Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

Travel Report from the first field trip within the SIDA supported project "Mini-grids supplied by renewable energy - improving technical and social feasibility : Including visits to Ihushi Development Center, Tweyambe Secondary School and Mavuno Project in Tanzania. Conducted in April 2011

This report describes the outcome of the first visit to Tanzania, within the project "Mini-grids supplied by renewable energy - improving technical and social feasibility". The trip included visits to three different organizations; Ihushi Development Center (IDC) near Mwanza, TIDESO near Bukoba, and Mavuno Project in Karagwe. At IDC, a brief evaluation of the current power system was done and measuring equipment for long term measurements were installed. At all three locations investigations regarding the current and future electricity demand were conducted and connections to people relevant to the study were established. The report is including as well some technical specifications as some observations regarding organization and management of the technical systems. The trip was including only short visits and therefore only brief introductions to the different organizations, based on observations done by the author. The report is hence describing the author’s understanding of the technical system and social structures after only short visits to each of the organizations, and may differ from observations done at another point in time, over a different time period, or by some other person.This report describes the outcome of the first visit to Tanzania, within the project "Mini-grids supplied by renewable energy - improving technical and social feasibility". The trip included visits to three different organizations; Ihushi Development Center (IDC) near Mwanza, TIDESO near Bukoba, and Mavuno Project in Karagwe. At IDC, a brief evaluation of the current power system was done and measuring equipment for long term measurements were installed. At all three locations investigations regarding the current and future electricity demand were conducted and connections to people relevant to the study were established. The report is including as well some technical specifications as some observations regarding organization and management of the technical systems. The trip was including only short visits and therefore only brief introductions to the different organizations, based on observations done by the author. The report is hence describing the author’s understanding of the technical system and social structures after only short visits to each of the organizations, and may differ from observations done at another point in time, over a different time period, or by some other person.

Usual clinical practice for early supported discharge after stroke with continued rehabilitation at home : an observational comparative study

Introduction: Based on randomised controlled trials, evidence exists that early supported discharge (ESD) from the hospital with continued rehabilitation at home has beneficial effects after stroke; however, the effects of ESD service in regular clinical practice have not been investigated. The purpose of the current study was to compare ESD service with conventional rehabilitation in terms of patient outcomes, caregiver burden at 3 and 12 months and the use and costs of healthcare during the first year after stroke. Material and methods: This study was a subgroup analysis of a longitudinal observational study of patients who received care in the stroke unit at Karolinska University Hospital in Sweden. Patients who met the inclusion criteria for ESD in previous experimental studies were included. The patients were referred to available rehabilitation services at discharge, and comparisons between those who received ESD service (the ESD group, n = 40) and those who received conventional rehabilitation (the NoESD group, n = 110) were performed with regard to independence in activities of daily living (ADL), the frequency of social activities, life satisfaction, and caregiver burden and the use and costs of healthcare during the first year after stroke. Results: At 3 and 12 months, no differences were observed with regard to patient outcomes; however, ESD was associated with a lower caregiver burden (p = 0.01) at 12 months. The initial length of stay (LOS) at the hospital was 8 days for the ESD group and 15 days for the NoESD group (p = 0.02). The median number of outpatient rehabilitation contacts was 20.5 for the ESD group (81% constituting ESD service) and 3 for the NoESD group (p<0.001). There was no difference between the groups with regard to overall healthcare costs. Conclusions: ESD service in usual clinical practice renders similar health benefits as conventional rehabilitation but a different pattern of resource use and with released capacity in acute stroke care.

