Analysis of polydicyclopentadiene-metal hybrid adhesive joints for automotive exterior body applications

An exterior body panel solution containing a polydicyclopentadiene skin attached to an interior metallic reinforcement through adhesive bonding is being studied to be applied in the MobiCar bonnet. With this solution is expected to achieve lightness, adequate structural integrity and cost-efficiency. However, there is uncertainty regarding to the bonnet adhesiveness since different metallic materials and adhesive types are being considered for its development. Thus, in this paper, several samples are tested through shear loading with the aim of understanding the loading magnitude expected by using polydicyclopentadiene, steel DC04+ZE and aluminum alloy AW5754-H111 as substrates adhesively bonded by an epoxy or a methacrylate. Methacrylate adhesive have shown greater shear strength in all types of adhesive joints. PDCPD joints presented the highest displacements. Surface degradation was considered adequate over abrading once none strength difference was seen between the different surface treatments. Steel treated by cataphoresis has shown the highest joint interface strength.

(Un)suitability of the use of pH buffers in biological, biochemical and environmental studies and their interaction with metal ions - a review

The use of buffers to maintain the pH within a desired range is a very common practice in chemical, biochemical and biological studies. Among them, zwitterionic N-substituted aminosulfonic acids, usually known as Good's buffers, although widely used, can complex metals and interact with biological systems. The present work reviews, discusses and updates the metal complexation characteristics of thirty one commercially available buffers. In addition, their impact on biological systems is also presented. The influences of these buffers on the results obtained in biological, biochemical and environmental studies, with special focus on their interaction with metal ions, are highlighted and critically reviewed. Using chemical speciation simulations, based on the current knowledge of the metal-buffer stability constants, a proposal of the most adequate buffer to employ for a given metal ion is presented.

Organic-inorganic hybrid sol-gelcoatings for metal corrosion protection: a review of recent progress

This paper is a review of the most recent and relevant achievements (from 2001 to 2013) on the development of organic–inorganic hybrid (OIH) coatings produced by sol–gel-derivedmethods to improve resistance to oxidation/corrosion of different metallic substrates and their alloys. This review is focused on the research of OIH coatings based on siloxanes using the sol–gel process conducted at an academic level and aims to summarize the materials developed and identify perspectives for further research. The fundamentals of sol–gel are described, including OIH classification, the interaction with the substrate, their advantages, and limitations. The main precursors used in the synthesis ofOIHsol–gel coatings for corrosion protection are also discussed, according to the metallic substrate used. Finally, a multilayer system to improve the resistance to corrosion is proposed, based on OIH coatings produced by the sol–gel process, and the future research challenges are debated.

Effect of acid or alkaline catalyst and of different capping agents on the optical properties of CdS nanoparticles incorporated within a diureasil hybrid matrix

CdS nanoparticles (NPs) were synthesized using colloidal methods and incorporated within a diureasil hybrid matrix. The surface capping of the CdS NPs by 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) organic ligands during the incorporation of the NPs within the hybrid matrix has been investigated. The matrix is based on poly(ethylene oxide)/poly(propylene oxide) chains grafted to a siliceous skeleton through urea bonds and was produced by sol–gel process. Both alkaline and acidic catalysis of the sol–gel reaction were used to evaluate the effect of each organic ligand on the optical properties of the CdS NPs. The hybrid materials were characterized by absorption, steady-state and time-resolved photoluminescence spectroscopy and High Resolution Transmission Electron Microscopy (HR-TEM). The preservation of the optical properties of the CdS NPs within the diureasil hybrids was dependent on the experimental conditions used. Both organic ligands (APTMS and MPTMS) demonstrated to be crucial in avoiding the increase of size distribution and clustering of the NPs within the hybrid matrix. The use of organic ligands was also shown to influence the level of interaction between the hybrid host and the CdS NPs. The CdS NPs showed large Stokes shifts and long average lifetimes, both in colloidal solution and in the xerogels, due to the origin of the PL emission in surface states. The CdS NPs capped with MPTMS have lower PL lifetimes compared to the other xerogel samples but still larger than the CdS NPs in the original colloidal solution. An increase in PL lifetimes of the NPs after their incorporation within the hybrid matrix is related to interaction between the NPs and the hybrid host matrix.

