Application of Ti/RuO(2)-Ta(2)O(5) electrodes in the electrooxidation of ethanol and derivants: Reactivity versus electrocatalytic efficiency

The influence of the preparation method on the performance of RuO(2)-Ta(2)O(5) electrodes was evaluated toward the ethanol oxidation reaction (EOR). Freshly prepared RuO(2)-Ta(2)O(5) thin films containing between 30 and 80 at.% Ru were prepared by two different methods: the modified Pechini-Adams method (DPP) and standard thermal decomposition (STD). Electrochemical investigation of the electrode containing RuO(2)-Ta(2)O(5) thin films was conducted as a function of electrode composition in a 0.5-mol dm(-3) H(2)SO(4) solution, in the presence and absence of ethanol and its derivants (acetaldehyde and acetic acid). At a low ethanol concentration (5 mmol dm(-3)), ethanol oxidation leads to high yields of acetic acid and CO(2). On the other hand, an increase in ethanol concentration (15-1000 mmol dm(-3)) favors acetaldehyde formation, so acetic acid and CO(2) production is hindered, in this case. Electrodes prepared by DPP provide higher current efficiency than STD electrodes for all the investigated ethanol concentrations. This may be explained by the increase in electrode area obtained with the DPP preparation method compared with STD. (c) 2008 Elsevier Ltd. All rights reserved.

Morphological and electrochemical investigation of RuO(2)-Ta(2)O(5) oxide films prepared by the Pechini-Adams method

Preparation methods can profoundly affect the structural and electrochemical properties of electrocatalytic coatings. In this investigation, RuO(2)-Ta(2)O(5) thin films containing between 10 and 90 at.% Ru were prepared by the Pechini-Adams method. These coatings were electrochemically and physically characterized by cyclic voltammetry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The composition and morphology of the oxide were investigated before and after accelerated life tests (ALT) by EDX and SEM. SEM results indicate typical mud-flat-cracking morphology for the majority of the films. High resolution SEMs reveal that pure oxide phases exhibit nanoporosity while binary compositions display a very compact structure. EDX analyses reveal considerable amounts of Ru in the coating even after total deactivation. XRD indicated a rutile-type structure for RuO(2) and orthorhombic structure for Ta(2)O(5). XPS data demonstrate that the binding energy of Ta is affected by Ru addition in the thin films, but the binding energy of Ru is not likewise influenced by Ta. The stability of the electrodes was evaluated by ALT performed at 750 mA cm(-2) in 80 degrees C 0.5 mol dm(-3) H(2)SO(4). The performance of electrodes prepared by the Pechini-Adams method is 100% better than that of electrodes prepared by standard thermal decomposition.

Estudos da eletrodeposição de metais em regime de subtensão

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

Reação de geração de oxigênio em eletrodos de Mn2O3 suportados em aço inoxidável

A study of the kinetics of oxygen evolution in alkaline conditions from ceramic films of Mn2O3 supported on stainless steel was carried out. This study has been done through the determination of transfer coefficients, Tafel slopes and exchange currents using potentiodynamic and quasi-potentiostatic measurements. The activation energy was determined as a function of the overpotential and, additionally, the electrode active surface was estimated. The results are consistent with data already published for other electrodes, implying that the methods used in this work were reliable and precise.

Novel Proteins Involved in Dynamics of The Photosynthetic Apparatus

During the past few years, a considerable number of research articles have been published relating to the structure and function of the major photosynthetic protein complexes, photosystem (PS) I, PSII, cytochrome (Cyt) b6f, and adenosine triphosphate (ATP) synthase. Sequencing of the Arabidopsis thaliana (Arabidopsis) genome together with several high-quality proteomics studies has, however, revealed that the thylakoid membrane network of plant chloroplasts still contains a number of functionally unknown proteins. These proteins may have a role as auxiliary proteins guiding the assembly, maintenance, and turnover of the thylakoid protein complexes, or they may be as yet unknown subunits of the photosynthetic complexes. Novel subunits are most likely to be found in the NAD(P)H dehydrogenase (NDH) complex, the structure and function of which have remained obscure in the absence of detailed crystallographic data, thus making this thylakoid protein complex a particularly interesting target of investigation. In this thesis, several novel thylakoid-associated proteins were identified by proteomics-based methods. The major goal of characterization of the stroma thylakoid associated polysome-nascent chain complexes was to determine the proteins that guide the dynamic life cycle of PSII. In addition, a large protein complex of ≥ 1,000 kDa, residing in the stroma thylakoid, was characterized in greater depth and it was found to be a supercomplex composed of the PSI and NDH complexes. A set of newly identified proteins from Arabidopsis thylakoids was subjected to detailed characterization using the reverse genetics approach and extensive biochemical and biophysical analysis. The role of the novel proteins, either as auxiliary proteins or subunits of the photosynthetic protein complexes, was revealed. Two novel thylakoid lumen proteins, TLP18.3 and AtCYP38, function as auxiliary proteins assisting specific steps of the assembly/repair of PSII. The role of the 10-kDa thylakoid lumen protein PsbR is related to the optimization of oxygen evolution of PSII by assisting the assembly of the PsbP protein. Two integral thylakoid membrane proteins, NDH45 and NDH48, are novel subunits of the chloroplast NDH complex. Finally, the thylakoid lumen immunophilin AtCYP20-2 is suggested to interact with the NDH complex, instead of PSII as was hypothesized earlier.

