Synthesis, characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb3+ doped CaZrO3 has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO3:Tb3+ exhibits three thermoluminescence (TL) glow peaks at 126 degrees C, 200 degrees C and 480 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 TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O- ion. Centre II with an axial symmetric g-tensor with principal values g(parallel to) = 1.9986 and g(perpendicular to) = 2.0023 is assigned to an F+ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F+ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F+ centre appear to correlate with the observed high temperature TL peak in CaZrO3:Tb3+ phosphor. (c) 2012 Elsevier B.V. All rights reserved.

Synthesis of self-assembled tubes in direct conjugated porphyrin-gold nanohybrid solution

We report on the formation of self-assembled meso-tetrakis (p-sulfonatofenyl) porphyrin (H2 TPP'S POT. 4-''IND. 4') tubes stabilized by gold nanoparticles (NPs) in basic solution and on their spectroscopic chareterization. The role of the gold NPs in the aggregation dynamics of free-base sulfonated porphyrin (H2TPP'S POT. 4-''IND. 4') is also investigated. The direct conjugation of the gold NPs to the H2TPPS4 molecule quenches the fluorescence intensity, while absorption peaks are blue-shifted, indicating predominant H-type aggregation. It is observed that porphyrin molecules adsorbed on the surface of the gold NP interact and form tubes of maximum diameter ∼1.5 μm and length >100 μm. Steady-state and time-resolved spectroscopic techniques confirm nonradiative energy transfer from porphyrin to gold NP.

From pyridoxalrhodanine to a novel 7-azacoumarin complex of dimethylthallium(III) in a one-pot synthesis

The hydrolysis of pyridoxalrhodanine in a basic medium containing the dimethylthallium(III) cation afforded the compound [TlMe2(L)]center dot H2O (1.H2O) [HL = 5-(hydroxymethyl)-8-methyl-3-thiol-7-azacoumarin]. This compound was characterized in solid state by IR spectroscopy and in solution by H-1 and C-13{H-1} NMR spectrometry. X-ray diffraction showed that the crystal consists of associated TlMe2(L) units and hydrogen bonded water molecules. The L- anion is bound to the metal mainly by a bridging S atom [Tl-S = 2.9458(18) angstrom; 2.9616(16) angstrom], although secondary interactions through O atoms (Tl-O: 2.861(5); 2.900(5) angstrom)] are also present. The longer Tl-O interaction and the hydrogen bonds of the water molecules give rise to a tridimensional polymeric structure. (C) 2012 Elsevier B.V. All rights reserved.

Urea-Based Synthesis of Zinc Oxide Nanostructures at Low Temperature

The preparation of nanometer-sized structures of zinc oxide (ZnO) from zinc acetate and urea as raw materials was performed using conventional water bath heating and a microwave hydrothermal (MH) method in an aqueous solution. The oxide formation is controlled by decomposition of the added urea in the sealed autoclave. The influence of urea and the synthesis method on the final product formation are discussed. Broadband photoluminescence (PL) behavior in visible-range spectra was observed with a maximum peak centered in the green region which was attributed to different defects and the structural changes involved with ZnO crystals which were produced during the nucleation process.

SYNTHESIS OF N-15-ENRICHED UREA (CO((NH2)-N-15)(2)) FROM (NH3)-N-15, CO, AND S IN A DISCONTINUOUS PROCESS

CO((NH2)-N-15)(2) enriched with the stable isotope N-15 was synthesized based on a reaction involving CO, (NH3)-N-15, and S in the presence of CH3OH. The method differs from the industrial method; a stainless steel reactor internally lined with polytetrafluoroethylene (PTFE) was used in a discontinuous process under low pressure and temperature. The yield of the synthesis was evaluated as a function of the parameters: the amount of reagents, reaction time, addition of H2S, liquid solution and reaction temperature. The results showed that under optimum conditions (1.36, 4.01, and 4.48 g of (NH3)-N-15, CO, and S, respectively, 40 ml CH3OH, 40 mg H2S, 100 degrees C and 120 min of reaction) 1.82 g (yield 76.5%) of the compound was obtained per batch. The synthesized CO((NH2)-N-15)(2) contained 46.2% N, 0.55% biuret, melting point of 132.55 degrees C and did not exhibit isotopic fractionation. The production cost of CO((NH2)-N-15)(2) with 90.0 at. % N-15 was US$ 238.60 per gram.

Synthesis, spectroscopic characterization, photochemical and photophysical properties and biological activities of ruthenium complexes with mono- and bi-dentate histamine ligand

The monodentate cis-[Ru(phen)(2)(hist)(2)](2+) 1R and the bidentate cis-[Ru(phen)(2)(hist)](2+) 2A complexes were prepared and characterized using spectroscopic (H-1, (H-1-H-1) COSY and (H-1-C-13) HSQC NMR, UV-vis, luminescence) techniques. The complexes presented absorption and emission in the visible region, as well as a tri-exponential emission decay. The complexes are soluble in aqueous and non-aqueous solution with solubility in a buffer solution of pH 7.4 of 1.14 x 10(-3) mol L-1 for (1R + 2A) and 6.43 x 10(-4) mol L-1 for 2A and lipophilicity measured in an aqueous-octanol solution of -1.14 and -0.96, respectively. Photolysis in the visible region in CH3CN converted the starting complexes into cis-[Ru(phen)(2)(CH3CN)(2)](2+). Histamine photorelease was also observed in pure water and in the presence of BSA (1.0 x 10(-6) mol L-1). The bidentate coordination of the histamine to the ruthenium center in relation to the monodentate coordination increased the photosubstitution quantum yield by a factor of 3. Pharmacological studies showed that the complexes present a moderate inhibition of AChE with an IC50 of 21 mu mol L-1 (referred to risvagtini, IC50 181 mu mol L-1 and galantamine IC50 0.006 mu mol L-1) with no appreciable cytotoxicity toward to the HeLa cells (50% cell viability at 925 mu mol L-1). Cell uptake of the complexes into HeLa cells was detected by fluorescence confocal microscopy. Overall, the observation of a luminescent complex that penetrates the cell wall and has low cytotoxicity, but is reactive photochemically, releasing histamine when irradiated with visible light, are interesting features for application of these complexes as phototherapeutic agents.

