Salinity tolerance in Schinopsis quebracho colorado: Seed germination, growth, ion relations and metabolic responses

Soil salinity is a major abiotic stress influencing plant productivity worldwide. Schinopsis quebracho colorado is one of the most important woody species in the Gran Chaco, an and and salt-prone subtropical biome of South America. To gain a better understanding of the physiological mechanisms that allow plant establishment under salt conditions, germination and seedling growth of S. quebracho colorado were examined under treatment with a range of NaCl solutions (germination: 0-300 mmol l(-1) NaCl; seedling growth: 0-200 mmol l(-1) NaCl). The aim was to test the hypothesis that S. quebracho colorado is a glycophite that shows different salt tolerance responses with development stage. Proline content, total soluble carbohydrates and Na+, K+ and Cl- concentrations in leaves and roots of seedlings, and the chlorophyll concentration and relative water content of leaves were measured. Germination was not affected by 100 mmol l(-1) NaCl, but decreased at a concentration of 200 mmol l(-1). At 300 mmol l(-1) NaCl, germination did not occur. Seedling growth decreased drastically with increasing salinity. An increase in NaCl from 0 to 100 mmol l(-1) also significantly reduced the leaf relative water content by 22% and increased the proline concentration by 60% in roots. In contrast, total soluble carbohydrates were not significantly affected by salinity. Seedlings showed a sodium exclusion capacity, and there was an inverse correlation between Cl- concentration and the total chlorophyll concentration. S. quebracho colorado was more tolerant to salinity during germination than in the seedling phase. The results suggest that this increased tolerance during germination might, in part, be the result of lower sensitivity to high tissue Na+ concentrations. The significant increment of proline in the roots suggests the positive role of this amino acid as a compatible solute in balancing the accumulation of Na+ and Cl- as a result of salinity. These results help clarify the physiological mechanisms that allow establishment of S. quebracho colorado on salt-affected soils in arid and semi-arid Gran Chaco. (c) 2008 Elsevier Ltd. All rights reserved.

Pt-RuO(2) electrodes prepared by thermal decomposition of polymeric precursors as catalysts for direct methanol fuel cell applications

The electrocatalytic activity of Pt and RuO(2) mixed electrodes of different compositions towards methanol oxidation was investigated. The catalysts were prepared by thermal decomposition of polymeric precursors and characterized by energy dispersive X-ray, scanning electronic microscopy, X-ray diffraction and cyclic voltammetry. This preparation method allowed obtaining uniform films with controlled stoichiometry and high surface area. Cyclic voltammetry experiments in the presence of methanol showed that mixed electrodes decreased the potential peak of methanol oxidation by approximately 100 mV (RHE) when compared to the electrode containing only Pt. In addition, voltammetric experiments indicated that the Pt(0.6)Ru(0.4)O(y) electrode led to higher oxidation current densities at lower potentials. Chronoamperometry experiments confirmed the contribution of RuO(2) to the catalytic activity as well as the better performance of the Pt(0.6)Ru(0.4)O(y) electrode composition. Formic acid and CO(2) were identified as being the reaction products formed in the electrolysis performed at 400 and 600 mV. The relative formation of CO(2) was favored in the electrolysis performed at 400 mV (RHE) with the Pt(0.6)Ru(0.4)O(y) electrode. The presence of RuO(2) in Pt-Ru-based electrodes is important for improving the catalytic activity towards methanol electrooxidation. Moreover, the thermal decomposition of polymeric precursors seems to be a promising route for the production of catalysts applicable to DMFC. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

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.

Recognition of cyclic, acyclic, exocyclic, and spiro Acetals via structurally diagnostic ion/molecule reactions with the (CH3)(2)N-C+=O acylium ion

Reactions of the model acylium ion (CH3)(2)N-C+=O with acyclic, exocyclic, and Spiro acetals of the general formula (RO)-O-1-(CRR4)-R-3-OR2-upole mass spectrometry. Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most common reactions observed were hydride and alkoxy anion [(RO-)-O-1 and (RO-)-O-2] abstraction. Other specific reactions were also observed: (a) a secondary polar [4(+) + 2] cycloaddition for acetals bearing alpha,beta-unsaturated R-3 or R-4 substituents and (b) OH- abstraction for exocyclic and spiro acetals. These structurally diagnostic reactions, in conjunction with others observed previously for cyclic acetals, are shown to reveal the class of the acetal molecule and its ring type and substituents and to permit their recognition and distinction from other classes of isomeric molecules.