Peça por peça: sistematização de um programa de responsabilidade social

O objetivo da dissertação foi analisar o processo de desenvolvimento e a aplicação de ações sociais e trabalho voluntário, que demonstram a preocupação da empresa com o seu papel social, através de uma participação mais ativa, concreta e efetiva, influenciando na ocorrência das mudanças que a sociedade necessita. O foco do estudo foi analisar um dessas empresas, notadamente a Robert Bosch Limitada, de capital alemão, radicada no Brasil desde o início da década de 1950. Sendo considerada, mais especificamente, uma de suas unidades, localizada no Paraná desde 1975. A Bosch Curitiba, através da implementação de um programa de ação social baseado principalmente na educação e no desenvolvimento sustentável, pretendeu criar condições para que a comunidade de um bairro da periferia de Curitiba pudesse identificar oportunidades de desenvolvimento econômico e social. Esta dissertação é o resultado dessa discussão e se desenvolveu por meio de um programa de ação social que evidencia a importância da participação ativa da empresa na comunidade, baseada em projetos que evidenciam a educação como a essência para o desenvolvimento social. A Vila Verde, comunidade da periferia de Curitiba, foi escolhida pela empresa para implantar o programa de responsabilidade social (Peça por Peça). Nessa comunidade, o foco principal foram os membros da faixa etária de O a 18 anos. O programa, portanto, teve a participação de uma empresa, dos seus colaboradores, como voluntários, e das escolas da comunidade envolvida. A coleta dos dados deu-se por diferentes procedimentos: pesquisa bibliográfica, pesquisa documental, observação participante e entrevistas. Os dados qualitativos foram comparados, e foram apresentados em forma de relatório. Os dados quantitativos foram tabulados e avaliados, servindo de apoio e confirmação aos resultados apresentados pela análise dos dados quantitativos. A atuação do programa social, Peça por Peça, foi no sentido de sensibilizar, estimular e criar condições de conscientizar os envolvidos que as mudanças necessárias somente serão efetivas na medida em que aumentar o seu nível de comprometimento, ou seja, tomar-se uma população capaz de se organizar e de preservar e defender seus interesses e anseios, desenvolvendo seu papel natural do exercício da cidadania e de uma convivência social que assegure direitos básicos para qualquer processo e evolução de uma sociedade. Sistematizar um programa de responsabilidade social, mais do que pretender criar soluções inovadoras, busca consolidar um outro pressuposto, em que a maioria das atividades sociais implementadas, sejam elas de cunho filantrópico ou não, dificilmente conseguem se manter e alegando várias razões, mas de que alguma forma sempre se reflete na falta de uma sistemática de trabalho, com metas, monitoramento, resultados esperados, com um planejamento estratégico que projete as ações a curto, médio e longo prazo. Isso também é uma evidência de que um projeto social não direcionado para atividades assistencialistas, mas sim para a busca de exercer efetivamente a responsabilidade social, não deve ter no fator tempo a principal referência de sucesso do empreendimento, mas sim de pequenas ações de melhoria de forma continuada e planejada, auto-sustentada, efetiva, mensurável e compartilhada.

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson's disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)(5)Ru-III-O-Ru-IV(NH3)(4)-O-Ru-III(NH3)(5)](6+) (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2 x 10(-4) and 1.0 x 10(-2) Mol l(-1) (r = 0.9988) with a detection limit of 8.5 x 10(-5) mol l(-1). The variation coefficient for a 1.0 x 10(-3) mol l(-1) L-dopa (n = 10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. (C) 2004 Elsevier B.V. All rights reserved.

On the dynamic behaviour of a mass supported by a parallel combination of a spring and an elastically connected damper

This paper presents a consistent and concise analysis of the free and forced vibration of a mass supported by a parallel combination of a spring and an elastically supported damper (a Zener model). The results are presented in a compact form and the physical behaviour of the system is emphasised. This system is very similar to the conventional single-degree-of freedom system (sdof)-(Voigt model), but the dynamics can be quite different depending on the system parameters. The usefulness of the additional spring in series with the damper is investigated, and optimum damping values for the system subject to different types of excitation are determined and compared.There are three roots to the characteristic equation for the Zener model; two are complex conjugates and the third is purely real. It is shown that it is not possible to achieve critical damping of the complex roots unless the additional stiffness is at least eight times that of the main spring. For a harmonically excited system, there are some possible advantages in using the additional spring when the transmitted force to the base is of interest, but when the displacement response of the system is of interest then the benefits are marginal. It is shown that the additional spring affords no advantages when the system is excited by white noise. (c) 2007 Elsevier Ltd. All rights reserved.

