On the apparent lack of preferential site occupancy and electrooxidation of CO adsorbed at low coverage onto stepped platinum surfaces

We report time evolution studies of low coverage CO adsorption (surface hydrogen site blocking < 40%) and oxidative stripping on stepped Pt(776) and Pt(554) surfaces. It was observed that there is no preferential site occupancy for CO adsorption on step or terrace. It is proposed that CO adsorption onto these surfaces is a random process, and after CO adsorption there is no appreciable shift from CO-(111) to CO-(110) sites. This implies that after adsorption, CO molecules either have a very long residence time, or that the diffusion coefficient is much lower than previously thought. After CO electrooxidation the sites released included both terrace (111) and step (110) orientations. For surface hydrogen site blocking > 40%, the lateral interactions might play a role in the preferential CO site occupancy. (C) 2011 Elsevier B.V. All rights reserved.

Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Spatiotemporal Pattern Formation in the Oscillatory Electro-Oxidation of Sulfide on a Platinum Disk

Spatiotemporal pattern formation in the electrocatalytic oxidation of sulfide on a platinum disk is investigated using electrochemical methods and a charge-coupled device (CCD) camera simultaneously. The system is characterized by different oscillatory regions spread over a wide potential range. An additional series resistor and a large electrode area facilitate observation of multiple regions of kinetic instabilities along the current/potential curve. Spatiotemporal patterns on the working electrode, such as fronts, pulses, spirals, twinkling eyes, labyrinthine stripes, and alternating synchronized deposition and dissolution, are observed at different operating conditions of series resistance and sweep rate.

The impact of water concentration on the catalytic oxidation of ethanol on platinum electrode in concentrated phosphoric acid

The electro-oxidation of ethanol on platinum in phosphoric acid opens the door to promote the oxidation reaction at higher temperatures. However, the effect of the presence of water is not well understood. In this work, the electro-oxidation of ethanol on platinum was studied in concentrated phosphoric acid containing different concentrations of water at room temperature. The results show that effect of bulk water on the rate electro-oxidation is highest at 0.60 V and decreases for increasing potentials. This was suggested as due to the increasing formation of oxygenated species on the electrode surface with potential, which in turn is more efficient than the increase of water content in the electrolyte. Altogether, these results were interpreted as an evidence of a Langmuir-Hinshelwood step involving oxygenated species as one of the adsorbed partners. (C) 2009 Elsevier B.V. All rights reserved.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Nanogravimetric study of the complex voltammetric response in the electro-oxidation of methanol on platinum

Instead of a time-invariant voltammetric profile, many electrochemical systems display a cycle-dependent current-potential response. This phenomenon has been referred to as complex voltammetric response and it has been observed during the electro-oxidation of several molecules such as methanol, ethanol, propanol and hydrogen. There are currently two explanations for the surface mechanism underlying this behavior. In one scenario, the complex voltammogram would result from the specific kinetic pathway taken during the forward sweep. In the other explanation, the phenomenon is discussed in terms of the interplay among the surface roughening and subsequent relaxation, and the ohmic drop coupled to a negative differential resistance. We report in this paper a nanogravimetric investigation of the complex voltammetric response in the electro-oxidation of methanol on platinum electrode in both acidic and alkaline media. Different periodic patterns composed of intercalated small and large hysteresis cycles were observed as a function of the applied voltage and the series resistance between the working electrode and the potentiostat. Independently, nanogravimetric results indicated no detectable difference in the delta-frequency versus voltage profile between small and large hysteresis cycles. These findings were interpreted as experimental evidence of the secondary, if any, role played by the very electrochemical reaction on the emergence of complex voltammetric response. (C) 2009 Elsevier Ltd. All rights reserved.

Voltammetric characterization of stepped platinum single crystal surfaces vicinal to the (110) pole

Platinum stepped surfaces vicinal to the (1 1 0) crystallographic pole have been investigated voltammetrically in 0.1 M HClO(4) and 0.1 M H(2)SO(4) solutions. Changes in the voltammetric profile with the step density suggest the existence of two types of surface sites, that has been ascribed to linear and bidimensional domains. This result indicates the existence of important restructuring processes that separate the real surface distribution from the nominal one. The electronic properties of the surfaces have been characterized with the CO charge displacement method and the potential of zero total charge has been calculated as a function of the step density. (c) 2009 Elsevier B.V. All rights reserved.

Estimating the term structure of volatility and fixed income derivative pricing

Estimating the parameters of the instantaneous spot interest rate process is of crucial importance for pricing fixed income derivative securities. This paper presents an estimation for the parameters of the Gaussian interest rate model for pricing fixed income derivatives based on the term structure of volatility. We estimate the term structure of volatility for US treasury rates for the period 1983 - 1995, based on a history of yield curves. We estimate both conditional and first differences term structures of volatility and subsequently estimate the implied parameters of the Gaussian model with non-linear least squares estimation. Results for bond options illustrate the effects of differing parameters in pricing.

Options listing and the volatility of the underlying asset: a study on the derivative market function

Os mercados de derivativos são vistos com muita desconfiança por inúmeras pessoas. O trabalho analisa o efeito da introdução de opções sobre ações no mercado brasileiro buscando identificar uma outra justificativa para a existência destes mercados: a alteração no nível de risco dos ativos objetos destas opções. A evidência empírica encontrada neste mercado está de acordo com os resultados obtidos em outros mercados - a introdução de opções é benéfica para o investidor posto que reduz a volatilidade do ativo objeto. Existe também uma tênue indicação de que a volatilidade se torna mais estocástica com a introdução das opções.

Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

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

Stability of multistep second derivative methods for integro-differential equations

The stability of multistep second derivative methods for integro-differential equations is examined through a test equation which allows for the construction of the associated characteristic polynomial and its region of stability (roots in the unit circle) at a proper parameter space. (c) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 4-aminoquinoline analogues and their platinum(II) complexes as new antileishmanial and antitubercular agents

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

A duplicated nitrotienyl derivative with antimycobacterial activity: synthesis, X-ray crystallography, biological and mutagenic activity tests

A duplicated nitrotienyl derivative was obtained as a by-product from the synthesis of a proposed molecular hybrid of a nitrotienyl derivative and isoniazid with an expected dual antimycobacteria mechanism. The structure was shown to be the 5,5'-dinitro-2(2,3-diaza-4-(2'-tienyl)buta-1,3-dienyl)tiophene by X-ray crystallography. The minimal inhibitory concentration (MIC) determination of this compound proved to be promising against Mycobacterium pathogenic strains such as M. avium and M. kansasei, although it had a high level of mutagenicity, as observed in mutagenic activity tests. (c) 2006 Elsevier Masson SAS. All rights reserved.

Synthesis, ex Vivo and in Vitro Hydrolysis Study of an Indoline Derivative Designed as an Anti-Inflammatory with Reduced Gastric Ulceration Properties

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Development and Validation of an UV-Derivative Spectrophotometric Method for Determination of Glimepiride in Tablets

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