Impedance characteristics of the diamond/carbon fiber electrodes for electrical double-layer capacitor

The electrochemical performance of carbon fibers (CF) and boron-doped diamond electrodes grown on carbon fiber substrate (BDD/CF) was studied. CF substrates were obtained from polyacrylonitrile precursor heat treated at two different temperatures of 1000 and 2000 degrees C to produce the desirable CF carbon graphitization index. This graphitization process influenced the CF conductivity and its chemical surface, also analyzed from X-ray photoelectron spectroscopy measurements. These three-dimensional CF structures allowed a high incorporation of diamond films compared to other carbon substrates such as glass carbon or HOPG. The electrochemical responses, from these four classes of electrodes, were evaluated focusing their application as electrical double-layer capacitors using cyclic voltammetry and impedance measurements. Cyclic voltammetry results revealed that the electrode formed from BDD grown on CF-2000 presented a typical capacitor behavior with the best rectangular shape, compared to those electrodes of CF or BDD/CF-1000. Furthermore, the BDD/CF-2000 electrode presented the lowest impedance, associated to its significant capacitance value of 1940 mu F/cm(2) taking into account the BDD films. This behavior was attributed to the strong dependence between diamond coating texture and the CF graphitization temperature. The largest surface area of BDD/CF-2000 was promoted by its singular film growth mechanism associated to the substrate chemical surface. (c) 2008 Elsevier B.V. All rights reserved.

Electrocatalytic oxidation of ethanol on Sn((1-x))Ir((x))O(2) electrodes in acid medium

The electrochemical oxidation of ethanol at Sn((1-x))Ir (x) O(2) electrodes (with x = 0.01, 0.05, 0.1 and 0.3) was studied in 0.1 mol L(-1) HClO(4) solution. Electrolysis experiments were carried out and the reaction products were analyzed by Liquid Chromatography. It was found that the amounts of the reaction products depended on the composition of the electrode. In situ infrared reflectance spectroscopy measurements were performed to identify the adsorbed intermediates and to postulate a reaction mechanism for ethanol electrooxidation on these electrode materials. As evidence, acetaldehyde and acetic acid were formed through a successive reaction process. Carbon dioxide was also identified as the end product, showing that the cleavage of the carbon-carbon bond occurred. These results indicate that the synthesized catalysts are able to lead to the total combustion of organic compounds. Analysis of the water bending band at different potentials illustrated its role at the electrode interface.

Spectroelectrochemistry and investigation of charge transport mechanisms of iron poly(pyridyl) redox polymers

In this work, we describe the characterization of the complex [Fe(tpy-NH2)(2)](PF6)(2) (tpy-NH2 = bis[4`-(3-aminophenyl)-2, 2`:6`,2 ``-terpyridine]. The complex was oxidatively electropolymerized on glassy.-carbon electrodes in CH3CN/0.1 M tetraethylammonium perchlorate (TEAP) to generate polymer films that exhibit reversible oxidative electrochemical behavior in a wide potential range (0.0-1.6 V), as well as high conductivity and stability/durability. In situ spectrocyclic voltammetry of this modified electrode was carried out on a photodiode array spectrophotometer attached to a potentiostat, which provided UV-Vis absorption spectra of the redox species during the potential sweep. We determined charge transport parameters as a function of time and thickness of the modified electrode, and the results showed that poly-[[Fe(tpy-NH2)(2)](2+)](n) can be made to exhibit three regimes of charge transport behavior by manipulation of the film thickness and the experimental time-scale. Morphological characterization of the film was provided by atomic force microscopy. (C) 2008 Elsevier Ltd. All rights reserved.

