Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies

Oxidation of ethanol on ruthenium-modified Pt(775) and Pt(332) stepped electrodes has been studied using electrochemical and FTIR techniques. It has been found that the oxidation of ethanol on these electrodes takes place preferentially on the step sites yielding CO(2) as the major final product. The cleavage of the C-C bond, which is the required step to yield CO(2), occurs only on this type of site. The presence of low ruthenium coverages on the step sites promotes the complete oxidation of ethanol since it facilitates the oxidation of CO formed on the step from the cleavage of the C-C bond. However, high ruthenium coverages have an important inhibiting effect since the adatoms block the step sites, which are required for the cleavage of the C-C bond. Under these conditions, the oxidation current diminishes and the major product in the oxidation process is acetic acid, which is the product formed preferentially on the (111) terrace sites.

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.

Nanogravimetric and voltammetric studies of a Pt-Rh alloy surface and its behavior for methanol oxidation

This paper describes the preparation of a Pt-Rh alloy surface electrodeposited on Pt electrodes and its electrocatalytic characterization for methanol oxidation. The X-ray photoelectronic spectroscopy ( XPS) results demonstrate that the surface composition is approximately 24 at-% Rh and 76 % Pt. The cyclic voltammetry (CV) and electrochemical quartz crystal (EQCN) results for the alloy were associated, for platinum, to the well known profile in acidic medium. For Rh, on the alloy, the generation of rhodium hydroxide species (Rh(OH)(3) and RhO(OH)(3)) was measured. During the successive oxidation-reduction cycles the mass returns to its original value, indicating the reversibility of the processes. It was not observed rhodium dissolution during the cycling. The 76/24 at % Pt-Rh alloy presented singular electrocatalytic activity for methanol electrooxidation, which started at more negative potentials compared to pure Pt (70 mV). During the sweep towards more negative potentials, there is only weak CO re-adsorption on both Rh and Pt-Rh alloy surfaces, which can be explained by considering the interaction energy between Rh and CO.

Effects of Molybdenum, Nickel, and Nitrogen Sources on the Mineral Nutrition and Growth of Rice Plants

Upland rice plants, cultivar `IAC 202,` were grown in nutrient solution until full tillering. Treatments consisted of ammonium nitrate (AN) or urea (UR) as nitrogen (N) source plus molybdenum (Mo) and/or nickel (Ni): AN + Mo + Ni, AN + Mo - Ni, AN - Mo + Ni, UR + Mo + Ni, UR + Mo - Ni, and UR - Mo + Ni. The experiment was carried out to better understand the effect of these treatments on dry-matter yield, chlorophyll, net photosynthesis rate, nitrate (NO3 --N), total N, in vitro activities of urease and nitrate reductase (NR), and Mo and Ni concentrations. In UR-grown plants, Mo and Ni addition increased yield of dry matter. Regardless of the N source, chlorophyll concentration and net photosynthesis rate were reduced when Mo or Ni were omitted, although not always significantly. The omission of either Mo or Ni led to a decrease in urease activity, independent of N source. Nitrate reductase activity increased in nutrient solutions without Mo, although NO3 --N increased. There was not a consistent variation in total N concentration. Molybdenum and Ni concentration in roots and shoots were influenced by their supply in the nutrient solution. Molybdenum concentration was not influenced by N sources, whereas Ni content in both root and shoots was greater in ammonium nitrate-grown plants. In conclusion, it can be hypothesized that there is a relationship between Mo and Ni acting on photosynthesis, although is an indirect one. This is the first evidence for a beneficial effect of Mo and Ni interaction on plant growth.

DFT and electrochemical studies on nortriptyline oxidation sites

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule`s activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.

Adsorption kinetic, thermodynamic and desorption studies of phosphate onto hydrous niobium oxide prepared by reverse microemulsion method

A type of Nb(2)O(5)center dot 3H(2)O was synthesized and its phosphate removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The phosphate adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model with which the maximum P adsorption capacity was estimated to be 18.36 mg-Pg(-1). The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. A phosphate desorbability of approximately 68% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. The immobilization of phosphate probably occurs by the mechanisms of ion exchange and physicochemical attraction. Due to its high adsorption capacity, this type of hydrous niobium oxide has the potential for application to control phosphorus pollution.

Quantification of MgO surface excess on the SnO(2) nanoparticles and relationship with nanostability and growth

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO(2) nanoparticles plays an important role in the system`s energetics and stability. Using Xray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO(2) with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO(2) nanoparticles stability. (C) 2010 Elsevier B.V. All rights reserved.