Activity of Mo(II) allylic complexes supported in MCM-41 as oxidation catalysts precursors

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

Compensatory lung growth in autologous lobar implant: Experimental study in dogs

Background. The best way to study compensatory lung growth (CLG) is in a transplant without rejection. Since immunosuppressive drugs may influence CLG, it is better to not use them. Therefore we studied CLG in a reimplant of only one lobe after its removal. The objective was to compare lobar transplant CLG with CLG after lobectomy.Methods. Forty eight dogs were distributed in three groups: G1 = control, G2 = left cranial lobectomy, and G3 = left pneumonectomy with reimplantation of the caudal lobe. Five months after surgery the animals underwent lung scintigraphy and were sacrificed for morphometric study.Results. There was no correlation between scintigraphy and lung mass or lung volume. There was both mass and residual volume CLG in the operated groups, both contralateral and ipsilateral to surgery. There was no compensation for total lung capacity or compliance in the remaining caudal lobe (G2) or the reimplanted caudal lobe (G3) at 5 months after surgery. There was more damage in the reimplanted lobe. As previous studies have shown that CLG starts with increased mass and residual volume and compliance is compensated later. This study seemed to document the beginning of CLG, with lung compliance being the limiting factor of CLG at 5 months.Conclusion. There was CLG in both the reimplanted lobe and the contralateral lung, but compliance was still reduced. CLG was similar in both groups, but in the implanted lobe compliance was more prejudiced.

Evaluation of low intensity laser's action on silicone mammary implant pseudocapsules in rats

OBJETIVO: Avaliar o efeito do laser de baixa intensidade sobre a contração da pseudocápsula que ocorre ao redor de implantes de silicone. MÉTODOS: 60 ratos machos divididos em dois grupos receberam implante de silicone. Grupo I: implante no subcutâneo da região dorsal, sem tratamento após a cirurgia; Grupo II: animais receberam sete sessões de irradiação com laser de baixa intensidade após o implante. Trinta, 60 e 180 dias após a cirurgia, foi feita a tonometria dos implantes, em seguida, os animais foram sacrificados, removendo-se o material de estudo que foi preparado para exame histológico, avaliando-se morfometricamente a espessura da pseudocápsula e a reação inflamatória. A análise estatistica pela técnica da Análise de Variância e Teste de Tukey (P<0.0 5). RESULTADOS: Pressões significativamente menores foram encontradas nos animais do grupo Grupo II. O estudo histológico não mostrou diferença significativa entre os grupos, destacando-se apenas maior quantidade de vasos intumescidos no Grupo II. A espessura da pseudocápsula foi menor no Grupo II. CONCLUSÃO: O laser de baixa intensidade altera o processo de reparação tecidual ao redor dos implantes, sugerindo que o mesmo possa ser útil para a modelação das contraturas que se estabelecem ao redor dos implantes de silicone.

Autologous implant of bone marrow mononuclear cells as treatment of induced equine tendinitis

Superficial digital flexor tendonitis is an important cause of lameness in horses and its incidence ranges from 13% to 30%, depending on the horse's activity. This injury can occur in yearlings and compromise its carriers by reinjury or even impossibility to return to athletic life. In spite of the long period required for tendon repair, the scar tissue presents lack of elasticity and stiffness. As current treatment strategies produce only marginal results, there has been great interest in research of therapies that influence the quality or the speed of tendon repair. Stem cell therapy has shown promising results in degenerative diseases and cases of deficient healing processes. This study aims to evaluate the influence of autologous mesenchymal bone marrow stem cells in tendon healing, comparing treated and non-treated tendons. Superficial digital flexor tendonitis lesions were induced by collagenase infiltration in both forelimbs of 6 horses, followed by autologous implant in one of the forelimbs of each animal. The horses were evaluated using clinical, ultrasonographic, histopathologic, and immunohistochemical parameters. Tendon biopsies were performed at Day 48. Results found in the treatment group, such as high inflammatory cells infiltration, extracellular matrix synthesis, reduced amount of necrosis areas, small increase in cellular proliferation (KI-67/MIB-1), and low immunoreactivity to transforming growth factor P I, suggested the acceleration of tendon repair in this group. Further studies should be conducted in order to verify the influence of this treatment on later phases of tendon repair. Overall, after analysis of the results, we can conclude that cellular therapy with the mononuclear fraction of bone marrow has accelerated tendon repair at 48 days after treatment.