Synthesis, thermal processing, and thin film morphology of poly(3-hexylthiophene)-poly(styrenesulfonate) block copolymers

A series of novel block copolymers, processable from single organic solvents and subsequently rendered amphiphilic by thermolysis, have been synthesized using Grignard metathesis (GRIM) and reversible addition-fragmentation chain transfer (RAFT) polymerizations and azide-alkyne click chemistry. This chemistry is simple and allows the fabrication of well-defined block copolymers with controllable block lengths. The block copolymers, designed for use as interfacial adhesive layers in organic photovoltaics to enhance contact between the photoactive and hole transport layers, comprise printable poly(3-hexylthiophene)-block-poly(neopentyl p-styrenesulfonate), P3HT-b-PNSS. Subsequently, they are converted to P3HT-b-poly(p-styrenesulfonate), P3HT-b-PSS, following deposition and thermal treatment at 150 °C. Grazing incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS) revealed that thin films of the amphiphilic block copolymers comprise lamellar nanodomains of P3HT crystallites that can be pushed further apart by increasing the PSS block lengths. The approach of using a thermally modifiable block allows deposition of this copolymer from a single organic solvent and subsequent conversion to an amphiphilic layer by nonchemical means, particularly attractive to large scale roll-to-roll industrial printing processes.

Can illness perceptions and coping predict psychological distress amongst allergy sufferers?

Objective. The aim of the present study was to measure the extent to which illness perceptions and coping strategies are associated with the levels of psychological distress amongst allergy sufferers. Design and method. One hundred and fifty-six allergy sufferers (all members of Allergy U.K.) completed a postal survey consisting of the Revised Illness Perception Questionnaire (IPQ-R) and the COPE. Psychological distress was measured using the General Health Questionnaire (GHQ-28) and the Perceived Stress Scale (PSS). Results. Multiple regression analyses indicated that illness perceptions explained between 6 and 26% of variance on measures of psychological distress; coping strategies explained between 12 and 25%. A strong illness identity and emotional representations of the allergy were associated with higher levels of psychological distress; as were less adaptive coping strategies such as focusing on and venting of emotions. Strong personal control beliefs were associated with the lower levels of distress, as were adaptive coping strategies such as positive reinterpretation and growth. Coping partially mediated the link between the illness perceptions and the outcome; however, illness identity, emotional representations and personal control retained an independent significant association with psychological distress. Conclusion. The findings support a role for illness perceptions and coping in explaining levels of psychological distress amongst allergy sufferers. This has implications for targeted health interventions aimed at reducing the strength of illness identity and emotional representations and increasing a sense of control and the use of more adaptive coping strategies.

A strategy formulation process for the delivery of technology enabled service delivery systems

The Product Service Systems, servitization, and Service Science literature continues to grow as organisations seek to protect and improve their competitive position. The potential of technology applications to deliver service delivery systems facilitated by the ability to make real time decisions based upon ‘in the field’ performance is also significant. Research identifies four key questions to be addressed. Namely: how far along the servitization continuum should the organisation go in a single strategic step? Does the organisation have the structure and infrastructure to support this transition? What level of condition monitoring should it employ? Is the product positioned correctly in the value chain to adopt condition monitoring technology? Strategy consists of three dimensions, namely content, context, and process. The literature relating to PSS, servitization, and strategy all discuss the concepts relative to content and context but none offer a process to deliver an aligned strategy to deliver a service delivery system enabled by condition based management. This paper presents a tested iterative strategy formulation methodology which is the result of a structured development programme.