Structural and morphological studies on SiOxNy thin films

In this work, the structure and morphology of silicon oxynitride films deposited by the PECVD technique were studied. The films were deposited under two different conditions: (a) SiOxNy with chemical compositions varying from SiO2 to Si3N4 via the control of a N2O + N-2 + SiH4 gas mixture, and (b) Si-rich SiOxNy films via the control of a N2O + SiH4 gas mixture. The analyses were performed using X-ray near edge spectroscopy (XANES) at the Si-K edge, transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS). For samples with chemical composition varying from SiO2 to Si3N4, the diffraction patterns obtained by TEM exhibited changes with the chemical composition, in agreement with the XANES results. For silicon-rich silicon oxynitride samples, the formation of a-Si clusters was observed and the possibility of obtaining Si nanocrystals after annealing depending on the composition and temperature was realized. (C) 2007 Elsevier B.V. All rights reserved.

Hormonal modulation of photomorphogenesis-controlled anthocyanin accumulation in tomato (Solanum lycopersicum L. cv Micro-Tom) hypocotyls: Physiological and genetic studies

Hormones are likely to be important factors modulating the light-dependent anthocyanin accumulation. Here we analyzed anthocyanin contents in hypocotyls of near isogenic Micro-Tom (MT) tomato lines carrying hormone and phytochrome mutations, as single and double-mutant combinations. In order to recapitulate mutant phenotype, exogenous hormone applications were also performed Anthocyanin accumulation was promoted by exogenous abscisic acid (ABA) and inhibited by gibberellin (GA), in accordance to the reduced anthocyanin contents measured in ABA-deficient (notabills) and GA-constitutive response (procera) mutants. Exogenous cytokinin also enhanced anthocyanin levels in MT hypocotyls. Although auxin-insensitive chageotropica mutant exhibited higher anthocyanin contents, pharmacological approaches employing exogenous auxin and a transport inhibitor did not support a direct role of the hormone in anthocyanin accumulation Analysis of mutants exhibiting increased ethylene production (epwastic) or reduced sensitivity (Never ripe), together with pharmacological data obtained from plants treated with the hormone, indicated a limited role for ethylene in anthocyanin contents. Phytochrome-deficiency (aurea) and hormone double-mutant combinations exhibited phenotypes suggesting additive or synergistic interactions, but not fully espistatic ones, in the control of anthocyanin levels in tomato hypocotyls. Our results indicate that phytochrome-mediated anthocyanin accumulation in tomato hypocotyls is modulated by distinct hormone classes via both shared and independent pathways. (C) 2010 Elsevier Ireland Ltd. All rights reserved

DOSES OF INDOLBUTYRIC ACID IN THE ROOTING AND GROWTH OF EUCALYPT CUTTINGS (Eucalyptus urophylla)

This work aimed to evaluate the effect of different concentrations of IBA (indolbutyric acid) in the rooting and growth of Eucalyptus urophylla cuttings. The experimental design used was the randomized blocks, in factorial with an arrangement of split plots, with three concentrations of IBA (2.000; 5.000 and 8.000 mg L(-1)), two ways of the application of plant gowth regulators (paste and powder), and three period of evaluations (30, 45 and 60 days). The experiment was carried out in the Farm Buriti de Prata, an entreprise property of Souza Cruz, in the city of Prata - MG in 2003. After the preparation of the cuttings, patterned in 10 cm of length and 0.8 cm of diameter, those were immersed in mixtures of IBA for 10 seconds, in the forms of dry powder and paste and than planted in plastic tubes contening Plantmax substrate with vermiculite. The cuttings were transported to greenhouse with controled humidity, where they remained for 60 days. The variables studied were: height of plant in the 30(th), 45(th) and 60(th) days after seeding; fresh mass of the aerial part and roots. The IBA applied in powder form as well as in paste form, resulted in an greater seedling growth. To the 60 days, the seedlings presented greater growth, being significantly superior to the heights measured in other times of evaluation. The application of 2.000 mg L(-1) and 5,000 mg L(-1) resulted in significant increases on weight of fresh mass of the aerial part and root system.

