High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

On the stabilization of conducting pernigraniline salt by the synthesis and oxidation of polyaniline in hydrophobic ionic liquids

The electrochemical polymerization of aniline in a hydrophobic room-temperature ionic liquid and the spectroelectrochemical characterization of the formed film are presented. The polymerization occurs without the presence of acid in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMITFSI), leading to a very stable electroactive material where no degradation was observed even at high applied potentials. Both in situ UV-Vis and Raman spectroscopic studies provided evidence for the stabilization of pernigraniline salt at high oxidation potentials and that this polyaniline state is the conducting form, as was corroborated by in situ resistance measurements. These data are indicative that low conductivity is not an intrinsic property of pernigraniline salt and this point must be reconsidered.

Dynamic light scattering and optical absorption spectroscopy study of pH and temperature stabilities of the extracellular hemoglobin of Glossoscolex paulistus

The extracellular hemoglobin of Glossoscolex paulistus (HbGp) is constituted of subunits containing heme groups, monomers and trimers, and nonheme structures, called linkers, and the whole protein has a minimum molecular mass near 3.1 x 10(6) Da. This and other proteins of the same family are useful model systems for developing blood substitutes due to their extracellular nature, large size, and resistance to oxidation. HbGp samples were studied by dynamic light scattering (DLS). In the pH range 6.0-8.0, HbGp is stable and has a monodisperse size distribution with a z-average hydrodynamic diameter (D-h) of 27 +/- 1 nm. A more alkaline pH induced an irreversible dissociation process, resulting in a smaller D-h of 10 +/- 1 nm. The decrease in D-h suggests a complete hemoglobin dissociation. Gel filtration chromatography was used to show unequivocally the oligomeric dissociation observed at alkaline pH. At pH 9.0, the dissociation kinetics is slow, taking a minimum of 24 h to be completed. Dissociation rate constants progressively increase at higher pH, becoming, at pH 10.5, not detectable by DILS. Protein temperature stability was also pH-dependent. Melting curves for HbGp showed oligomeric dissociation and protein denaturation as a function of pH. Dissociation temperatures were lower at higher pH. Kinetic studies were also performed using ultraviolet-visible absorption at the Soret band. Optical absorption monitors the hemoglobin autoxidation while DLS gives information regarding particle size changes in the process of protein dissociation. Absorption was analyzed at different pH values in the range 9.0-9.8 and at two temperatures, 25 degrees C and 38 degrees C. At 25 degrees C, for pH 9.0 and 9.3, the kinetics monitored by ultraviolet-visible absorption presents a monoexponential behavior, whereas for pH 9.6 and 9.8, a biexponential behavior was observed, consistent with heme heterogeneity at more alkaline pH. The kinetics at 38 degrees C is faster than that at 25 degrees C and is biexponential in the whole pH range. DLS dissociation rates are faster than the autoxidation dissociation rates at 25 degrees C. Autoxiclation and dissociation processes are intimately related, so that oligomeric protein dissociation promotes the increase of autoxidation rate and vice versa. The effect of dissociation is to change the kinetic character of the autoxidation of hemes from monoexponential to biexponential, whereas the reverse change is not as effective. This work shows that DLS can be used to follow, quantitatively and in real time, the kinetics of changes in the oligomerization of biologic complex supramolecular systems. Such information is relevant for the development of mimetic systems to be used as blood substitutes.

Near infrared spectroscopy for soil bulk density assessment

P>Soil bulk density values are needed to convert organic carbon content to mass of organic carbon per unit area. However, field sampling and measurement of soil bulk density are labour-intensive, costly and tedious. Near-infrared reflectance spectroscopy (NIRS) is a physically non-destructive, rapid, reproducible and low-cost method that characterizes materials according to their reflectance in the near-infrared spectral region. The aim of this paper was to investigate the ability of NIRS to predict soil bulk density and to compare its performance with published pedotransfer functions. The study was carried out on a dataset of 1184 soil samples originating from a reforestation area in the Brazilian Amazon basin, and conventional soil bulk density values were obtained with metallic ""core cylinders"". The results indicate that the modified partial least squares regression used on spectral data is an alternative method for soil bulk density predictions to the published pedotransfer functions tested in this study. The NIRS method presented the closest-to-zero accuracy error (-0.002 g cm-3) and the lowest prediction error (0.13 g cm-3) and the coefficient of variation of the validation sets ranged from 8.1 to 8.9% of the mean reference values. Nevertheless, further research is required to assess the limits and specificities of the NIRS method, but it may have advantages for soil bulk density predictions, especially in environments such as the Amazon forest.