The association of depression and perceived stress with beta cell function between African and Haitian Americans with and without type 2 diabetes

Background: Diabetes and diabetes-related complications are major causes of morbidity and mortality in the United States. Depressive symptoms and perceived stress have been identified as possible risk factors for beta cell dysfunction and diabetes. The purpose of this study was to assess associations between depression symptoms and perceived stress with beta cell function between African and Haitian Americans with and without type 2 diabetes. Participants and Methods: Informed consent and data were available for 462 participants (231 African Americans and 231 Haitian Americans) for this cross-sectional study. A demographic questionnaire developed by the Primary Investigator was used to collect information regarding age, gender, smoking, and ethnicity. Diabetes status was determined by self-report and confirmed by fasting blood glucose. Anthropometrics (weight, and height and waist circumference) and vital signs (blood pressure) were taken. Blood samples were drawn after 8 10 hours over-night fasting to measure lipid panel, fasting plasma glucose and serum insulin concentrations. The homeostatic model assessment, version 2 (HOMA2) computer model was used to calculate beta cell function. Depression was assessed using the Beck Depression Inventory-II (BDI-II) and stress levels were assessed using the Perceived Stress Scale (PSS). Results: Moderate to severe depressive symptoms were more likely for persons with diabetes (p = 0.030). There were no differences in perceived stress between ethnicity and diabetes status (p = 0.283). General linear models for participants with and without type 2 diabetes using beta cell function as the dependent variable showed no association with depressive symptoms and perceived stress; however, Haitian Americans had significantly lower beta cell function than African Americans both with and without diabetes and adjusting for age, gender, waist circumference and smoking. Further research is needed to compare these risk factors in other race/ethnic groups.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

Relação entre estresse percebido e qualidade de vida em pessoas idosas

O envelhecimento é um processo multifatorial, influenciado por mudanças biológicas, sociais e psicológicas que pode estar associado ao desenvolvimento de estresse e ao comprometimento da qualidade de vida. O objetivo deste trabalho foi investigar a relação entre o estresse percebido e a qualidade de vida em idosos no município de Campina Grande, PB. O estudo teve um delineamento transversal e descritivo, com abordagem quantitativa, amostragem do tipo snowboll e não probabilística, com amostra composta por 326 idosos, considerando as perdas, totalizaram 253 idosas para a análise dos dados. Foram realizados análises descritivas e testes paramétricos e não-paramétricos entre as características da amostra, adotando um nível de significância de 5%. Utilizou-se como instrumentos um questionário sócio-demográfico e epidemiológico, o Índice de Barthel, a Escala de Atividades Instrumentais de Vida Diária de Lawton e Brody, as Escalas de Estresse Percebido, PSS14 e PSS10 e o SF-36, para avaliar a qualidade de vida relacionada à saúde. As idosas participantes apresentaram o seguinte perfil sócio-demográfico e epidemiológico: idade média de 71,3 anos; 80,2% casadas ou viúvas; 55,3% praticam alguma atividade física; aproximadamente 50% tinham menos de 8 anos de estudo; 76,7% recebiam até dois salários mínimos por mês; a maioria, 82,2%, vivia com a família; e 87,4% apresentava alguma doença crônica. Com relação ao estresse percebido, foi possível identificar que as pontuações da P SS-14 e PSS-10 variaram entre, 2-53 e 4-39, respectivamente, sendo que a quantidade de participantes com valores PSS-14  28 e PSS-10  21 foram de 15.8% (n = 40) e 20.6% (n= 52), respectivamente. Na avaliação da qualidade de vida relacionada à saúde, os escores do SF-36 foram menores nas dimensões de dor (62,7) e aspectos físicos (63,6), e maiores nas dimensões aspectos sociais (84,4) e saúde mental (75,6). Observou-se uma correlação negativa e estatisticamente significativa entre os valores de estresse percebido e os domínios do SF-36 (p <0,001). O estresse percebido relacionou-se tanto com os aspectos físicos e funcionais como com a saúde mental das idosas, apresentando uma associação com a qualidade de vida de forma global, sendo um ótimo indicador da qualidade de vida das idosas.

