Determination of sugar cane herbicides in soil and soil treated with sugar cane vinasse by solid-phase extraction and HPLC-UV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Changes in optical properties caused by UV-irradiation of aquatic humic substances from the amazon river basin: Seasonal variability evaluation

Aquatic humic substances (AHS) isolated from two characteristic seasons of the Negro river, winter and summer corresponding to floody and dry periods, were structurally characterized by (13)C nuclear magnetic ressonance. Subsequently, AHS aqueous solutions were irradiated with a polychromatic lamp (290-475 nm) and monitored by its total organic carbon (TOC) content, ultraviolet-visible (UV-vis) absorbance, fluorescence and Fourier transformed infrared spectroscopy (FTIR). As a result, a photobleaching upto 80% after irradiation of 48 h was observed. Conformational rearrangements and formation of low molecular complexity structures were formed during the irradiation, as deduced from the pH decrement and the fluorescence shifting to lower wavelengths. Additionally a significant mineralization with the formation of CO(2), CO, and inorganic carbon compounds was registered, as assumed by TOC losses of up to 70%. The differences in photodegradation between samples expressed by photobleaching efficiency were enhanced in the summer sample and related to its elevated aromatic content. Aromatic structures are assumed to have high autosensitization capacity effects mediated by the free radical generation from quinone and phenolic moieties.

Effect of lactic acid and UV irradiation on the cassava and corn starches

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Planar and UV written channel optical waveguides prepared with siloxane poly(oxyethylene)-zirconia organic-inorganic hybrids. Structure and optical properties

Organic-inorganic hybrids were prepared using ureapropyltriethoxysilane, methacryloxypropyltrimethoxysilane and acrylic acid modified zirconium(IV) n-propoxide precursors and were characterized by small angle X-ray scattering, X-ray diffraction and photoluminescence spectroscopy. The results indicate an effective interaction between the zirconium-based nanoparticles and the siliceous nanodomains that induces changes in the hybrids' emission features. Planar waveguides were obtained by spin-coating of the prepared sols on sodalime and silica substrates. Refractive index, thickness, number of propagating modes, and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm by the prism coupling technique. The synergism between the two hybrid precursors resulted in monomode planar waveguides with low losses in the infrared ( from 0.6-1.1 dB cm(-1)) which also support a number of propagating modes in the visible ( losses from 0.4-1.5 dB cm(-1)). Channel waveguides were also obtained by UV photopatterning using amplitude or phase masks and propagating modes were observed at 1550 nm.

Determination of carbofuran and 3-hydroxycarbofuran residues in coconut water by solid-phase extraction and liquid chromatography with UV detection

A simple method was developed to determine carbofuran and 3-hydroxycarbofuran in coconut water. The procedure involved solid-phase extraction using C-18 cartridges with acetonitrile for elution. The analysis of these compounds was carried out by liquid chromatography with UV detection at 275 nm using a gradient solvent system. The method was validated with fortified samples at different concentration levels (0.01-2.5 mu g/mL). Average recoveries ranged from 81 to 95% with relative standard deviation between 1.6 and 12.5%. Each recovery analysis was repeated at least five times. Detection limits ranged from 0.008 to 0.01 mu g/mL. The analytical procedure was applied to coconut water samples from palms submitted to treatment with commercial formulation under field conditions.

UV-visible absorption characteristics of TEOS-derived and Cr-doped silica sonogels aged in different pH solutions and heat treated up to 600 degrees C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl3.6H(2)O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600degreesC and analyzed by UV-visible absorption spectroscopy. Cr3+ is the preferable oxidation state of the chromium ion in the gels annealed up to 250-300degreesC, in the case of aging in solutions of pH=5 and 11. A high UV absorption below similar to320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below similar to250degreesC, in the case of aging in solutions of pH=1 and 2. These absorption bands have not been assigned. Above 300degreesC up to 600degreesC, Cr5+, and possibly Cr6+, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.

