Photoelectrocatalytic production of active chlorine on nanocrystalline titanium dioxide thin-film electrodes

The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L-1 of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L-1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.

Determination of Cu, Ni and Pb in Aqueous Medium by FAAS after Pre-Concentration on 2-Aminothiazole Modified Silica Gel

This work describes the synthesis and characterization of 2-aminothiazole modified silica gel (SiAT), and the results of a study of the adsorption and pre-concentration (in batch and using a flow-injection system coupled to an absorption atomic spectrometer) of Cu(II), Ni(II) and Pb(II) in aqueous medium. The adsorption capacities for each metal ions in mmol g -1 were: Cu(II)= 1.18, Ni(II)= 1.15 and Pb(II)= 1.10. The results obtained in the flow experiments showed a recovery of practically 100% of the metal ions adsorbed in a mini-column packed with 100 mg of SiAT, using 100 μL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the application of a flow-injection system for the pre-concentration and quantification by FAAS of metal ions at trace level in natural water samples digested and not digest by an oxidizing UV photolysis.

Dynamics of energy transfer and frequency upconversion in Tm3+ doped fluoroindate glass

The spectroscopic properties of Tm3+-doped fluoroindate glasses (FIG) were described by single wavelength pumping in the red region. The Judd-Ofelt (J-O) theory was used to obtain the quantum efficiency of the 4f-4f transitions and other spectroscopic parameters. The dynamics of the fluorescence was investigated and energy transfer (ET) processes among Tm3+ ions were studied. The results indicate that a two-step one-photon absorption process is responsible for the ultraviolet upconversion (UC) emissions, and dipole-dipole interaction provides the main contribution for ET rate is equal to the decay rate of noninteracting among active ions.

Studies on the interaction between humic substances and conducting polymers for sensor application

The interaction between humic substances and poly(o-ethoxyaniline) (POEA), a conducting polymer, was investigated for both solution and self-assembled films. The results have shown that the humic substances induce a doping of POEA by protonation, as indicated by UV-Vis and Raman spectroscopies. The atomic force microscopy (AFM) studies on the self-assembled films have shown that the average roughness of the polymer film has increased after exposing it to humic substances (fulvic and humic acids), consistent with the interaction between POEA and humic substances. However, this change in morphology is reversible by washing the films with water in agreement with the electrical data allowing using this system in sensor applications. Here, the sensor formed by an array of different sensing units was able to detect and distinguish humic substances in aqueous solution, as shown by multivariate analysis (principal component analysis). The motivation to detect humic substance comes due to its importance in terms of quality control of water or soil. ©2005 Sociedade Brasileira de Química.

An alternative LC-UV procedure for the determination of prochloraz residues in fruits

An alternative method using liquid chromatography with UV detection for the determination of prochloraz as 2,4,6-trichlorophenol in mango, papaya and orange is described. Ethyl acetate, acetone and dichloromethane were tested for extraction of prochloraz from the fruits. After extraction the residue of prochloraz was derivatized with pyridine hydrochloride. The analysis was carried out using liquid chromatography with UV detection and gas chromatography with electron-capture detection. Average recoveries of prochloraz from spiked fruits (0.1 and 0.2 mg kg-1) ranged from 80% to 94% with relative standard deviations between 5.6% and 12.6% (n=8). Detection and quantification limits were 0.05 and 0.1 mg kg-1, respectively. The LC-UV method was applied to mango and papaya samples submitted to dip treatment with a prochloraz formulation under laboratory conditions. In addition, fruit samples obtained from local markets were analysed. ©2005 Sociedade Brasileira de Química.

Development and validation of an UV spectrophotometric method for determination of gatifloxacin in tablets

A simple, sensitive and accurate spectrophotometric method was developed for the assay of gatifloxacin in raw material and tablets. Validation of the method yielded good results concerning range, linearity, precision and accuracy. The absorbance was measured at 287 nm for gatifloxacin tablet solutions. The linearity range was found to be 4.0-14.0 μg/mL for gatifloxacin. It was also found that the excipients in the commercial tablets did not interfere with the method.

Validation of UV spectrophotometric method for determination of lomefloxacin in pharmaceutical dosage form

A simple and reproducible method was developed for the assay of lomefloxacin in tablets. The excipients in the commercial tablet preparation did not interfere with the assay. Beer's law is obeyed in the range 2.0-9.0 μg.mL-1 at λmax 280 nm. The molar absorptivity was calculated. Six triplicate analyses of solutions containing six different concentrations of the examined drug were carried out and gave a mean correlation coefficient 0.9997. The proposed method was applied to the determination of the examined drug in coated tablet and the results demonstrated that the method is equally accurate, precise and reproducible as the official methods.