Electronic structure and optical signatures of semiconducting transition metal dichalcogenide nanosheets

CONSPECTUS: Two-dimensional (2D) crystals derived from transition metal dichalcogenides (TMDs) are intriguing materials that offer a unique platform to study fundamental physical phenomena as well as to explore development of novel devices. Semiconducting group 6 TMDs such as MoS2 and WSe2 are known for their large optical absorption coefficient and their potential for high efficiency photovoltaics and photodetectors. Monolayer sheets of these compounds are flexible, stretchable, and soft semiconductors with a direct band gap in contrast to their well-known bulk crystals that are rigid and hard indirect gap semiconductors. Recent intense research has been motivated by the distinct electrical, optical, and mechanical properties of these TMD crystals in the ultimate thickness regime. As a semiconductor with a band gap in the visible to near-IR frequencies, these 2D MX2 materials (M = Mo, W; X = S, Se) exhibit distinct excitonic absorption and emission features. In this Account, we discuss how optical spectroscopy of these materials allows investigation of their electronic properties and the relaxation dynamics of excitons. We first discuss the basic electronic structure of 2D TMDs highlighting the key features of the dispersion relation. With the help of theoretical calculations, we further discuss how photoluminescence energy of direct and indirect excitons provide a guide to understanding the evolution of the electronic structure as a function of the number of layers. We also highlight the behavior of the two competing conduction valleys and their role in the optical processes. Intercalation of group 6 TMDs by alkali metals results in the structural phase transformation with corresponding semiconductor-to-metal transition. Monolayer TMDs obtained by intercalation-assisted exfoliation retains the metastable metallic phase. Mild annealing, however, destabilizes the metastable phase and gradually restores the original semiconducting phase. Interestingly, the semiconducting 2H phase, metallic 1T phase, and a charge-density-wave-like 1T' phase can coexist within a single crystalline monolayer sheet. We further discuss the electronic properties of the restacked films of chemically exfoliated MoS2. Finally, we focus on the strong optical absorption and related exciton relaxation in monolayer and bilayer MX2. Monolayer MX2 absorbs as much as 30% of incident photons in the blue region of the visible light despite being atomically thin. This giant absorption is attributed to nesting of the conduction and valence bands, which leads to diversion of optical conductivity. We describe how the relaxation pathway of excitons depends strongly on the excitation energy. Excitation at the band nesting region is of unique significance because it leads to relaxation of electrons and holes with opposite momentum and spontaneous formation of indirect excitons.

Imidazo-benzocrown ether functionalised amino acids: synthesis and fluorimetric chemosensing studies with metal cations

Comunicação em painel - P59

Towards an engine for coordination-based architectural reconfigurations

Software reconfigurability became increasingly relevant to the architectural process due to the crescent dependency of modern societies on reliable and adaptable systems. Such systems are supposed to adapt themselves to surrounding environmental changes with minimal service disruption, if any. This paper introduces an engine that statically applies reconfigurations to (formal) models of software architectures. Reconfigurations are specified using a domain specific language— ReCooPLa—which targets the manipulation of software coordinationstructures,typicallyusedinservice-orientedarchitectures(soa).Theengine is responsible for the compilation of ReCooPLa instances and their application to the relevant coordination structures. The resulting configurations are amenable to formal analysis of qualitative and quantitative (probabilistic) properties.

Toxicity induced by a metal mixture (Cd, Pb and Zn) in the yeast Pichia kudriavzevii: The role of oxidative stress

The present work aims to contribute for the elucidation of the role of oxidative stress in the toxicity associated with the exposure of Pichia kudriavzevii to multi-metals (Cd, Pb and Zn). Cells of the non-conventional yeast P. kudriavzevii exposed for 6 h to the action of multi-metals accumulated intracellular reactive oxygen species (ROS), evaluated through the oxidation of the probe 2,7-dichlorodihydrofluorescein diacetate. A progressive loss of membrane integrity (monitored using propidium iodide) was observed in multi-metal-treated cells. The triggering of intracellular ROS accumulation preceded the loss of membrane integrity. These results suggest that the disruption of membrane integrity can be attributed to the oxidative stress. The exposure of yeast cells to single metal showed that, under the concentrations tested, Pb was the metal responsible for the induction of the oxidative stress. Yeast cells coexposed to an antioxidant (ascorbic acid) and multi-metals did not accumulate intracellular ROS, but loss proliferation capacity. Together, the data obtained indicated that intracellular ROS accumulation contributed to metal toxicity, namely for the disruption of membrane integrity of the yeast P. kudriavzevii. It was proposed that Pb toxicity (the metal responsible for the toxic symptoms under the conditions tested) result from the combination of an ionic mechanism and the intracellular ROS accumulation.