In situ UV-vis and EXAFS studies of ZnO quantum-sized nanocrystals and Zn-HDS formations from sol-gel route

We have pointed Out that. zinc-based particles obtained from zinc acetate sol-gel route is a mixture of quantum-sized ZnO nanoparticles, zinc acetate, and zinc hydroxide double salt (Zn-HDS). Aiming the knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, the thermohydrolysis of ethanolic zinc acetate solutions induced by lithium hydroxide ([LiOH]/[Zn2+] = 0.1) or water ([H2O]/[Zn2+] = 0.05) addition was investigated at different isothermal temperatures (40, 50, 60 and 70 degrees C) by in situ measurements of turbidity, UV-vis absorption spectra and extended X-ray absorption fine structures (EXAFS). Only the growth of ZnO nanoparticles was observed in sol prepared with LiOH, while a two-step process was observed in that prepared with water addition, leading the fast growth of Zn-HDS and the formation of ZnO nanoparticles at advanced stage. A mechanism of dissolution/reprecipitation governed by the water/ethanol proportion is proposed to account for relative amount of ZnO. (c) 2007 Elsevier Ltd. All rights reserved.

Light-induced relief gratings and a mechanism of metastable light-induced expansion in chalcogenide glasses

We report on a metastable light-induced volume expansion in Ge25+xGa10-xS65 glasses under irradiation with band gap (UV) light, which can result in recording of relief gratings on their surface in the case of irradiation with two interfering beams. We propose a mechanism for the expansion, which is based on the light-induced change in the polarizability of secondary (van der Waals type) bonds and the effect of this change on primary (covalent type) bonds of the glass. The effect is suggested to be due to an interference of electrons, which belong to a chalcogen atom and participate in the formation of secondary and primary bonds, respectively. We suggest that a minimum point of the Lennard-Jones potential, which corresponds to the equilibrium position of a chalcogen atom is shifted in the course of irradiation to a larger interatomic distance. This shift causes a volume expansion and allows a diffusion of chalcogen atoms into the irradiated area. We show that light-induced polymerization of the glass network is an important attribute of the light-induced volume expansion.

Holographic recording in [Sb(Po-3)(3)](n)-Sb2O3 glassy films by photoinduced volume and refraction index changes

Glassy films of 0.2[Sb(PO3)(3)]-0,8Sb(2)O(3) with 0.8 mum-thickness were deposited on quartz substrates by electron beam evaporation. A contraction in the film thickness (photoinduced decrease in volume) and photobleaching effect associated with a decrease of up to 25% in the index of refraction has been observed in the films after irradiation near the bandgap (3.89 eV), using the 350.7 nm (3.54 eV) Kr+ ion laser line with 2.5 W/cm(2) for 30 min. A loss of 30% in the phosphorus concentration was measured by wavelength dispersive X-ray microanalysis in the film after laser irradiation with 5.0 W/cm(2) for 1.0 h. These photoinduced changes in the samples are dependent on the power density and intensity profile of the laser beam. Using a Lloyd's mirror setup for continuous wave holography it was possible to record holographic gratings with period from 500 nm up to 20 mum and depth profile of similar to50 nm in the films after laser irradiation with 5.0 W/cm(2) for 1 h. Real-time diffraction efficiency measurements have shown that ultraviolet irradiation induces first a refractive index grating formation, and after this, the photocon traction effect takes place generating an irreversible relief grating. Diffraction efficiency up to 10% was achieved for the recorded gratings. 3D-refraction index measurements and atomic force microscopy images are presented. (C) 2004 Elsevier B.V. All rights reserved.

Optical recording in Se(Te)/As2S3 multilayers

The development of Te containing nanoscaled, compositionally modulated Te/As2S3 multilayer structures enables the realisation of optical recording in real time with a CW He-Ne laser illumination (lambda=633 nm) with improved recording parameters in comparison with known Se/As2S3 structures. It is established that the efficiency of the recording process depends on the light stimulated interdiffusion and thickness of sub-layers.

Comparison of different clean-up procedures for the determination of N-methylcarbamate insecticides in vegetable matrices by high-performance liquid chromatography with UV detection

Several clean-up procedures which included the use of glass chromatography columns (silica gel, alumina, Florisil, silanized Celite-charcoal), Sep-Pak cartridges and standard solutions were compared for the determination of the following N-methylcarbamate (NMC) insecticides: aldicarb, carbaryl, carbofuran, methomyl and propoxur. According to recovery results of the compounds after elution in a glass column, the most efficient systems employed 4.6% deactivated alumina and a silanized Celite-charcoal (4:1) as adsorbents, using dichloromethane-methanol (99:1) and toluene-acetonitrile (75:25) mixtures, respectively, as binary eluents. The recoveries of the compounds studied varied from 84 to 120%. Comparable recoveries (75-100%) for Sep-Pak cartridges in normal phase (NH2, CN) and reversed phase (C-8) were observed. Different temperatures were tested during the concentration step in a rotary evaporator, and we verified a strong influence of this parameter on the stability of some compounds, such as carbofuran and carbaryl. Recovery studies employing the best clean up procedures were performed at the Brazilian agricultural level in potato and carrot samples; Validation methodology of the US Food and Drug Administration was adapted for the N-methylcarbamate analysis. Their recoveries ranged between 79 and 93% with coefficients of variation of 2.3-8%. (C) 1998 Elsevier B.V. B.V.