Photodegradation of sparfloxacin and isolation of its degradation products by preparative HPLC

Sparfloxacin, a third generation fluoroquinolone derivative, is a potent antibacterial agent active against a wide range of Gram-positive and Gram-negative organisms including Streptococcus pneuinoniae, Staphylococcus aureus, methicillin resistant S. aureus, Legionella spp., Mycoplasina spp., Chlamydia spp. and Mycobacterium spp. A drawback of fluoroquinolones is their photoreactivity. Sparfloxacin has been studied in terms of therapeutic activities. However, there are few published of analytical methods being applied to sparfloxacin. The aim in this study was to determine the photodegradation products of sparfloxacin, when submitted to UV light, and to characterize two of these products, designated SPAX-PDP1 and SPAX-PDP2. An accelerated study of stability in methanol solution was carried out by exposing a solution of sparfloxacin to UV light (peak wavelength 290 nm) for 36 hours at room temperature. The products were analyzed by NMR spectrophotometry, IR spectrometry and mass spectrophotometry. The results suggest that the products isolated here could be used to estimate the degradation of sparfloxacin in a stability study. However, the low activity exhibited by UV-irradiated sparfloxacin is a source of concern that demands further investigation of the mechanism of its photodegradation mechanism.

Energy transfer and frequency upconversion involving triads of Pr3+ ions in (Pr3+, Gd3+) doped fluoroindate glass

Blue and ultraviolet luminescence in (Pr3+, Gd3+) doped fluoroindate glass is studied for excitation in the red region (≈590 nm). Frequency upconversion (UC) is observed due to energy transfer (ET) among three Pr3+ ions initially excited to the D21 state corresponding to the ET process D21 + D21 + D21 → S01 + H53 + H53. Additionally, UC luminescence from states P 72 6 and I 72 6 of Gd3+ is observed for an excitation wavelength resonant with transitions of the Pr3+ ions. The characterization of the luminescence signals allowed to determine ET rate among the Pr3+ ions and provides evidence of interconfigurational ET between Gd3+ and Pr3+ ions. © 2006 American Institute of Physics.

Ten years of NO2 comparisons between ground-based SAOZ and satellite instruments (GOME, SCIAMACHY, OMI)

SAOZ (Systeme d'Analyse par Observations Zenithales) is a ground-based UV-Visible zenith-sky spectrometer installed between 1988 and 1995 at a number of NDSC stations at various latitudes on the globe. The instrument is providing ozone and NO2 vertical columns at sunrise and sunset using the Differential Optical Absorption Spectroscopy (DOAS) technique in the visible spectral range. The ERS-2 GOME Ozone Monitoring Experiment (GOME) in 1995 was the first satellite mission to provide a global picture of atmospheric NO 2 with reasonable spatial and temporal resolution. It was then followed by SCanning ImAging spectroMeter for Atmospheric ChartographY (SCIAMACHY) onboard ENVISAT in 2002, and Ozone Monitoring Instrument (OMI) onboard EOS-AURA in 2004, with a similar capacity to monitor total NO 2. All these instruments are nadir viewing mapping spectrometers, applying the DOAS technique in the visible for deriving the NO2 total column. Here we present the results of NO2 long-term comparisons between GOME and SAOZ for the whole period of GOME operation since 1995 at all latitudes - tropics, mid-latitudes and polar regions - in both hemispheres. Comparisons are also shown with the most recently available SCIAMACHY and OMI data in 2004-2005. Overall, the daytime satellite measurements (around noon) are found consistent with sunrise ground-based data, with an average smaller difference at the tropics and mid-latitudes than in the polar areas in the summer. The agreement is even improved after correcting for the NO2 photochemical change between sunrise and the satellite overpass using a box model. However, some seasonal dependence of the difference between ground-based and satellite total NO2 still remains, related to the accuracy of photochemical simulations and the set of NO2 air mass factors used in the retrievals of both systems.

End-to-end validation of EPS / MetOp GOME-2 trace gas data

Within the next decade, the improved version 2 of Global Ozone Monitoring Experiment (GOME-2), a ultraviolet-visible spectrometer dedicated to the observation of key atmospheric trace species from space, will be launched successively on board three EUMETSAT Polar System (EPS) MetOp satellites. Starting with the launch of MetOp-1 scheduled for summer 2006, the GOME-2 series will extend till 2020 the global monitoring of atmospheric composition pioneered with ERS-2 GOME-1 since 1995 and enhanced with Envisat SCIAMACHY since 2002 and EOS-Aura OMI since 2004. For more than a decade, an international pool of scientific teams active in ground-and space-based ultraviolet-visible remote sensing have contributed to the successful post-launch validation of trace gas data products and the associated maturation of retrieval algorithms for the latter satellites, ensuring that geophysical data products are/become reliable and accurate enough for intended research and applications. Building on this experience, this consortium plans now to develop and carry out appropriate validation of a list of GOME-2 trace gas column data of both tropospheric and stratospheric relevance: nitrogen dioxide (NO 2), ozone (O 3), bromine monoxide (BrO), chlorine dioxide (OClO), formaldehyde (HCHO), and sulphur dioxide (SO 2). The proposed investigation will combine four complementary approaches resulting in an end-to-end validation of expected column data products.

