cd probe atoms were investigated in detail.

Microstructural, structural and electrical properties of La(3+)-modified Bi(4)Ti(3)O(12) ferroelectric ceramics

Bi(4-x)La(x)Ti(3)O(12) (BLT) ceramics were prepared and studied in this work in terms of La(3+)-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (XL) of La(3+) into the Bi(4)Ti(3)O(12) (BIT) matrix was here found to locate slightly above x = 1.5. Further, La(3+) had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric-paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La(3+) content. (c) 2008 Elsevier Ltd. All fights reserved.

Four novel mononuclear and polynuclear Cu(I) thiosaccharinates with triphenylphosphane and bis(diphenylposphino)methane. Synthesis and structural study of Cu(4)(tsac)(4)(PPh(3))(3), Cu(tsac)(PPh(3))(2), Cu(4)(tsac)(4)(dppm)(2), and Cu(2)(tsac)(2)(dppm)(2)

Four new ternary complexes of copper(I) with thiosaccharin and phosphanes were prepared. The reaction of [Cu(4)(tsac)(4)(CH(3)CN)(2)] (1) (tsac: thiosaccharinate anion) with PPh(3) in molar ratios Cu(I)/PPh(3) 1:075 and 1:2 gave the complexes [Cu(4)(tsac)(4)(PPh(3))(3)] center dot CH(3)CN (2) and Cu(tsac)(PPh(3))(2) (3), respectively. The reaction of 1 with Ph(2)PCH(2)PPh(2) (dppm) in molar ratios Cu(I)/dppm 2:1 and 1:1 gave the complexes [Cu(4) (tsac)(4)(dppm)(2)] center dot 2CH(2)Cl(2) (4) and [Cu(2)(tsac)(2)(dppm)(2)] center dot CH(2)Cl(2) (5), respectively. All the compounds have been characterized by spectroscopic and X-ray crystallographic methods. Complex 2 presents a tetra-nuclear arrangement with three metal centers in distorted tetrahedral S(2)NP environments, the fourth one with the Cu(I) ion in a distorted trigonal S(2)N coordination sphere, and the tsac anions acting as six electron donor ligands in mu(3)-S(2)N coordination forms. Complex 3 shows mononuclear molecular units with copper(I) in a distorted trigonal planar coordination sphere, built with the exocyclic S atom of a mono-coordinated thiosaccharinate anion and two P-atoms of triphenylphosphane molecules. With dppm as secondary ligand the structures of the complexes depends strongly on the stoicheometry of the preparation reaction. Complex 4 has a centrosymmetric structure. Two triply bridged Cu(2)(tsac)(2)(dppm) units are joined together by the exocyclic S-atoms of two tsac anions acting effectively as bridging tridentate ligands. Complex 5 is conformed by asymmetric dinuclear moieties where the two dppm and one tsac ligands bridge two Cu(I) atoms and the second tsac anion binds one of the metal centers through its exocyclic S-atom. (C) 2009 Elsevier B.V. All rights reserved.

Lead(II)-induced formation and coordination of 3,4-dihydro-3-thioxo-1,2,4-triazin-5(2H)-one

Cyclization of (n)butyl glyoxylate thiosemicarbazone (HBuTSC) under reflux in the presence of Pb(OAc)(2) led to tile formation of the complex [Pb(HTz)(2)] (H(2)Tz = 3,4-dihydro-3-thioxo-1,2,4-triazin-5(2H)-one), which after recrystallization from DMSO afforded the polymer [Pb(Tz)](n), the first example of a Tz(2-) metal complex. (C) 2008 Elsevier B.V. All rights reserved.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Photoswitches and Luminescent Rigidity Sensors Based on fac-[Re(CO)(3)(Me(4)phen)(L)](+)

The fac-[Re(CO)(3)(Me(4)phen)(trans-L)](+) complexes, Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline and L = 4-styrylpyridine, stpy, or 1,2-bis(4-pyridyl)ethylene, bpe, were synthesized and characterized by their spectroscopic, photochemical, and photophysical properties. The complexes exhibit trans-to-cis isomerization upon 313, 334, 365, and 404 nm irradiation, and the true quantum yields can be efficiently determined by absorption changes combined with (1)H NMR data. For fac-[Re(CO)(3)(Me(4)phen)(trans-bpe)](+) similar quantum yields were determined at all wavelengths investigated. However, a lower value (phi(true) = 0.35) was determined for fac-[Re(CO)(3)(Me(4)phen)(trans-stpy)](+) at 404 nm irradiation, which indicates different pathways for the photoisomerization process. The photoproducts, fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+), exhibit luminescence at room temperature with two maxima ascribed to the (3)IL(Me4phen) and (3)MLCT(Re -> Me4phen) excited states. The luminescence properties were investigated in different media, and the behavior in glassy EPA at 77 K showed that the contribution of each emissive state is dependent on the excitation wavelength. The photochemical and photophysical behavior of the complexes were rationalized in terms of the energy gap of excited states and can be exploited in photoswitchable luminescent rigidity sensors.