Evaluation of laser induced breakdown spectroscopy for cadmium determination in soils

Cadmium is known to be a toxic agent that accumulates in the living organisms and present high toxicity potential over lifetime. Efforts towards the development of methods for microanalysis of environmental samples, including the determination of this element by graphite furnace atomic absorption spectrometry (GFAAS). inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma-mass spectrometry (ICP-MS) techniques, have been increasing. Laser induced breakdown spectroscopy (UBS) is an emerging technique dedicated to microanalysis and there is a lack of information dealing with the determination of cadmium. The aim of this work is to demonstrate the feasibility of LIBS for cadmium detection in soils. The experimental setup was designed using a laser Q-switched (Nd:YAG, 10 Hz, lambda = 1064 nm) and the emission signals were collimated by lenses into an optical fiber Coupled to a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Samples were cryogenically ground and thereafter pelletized before LIBS analysis. Best results were achieved by exploring a test portion (i.e. sampling spots) with larger surface area, which contributes to diminish the uncertainty due to element specific microheterogeneity. Calibration curves for cadmium determination were achieved using certified reference materials. The metrological figures of merit indicate that LIBS can be recommended for screening of cadmium contamination in soils. (C) 2009 Elsevier B.V. All rights reserved.

Simultaneous optimization by neuro-genetic approach for analysis of plant materials by laser induced breakdown spectroscopy

A simultaneous optimization strategy based on a neuro-genetic approach is proposed for selection of laser induced breakdown spectroscopy operational conditions for the simultaneous determination of macronutrients (Ca, Mg and P), micro-nutrients (B, Cu, Fe, Mn and Zn), Al and Si in plant samples. A laser induced breakdown spectroscopy system equipped with a 10 Hz Q-switched Nd:YAG laser (12 ns, 532 nm, 140 mJ) and an Echelle spectrometer with intensified coupled-charge device was used. Integration time gate, delay time, amplification gain and number of pulses were optimized. Pellets of spinach leaves (NIST 1570a) were employed as laboratory samples. In order to find a model that could correlate laser induced breakdown spectroscopy operational conditions with compromised high peak areas of all elements simultaneously, a Bayesian Regularized Artificial Neural Network approach was employed. Subsequently, a genetic algorithm was applied to find optimal conditions for the neural network model, in an approach called neuro-genetic, A single laser induced breakdown spectroscopy working condition that maximizes peak areas of all elements simultaneously, was obtained with the following optimized parameters: 9.0 mu s integration time gate, 1.1 mu s delay time, 225 (a.u.) amplification gain and 30 accumulated laser pulses. The proposed approach is a useful and a suitable tool for the optimization process of such a complex analytical problem. (C) 2009 Elsevier B.V. All rights reserved.

Evaluation of laser induced breakdown spectroscopy for the determination of micronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has been evaluated for the determination of micronutrients (B, Cu, Fe, Mn and Zn) in pellets of plant materials, using NIST, BCR and GBW biological certified reference materials for analytical calibration. Pellets of approximately 2 mm thick and 15 mm diameter were prepared by transferring 0.5 g of powdered material to a 15 mm die set and applying 8.0 tons cm(-2). An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm (200 mJ per pulse, 10 Hz) and an Echelle spectrometer with ICCD detector. Repeatability precision varied from 4 to 30% from measurements obtained in 10 different positions (8 laser shots per test portion) in the same sample pellet. Limits of detection were appropriate for routine analysis of plant materials and were 2.2 mg kg(-1) B, 3.0 mg kg(-1) Cu, 3.6 mg kg(-1) Fe, 1.8 mg kg(-1) Mn and 1.2 mg kg(-1) Zn. Analysis of different plant samples were carried out by LIBS and results were compared with those obtained by ICP OES after wet acid decomposition. (C) 2009 Elsevier B.V. All rights reserved.