Determination of carbamate insecticides in apples, pears, and lettuce by LC with UV detector

A simple and rapid method was developed for determination of 8 carbamate insecticides and 10 of their metabolites in apples, pears, and lettuce by liquid chromatography with UV diode array detector. With this method no derivatization is needed. Carbamates not belonging to the N-methylcarbamate class and metabolites without the N-methyl group can also be determined.

Rapid and sensitive method for the determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with UV-Vis detection

A high-performance liquid chromatography (HPLC) method for the determination of acetaldehyde in fuel ethanol was developed. Acetaldehyde was derivatized with 0.900 mL 2,4-dinitrophenylhydrazine (DNPHi) reagent and 50 mu L phosphoric acid 1 mol L-1 at a controlled room temperature of 15 degrees C for 20 min. The separation of acetaldehyde- DNPH (ADNPH) was carried out on a Shimadzu Shim-pack C-18 column, using methanol/LiCl(aq) 1.0 mM (80/20, v/v) as a mobile phase under isocratic elution and UV-Vis detection at 365 nm. The standard curve of ADNPH was linear in the range 3-300 amg L-1 per injection (20 mu L) and the limit of detection (LOD) for acetaldehyde was 2.03 mu g L-1, with a correlation coefficient greater than 0.999 and a precision (relative standard deviation, RSD) of 5.6% (n=5). Recovery studies were performed by fortifying fuel samples with acetaldehyde at various concentrations and the results were in the range 98.7-102%, with a coefficient of variation (CV) from 0.2% to 7.2%. Several fuel samples collected from various gas stations were analyzed and the method was successfully applied to the analysis of acetaldehyde in fuel ethanol samples.

Photoinduced structural changes in antimony polyphosphate based glasses

A photocontraction effect in amorphous films of the binary glass system 0.20 [Sb(PO3)(3)](n)-0.80 Sb2O3 has been observed after UV irradiation using the 350.7 nm Kr+ ion laser line with 5.0 W/cm(2). Good optical quality films up to 4.0 mum were deposited on silica substrates at room temperature in vacuum by electron beam physical vapor deposition (EB-PVD) and characterized using WDX, XRD, optical absorption, infrared reflectance, profilometry and atomic force microscopy (AFM) techniques. Very stable glasses were prepared by the melt quenching technique and used as evaporation source for the production of films. The photoinduced structural change (PSC) was observed as a variation of about 6% in the film thickness and this effect is accompanied by a photobleaching of the irradiated area with a blue shift of the optical absorption edge. Otherwise this photoinduced change in the film thickness is very sensitive to the variations in the shape and intensity of the laser beam; therefore several possibilities in optical recording arise from these results. (C) 2003 Published by Elsevier B.V.

Characterization of iron(III)porphyrin-hydroxo complexes in organic media through UV-Vis and EPR spectroscopies

The interaction of OH- with Fe(TPP)(+), Fe(TDCPP)(+), Fe(TMP)(+) and Fe(TFPP)(+) in 1,2-dichloroethane was studied by titrating FeP solutions with aliquots of a solution of tetrabutylammonium hydroxide in acetonitrile. The number of OH- ions (n) coordinated to the FeP and the stability constants (beta(n)) for the FeP-OH- complexes were calculated from UV-Vis absorbance data and iron spin states were determined through EPR spectroscopy, Fe(TMP) (+) forms a high-spin mono-hydroxo complex, while Fe(TPP)I and Fe(TDCPP)(+) form high-spin bis-hydroxo complexes. To our knowledge, this is the first time that the formation of bis-hydroxo complexes from Fe(TPP) (+) has been reported, and this was possible because the studies were carried out in basic organic media, In this same medium, Fe-III-Fe-II reduction upon OH- addition to Fe(TFPP) (+) was observed, without concomitant formation of the mu-oxo dimeric species [Fe(TFPP)](2)O. (C) 1999 Elsevier B.V., All rights reserved.