Excited-State Dynamics in fac-[Re(CO)(3)(Me(4)phen)(L)](+)

Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, 3IL(cis-L), (3)MLCT(Re -> me4phen), and (3)IL(Me4phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re -> Me4phen) and (3)IL(Me4phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (Delta E(a)) for interconversion between (3)MLCT(Re -> me4Phen) and (3)IL(Me4phen) emitting states were determined. For L = cis-stpy, Delta E(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, Delta E(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(me4phen) state to (3)MLCT(Re -> Me4phen), k(i) congruent to 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.

4-Fluoro-2-methoxyphenol, an apocynin analog with enhanced inhibitory effect on leukocyte oxidant production and phagocytosis

Apocynin, a methoxy-substituted catechol (4-hydroxy-3-methoxyacetophenone), originally extracted from the roots of Picrorhiza kurroa, has been extensively used as a non-toxic inhibitor of the multienzymatic complex NADPH oxidase. We discovered that the analogous methoxy-substituted catechol, 4-Fluoro-2-methoxyphenol (F-apocynin), in which the acetyl group present in apocynin was changed to a fluorine atom, was significantly more potent as an inhibitor of NADPH oxidase activity, myeloperoxidase (MPO) chlorinating activity and phagocytosis of microorganisms by neutrophils; it was also as potent as apocynin in inhibiting tumor necrosis factor-alpha (TNF alpha) release by peripheral blood mononuclear cells. We attribute the increased potency of F-apocynin to its increased lipophilicity, which could facilitate the passage of the drug through the cell membrane. The inhibition of MPO chlorination activity, phagocytosis and TNF alpha release shows that apocynin and F-apocynin actions are not restricted to reactive oxygen species inhibition, but further studies are needed to clarify if these mechanisms are related. Like apocynin, F-apocynin did not show cell toxicity, and is a strong candidate for use in the treatment of inflammatory diseases. (C) 2011 Elsevier B.V. All rights reserved.

Infrared emissions, visible up-conversion, thermoluminescence and defect centres in Er(3)Al(5)O(12) phosphor obtained by solution combustion reaction

The Er(3)Al(5)O(12) phosphor powders were prepared using the solution combustion method. Formation and homogeneity of the Er(3)Al(5)O(12) phosphor powders have been verified by X-ray diffraction and energy-dispersive X-ray analysis respectively. The frequency up-conversion from Er(3)Al(5)O(12) phosphor powder corresponding to the (2)H(9/2) -> (4)I(15/2), (2)H(11/2) -> (4)I(15/2), (4)S(3/2) -> (4)I(15/2), (4)F(9/2) -> (4)I(15/2) and the infrared emission (IR) due to the (4)I(13/2) -> (4)I(15/2) transitions lying at similar to 410, similar to 524, similar to 556, 645-680 nm and at similar to 1.53 mu m respectively upon excitation with a Ti-Sapphire pulsed/CW laser have been reported. The mechanism responsible for the frequency up-conversion and IR emission is discussed in detail. Defect centres induced by radiation were studied using the techniques of thermoluminescence and electron spin resonance. A single glow peak at 430A degrees C is observed and the thermoluminescence results show the presence of a defect center which decays at high temperature. Electron spin resonance studies indicate a center characterized by a g-factor equal to 2.0056 and it is observed that this center is not related to the thermoluminescence peak. A negligibly small concentration of cation and anion vacancies appears to be present in the phosphor in accordance with the earlier theoretical predictions.