Coordinación socio-política. Redes de influencia y estructuras de poder en CórdobaSocio-political coordination. Influence Networks and power structures in Córdoba.

Los mecanismos de producción y reproducción de la influencia política es una importante área de estudio de la ciencia política en las últimas décadas. En la misma se han disputado diferentes teorías, desde las que plantean la influencia predominante de grupos de poder y sectores corporativos tanto en las decisiones del estado como en las no decisiones, hasta los que plantean que existe la puja de diferentes intereses dentro del Estado pero que no existe ningún grupo predominante. El análisis de redes (network analysis) permite estudiar este objeto mediante la observación de la estructura de relaciones de los actores influyentes dentro de la política provincial. En esta area de estudio, este proyecto propone estudiar de qué manera se produce y reproduce la influencia política en la Provincia de Córdoba.Las hipótesis que plantea el proyecto son las siguientes: H1- La estructura del poder socio-político provincial adquiere una configuración reticular en la que existe un núcleo de actores que representan intereses tradicionales organizados y permite un escaso acceso de nuevas organizaciones que defienden intereses sociales difusos. H2- En el proceso de influencia sociopolítica provincial operan mecanismos de influencia interpersonales directos e indirectos (Brokerage) que permiten a los actores acceder e influir en los decisores públicos. H3- En el proceso de influencia socio-política interviene una diversidad de recursos de poder que los actores utilizan para influir las políticas públicas. Para esto se propone como objetivos del proyecto los siguientes: 1- Identificar y analizar la estructura de poder e influencia que subyace a la política provincial. 2- Analizar los intereses, actores y sectores incluidos y excluidos de la estructura de influencia política. 3- Analizar los mecanismos y recursos de producción y reproducción del poder y la influencia. 4- Analizar las áreas de política del estado provincial que resultan lugar de influencia de los actores y sectores que configuran la estructura de poder socio-política. 5- Analizar el sistema de decisión colectiva (policy domain) en dos áreas de política provincial. 6- Analizar los recursos que posibilitan a los actores ejercer poder e influencia en las áreas de políticas estudiadas. Para la verificación empírica de las hipótesis se realiza un diseño de investigación que incluye el mapeo y análisis de dos tipos de redes políticas diferentes, la "red de influencia en la política provincial" y la red de influencia en un "área de políticas públicas". La reconstrucción de las redes políticas se realizará mediante entrevistas semi-estructuradas a actores sociales y políticos en un muestreo no probabilístico de tipo "bola de nieve". La investigación pretende realizar un aporte a la comprensión de la coordinación política y, en tal sentido, espera alcanzar una adecuada descripción y comprensión de los procesos de influencia y de estructuración del poder en la Provincia de Córdoba.

Intervenção coronária percutânea utilizando Full Metal Jacket com stents farmacológicos: eventos cardíacos adversos maiores em um ano

FUNDAMENTO: O benefício clínico de intervenção coronária percutânea (ICP) para lesões coronárias longas é incerto; além disso, foram levantadas dúvidas questões sobre a sua segurança. OBJETIVO: Avaliar os preditores de eventos cardíacos adversos maiores (ECAM) associados à ICP utilizando Full Metal Jacket (FMJ), definido como a sobreposição de stents farmacológicos (SF) medindo >60 mm de comprimento, para lesões muito longas. MÉTODOS: Foram incluídos 136 pacientes consecutivos com lesões coronárias longas, requerendo FMJ em nosso cadastro de centro único. O desfecho primário incluiu a ocorrência combinada de todas as causas de morte, infarto do miocárdio (IM) e revascularização do vaso alvo (RVA). Variáveis demográficas, clínicas, angiográficas e de procedimento foram avaliadas por meio de análise de regressão de Cox para determinar os preditores independentes de desfecho. RESULTADOS: O comprimento médio do stent por lesão foi de 73,2 ± 12,3 mm e o diâmetro médio do vaso de referência foi de 2,9 ± 0,6 mm. O sucesso angiográfico foi de 96,3%. A ausência de ECAM foi de 94,9% em 30 dias e 85,3% em um ano. No acompanhamento de um ano, a taxa de mortalidade por todas as causas foi de 3,7% (1,5% por mortes cardíacas), a taxa de IM foi de 3,7%, e a incidência de trombose de stent (TS) definitiva ou provável foi de 2,9%. O gênero feminino [risco relativo (RR), 4,40; intervalo de confiança de 95% (IC), 1,81-10,66, p = 0,001) e ICP de artéria coronária não direita (RR, 3,49; p = 0,006; IC 95%, 1,42-8,59) foram preditores independentes de ECAM em um ano. A ausência de eventos adversos em um ano foi maior em pacientes com angina estável submetidos à ICP (RR, 0,33; IC 95% 0,13-0,80, p = 0,014). CONCLUSÕES: A ICP utilizando FMJ com SF para lesões muito longas foi eficaz, mas associada a uma alta taxa de TS em acompanhamento de um ano. No entanto, a taxa de mortalidade cardíaca, IM não relacionado a procedimento, e ECAM foi relativamente baixa. ICP de vaso coronário alvo, apresentação clínica, e gênero feminino são novos fatores clínicos contemporâneos que parecem apresentar efeitos adversos sobre o resultado da ICP utilizando FMJ para lesões longas.