Influência das condições de resfriamento sobre as propriedades superficiais e eletroquímicas de anodos dimensionalmente estáveis

Surface and electrochemical properties of the dimensionally stable anode Ti/(Ru0.3Ti0.7)O2 were studied as a function of the annealing temperature using different conditions in order to perform the cooling process of the oxide films (conventional thermal shock and the slow cooling processes). It was found that surface and electrochemical properties for the oxygen evolution reaction are both affected through the cooling process, being the electrode prepared at 400 ºC using the slow cooling process the less susceptible to wear. The Tafel slope obtained in the high overpotential domain was analysed in light of the apparent charge transfer coefficient.

An investigation into the functional role of the D1:1 and D1:2 polypeptides in photosystem II in cyanobacteria : the effect of changing PSI/PSII ratio on photoinhibition in Synechococcus sp. PCC7942 /

The cyanobacterium Synechococcus sp. PCC 7942 (Anacystis nidulans R2) adjusts its photosynthetic function by changing one of the polypeptides of photosystem II. This polypeptide, called Dl, is found in two forms in Synechococcus sp. PCC 7942. Changing the growth light conditions by increasing the light intensity to higher levels results in replacement of the original form of D 1 polypeptide, D 1: 1, with another form, D 1 :2. We investigated the role of these two polypeptides in two mutant strains, R2S2C3 (only Dl:l present) and R2Kl (only Dl:2 present) In cells with either high or low PSI/PSII. R2S2C3 cells had a lower amplitude for 77 K fluorescence emission at 695 nm than R2Kl cells. Picosecond fluorescence decay kinetics showed that R2S2C3 cells had shorter lifetimes than R2Kl cells. The lower yields and shorter lifetimes observed in the D 1 and Dl:2 containing cells. containing cells suggest that the presence of D 1: 1 results in more photochemical or non-photochemical quenching of excitation energy In PSII. One of the most likely mechanisms for the increased quenching in R2S2C3 cells could be an increased efficiency in the transfer of excitation energy from PSII to PSI. However, photophysical studies including 77 K fluorescence measurements and picosecond time resolved decay kinetics comparing low and high PSI/PSII cells did not support the hypothesis that D 1: 1 facilitates the dissipation of excess energy by energy transfer from PSII to PSI. In addition physiological studies of oxygen evolution measurements after photoinhibition treatments showed that the two mutant cells had no difference in their susceptibility to photoinhibition with either high PSI/PSII ratio or low PSI/PSII ratio. Again suggesting that, the energy transfer efficiency from PSII to PSI is likely not a factor in the differences between Dl:l and Dl:2 containing cells.

Alkali insoluble glucan extracted from Acremonium diospyri is a more potent immunostimulant in the Indian White Shrimp, Fenneropenaeus indicus than alkali soluble glucan

E¡ect of an extraction method on the structure of glucan and its immunostimulatory response in Fenneropenaeus indicus was investigated. Here we extracted alkali insoluble glucan (AIG) and alkali soluble glucan (ASG) from a ¢lamentous fungi Acremonium diospyri following alkali^acid hydrolysis and the sodium hypochlorite oxidation and dimethyl sulphoxide extraction method respectively. Structural analysis showed that 85% of glucan in AIG was a (1 !3)-b-D-glucan and it increased the prophenoloxidase and reactive oxygen intermediate activity when administered to F. indicus. On the other hand, ASG, which contained 93% (1 !3)-a-glucan, did not induce signi¢cant immune response in shrimp. Here we report that the di¡erence in immunostimulatory potential between AIG and ASG is due to the di¡erence in the percentage of (1 !3)-b-D-glucans present in each preparation, which varies with the method of extraction employed. Also our observations suggest that glucan can be used as a potential immunostimulant to shrimp, provided it contains (1 !3)-b-D-glucan as the major fraction.