NIR to visible up-conversion, infrared luminescence, thermoluminescence and defect centres in Y(2)O(3) : Er phosphor

Er(3+) doped Y(2)O(3) phosphor was prepared by the solution combustion method and characterized using powder x-ray diffraction and energy-dispersive analysis of x-ray mapping studies. Room temperature near infrared (NIR) to green up-conversion (UC) emissions in the region 520-580 nm {((2)H(11/2), (4)S(3/2)) -> (4)I(15/2)} and red UC emissions in the region 650-700 nm ((4)F(9/2) -> (4)I(15/2)) of Er(3+) ions have been observed upon direct excitation to the (4)I(11/2) level using similar to 972 nm laser radiation of nanosecond pulses. The possible mechanisms for the UC processes have been discussed on the basis of the energy level scheme, the pump power dependence as well as based on the temporal evolution. The excited state absorption is observed to be the dominant mechanism for the UC process. Y(2)O(3) : Er exhibits one thermally stimulated luminescence (TSL) peak around 367 degrees C. Electron spin resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TSL peak. Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of at least three distinct centres. One of them (centre I) with principal g-values g(parallel to) = 2.0415 and g(perpendicular to) = 2.0056 is identified as O(2)(-) centre while centre II with an isotropic g-factor 2.0096 is assigned to an F(+)-centre (singly ionized oxygen vacancy). Centre III is also assigned to an F(+)-centre with a small g-factor anisotropy (g(parallel to) = 1.974 and g(perpendicular to) = 1.967). Additional defect centres are observed during thermal annealing experiments and one of them appearing around 330 degrees C grows with the annealing temperature. This centre (assigned to an F(+)-centre) seems to originate from an F-centre (oxygen vacancy with two electrons) and the F-centre appears to correlate with the observed TSL peak in Y2O3 : Er phosphor. The trap depth for this peak has been determined to be 0.97 eV from TSL data.

Reactions of 1,2.,5-thiadiazole 1,1-dioxide derivatives with nitrogen nucleophiles. Part IV. Addition of alpha-diamines

alpha-diamines, such as ethylendiamine and o-phenylendiamine, add to 3,4-aryl-disubstituted 1,2,5-thiadiazole 1,1-dioxides to give dihydropyrazines or quinoxalines, respectively and sulfamide. The new compound acenaphtho [5,6-b]-2,3-dihydropyrazine was synthesized and characterized. The addition of ethylendiamine to 3,4-diphenyl-1,2,5-thiadiazoline 1,1-dioxide gives 3,4-disubstituted thiadiazoildine 1,1-dioxide, dihydropyrazines, or pyrazines, depending on the reaction condition used. The reactions were followed by cyclic voltammetry and NMR spectroscopy which, in some cases, allowed the detection of the thiadiazolidine intermediate. Copyright (c) 2008 John Wiley & Sons, Ltd.

Synthesis, Structure, and Phosphatase-Like Activity of a New Trinuclear Gd Complex with the Unsymmetrical Ligand H(3)L As a Model for Nucleases

The new trinuclear gadolinium complex [Gd(3)L(2)(NO(3))(2)(H(2)O)(4)]NO(3)center dot 8H(2)O (1) with the unsymmetrical ligand 2-[N-bis-(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-bis(2-hydroxy-2-oxoethyl)aminomethyl] phenol (H(3)L) was synthesized and characterized. The new ligand H(3)L was obtained in good yield. Complex I crystallizes in an orthorhombic cell, space group Pcab. Kinetic studies show that complex 1 is highly active in the hydrolysis of the substrate 2,4-bis(dinitrophenyl)phosphate (K(m) = 4.09 mM, V(max) = 2.68 x 10(-2) mM s(-1), and k(cat) = V(max)/[1] = 0.67 s(-1)). Through a potentiometric study and determination of the kinetic behavior of 1 in acetonitrile/water solution, the species present in solution could be identified, and a trinuclear monohydroxo species appears to be the most prominent catalyst under mild conditions. Complex 1 displays high efficiency in DNA hydrolytic cleavage, and complete kinetic studies were carried out (K(m) = 4.57 x 10(-4) M, K(cat)` = 3.42 h(-1), and k(cat)`/K(m) = 7.48 x 10(3) M(-1) h(-1)). Studies with a radical scavenger (dimethyl sulfoxide, DMSO) showed that it did not inhibit the activity, indicating the hydrolytic action of 1 in the cleavage of DNA, and studies on the incubation of distamycin with plasmid DNA suggest that 1 is regio-specific, interacting with the minor groove of DNA.

Efficient sonothemical synthesis of thiazolidinones from piperonilamine

An efficient multicomponent reaction of arenealdehydes, mercaptoacetic acid and piperonilamine under ultrasound irradiation to afford 2-aryl-3-(piperonylmethyl)-1,3-thiazolidin-4-ones is reported. Applying this methodology, eleven heterocycles were synthesized and isolated in good yields after short reaction times. (C) 2010 Elsevier B.V. All rights reserved.