Evaluation of laser induced breakdown spectroscopy for the determination of macronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has become an analytical tool for the direct analysis of a large variety of materials in order to provide qualitative and/or quantitative information. However, there is a lack of information for LIBS analysis of agricultural and environmental samples. In this work a LIBS system has been evaluated for the determination of macronutrients (P, K, Ca, Mg) in pellets of vegetal reference materials. An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with ICCD detector. The plasma temperature was estimated by Boltzmann plots and instrumental paragmeters such as delay time, lens-to-sample distance and pulse energy were evaluated. Certified reference materials as well as reference materials were used for analytical calibrations of P, K, Ca, and Mg. Most results of the direct analysis of plant samples by LIBS were in reasonable agreement with those obtained by ICP OES after wet acid decomposition. (C) 2008 Elsevier B.V. All rights reserved.

Laser-induced breakdown spectroscopy and chemometrics for classification of toys relying on toxic elements

Quality control of toys for avoiding children exposure to potentially toxic elements is of utmost relevance and it is a common requirement in national and/or international norms for health and safety reasons. Laser-induced breakdown spectroscopy (LIBS) was recently evaluated at authors` laboratory for direct analysis of plastic toys and one of the main difficulties for the determination of Cd. Cr and Pb was the variety of mixtures and types of polymers. As most norms rely on migration (lixiviation) protocols, chemometric classification models from LIBS spectra were tested for sampling toys that present potential risk of Cd, Cr and Pb contamination. The classification models were generated from the emission spectra of 51 polymeric toys and by using Partial Least Squares - Discriminant Analysis (PLS-DA), Soft Independent Modeling of Class Analogy (SIMCA) and K-Nearest Neighbor (KNN). The classification models and validations were carried out with 40 and 11 test samples, respectively. Best results were obtained when KNN was used, with corrected predictions varying from 95% for Cd to 100% for Cr and Pb. (C) 2011 Elsevier B.V. All rights reserved.

Treatment of wastewater from a cotton dyeing process with UV/H(2)O(2) using a photoreactor covered with reflective material

Wastewater containing several dyes, including sulfur black from the dyeing process in a textile mill, was treated using a UV/H(2)O(2) process. The wastewater was characterized by a low BOD/ COD ratio, intense color and high acute toxicity to the algae species Pseudokirchneriella subcaptata. The influence of the pH and H(2)O(2) concentration on the treatment process was evaluated by a full factorial design 2(2) with three replicates of the central experiment. The removal of aromatic compounds and color was improved by an increase in the H(2)O(2) concentration and a decrease in pH. The best results were obtained at pH 5.0 and 6 g L(-1). With these conditions and 120 min of UV irradiation, the removal of the color, aromatic compounds and COD were 74.1, 55.1 and 44.8%, respectively. Under the same conditions, but using a photoreactor covered with aluminum foil, the removal of the color, aromatic compounds and COD were 92.0, 77.6 and 59.4%, respectively. Moreover, the use of aluminum foil reduced the cost of the treatment by 40.8%. These results suggest the potential application of reflective materials as a photoreactor accessory to reduce electric energy consumption during the UV/H(2)O(2) process.

LEACHATE TREATMENT PROCESS AT A MUNICIPAL STABILIZED LANDFILL BY CATALYTIC OZONATION: AN EXPLORATORY STUDY FROM TAGUCHI ORTHOGONAL ARRAY

Catalytic ozonation has been recognized in the scientific community as an efficient technique, reaching elevated rates of recalcitrant organic material mineralization, even at the presence of scavenger species of hydroxyl free radicals. This study presents the most significant factors involving the leachate treatment stabilized by the municipal landfill of the city of Guaratingueta, State of Sao Paulo, Brazil, by using a catalytic ozonation activated by metallic ions Fe(3+), Zn(2+), Mn(2+), Ni(2+) and Cr(3+). The Taguchi L(16) orthogonal array and its associated statistical methods were also used in this study. Among the researched ions, the most notable catalysis was obtained with ferric ion, statistically significant in the reduction of COD with a confidence level of 99.5%.