Long-term Outcomes of Drug-eluting versus Bare-metal stent for ST-elevation Myocardial Infarction

Background:Long-term outcomes of drug-eluting stents (DES) versus bare-metal stents (BMS) in patients with ST-segment elevation myocardial infarction (STEMI) remain uncertain.Objective:To investigate long-term outcomes of drug-eluting stents (DES) versus bare-metal stents (BMS) in patients with ST-segment elevation myocardial infarction (STEMI).Methods:We performed search of MEDLINE, EMBASE, the Cochrane library, and ISI Web of Science (until February 2013) for randomized trials comparing more than 12-month efficacy or safety of DES with BMS in patients with STEMI. Pooled estimate was presented with risk ratio (RR) and its 95% confidence interval (CI) using random-effects model.Results:Ten trials with 7,592 participants with STEMI were included. The overall results showed that there was no significant difference in the incidence of all-cause death and definite/probable stent thrombosis between DES and BMS at long-term follow-up. Patients receiving DES implantation appeared to have a lower 1-year incidence of recurrent myocardial infarction than those receiving BMS (RR = 0.75, 95% CI 0.56 to 1.00, p= 0.05). Moreover, the risk of target vessel revascularization (TVR) after receiving DES was consistently lowered during long-term observation (all p< 0.01). In subgroup analysis, the use of everolimus-eluting stents (EES) was associated with reduced risk of stent thrombosis in STEMI patients (RR = 0.37, p=0.02).Conclusions:DES did not increase the risk of stent thrombosis in patients with STEMI compared with BMS. Moreover, the use of DES did lower long-term risk of repeat revascularization and might decrease the occurrence of reinfarction.

Spectral Analysis Related to Bare-Metal and Drug-Eluting Coronary Stent Implantation

Background: The autonomic nervous system plays a central role in cardiovascular regulation; sympathetic activation occurs during myocardial ischemia. Objective: To assess the spectral analysis of heart rate variability during stent implantation, comparing the types of stent. Methods: This study assessed 61 patients (mean age, 64.0 years; 35 men) with ischemic heart disease and indication for stenting. Stent implantation was performed under Holter monitoring to record the spectral analysis of heart rate variability (Fourier transform), measuring the low-frequency (LF) and high-frequency (HF) components, and the LF/HF ratio before and during the procedure. Results: Bare-metal stent was implanted in 34 patients, while the others received drug-eluting stents. The right coronary artery was approached in 21 patients, the left anterior descending, in 28, and the circumflex, in 9. As compared with the pre-stenting period, all patients showed an increase in LF and HF during stent implantation (658 versus 185 ms2, p = 0.00; 322 versus 121, p = 0.00, respectively), with no change in LF/HF. During stent implantation, LF was 864 ms2 in patients with bare-metal stents, and 398 ms2 in those with drug-eluting stents (p = 0.00). The spectral analysis of heart rate variability showed no association with diabetes mellitus, family history, clinical presentation, beta-blockers, age, and vessel or its segment. Conclusions: Stent implantation resulted in concomitant sympathetic and vagal activations. Diabetes mellitus, use of beta-blockers, and the vessel approached showed no influence on the spectral analysis of heart rate variability. Sympathetic activation was lower during the implantation of drug-eluting stents.

Coordination chemistry of acrylamide and N-pyrazolylpropanamide : syntheses and structures

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2006

Simulation of metal quenching processes for the minimization of distortion and stresses

Quenching process, TRIP, J2-plasticity theory, phase transition, distortion