Investigation of the electrical and electrochemical properties of nanocomposites from V2O5, polypyrrole, and polyaniline

In this work, an investigation of the electrical and electrochemical properties responsible for the energy storage capability of nanocomposites has been carried out. We demonstrate that, in the case of the V2O5 xerogel and the nanocomposites polypyrrole (Ppy)/V2O5 and polyaniline (PANI)/V2O5, the quadratic logistic equation (QLE) can be used to fit the inverse of the resistance values as a function of the injected charge in non-steady-state conditions. This contributes to a phenomenological understanding of the lithium ion and electron transport. The departure of the experimental curve from the fitting observed for the V2O5 xerogel can be attributed to the trapping sites formed during the lithium electroinsertion, which was observed by electrochemical impedance spectroscopy. The amount of trapping sites was obtained on the basis of the QLE. Similar values used to fit the inverse of the resistance were also used to fit the absorbance changes, which is also associated with the small polaron hopping from the V(IV) to the V(V) sites. On the other hand, there was good agreement between the experimental and the theoretical data when the profile of the inverse of the resistance as a function of the amount of inserted lithium ions of the nanocomposites Ppy/V2O5 and PANI/ V2O5 was concerned. We suggest that the presence of the conducting polymers is responsible for the different electrical profile of the V2O5 xerogel compared with those of the nanocomposites. In the latter case, interactions between the lithium ions and oxygen atoms from V2O5 are shielded, thus decreasing the trapping effect of lithium ions in the V2O5 sites. The different values of the lithium ion diffusion coefficient into these intercalation materials are in agreement with this hypothesis.

A new oxovanadium(IV)-cucurbit[6]uril complex: Properties and potential for confined heterogeneous catalytic oxidation reactions

This work presents a new oxovanadium(IV)-cucurbit[6]uril complex, which combines the catalytic properties of the metal ion with the size-excluding properties of the macrocycle cavity. In this coordination compound, the VO(2-) ions are coordinated to the oxygen atoms located at the rim of the macrocycle in slightly distorted square-pyramidal configurations, which are in fact C(2v) symmetries. This combination results in a size-selective heterogeneous catalyst, which is able to oxidize linear alkanes like n-pentane at room temperature, but not styrene, cyclohexane or z-cyclooctene, which are too big to enter the cucurbit[6]uril cavity. The results presented here contribute to understanding the mechanism of alkane catalytic oxidation by oxovanadium(IV) complexes. (C) 2010 Elsevier Ltd. All rights reserved.

Characterization and voltammetric behavior of Pt(y)Mo(z)O(x)/C electrodes prepared by the thermal decomposition of polymeric precursors

Carbon-supported catalysts containing platinum and molybdenum oxide are prepared by thermal decomposition of polymeric precursors. The Pt(y)Mo(z)O(x)/C materials are characterized by energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The catalysts present a well-controlled stoichiometry and nanometric particles. Molybdenum is present mainly as the MoO(3) orthorhombic structure, and no Pt alloys are detected. The voltammetric behavior of the electrodes is investigated; a correlation with literature results for PtMo/C catalysts prepared by other methods is established. The formation of soluble species and the aging effect are discussed. (C) 2009 Elsevier B.V. All rights reserved.

Self-assembled films from WO(3): Electrochromism and lithium ion diffusion

WO(3)/chitosan and WO(3)/chitosan/poly(ethylene oxide) (PEO) films were prepared by the layer-by-layer method. The presence of chitosan enabled PEO to be carried into the self-assembled structure, contributing to an increase in the Li(+) diffusion rate. On the basis of the galvanostatic intermittent titration technique (GITT) and the quadratic logistic equation (QLE), a spectroelectrochemical method was used for determination of the ""optical"" diffusion coefficient (D(op)), enabling analysis of the Li(+) diffusion rate and, consequently, the coloration front rate in these host matrices. The D(op) values within the WO(3)/chitosan/PEO film were significantly higher than those within the WO(3)/chitosan film, mainly for higher values of injected charge. The presence of PEO also ensured larger accessibility to the electroactive sites, in accordance with the method employed here. Hence, this spectroelectrochemical method allowed us to separate the contribution of the diffusion process from the number of accessible electroactive sites in the materials, thereby aiding a better understanding of the useful electrochemical and electrochromic properties of these films for use in electrochromic devices. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization and electrochemical behavior of the vanadium pentoxide/cetyl pyridinium chloride hybrid material