Síntese e caracterização de PSFC (Pr0,5Sr0,5Fe1-xCuxO3-δ, sendo x=0,2 e x=0,4) para aplicação como catodo de células a combustível de óxido sólido

The PSFC (Pr0.5Sr0.5Fe1-xCuxO3-δ) is a new mixed oxide perovskite and has been studied and evaluated the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs), mainly due to its good compatibility with the electrolyte (CGO) and its high ionic conductivity and electronic in intermediate temperature. In this work, PSFC powders with two different compositions (Pr0,5Sr0,5Fe0,8Cu0,2O3- PSFC5582 and Pr0,5Sr0,5Fe0,6Cu0,4O3-PSFC5564) were synthesized by the citrate method using a new route. The powders obtained were characterized by thermal analysis (Differential Scanning Calorimetry and Thermogravimetry), and the material calcined at 800, 900 and 1000 °C for 5h were analyzed by X-ray diffractometry (XRD), with the Rietveld refinement of the diffraction data and dilatometry. PSFC5582 composite films were obtained by screen printing of powder calcined at 1000 °C. The films were deposited on substrate ceria doped with gadolinia (CGO) and then sintered at 1050 °C for 2h. The electrochemical performance of the electrodes was evaluated by impedance spectroscopy and the interface electrode/electrolyte was observed by scanning electron microscopy (SEM). The specific resistance area (ASR) was 0.44 Ω.cm² at 800 °C, slightly lower than those reported in the literature for cathodes containing cobalt. The thermal expansion coefficients of both the PSFC compositions were obtained and varied between 13 and 15 x 10-6 °C-1 , in a temperature range of 200 to 650 °C, demonstrating the good thermal compatibility of cathodes with Ce0,9Gd0,1O1,95 electrolytes (CET = 12 x 10-6 °C).

Progettazione, realizzazione e caratterizzazione funzionale di sorgenti di plasma atmosferico di non equilibrio per l'idrofobizzazione di fibre tessili

L’attività di tesi ha previsto la progettazione e realizzazione di sorgenti di plasma di non equilibrio a pressione atmosferica e l’individuazione delle condizioni operative ottimali per l’idrofobizzazione di materiali tessili. La prima parte delle attività di tesi hanno riguardato lo studio e l’approfondimento della letteratura scientifica al fine di individuare le sorgenti e i processi plasma assistiti per l’idrofobizzazione dei materiali. Relativamente alle sorgenti di plasma di non-equilibrio a pressione atmosferica, studi di letteratura riportano che sorgenti di tipo APPJ (Atmospheric Pressure Plasma Jet) consentono di effettuare un trattamento localizzato in un punto, mentre sorgenti DBD (Dielectric Barrier Discharge) risultano idonee a trattamenti di materiali large area. Per quanto riguarda i processi plasma assistiti, sulla base di quanto riportato in letteratura il processo di idrofobizzazione può avvenire principalmente mediante polimerizzazione di gas organici contenenti fluoro, introdotti nella regione di plasma, con la conseguente deposizione di coating fluorurati. Le attività sperimentali condotte durante la tesi hanno avuto l’obbiettivo di valutare la possibilità di rendere idrofobico un filato di fibra tessile naturale mediante l’utilizzo di una sorgente plasma jet operante con miscela di argon e gas organoflorurato. Il filato, messo in moto a diverse velocità, è stato fatto transitare attraverso la piuma di plasma. In particolare, si è passati da una velocità di movimentazione di 1 m/min a una di 10 m/min. I risultati ottenuti hanno evidenziato che maggiore è la velocità di movimentazione del filato attraverso la piuma di plasma, minore è il grado di idrofibizzazione raggiungibile sul filato stesso, in quanto minore è il tempo di esposizione del materiale al plasma. Infine, nell’ultima parte dell’attività di tesi, è stata progettata una sorgente DBD, che caratterizzata da una maggiore area di generazione del plasma rispetto alla sorgente plasma jet, consente di incrementare il tempo di esposizione del filato al plasma a parità di velocità di movimentazione del filato.

Crenças e experiências de professores no PIBID de Língua Inglesa : interação e ressignificação?