Polyazomethine with vinylene and phenantridine moieties in the main chain: Synthesis, characterization, opto(electrical) properties and theoretical calculations

The opto(electrical) properties and theoretical calculations of polyazomethine with vinylene and phenantridine moieties in the main chain were investigated in the present study. 2,5-Bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerized in solution with 3,8-diamino-6-phenylphenanthridine (PAZ-PV-Ph). The temperatures of 5% weight loss (T-5%) of the polyazomethine was observed at 356 degrees C in nitrogen. Electrochemical properties of thin film of the polymer were studied by differential pulse voltammetry. The HOMO level of the PAZ-PV-Ph was at -4.97 eV. The energy band gap (E-g) was detected of approximately similar to 1.9 eV. Energy band gap (E-gopt) was additionally calculated from absorption spectrum and absorption coefficient alpha. The absorption UV-vis spectra of polyazomethine recorded in solution showed a blue shift in comparison with the solid state. HOMO-LUMO levels and E-g were additionally calculated theoretically by density functional theory and molecular simulations of PAZ-PV-Ph are presented. Current density-voltage (J-U) measurements were performed on ITO/PAZ-PV-Ph/Al, ITO/TiO2/PAZ-PV-Ph/Al and ITO/PEDOT/PAZ-PV-Ph:TiO2/Al devices in the dark and during irradiation with light (under illumination of 1000 W m(-2)). The polymer was tested using AFM technique and roughness (R-a, R-ms) along with skew and kurtosis are presented.

Synthesis of high-surface-area gamma-Al2O3 from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

Several types of alumina were synthesized from sodium aluminate (NaAlO2) by precipitation with sulfuric acid (H2SO4) and subsequently calcination at 500 degrees C to obtain gamma-Al2O3. The precursor aluminate was derived from aluminum scrap. The various gamma-Al2O3 synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption-desorption of N-2 (S-BET) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al2O3 were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m(2) g(-1)) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Synthesis of 15N-enriched urea (CO(15NH2)2) from 15NH3, CO, and S in a discontinuous process

CO(15NH2)2 enriched with the stable isotope 15N was synthesized based on a reaction involving CO, 15NH3, and S in the presence of CH3OH. The method differs from the industrial method; a stainless steel reactor internally lined with polytetrafluoroethylene (PTFE) was used in a discontinuous process under low pressure and temperature. The yield of the synthesis was evaluated as a function of the parameters: the amount of reagents, reaction time, addition of H2S, liquid solution and reaction temperature. The results showed that under optimum conditions (1.36, 4.01, and 4.48 g of 15NH3, CO, and S, respectively, 40 ml CH3OH, 40 mg H2S, 100 ºC and 120 min of reaction) 1.82 g (yield 76.5%) of the compound was obtained per batch. The synthesized CO(15NH2)2 contained 46.2% N, 0.55% biuret, melting point of 132.55 ºC and did not exhibit isotopic fractionation. The production cost of CO(15NH2)2 with 90.0 at. % 15N was US$ 238.60 per gram.

Effects of synthesis conditions on the nanostructre of CexZr1-xO2 mesoporous ceramics.

CexZr1-xO2 (0.5 ≤ x ≤ 0.9) were synthesized with Zr and Ce chloride precursors, using the triblock copolymer Pluronic P123 and HCl (2 mol/L). The pH adjustment was performed in two ways: synthesis A used 11.4 mL of a NH4OH solution added at once to the initial mixture, composed by metal precursors and template in HCl; synthesis B was done by dripping slowly until the change of pH value (between 3 and 6). In this work, CexZr1-xO2 samples synthesized by these two processes are compared. The effects of pH values in materials characteristics were also evaluated. These samples were analysed by X-Ray Diffraction (XRD) with Rietveld refinement, and Nitrogen Adsorption/Desorption. In both processes, the studied materials presented two crystalline phases of CexZr1-xO2 solid solution: cubic and tetragonal. The synthesis A also presented a tetragonal phase of ZrO2. The average crystallite size and the Brunauer- Emmett-Teller (BET) surface area are bigger in process A. Both processes give samples with a mesoporous structure.

Electrochemically prepared polypyrrole-2-carboxylic acid films: synthesis protocols and studies on biosensors

The process for obtaining polypyrrole-2-carboxylic acid (PPY-2-COOH) films in acetonitrile was investigated using cyclic voltammetry, electrochemical quartz crystal microgravimetry (EQCM), and infrared spectroscopy (FTIR). Different potential ranges were applied during cyclic voltammetry experiments with the aim of obtaining films without and with the presence of controlled amounts of water added in acetonitrile. The FTIR spectra of the films have evidenced that cations and anions from the electrolyte solution were incorporated into the PPY-2-COOH structure, with a preferential adsorption of cations. After chemically immobilizing polyphenoloxidase (tyrosinase, PPO), PPY-2-COOH/PPO films were build for amperometric detection of catechol, establishing a linear limit of concentrations ranging from 5.0 x 10-4 to 2.5 x 10-2 mol L-1.