New mono- and dinuclear ruthenium complexes containing the 3,5-bis(2-pyridyl)pyrazole ligand. Synthesis, characterization and applications

Se han sintetizado dos nuevos complejos mononucleares de Ru, con formula [RuCl2(Hbpp)(dmso)2], a partir de la reacción entre [RuCl2(dmso)4] y Hbpp (3,5-bis(2-piridil)pirazola). El hecho que sólo tres de los seis posibles estereoisómeros se obtengan a partir de esta reacción, se ha racionalizado en base a factores estructurales y electrónicos. Estos complejos se han caracterizado de forma estructural, espectroscópica y electroquímica. En acetonitrilo en medio básico, el isómero trans,cis-[RuCl2(Hbpp)(dmso)2] da lugar a procesos de isomerización de enlace de un ligando dmso cuando el Ru(II) se oxida a Ru(III). Las constantes termodinámicas y cinéticas para el proceso se han determinado por voltametria cíclica. La irradiación de trans,cis-[RuCl2(Hbpp)(dmso)2] y cis(out),cis-[RuCl2(Hbpp)(dmso)2] con luz UV o solar da lugar a reacciones de fotosustitución de un ligando dmso por una molécula de acetonitrilo para dar un nuevo compuesto el cual ha sido caracterizado en solución por técnicas espectroscópicas y electroquímicas. Ambos complejos resultan catalizadores útiles en la transferencia de hidrógeno de isopropanol a acetofenona, obteniéndose 1-feniletanol como único producto y un 42.1% de conversión (36.1 ciclos metálicos) a 80ºC con el isómero trans,cis-[RuCl2(Hbpp)(dmso)2], que resulta significativamente más eficaz que el complejo cis(out),cis-[RuCl2(Hbpp)(dmso)2]. La reacción de cis(out),cis-[RuCl2(Hbpp)(dmso)2] con trpy (2,2':6',2"-terpiridina) da lugar a los dos isómeros geométricos del complejo [Ru(Hbpp)(trpy)(Cl)]+, el in y el out. Estos complejos se han aislado y caracterizado por técnicas estructurales, espectroscópicas y electroquímicas. Estos cloro complejos han sido utilizados como precursores para la síntesis de los complejos análogos con ligandos aqua (in,out-[Ru(Hbpp)(trpy)(H2O)]2+) y piridina (in,out-[Ru(Hbpp)(trpy)(py)]2+), los cuales también han sido aislados y caracterizados. Las propiedades ácido-base de los aqua complejos, y del complejo out-py se han estudiado detalladamente por voltametria cíclica y mediante valoraciones espectrofotométricas ácido-base. El tratamiento matemático de los datos así obtenidos nos ha permitido determinar los valores de pKa para los distintos equilibrios de protonación de los complejos en los estados de oxidación II y III. El complejo out-aqua ha demostrado ser un buen catalizador para la oxidación electroquímica del alcohol benzílico, presumiblemente a benzaldehido. La constante de velocidad de segundo orden para el proceso ha sido determinada como 17.1 M-1 s-1, por simulación matemática. El dímero con un puente cloro, [Ru2Cl(bpp)(trpy)2]2+ ha sido preparado por dos rutas sintéticas diferentes. El dímero análogo con un puente acetato se ha obtenido por reacción del cloro dímero con un exceso de acetato sódico. El dímero con dos ligandos aqua [Ru2(bpp)(trpy)2(OH2)2]3+ puede obtenerse por hidrólisis ácida del complejo con un acetato puente o por hidrólisis básica del complejo con un puente cloro. Estos complejos han sido caracterizados por técnicas estructurales, espectroscópicas y electroquímicas. Las soluciones del dímero con dos ligandos aqua en medio ácido resultan inestables a la coordinación de aniones de la solución con el tiempo. Las propiedades ácido-base del dímero con dos aguas coordinadas han sido estudiadas por voltametria cíclica y mediante experimentos de electrólisis a potencial controlado. El pKa para la desprotonación de uno de los ligandos aqua ha sido determinado mediante una valoración espectrofotométrica ácido-base como 6.7. Este valor tan bajo de pKa se atribuye a la formación de la entidad {Ru2O2H3}, favorable termodinámicamente. Los espectros UV-vis para los distintos estados de oxidación del aqua dímero, de RuIIRuII a RuIIIRuIV, han sido obtenidos por oxidación química y electroquímica del complejo. Se han llevado a cabo estudios cinéticos de la oxidación, paso a paso, de RuII,II a RuIV,IV , y se han determinado las constantes de oxidación de segundo orden para los distintos procesos de oxidación. La capacidad del aqua dímero en la oxidación del agua a oxígeno molecular ha sido investigada en solución homogénea utilizando CeIV como oxidante. La evolución de oxígeno se ha demostrado por cromatografia de gases. Se ha obtenido una eficiencia del 73% y 18.6 ciclos catalíticos, cuando 1.83 x 10-6 moles de dímero se han mezclado con un exceso de 100 equivalentes de cerio. El dímero con dos aguas cataliza también la oxidación del agua de forma heterogénea, con el complejo adsorbido sobre una membrana de nafion, aunque la eficiencia es menor. Se ha propuesto un mecanismo intramolecular para la reacción de oxidación del agua. Consiste en la oxidación a 4 electrones del dímero, de RuII,II a RuIV,IV, el cual reacciona con el agua para formar oxígeno y revierte nuevamente al estado de oxidación II,II. Este modelo es consistente con estudios catalíticos de la evolución de oxígeno en función de las concentraciones de cerio y catalizador, llevados a cabo en solución ácida homogénea, que demuestran que la oxidación a 4 electrones del agua se encuentra catalizada por una sola molécula de complejo bajo concentraciones elevadas de cerio. La constante de pseudo-primer-orden para la evolución de oxígeno tiene un valor de 1.4 x 10-2 s-1, que es uno de los valores de constante más elevados obtenidos hasta la fecha. Desafortunadamente, el aqua dímero se desactiva durante el proceso de catálisis dando lugar a una especie naranja, la cual estamos actualmente tratando de caracterizar.