There are diverse studies about beliefs in Applied Linguistics since 1970 or so (BARCELOS, 2004), especially beliefs about teaching and learning Foreign Languages. The research about beliefs and experiences of English language teachers, who take part in a program of teaching incentive (Pibid), and, therefore, are immersed in public schools for elementary education, is relevant, once the (ac)knowledgment of these beliefs related to their teaching and learning experiences allows these teachers to reflect about the aspects that involve their teaching practice and their role as teachers of English language. The present work aims to investigate the interaction of beliefs and experiences related to foreign language teaching and learning of teachers who are participants of Pibid, in the subproject of English Language at the Federal University of Uberlândia (UFU), in 2013. The objective is to identify the beliefs and experiences about teaching and learning that the pre-service teachers (PI), the coordinator teacher (PF) and the supervisor teachers (PS) of the program show and how their beliefs and experiences influence each other and can or cannot be redefined. This is a qualitative and interpretative master’s research, in which I analized one narrative of each PI, one interview of PF and another of each PS, and, also, two meetings – the first between the PF and the PIs, and the second between all the participants in the subproject. All the data was collected at the end of their participation in Pibid, approximately one year and six months later. Therefore, I raised some beliefs and experiences about English language teaching and learning present in the teachers’ discourse and analized excerpts in their speech that evidenced the interaction with other participants and its influence to the formation, confirmation, demystification and redefinition of their beliefs. The results of this analysis bring elements that may help the constant reflection of university teachers, teachers in practice and pre-service teachers about the aspects that involve the teaching experiences in public schools.

Preparação de catalisadores para reações de esterificação do ácido oleico baseados em matrizes polímericas sulfonadas POLI(1- FENILETILENO) (PS) e POLI(1-CLOROETILENO) (PVC)

Chemical modification of polymer matrices is an alternative way to change its surface properties. The introduction of sulfonic acid groups in polymer matrices alter properties such as adhesion, wettability, biocampatibility, catalytic activity, among others. This paper describes the preparation of polymeric solid acid based on the chemical modification of poly (1-fenietileno) (PS) and Poly (1-chloroethylene) (PVC) by the introduction of sulfonic acid groups and the application of these polymers as catalysts in the esterification reaction of oleic acid with methanol. The modified materials were characterized by Infrared Spectroscopy, Elemental Analysis and titration acid-base of the acid groups. All techniques confirmed the chemical changes and the presence of sulfur associated with sulfonic acid groups or sulfates. The modified polymers excellent performance in the esterification reaction of oleic acid with methanol a degree of conversion higher than 90% for all investigated polymers (modified PS and PVC (5% w / w)), with a mass ratio of oleic acid: methanol 1:10 to 100 ° C. The best performance was observed for the modified PVC catalyst (PVCS) which showed low degree of swelling during the reactions is recovered by filtration different from that observed for polystyrene sulfonate (PSS). Given these facts, the PVCS was employed as a catalyst in the esterification reaction of oleic acid in different times and different temperatures to obtain the kinetic parameters of the reaction. Experimental data show a great fit for pseudo-homogeneous model of second order and activation energy value of 41.12 kJ mol -1, below that found in the literature for the uncatalyzed reaction, 68.65 kJ mol -1 .The PVCS exhibits good catalytic activity for 3 times of reuse, with a slight decrease in the third cycle, but with a conversion of about 78%. The results show that solid polymeric acid has good chemical stability for the application in esterification reaction of commercial importance with possible application in the biodiesel production. The advantages in use of this system are the increased reaction rate at about 150 times, at these test conditions, the replacement of sulfuric acid as a catalyst for this being the most corrosive and the possibility of reuse of the polymer for several cycles.