In situ and ex situ studies concerning the new hybrid material vanadium pentoxide xerogel in the presence of the cationic surfactant cetyl pyridinium chloride (V(2)O(5)/CPC) are presented. The in situ characterization studies revealed the presence of a lamellar structure for the V(2)O(5)/CPC hybrid material. The intercalation reaction was evidenced on the basis of the increase in the d-spacing as well as the displacement of the infrared bands toward lower energy levels. Electrochemical studies comprising the cyclic voltammetry and the electrochemical impedance spectroscopy techniques showed that the behavior of the hybrid material is considerably influenced by the electrolyte composition. The ion insertion/de-insertion into the V(2)O(5) xerogel structure accompanying the charge transfer process is influenced by the solid-state diffusion process modeled by using the finite-space Warburg element.

Synthesis and electrochemical properties of vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films

Vanadyl phosphate and its hybrid compounds have proven to undergo electrochemical intercalation and de-intercalation of lithium ions, which enables its use as cathode material for Li ion rechargeable batteries. In this context, vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films were synthesized via the exfoliation and reconstruction approach in order to evaluate their potential use as cathode in ion lithium batteries. X-ray diffraction patterns indicate that the lamellar structure of the inorganic matrix is maintained, consistent with the topotactic process. In the scanning electron micrographs, hybrid films exhibit rough surface consisting of warped and cracked crystallites, quite different from vanadyl phosphate di-hydrate square platelets crystallites. Electrochemical evaluation using cyclic voltammetry and charge-discharge galvanostatic techniques shows small differences between the charge and the discharge curves, indicating an irreversibility of the hybrid systems. (C) 2009 Elsevier B.V. All rights reserved.

Total synthesis of (+/-)-dihydroactinidiolide using selenium-stabilized carbenium ion

A new, short total synthesis of dihydroactinidiolide 1 is described using selenium carbenium ion-promoted carbon-carbon bond formation as the key step. Our synthetic strategy starts with a lactonization reaction between 1,3,3-trimethylcyclohexene 13 and alpha-chloro-alpha-phenylseleno ethyl acetate 14, affording the key intermediate, alpha-phenylseleno-gamma-butyro lactone 15, which reacted via a selenoxide elimination to the target compound 1. (C) 2009 Elsevier Ltd. All rights reserved.

Selective involvement of GABAergic mechanisms of the dorsal periaqueductal gray and inferior colliculus on the memory of the contextual fear as assessed by the fear potentiated startle test

The inferior colliculus (IC) together with the dorsal periaqueductal gray (dPAG), the amygdala and the medial hypothalamus make part of the brain aversion system, which has mainly been related to the organization of unconditioned fear. However, the involvement of the IC and dPAG in the conditioned fear is still unclear. It is certain that GABA has a regulatory role on the aversive states generated and elaborated in these midbrain structures. In this study, we evaluated the effects of injections of the GABA-A receptor agonist muscimol (1.0 and 2.0 nmol/0.2 mu L) into the IC or dPAG on the freezing and fear-potentiated startle (FPS) responses of rats submitted to a context fear conditioning. Intra-IC injections of muscimol did not cause any significant effect on the FPS or conditioned freezing but enhanced the startle reflex in non-conditioned animals. In contrast, intra-dPAG injections of muscimol caused significant reduction in FPS and conditioned freezing without changing the startle reflex in non-conditioned animals. Thus, intra-dPAG injections of muscimol produced the expected inhibitory effects on the anxiety-related responses, the FPS and the freezing whereas these injections into the IC produced quite opposite effects suggesting that descending inhibitory pathways from the IC, probably mediated by GABA-A mechanisms, exert a regulatory role on the lower brainstem circuits responsible for the startle reflex. (C) 2008 Elsevier Inc. All rights reserved.