Intralamellar structural modifications related to the proton exchanging in K(4)Nb(6)O(17) layered phase

Basic structural aspects about the layered hexaniobate of K(4)Nb(6)O(17) composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K(4)Nb(6)O(17) and H(2)K(2)Nb(6)O(17)center dot H(2)O show significant modifications in the 950-800 cm(-1) region (Nb-O stretching mode of highly distorted NbO(6) octahedra). The band at 900 cm(-1) shifts to 940 cm(-1) after the replacement of K(+) ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H(2)K(2)Nb(6)O(17) was dehydrated: the relative intensity of the band at 940 cm(-1) decreases and new bands seems to be present at about 860-890 cm(-1). The H(+) ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H(+) ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials. 2009 Elsevier Ltd. All rights reserved.

Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

The effect of ultra-low proton concentration on the electrocatalytic reduction of nitrate over platinum

The electrocatalytic reduction of NO3- (aq) over platinum has been investigated in sulfuric acid solutions with proton concentrations between 1 mM and 50 mM. Cyclic voltammetry indicates that for [H+] < 10 mM, NO3- (aq) is reduced in two distinct regions of potential: one reduction peak occurs at approximately 0.1 V vs. RHE and one occurs at -0.13 V vs. RHE. This second reduction peak has never before been observed, and is not present for proton concentrations >10 mM, where hydrogen electroreduction prevails below 0.0 V vs. RHE. Chronoamperometry shows that the kinetics of the two reduction peaks are distinct, suggesting that the two reduction peaks may correspond to the evolution of different products. Results are discussed in the context of tuning the product selectivity of the electrocatalytic reduction of NO3- (aq). (C) 2007 Elsevier B.V. All rights reserved.

Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode

We report in this paper the occurrence of potential oscillations in a proton exchange membrane fuel cell (PEMFC) with a Pd-Pt/C anode, fed with H(2)/100 ppm CO, and operated at 30 degrees C. We demonstrate that the use of Pd-Pt/C anode enables the emergence of dynamic instabilities in a PEMFC. Oscillations are characterized by the presence of very high oscillation amplitude, ca. 0.8 V. which is almost twice that observed in a PEMFC with a Pt-Ru/C anode under similar conditions. The effects of the H(2)/CO flow rate and cell current density on the oscillatory dynamics were investigated and the mechanism rationalized in terms of the CO oxidation and adsorption processes. We also discuss the fundamental aspects concerning the operation of a PEMFC under oscillatory regime in terms of the benefit resulting from the higher average power output. (c) 2010 Elsevier B.V. All rights reserved.

Multimilligram enantioresolution of sulfoxide proton pump inhibitors by liquid chromatography on polysaccharide-based chiral stationary phase

The enantiomers of sulfoxide proton pump inhibitors - omeprazole, lansoprazole, rabeprazole and Ro 18-5364 - were enantiomerically separated by liquid chromatography at multimilligram scale on a poly saccharide-based chiral stationary phase using normal and polar organic conditions as mobile phase. The values of the recovery and production rate were significant for each enantiomer; better results were achieved using a solid-phase injection system. However, this system was applied just for the enantionteric separation of omeprazole to demonstrate the applicability of this injection mode at milligram scale. The chiroptical characterization of the compounds was performed using a polarimeter and a circular dichroism detector. The higher enantiomeric purity obtained for the isolated enantiomers suggests that the methods here described should be considered as a simple and rapid way to obtain enantiomeric pure standards for analytical purpose. (C) 2007 Elsevier B.V. All rights reserved.

Physiological response of American bullfrog tadpoles to stressor conditions of capture and hypoxia

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

Biological indicators of stress in pacu (Piaractus mesopotamicus) after capture

Os efeitos da captura (perseguição, contenção em puçá e exposição aérea) no perfil sanguíneo do cortisol, glicose, cloreto, sódio, potássio, cálcio e na osmolaridade, hematócrito, hemoglobina, número de células vermelhas (CV) e volume corpuscular médio (VCM) foram investigados no pacu (Piaractus mesopotamicus). Um total de 132 peixes (49,7 ± 11,7 g) foi submetido à captura com 3 ou 5 minutos de exposição aérea. Nove peixes de cada tratamento foram amostrados 5, 15, 30, 60 minutos e 24 horas depois e outros nove peixes foram amostrados antes da captura e considerados controle. A captura resultou em aumento do cortisol e glicose no sangue 30 e 5 minutos depois da captura, respectivamente, independente do tempo de exposição aérea. Ambos os indicadores recuperaram os valores controle em 24 horas. Nos dois grupos de peixes, o cloreto plasmático diminuiu 60 minutos após captura e não recuperou os valores controle, enquanto o sódio sérico aumentou entre 15 e 30 minutos recuperando a condição controle em 24 horas. Não houve alteração significativa nos valores de potássio, cálcio, osmolaridade ou no hematócrito, hemoglobina, CV e VCM como consequência da captura. Os estressores sequenciais aplicados no pacu durante a captura ativaram o eixo cérebro-pituitária-interrenal (respostas do cortisol e glicose), mas a ativação do eixo cérebro-sistema simpático-células cromafins foi aparentemente moderada (respostas iônicas e hematológicas).