Advanced process of microbiological control of wastewater in combined system of disinfection with UV radiation

The purpose of this study was to present a methodology with superior efficiency for inactivating pathogenic indicators commonly found in domestic sewage. The adopted method was based on synergistic effect resulting from the introduction of a UV radiation pre-disinfection stage of sewage followed by secondary treatment. A pilot unit was installed in the sewage treatment plant of the University of Sao Paulo to simulate the combined system in full-scale operational conditions. Its performance was evaluated through microbiological examinations for determining Escherichia coli, total coliforms and coliphages. The application of UV radiation at 5.1mW/cm(2) for 10 s of exposure in the first disinfection stage was enough to reduce the surviving number of E. coli around 100 times, in comparison to the conventional method. Therefore, based on experimental data, it is possible to conclude that combining treatment and pre-disinfection stage is an effective potential technique to produce effluents with lower degree of contamination by pathogenic organisms.

Combination of an anaerobic process with O(3), UV and O(3)/UV for cellulose pulp bleaching effluent treatment

Recent studies have shown that partial oxidation by advanced oxidation processes (AOP) is able to transform hard-to-degrade compounds and increase their biodegradability. In this work, anaerobic treatment was followed by ozonation, UV radiation and ozonation in the presence of UV radiation, to treat bleaching effluents from a cellulose kraft Pulp plant. The anaerobic reactor (horizontal anaerobic immobilized Sludge bed, HAISB) was Used as a pretreatment to reduce the efficient organic load before applying ACIP. The ozone treatments were applied in three different pH environments (3, 8 and 10) with retention times of 10, 30, 45 and 60 min. COD and adsorbable organic halogens (AOX) removal efficiencies at the HAISB were approximately 50%, while the BOD removal efficiency reached 80%. Ozonation promoted further removal of AOX and COD so that the combined efficiency reached 96% for AOX and 70% for COD. In the oxidation process, BOD was either removed in small quantities or actually increased, as intended, so that a second biological treatment would be able to complete the treatment. The maximum increase in the BOD(5)/COD ratio (biodegradability indicator) Occurred at pH 8, reaching 104% for ozonation at a dosage of 1540 mg(O3).L(-1). Applying UV radiation alone resulted in lower values: a 34% increase ill the BOD(5)/COD ratio and a 76% AOX removal efficiency. These results indicate that the combination of anaerobic treatment with ozonation or ozonation/UV radiation improves the treatability of cellulose pulp bleaching efficients and that the resulting wastewater is suitable for further biological treatment under aerobic conditions with a low level of toxic compounds from the halogenated family.

Information Filtering and Array Algorithms for Discrete-Time Markovian Jump Linear Systems

This technical note develops information filter and array algorithms for a linear minimum mean square error estimator of discrete-time Markovian jump linear systems. A numerical example for a two-mode Markovian jump linear system, to show the advantage of using array algorithms to filter this class of systems, is provided.

Modeling and experimental study of nucleate boiling on a vertical array of horizontal plain tubes

An investigation of nucleate boiling on a vertical array of horizontal plain tubes is presented in this paper. Experiments were performed with refrigerant RI 23 at reduced pressures varying from 0.022 to 0.64, tube pitch to diameter ratios of 1.32, 1.53 and 2.00, and heat fluxes from 0.5 to 40 kW/m(2). Brass tubes with external diameters of 19.05 mm and average roughness of 0.12 mu m were used in the experiments. The effect of the tube spacing on the local heat transfer coefficient along the tube array was negligible within the present range of experimental conditions. For partial nucleate boiling, characterized by low heat fluxes, and low reduced pressures, the tube positioning shows a remarkable effect on the heat transfer coefficient. Based on these data, a general correlation for the prediction of the nucleate boiling heat transfer coefficient on a vertical array of horizontal tubes under flooded conditions was proposed. According to this correlation, the ratio between the heat transfer coefficients of a given tube and the lowest tube in the array depends only on the tube row number, the reduced pressure and the heat flux. By using the proposed correlation, most of the experimental heat transfer coefficients obtained in the present study were predicted within +/- 15%. The new correlation compares reasonably well with independent data from the literature. (C) 2008 Elsevier Inc. All rights reserved.