QUALIDADE DE VIDA – UM ESTUDO REALIZADO COM DIRETORES DE ESCOLAS PÚBLICAS

A estrutura política e econômica brasileira promove uma sociedade marcada por desigualdades sociais, gerando indignações e diversos conflitos. Estresse, ansiedade, depressão, mal estar profissional, infraestrutura precária, alimentação inadequada, sedentarismo, (i)mobilidade urbana, fragilidade dos vínculos sociais, poluição, dentre outros, são fatores contemporâneos que afetam a qualidade de vida dos seres humanos. Este cenário merece atenção peculiar quando nos remetemos ao ambiente escolar. Este estudo teve por objetivo avaliar a qualidade de vida bem como identificar o grau de estresse percebido em diretores de Escolas Municipais de Educação Infantil (EMEIs) na Cidade de São Paulo. Participaram do estudo 86 Diretores de Escolas, correspondendo a 16,04% do total de diretores de EMEIs da Rede Municipal de Educação (RME). Os instrumentos utilizados foram: Questionário sociodemográfico, Instrumento de Avaliação de Qualidade de Vida-abreviado - WHOQOL-bref e a Escala de Estresse Percebido – PSS. Os resultados revelaram que, em média, 70,9% possuem uma excessiva rotina de trabalho, caracterizadas por: chegar mais cedo e/ou sair mais tarde do expediente normal; receber e/ou fazer ligações, mensagens, e-mails ou similares, relacionados à direção, fora do expediente de trabalho e levar serviços para casa e/ou se preocupar com questões relativas à direção, após encerrar o expediente. A maioria (60,05%) acredita que as condições de trabalho, enquanto Diretor de Escola influenciam negativamente na saúde pessoal. Tanto o índice geral da Qualidade de Vida quanto em relação aos domínios do WHOQOL-bref mostraram médias significativamente abaixo dos dados normativos brasileiros 12,7±3,1 (p<0,001). Quanto ao nível de estresse percebido, inicialmente analisamos as frequências referentes aos respectivos níveis. Os resultados mostraram que o nível de estresse percebido se situa entre 48,8% de “às vezes” para 41,9% de “quase sempre”. Este resultado se apresenta estatisticamente significativo (χ2 p<0,05). Com base neste estudo pudemos observar a escassez de estudos sobre QV e estresse com Diretores de Escolas e que a QV se apresentou significativamente baixa, bem como a percepção de estresse em quase metade da amostra estudada.

Utilização de dispositivos de armazenamento de energia em apoio ao funcionamento de redes isoladas

Temos assistido nos últimos anos à proliferação da produção distribuída de electricidade, sobretudo, com recurso a fontes de energia renováveis, implicando a natural reestruturação das redes eléctricas existentes, desde a produção até ao consumidor final. As constantes preocupações na garantia da qualidade de serviço e até mesmo em termos ambientais, levam a que a operacionalidade das redes seja cada vez mais eficiente, visando a integração de tecnologias emergentes como é o caso dos sistemas de armazenamento de energia. A aposta nas energias de origem renovável nomeadamente a solar e a eólica, representa uma forma cada vez mais presente de geração de electricidade, tendo como grande inconveniente o regime de intermitência a que estão sujeitas, não se conseguindo tirar proveitos absolutos de todas as potencialidades que estas fontes proporcionam. Existem actualmente sistemas de armazenamento de energia que permitem optimizar o comportamento das redes. Nesta dissertação é feita uma abordagem a alguns desses sistemas, tendo como objectivo principal a demonstração das potencialidades de optimização dos sistemas de produção e distribuição de energia eléctrica com recurso a sistemas de armazenamento de energia, em redes isoladas e interligadas. É também feito um estudo do comportamento dinâmico de uma rede com vários cenários de ocorrência de defeitos, com e sem armazenamento de energia. Para isso a base deste trabalho consistiu na familiarização com uma ferramenta de grande potencial na simulação dinâmica de redes eléctricas, utilizado por prestigiados grupos de energia a nível mundial, na qual foi implementada a rede de teste e efectuadas as simulações do estudo.