Lactate sequestration by osteoderms of the broad-nose caiman, Caiman latirostris, following capture and forced submergence

Lactate accumulation in osteoderms; of the broad-nose caiman, Caiman latirostris, was determined following capture and surgery and after a period of forced submergence and related to concurrent values in blood. Control samples of bone and blood were taken after recovery from surgery and before submergence. In addition, samples of osteoderm were incubated in a lactate solution to determine equilibrium concentration, and additional samples were analyzed for elemental and CO2 concentrations. The composition of the osteoderms closely resembles that of typical vertebrate bone, with a high concentration of calcium and phosphate. Plasma and osteoderm lactate concentrations were both elevated following surgery and decreased significantly after 1 day of recovery. Submergence produced a typical lactate pattern in the plasma, with only a modest increase during the dive and then a sharp increase during recovery to a peak of 31.2 +/- 1.9 mumol ml(-1) after 1 h. When caimans were anesthetized 2 h after submergence, osteoderm lactate in the same animals was significantly increased to 14.8 mumol g(-1) wet mass. The ratio of the osteoderm: plasma lactate concentration after submergence was similar to the ratio observed in the incubated samples, suggesting that osteoderm lactate concentrations in vivo were equilibrated with circulating plasma levels. We conclude that caiman osteoderms sequester lactate during lactic acidosis and that the time course is fast enough to have benefit to these animals following normal anaerobic burst activity.

A technique for the capture of free-ranging marsh deer (blastocerus dichotomus)

The marsh deer (Blastocerus dichotomus) is an endangered species froth the marshlands of central South America. Its population has declined in several regions due to the loss of available habitat caused by human activities, especially the construction of hydroelectric darns. The capture of individual deer is critical for research programs and population management. This report describes a novel live-capture technique, which uses a helicopter to drive the animals into a terrain that restricts their movement such as thick vegetation or deep water (60-120 cm in depth). Following confinement, animals are manually restrained. The short pursuit time (median = 2 thin), low mortality rate (0.82-3.28%), and the absence of injury to both the capture team and animals suggest that this method is appropriate for the safe capture of this species. Body temperature correlated with the pursuit time (R-2 = 0.15) but was not significantly altered with pursuit times <3 min.

A comparative solid state C-13 NMR and thermal study of CO2 capture by amidines PMDBD and DBN

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

Are light traps baited with kairomones effective in the capture of Lutzomyia longipalpis and Lutzomyia intermedia? An evaluation of synthetic human odor as an attractant for phlebotomine sand flies (Diptera: Psychodidae: Phlebotominae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Supercritical fluid extraction for pesticide multiresidue analysis in honey: determination by gas chromatography with electron-capture and mass spectrometry detection

An analytical procedure using supercritical fluid extraction (SFE) and capillary gas chromatography with electron-capture detection was developed to determine simultaneously residues of different pesticides (organochlorine, organophosphorus, organonitrogen and pyrethroid) in honey samples. Fortification experiments were conducted to test conventional extraction (liquid-liquid) and optimize the extraction procedure in SFE by varying the CO2-modifier, temperature, extraction time and pressure. Best efficiency was achieved at 400 bar using acetonitrile as modifier at 90 degreesC. For the clean-up step, Florisil cartridges were used for both methods LLE and SFE. Recoveries for majority of pesticides from fortified samples of honey at fortification level of 0.01-0.10 mg/kg ranged 75-94% from both methods. Limits of detection found were less than 0.01 mg/kg for ECD and confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in selected-ion monitoring mode. The multiresidue methods in real honey samples were applied and the results of developed methods were compared. (C) 2004 Elsevier B.V. All rights reserved.

Multiresidue analysis of pesticides in soil by supercritical fluid extraction/gas chromatography with electron-capture detection and confirmation by gas chromatography-mass spectrometry

The applicability of supercritical fluid extraction (SFE) in pesticide multiresidue analysis (organohalogen, organonitrogen, organophosphorus, and pyrethroid) in soil samples was investigated. Fortification experiments were conducted to test the conventional extraction (solid-liquid) and to optimize the extraction procedure in SFE by varying the CO2 Modifier, temperature, extraction time, and pressure. The best efficiency was achieved at 400 bar using methanol as modifier at 60 degreesC. For the SFE method, C-18 cartridges were used for the cleanup. The analytical screening was performed by gas chromatography equipped with electron-capture detection (ECD). Recoveries for the majority of pesticides from spiked samples of soil at different residence times were 1, 20, and 40 days at the fortification level of 0.04-0.10 mg/kg ranging from 70 to 97% for both methods. The detection limits found were <0.01 mg/kg for ECD, and the confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in a selected-ion monitoring mode. Multiresidue methods were applied in real soil samples, and the results of the methods developed were compared.