Gluon mass generation in the PT-BFM scheme

In this article we study the general structure and special properties of the Schwinger-Dyson equation for the gluon propagator constructed with the pinch technique, together with the question of how to obtain infrared finite solutions, associated with the generation of an effective gluon mass. Exploiting the known all-order correspondence between the pinch technique and the background field method, we demonstrate that, contrary to the standard formulation, the non-perturbative gluon self-energy is transverse order-by-order in the dressed loop expansion, and separately for gluonic and ghost contributions. We next present a comprehensive review of several subtle issues relevant to the search of infrared finite solutions, paying particular attention to the role of the seagull graph in enforcing transversality, the necessity of introducing massless poles in the three-gluon vertex, and the incorporation of the correct renormalization group properties. In addition, we present a method for regulating the seagull-type contributions based on dimensional regularization; its applicability depends crucially on the asymptotic behavior of the solutions in the deep ultraviolet, and in particular on the anomalous dimension of the dynamically generated gluon mass. A linearized version of the truncated Schwinger-Dyson equation is derived, using a vertex that satisfies the required Ward identity and contains massless poles belonging to different Lorentz structures. The resulting integral equation is then solved numerically, the infrared and ultraviolet properties of the obtained solutions are examined in detail, and the allowed range for the effective gluon mass is determined. Various open questions and possible connections with different approaches in the literature are discussed. © SISSA 2006.

GDP 4.0 transfer to SGP 3.0 for SCIAMACHY no2 column processing: Verification with SDOAS / GDOAS prototype algorithms and delta-validation with NDACC / UV-visible network data

Until mid 2006, SCIAMACHY data processors for the operational retrieval of nitrogen dioxide (NO2) column data were based on the historical version 2 of the GOME Data Processor (GDP). On top of known problems inherent to GDP 2, ground-based validations of SCIAMACHY NO2 data revealed issues specific to SCIAMACHY, like a large cloud-dependent offset occurring at Northern latitudes. In 2006, the GDOAS prototype algorithm of the improved GDP version 4 was transferred to the off-line SCIAMACHY Ground Processor (SGP) version 3.0. In parallel, the calibration of SCIAMACHY radiometric data was upgraded. Before operational switch-on of SGP 3.0 and public release of upgraded SCIAMACHY NO2 data, we have investigated the accuracy of the algorithm transfer: (a) by checking the consistency of SGP 3.0 with prototype algorithms; and (b) by comparing SGP 3.0 NO2 data with ground-based observations reported by the WMO/GAW NDACC network of UV-visible DOAS/SAOZ spectrometers. This delta-validation study concludes that SGP 3.0 is a significant improvement with respect to the previous processor IPF 5.04. For three particular SCIAMACHY states, the study reveals unexplained features in the slant columns and air mass factors, although the quantitative impact on SGP 3.0 vertical columns is not significant.

Analyzing dynamical gluon mass generation

We study the necessary conditions for obtaining infrared finite solutions from the Schwinger-Dyson equation governing the dynamics of the gluon propagator. The equation in question is set up in the Feynman gauge of the background field method, thus capturing a number of desirable features. Most notably, and in contradistinction to the standard formulation, the gluon self-energy is transverse order-by-order in the dressed loop expansion, and separately for gluonic and ghost contributions. Various subtle field-theoretic issues, such as renormalization group invariance and regularization of quadratic divergences, are briefly addressed. The infrared and ultraviolet properties of the obtained solutions are examined in detail, and the allowed range for the effective gluon mass is presented.

Preparation and characterization of castor oil-based polyurethane/poly(o- methoxyaniline) blend film

Blends made up of castor oil-based polyurethane (PU) and poly(o-methoxyaniline) (POMA) were obtained in the form of films by casting and characterized by FTIR, UV-Vis-NIR spectroscopy, and electrical conductivity measurements. Doping was carried out by immersing the films in 1.0M HCl aqueous solution. Chemical bonds between NCO group of PU and NH group of POMA were observed by means of FTIR spectra. The UV-Vis-NIR spectra indicated that the presence of the PU in the blend does not affect doping and formation of the POMA phase. The electrical conductivity research was in the range of 10-3 S/cm. © 2007 Wiley Periodicals, Inc.