Color and structural analysis of CoxZn7-xSb2O12 pigments

The polymeric precursor method was successfully used to synthesize CoxZn7-xSbO12 (x = 0-7) powders. Pigments were evaluated using colorimetry, X-ray diffraction, UV-vis and infrared spectroscopy. The optical band gap values vary with the Co2+ substitution. These results suggest that the concomitant presence of Co and Zn in the spinel lattice leads to the rupture of the Vegard law, as well as other properties of the studied system, such as unit cell volume. The Co-richer samples display a higher absorbance than the Co-lean samples. The high absorption of the Co7Sb2O12 sample at most of the visible region makes this compound a candidate for a black pigment. It was shown that color depends on the site where the chromophore ion is located, in agreement with the ligand field theory. (c) 2006 Elsevier Ltd. All rights reserved.

Dynamical study of ZnO nanocrystal and Zn-HDS layered basic zinc acetate formation from sol-gel route

We have pointed out that zinc based particles obtained from ethanolic solution of a zinc acetate derivative (zinc oxy-acetate, Zn4O(Ac)(6)) are a mixture of nanometer sized ZnO, zinc oxy-acetate, and zinc hydroxide double salt (Zn-HDS). The knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, and the evolution of Zn species in reaction medium was monitored in situ during 14 h by simultaneous measurements of UV-vis absorption and extended X-ray absorption fine structures (EXAFS) spectra. This spectroscopic monitoring was initialized just after the addition of an ethanolic lithium hydroxide solution ([LiOH]/[Zn] = 0. 1) to the reaction medium kept under controlled temperature (40 degrees C). This study points out the first direct evidence of the reaction between ZnO nanoparticles and unreacted zinc oxy-acetate to form a Zn-HDS phase. The dissolution of ZnO and the reprecipitation of Zn-HDS are induced by the gradual release of water mainly produced by ethanol esterification well evidenced by gas chromatography coupled to mass spectroscopy and FT-IR measurements.

Simultaneous determination of quinoline and pyridine compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

Manganese(III) porphyrins: Catalytic activity and intermediate studies in homogeneous systems

We studied how solvent, stirring method, PhIO/MnP molar ratio, presence of water and axial ligand affect the catalytic activities of Mn(TPP)Cl, Mn(MNPP)Cl, Mn(TDCPP)Cl and Mn(TFPP)Cl in the oxidation of cyclohexane by PhIO. A study of the catalytic intermediates in the reaction between Mn(TPP)Cl or Mn(TDCPP)Cl and PhIO was also carried out by UV-Vis and EPR spectroscopies. The reaction of Mn(TPP)Cl with PhIO showed the formation of a mixture of species Mn-IV(OP+ and Mn-V(O)P as intermediates, which were confirmed by the deconvolution of the UV-Vis spectra. Addition of imidazole as cocatalyst favoured the formation of the intermediate species Mn-V(O)P, evidenced by the UV-Vis band at 408 nm. The corresponding EPR spectra gave evidence that in the presence of imidazole, Mn-IV(OP+ species are formed only in very low amounts. For Mn(TDCPP)Cl the dominating intermediate species is Mn-IV(OP+. Addition of imidazole to halogen-substituted MnP systems does not result in increase of the C-ol yields because very stable bis-imidazole-MnP complexes are formed. Anchoring of such MnP on imidazole propyl gel (IPG) results in better catalytic activity because in this case, the catalyst is mono-coordinated to the support and imidazole favours the formation of the intermediate species Mn-V(O)P.

The nature of the photo luminescence in amorphized PZT

The polymeric precursor method was used to synthesize lead zirconate titanate powder (PZT). The crystalline powder was then amorphized by a high-energy ball milling process during 120h. A strong photoluminescence emission was observed at room temperature for the amorphized PZT powder. The powders were characterized by XRD and the percentage of amorphous phase was calculated through Rietveld refinement. The microstructure for both phases was investigated by TEM. The optical gap was calculated through the Wood and Tauc method using the UV-Vis. data. Quantum mechanical calculations were carried out to give an interpretation of the photoluminescence in terms of electronic structure. (C) 2004 Elsevier B.V. All rights reserved.

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Photoluminescence of crystalline and disordered BTO : Mn powder: Experimental and theoretical modeling

Disordered and crystalline Mn-doped BaTiO3 (BTO:Mn) powders were synthesized by the polymeric precursor method. After heat treatment, the nature of visible photoluminescence (PL) at room temperature in amorphous BTO:Mn was discussed, considering results of experimental and theoretical studies. X-ray diffraction (XRD), PL, and UV-vis were used to characterize this material. Rietveld refinement of the BTO:Mn from XRD data was used to built two models, which represent the crystalline BTO:Mn (BTO:Mn,) and disordered BTO:Mn (BTO:Mn-d) structures. Theses models were analyzed by the periodic ab initio quantum mechanical calculations using the CRYSTAL98 package within the framework of density functional theory at the B3LYP level. The experimental and theoretical results indicated that PL is related with the degree of disorder in the BTO:Mn powders and also suggests the presence of localized states in the disordered structure. (c) 2006 Elsevier B.V. All rights reserved.

Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-1 for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8 +/- 0.3 and 64.6 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-1, respectively. The recovery was evaluated and the results shown the values of 88.9 +/- 0.4 and 90.2 +/- 0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests. (C) 2007 Elsevier B.V. All rights reserved.

Conditions giving rise to intense visible room temperature photoluminescence in SrWO4 thin films: the role of disorder

The nature of intense visible photoluminescence at room temperature of SrWO4 (SWO) non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The SWO thin films were synthesized by the polymeric precursors method. Their structural properties have been obtained by X-ray diffraction data and the corresponding photoluminescence (PL) spectra have been measured. The UV-vis optical spectra measurements suggest the creation of localized states in the disordered structure. The photoluminescence measurements reveal that the PL changes with the degree of disorder in the SWO thin film. To understand the origin of visible PL at room temperature in disordered SWO, we performed quantum-mechanical calculations on crystalline and disordered SWO periodic models. Their electronic structures are analyzed in terms of DOS, hand dispersion and charge densities. We used DFT method with the hybrid non-local B3LYP approximation. The polarization induced by the symmetry break and the existence of localized levels favors the creation of trapped holes and electrons, giving origin to the room temperature photoluminescence phenomenon in the SWO thin films. (c) 2004 Elsevier B.V. All rights reserved.

Nanoscale processing of polyaniline and phthalocyanines for sensing applications

Nanostructured polyaniline-modified electrodes were fabricated via the electrostatic layer-by-layer (LbL) technique where polyaniline (PANI) was assembled with one of three tetrasulfonated metallic phthalocyanines, viz. iron (FeTsPc), nickel (NiTsPc) and copper (CuTsPc). The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the 800 run absorption band due to PANI. Infrared spectroscopy in the transmission mode suggested specific interactions between PANI and the phthalocyanines, such as those between SO3- groups from the phthalocyanines and the protonated NH group from PANI. The films were employed to detect dopamine (DA) using cyclic voltammetry. In the presence of dopamine the PANI-based LbL films showed additional redox peaks at ca. 230 and 190 mV the oxidation peak increased linearly with the concentration of DA in the electrolytic solution. Films comprising PANI/FeTsPc were able to distinguish between DA and ascorbic acid (AA), which acts as a natural interferent in biological fluids. (c) 2005 Elsevier B.V. All rights reserved.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel

In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.

Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

Structural evolution up to 1100 degrees C of xerogels prepared from TEOS sonohydrolysis and liquid phase exchanged by acetone

Silica xerogels were prepared from sonohydrolysis of tetraethoxysilane and exchange of the liquid phase of the wet gel by acetone. Monolithic xerogels were obtained by slow evaporation of acetone. The structural characteristics of the xerogels were studied as a function of temperature up to 1100 degrees C by means of bulk and skeletal density measurements, linear shrinkage measurements and thermal analyses (DTA, TG and DL). The results were correlated with the evolution in the UV-Vis absorption. Particularly, the initial pore structure of the dried acetone-exchanged xerogel was studied by small-angle X-ray scattering and nitrogen adsorption. The acetone-exchanged xerogels exhibit greater porosity in the mesopore region presenting greater mean pore size (similar to 4 nm) when compared to non-exchanged xerogels. The porosity of the xerogels is practically stable in the temperature range between 200 degrees C and 800 degrees C. Evolution in the structure of the solid particles (silica network) is the predominant process upon heating up to about 400 degrees C and pore elimination is the predominant process above 900 degrees C. At 1000 degrees C the xerogels are still monolithic and retain about 5 vol.% pores. The xerogels exhibited foaming phenomenon after hold for 10 h at 1100 degrees C. This temperature is even higher than that found for foaming of non-exchanged xerogels. (c) 2005 Elsevier B.V. All rights reserved.

Surface-enhanced resonance Raman scattering as an analytical tool for single molecule detection

A perylene derivative, n-(n-butyl)-n'-(4-aminobutyl) perylene-3,4,9,10-tetracarboxylic acid diimide (simplified as nBu-PTCD-(CH2)(4)-NH2) has been chosen as the target molecule for studies involving single molecule detection (SMD) using Raman scattering. The enhancement of the Raman signal is the result of the multiplicative effects of two phenomena, resonance Raman scattering (RRS) and surface-enhanced Raman scattering (SERS), which leads to the resulting surface-enhanced resonance Raman scattering (SERRS) process. The SERRS spectra from a single molecule have been collected using both silver and gold colloids. The SMD detection of the fundamental vibrational frequencies characteristic of nBu-PTCD-(CH2)(4)-NH2 is complemented with the detection of some overtones and combinations from ring stretching modes at the single molecule level. The background characterization of the ensemble vibrational spectroscopy of the target perylene and its SERRS is also presented, which includes the UV-vis absorption, experimental and calculated Raman scattering and infrared absorption, and molecular organization using reflection-absorption infrared spectroscopy (RAIRS).