Effects of N supply on the accumulation of photosynthetic pigments and photoprotectors in Gracilaria tenuistipitata (Rhodophyta) cultured under UV radiation

We have studied the effects of nitrate supply under photosynthetic active radiation (PAR) plus ultraviolet radiation (UVR) exposure on photosynthetic pigments (chlorophyll a and carotenoids), photoprotective UV screen mycosporine-like amino acids (MAAs), and photosynthetic parameters, including the maximum quantum yield (F(v)/F(m)) and electron transport rate (ETR) on the red agarophyte Gracilaria tenuistipitata. Apical tips of G. tenuistipitata were cultivated under ten different concentrations of NO(3)(-) for 7 days. It has been shown that G. tenuistipitata cultured under laboratory conditions has the ability to accumulate high amounts of MAAs following a nitrate concentration-dependent manner under PAR+UVR. Two MAAs were identified, shinorine and porphyra-334. The relative concentration of the first increased under high concentrations of nitrate, while the second one decreased. The presence of antheraxanthin is reported for the first time in this macro-algae, which also contains zeaxanthin, lutein, and beta-carotene. The accumulation of pigments, photoprotective compounds, and photosynthetic parameters of G. tenuistipitata is directly related to N availability. All variables decreased under low N supplies and reached constant maximum values with supplements higher than 0.5 mM NO(3)(-). Our results suggest a high potential to acclimation and photoprotection against stress factors (including high PAR and UVR) directly related to N availability for G. tenuistipitata.

A New Insight on the Preparation of Stabilized Alpha-Nickel Hydroxide Nanoparticles

Nickel hydroxide can provide an outstanding cathode material in alkaline secondary batteries, however the progressive decrease of the charge capacity as a function of the number of oxidation/reduction cycles is a challenging problem to be solved. New improvements on the electrochemical properties of electrode materials can be achieved by exploiting the much better performance of alpha-nickel hydroxide. Such materials were obtained in a stable form by sol-gel method and characterized by thermogravimetric analyses, UV-Vis spectroscopy, X-ray diffractometry, scanning and transmission electron microscopy, cyclic voltammetry and electrochemical quartz crystal microbalance techniques. The results revealed not only the formation of the alpha-Ni(OH)(2) phase, but also a much better electrochemical reversibility and stability as compared with similar materials obtained by electrochemical precipitation method.

Electrocombustion of humic acid and removal of algae from aqueous solutions

This paper reports experiments involving the electrochemical combustion of humic acid (HA) and removal of algae from pond water. An electrochemical flow reactor with a boron-doped diamond film anode was used and constant current experiments were conducted in batch recirculation mode. The mass transfer characteristics of the electrochemical device were determined by voltammetric experiments in the potential region of water stability, followed by a controlled current experiment in the potential region of oxygen evolution. The average mass transfer coefficient was 5.2 x 10(-5) m s(-1). The pond water was then processed to remove HA and algae in the conditions in which the reaction combustion occurred under mass transfer control. To this end, the mass transfer coefficient was used to estimate the initial limiting current density applied in the electrolytic experiments. As expected, all the parameters analyzed here-solution absorbance at 270 nm, total phenol concentration and total organic carbon concentration-decayed according to first-order kinetics. Since the diamond film anode successfully incinerated organic matter, the electrochemical system proved to be predictable and programmable.