Molecular modeling and QSAR studies of a set of indole and benzimidazole derivatives as H(4) receptor antagonists

Histamine is an important biogenic amine, which acts with a group of four G-protein coupled receptors (GPCRs), namely H(1) to H(4) (H(1)R - H(4)R) receptors. The actions of histamine at H(4)R are related to immunological and inflammatory processes, particularly in pathophysiology of asthma, and H(4)R ligands having antagonistic properties could be helpful as antiinflammatory agents. In this work, molecular modeling and QSAR studies of a set of 30 compounds, indole and benzimidazole derivatives, as H(4)R antagonists were performed. The QSAR models were built and optimized using a genetic algorithm function and partial least squares regression (WOLF 5.5 program). The best QSAR model constructed with training set (N = 25) presented the following statistical measures: r (2) = 0.76, q (2) = 0.62, LOF = 0.15, and LSE = 0.07, and was validated using the LNO and y-randomization techniques. Four of five compounds of test set were well predicted by the selected QSAR model, which presented an external prediction power of 80%. These findings can be quite useful to aid the designing of new anti-H(4) compounds with improved biological response.

HPLC-UV determination of metformin in human plasma for application in pharmacokinetics and bioequivalence studies

In this study, a simple, rapid and sensitive HPLC method with UV detection is described for determination of metformin in plasma samples from bioequivalence assays. Sample preparation was accomplished through protein precipitation with acetonitrile and chromatographic separation was performed on a reversed-phase phenyl column at 40 degrees C. Mobile phase consisted of a mixture of phosphate buffer and acetonitrile at flow rate of 1.0 ml/min. Wavelength was set at 236 nm. The method was applied to a bioequivalence study of two drug products containing metformin, and allowed determination of metformin at low concentrations with a higher throughput than previously described methods. (c) 2007 Elsevier B.V. All rights reserved.

Re-examination of the anion derivatives of isoflavones by radical fragmentation in negative electrospray ionization tandem mass spectrometry: experimental and computational studies

This paper reports theoretical and experimental studies of gas-phase fragmentation reactions of four naturally occurring isoflavones. The samples were analyzed in negative ion mode by direct infusion in ESI-QqQ, ESI-QqTOF and ESI-Orbitrap systems. The MS/MS and MS(n) spectra are in agreement with the fragmentation proposals and high-resolution analyses have confirmed the formulae for each ion observed. As expected, compounds with methoxyl aromatic substitution have showed a radical elimination of center dot CH(3) as the main fragmentation pathway. A second radical loss (center dot H) occurs as previously observed for compounds which exhibit a previous homolytic center dot CH(3) cleavage (radical anion) and involves radical resonance to stabilize the anion formed. However, in this study we suggest another mechanism for the formation of the main ions, on the basis of the enthalpies for each species. Compounds without methoxy substituent dissociate at the highest energies and exhibit the deprotonated molecule as the most intense ion. Finally, energy-resolved experiments were carried out to give more details about the gas-phase dissociation reaction of the isoflavones and the results are in agreement with the theoretical approaches. Copyright (C) 2011 John Wiley & Sons, Ltd.

Photophysical and Complexation Studies of Chloro-Aluminum Phthalocyanine with Beta-Cyclodextrin and Hydroxypropyl-Beta-Cyclodextrin

A variety of nanostructures are being investigated as functional drug carriers for treatment of a wide range of diseases, most notably cardiovascular defects, autoimmune diseases, and cancer. The aim of this present contribution is to evaluate potentially applicable nanomaterials in the diagnosis and treatment of cancer due to their photophysical and photobiological properties and complexation behavior. The delivery systems consisted of chloro-aluminum phthalocyanine associated with beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin. The preparation of the complex and its stoichiometry in an ethanol/buffer (3:1) solution were studied by spectroscopic techniques, which were defined as 1:2. The inclusion complex in the nanometer scale was observed on the basis of changes to the spectroscopic properties. The singlet oxygen production and complex photophysical parameters were determined by measuring luminescence at 1270 nm and by steady state and time resolved spectroscopic, respectively. The preparation of the complex was tested and analyzed with regard to cellular damage by visible light activation. The inclusion complex showed a higher singlet oxygen quantum yield compared with other systems and other photoactive dyes. There was also a reduction in the fluorescence quantum yield compared with the results obtained for zinc phthalocyanine in organic medium. The results reported clearly that the inclusion complex chloro-aluminum phthalocyanine/cyclodextrin showed some changes in its spectroscopy properties leading to better biodistribution and biocompatibility with a potential application in photodynamic therapy, especially in the case of neoplasy. Additionally, it also has non-oncological applications as a drug delivery system.