Conceptual designs of multi-degree of freedom compliant parallel manipulators composed of wire-beam based compliant mechanisms

This paper proposes conceptual designs of multi-degree(s) of freedom (DOF) compliant parallel manipulators (CPMs) including 3-DOF translational CPMs and 6-DOF CPMs using a building block based pseudo-rigid-body-model (PRBM) approach. The proposed multi-DOF CPMs are composed of wire-beam based compliant mechanisms (WBBCMs) as distributed-compliance compliant building blocks (CBBs). Firstly, a comprehensive literature review for the design approaches of compliant mechanisms is conducted, and a building block based PRBM is then presented, which replaces the traditional kinematic sub-chain with an appropriate multi-DOF CBB. In order to obtain the decoupled 3-DOF translational CPMs (XYZ CPMs), two classes of kinematically decoupled 3-PPPR (P: prismatic joint, R: revolute joint) translational parallel mechanisms (TPMs) and 3-PPPRR TPMs are identified based on the type synthesis of rigid-body parallel mechanisms, and WBBCMs as the associated CBBs are further designed. Via replacing the traditional actuated P joint and the traditional passive PPR/PPRR sub-chain in each leg of the 3-DOF TPM with the counterpart CBBs (i.e. WBBCMs), a number of decoupled XYZ CPMs are obtained by appropriate arrangements. In order to obtain the decoupled 6-DOF CPMs, an orthogonally-arranged decoupled 6-PSS (S: spherical joint) parallel mechanism is first identified, and then two example 6-DOF CPMs are proposed by the building block based PRBM method. It is shown that, among these designs, two types of monolithic XYZ CPM designs with extended life have been presented.

Sintesi e Caratterizzazione di Elettrodi Modificati Chimicamente con nuovi complessi Carbenici del Ferro

The Chemically Modified Electrodes (CME) are widely used in electroanalytical chemistry as chemical sensors. The interest in the covalent anchoring of a redox mediator on the electrode surface is increasing, because it allows the sensibility and the selectivity of this kind of systems to improve. My work is situated in this field of research and involves the synthesis of new Iron(0) complexes that contain cyclopentadienone, N-heterocyclic carbene (NHC) and carbonyl ancillary ligands. These complexes have shown electrochemical properties similar to those of ferrocene (organometallic compound widely used as electrochemical sensor). These complexes have been properly functionalized with a EDOT group in the NHC ligand side chain that it was after used for the realization of Electrochemically Modified PEDOT thanks to copolymerization reaction between the functionalized complex and the EDOT in different amounts. All the synthetic steps were assisted by suitable characterizations (NMR, IR, ESI-MS, cyclic voltammetry and X-ray for the monomeric compound as imidazolium salt and NHC functionalized complexes; cyclic voltammetry, IR e SEM for the copolymers). The properties of the polymer as a selective sensor was preliminarily investigated for dopamine and 2-propanol.

Incapsulamento di complessi organometallici e lantanoidei con silice e sviluppo come traccianti di supporti ceramici

Lo scopo di questo lavoro di tesi sperimentale consiste nell’ideazione e nell’ottimizzazione di nuove forme d’ingegnerizzazione di sistemi nano e micrometrici di silice (SiO2) in cui sono stati incorporati complessi di metalli di transizione e lantanoidei. Lo studio è scaturito dalla prospettiva di poter trasferire le caratteristiche di luminescenza dei complessi dalla scala molecolare di sintesi a quella macroscopica, attraverso l’utilizzo di una opportuna matrice veicolante. Dopo una intensa sessione di lavoro dedicata all’ottimizzazione della sintesi e delle caratteristiche di stabilità e resistenza dei sistemi, dalla fase sol fino ai micronizzati, si è sviluppata una possibile applicazione industriale come substrato tessile dotato di funzioni eventualmente antibatteriche. This experimental work is aimed at exploiting and optimizing new and convenient ways to incorporate organometallic and lanthanoid complexes into silica-based colloid matrices. Following a similar approach, the luminescent properties of both organometallic and lanthanoid complexes could be kept unaltered on passing from the molecular to nanometric scale (sol), ending up to micrometer sized systems (micro-powders). The subsequent optimization of the processes led to systems that were loaded onto the surface of fabric, which were successively studied for their light-induced antimicrobial abilities.