Photosynthetic characteristics of the freshwater red alga Batrachospermum delicatulum (Skuja) Necchi & Entwisle

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

Light-related photosynthetic characteristics of freshwater rhodophytes

Photosynthetic characteristics in response to irradiance were analysed in 21 field and culture populations of thirteen freshwater red algal species applying two distinct techniques (chlorophyll fluorescence and oxygen evolution). Photosynthesis-irradiance (PI) curves indicated adaptations to low irradiances in all species analysed, essentially characterized by occurrence of photoinhibition, low values of the saturation parameter (I-k < 225 mu mol m(-2) s(-1)) and compensation irradiance (I-c < 20 mu mol m(-2) s(-1)) and relatively high values of the effective quantum yield of photosystem II (Delta F/F'(m) >= 45). These characteristics have been reported in freshwater red algae and were confirmed from data based on the two techniques, indicating they are typically shade-adapted plants. on the other hand, some species (e.g. Batrachospermum delicatulum) can tolerate high irradiances (up to 2400 mu mol m(-2) s(-1)), suggesting they have mechanisms that enable them to avoid photodarnage of the photosynthetic apparatus. One of these mechanisms is the increase in dissipation of excessive energy captured by reaction centres after exposure to continuous irradiance, as reflected by the non-photochemical quenching fluorescence parameter in dark/light induction curves. Photo-inhibition occurred in all algae tested by both techniques. Light acclimation was evident particularly in field populations, as revealed by lower values of the saturation parameter (Ik) and the compensation irradiance (I-c) and higher values of Delta F/F'(m) in algae under low irradiances (shaded or heavily shaded stream segments), and vice-versa. Forms living within the boundary layer (e.g. crusts), in a region of reduced current velocity, tended to be more shade-adapted than semi-erect plants (e.g. non-mucilaginous or mucilaginous filaments), as indicated by highest values of photosynthetic efficiency (alpha = 0.31) and effective quantum yield (Delta F/F'(m) = 0.88) under natural conditions. Higher photo- synthetic rates (P-max) for the same species or population were observed under culture than field conditions when measured with the oxygen evolution technique, whereas the opposite trend was observed using chlorophyll fluorescence. (c) 2005 Elsevier B.V. All rights reserved.

Light-related photosynthetic characteristics of lotic macroalgae

Photosynthetic characteristics in response to irradiance were analysed in 42 populations of 33 macroalgal species by two distinct techniques (chlorophyll fluorescence and oxygen evolution). Photosynthesis-irradiance (PI) curves based on the two techniques indicated adaptations to low irradiance reflected by low saturation values, high to moderate values of photosynthetic efficiency (alpha) and photoinhibition (beta), for Bacillariophyta and Rhodophyta, which suggests they are typically shade-adapted algae. In contrast, most species of Chlorophyta were reported as sun adapted algae, characterized by high values of I-k and low of alpha, and lack of or low photoinhibition. Cyanophyta and Xanthophyta were intermediate groups in terms of light adaptations. Photoinhibition was observed in variable degrees in all algal groups, under field and laboratory conditions, which confirms that it is not artificially induced by experimental conditions, but is rather a common and natural phenomenon of the lotic macroalgae. Low values of compensation irradiance (I-c) were found, which indicate that these algae can keep an autotrophic metabolism even under very low irradiances. High ratios (>2) of photosynthesis/respiration were found in most algae, which indicates a considerable net gain. These two physiological characteristics suggest that macroalgae may be important primary producers in lotic ecosystems. Saturation parameters (I-k and I-s) occurred in a relatively narrow range of irradiances (100-400 mumol photons m(-2) s(-1)), with some exceptions (higher in some filamentous green algae or lower in red algae). These parameters were way below the irradiances measured at collecting sites for most algae, which means that most of the available light energy was not photochemically converted via photosynthesis. Acclimation to ambient PAR was observed, as revealed by lower values of I-k and I-c and higher values of alpha and quantum yield in algae from shaded streams, and vice versa. Forms living within the boundary layer (crusts) showed responses of shade-adapted species and had the highest values of P-max, alpha and quantum yield, whereas the opposite trend was observed in gelatinous forms (colonies and. laments). These results suggests adaptation to the light regime rather than functional attributes related to the growth form.