Synthesis of new beta-amidodehydroaminobutyric acid derivatives and of new tyrosine derivatives using copper catalyzed C-N and C-O coupling reactions

Several beta-amidodehydroaminobutyric acid derivatives were prepared from N,C-diprotected beta-bromodehydroaminobutyric acids and amides by a copper catalyzed C-N coupling reaction. The best reaction conditions include the use of a catalytic amount of CuI, N,N’-dimethylethylenediamine as ligand and K2CO3 as base in toluene at 110 ºC. The stereochemistry of the products was determined using NOE difference experiments and the results obtained are in agreement with an E-stereochemistry. Thus, the stereochemistry is maintained in the case of the E-isomers of beta-bromodehydroaminobutyric acid dervatives, but when the Z-isomers were used as substrates the reaction proceeds with inversion of configuration. The use of beta-bromodehydrodipeptides as substrates was also tested. It was found that the reaction outcome depend on the stereochemistry of the beta-bromodehydrodipeptide and on the nature of the first amino acid residue. The products isolated were the beta-amidodehydrodipeptide derivatives and/or the corresponding dihydropyrazines. The same catalytic system (CuI/N,N’-dimethylethylene diamine) was used in the C-O coupling reactions between a tyrosine derivative and aryl bromides. The new O-aryltyrosine derivatives were isolated in moderate to good yields. The photophysical properties of two of these compounds were studied in four solvents of different polarity. The results show that these compounds after deprotection can used as fluorescence markers.This work was financed by FEDER through "Programa Operacional Factores de Competitividade"-COMPETE and by FCT-"Fundacao para a Ciencia e Tecnologia" through project "Projecto Estrategico-UI 686-2011-2012" Ref: PEst-C/QUI/UI0686/2011. The NMR spectrometer is part of the National NMR Network (RNRMN) and was purchased in the framework of the National Programme for Scientific Re-equipment, contract REDE/1517/RMN/2005, with funds from POCI 2010 (FEDER) and Fundacao para a Ciencia e a Tecnologia (FCT) and is supported with funds from FCT. G. P. acknowledges FCT for a PhD grant SFRH/BD/38766/2007. H. V. acknowledges FCT for a PhD grant SFRH/BD/7265/2010

Teamwork and negotiation with family in pediatrics

Objetivo: Analizar el proceso de negociación e interacción en la práctica enfermera con las madres de los niños hospitalizados en Pediatría desde la perspectiva del trabajo en equipo. Método: Estudio cualitativo, basado en la teoría fundamentada y tomando como referencia el interaccionismo simbólico. Participaron en el estudio 12 enfermeras de la unidad pediátrica y 18 madres cuyos hijos se encontraban hospitalizados en dicha unidad. El número de participantes fue definido con respecto al criterio de la saturación de los datos. Para la recogida de datos se utilizó la observación participante y la entrevista semiestructurada, y posteriormente se analizaron mediante el programa NVivo8. Resultados: Del análisis efectuado emergió la categoría central, «debilidades en el proceso de negociación», en las interacciones que las enfermeras establecen con las madres. Las enfermeras revelaron dificultades en la comunicación; no contemplaron la necesaria clarificación de los roles junto a las madres para su participación en el proceso de cuidados y fue evidente un desequilibrio de poder en las relaciones que establecían con ellas. Conclusiones: En el contexto estudiado, se observaron importantes carencias en el desarrollo deltrabajo colaborativo con las madres de los niños hospitalizados. Las debilidades en el proceso de negociación, en particular, las dificultades en la comunicación, la falta de clarificación de los roles y tareas que cada uno debe asumir así como el desequilibrio de poder percibido en las relaciones obstaculizan el compromiso de las madres en el proceso de atención del niño, lo cual es esencial para conseguir una mayor implicación, unos mejores resultados en términos de salud y un menor impacto de la hospitalización en el niño.Objective: Analyze the negotiation and interaction process within nurses’ practice with mothers of hospitalized children in pediatric unit from the teamwork perspective. Method: A qualitative approach was used in this study, based on the Grounded Theory from the symbolic interaction perspective. The study included 12 nurses of the pediatric unit and 18 mothers who stayed in the hospital with their hospitalized children. The number of participants was defined according to data saturation. Participant observation and semi-structured interviews were chosen as data collection techniques and it was analyzed using the program NVivo8. Results: From the analysis performed, the central category identified was «weaknesses in the negotiation process», within the interactions between nurses and mothers. Nurses revealed difficulties in the communication process, they did not include roles definition with mothers in order to establish their participation in the care process and a power imbalance was also evidenced. Conclusion: Within the studied settings, an important lack of collaborative work with hospitalized children’s mothers was observed. The weaknesses in the negotiation process and specifically the difficulties found in communication; the lack of roles and tasks clarification and the perceived power imbalance regarding relationships, prevent mothers involvement in their children care process, considered a basic component to achieve a greater mother implication, better results in terms of health and a lower impact of hospitalization in the children

A relação entre a consciência fonológica e o domínio da ortografia: um estudo com alunos do 1º ano de escolaridade

Mestrado em Ensino do 1º e do 2º Ciclo do Ensino BásicoEste relatório aborda a consciência fonológica e a capacidade ortográfica de crianças do 1.º ano de escolaridade, com o principal objetivo de estudar a rela-ção existente entre estas duas competências. Sob o ponto de vista de vários autores especialistas na área, procuramos abordar o conceito de consciência fonológica, a entrada no mundo da escrita e as dificuldades que a criança en-frenta no início da alfabetização, para assim estudar o modo como a criança desenvolve a sua capacidade ortográfica e relacionar esta capacidade com a consciência fonológica. Para estabelecer tal relação, aplicámos a Bateria de Provas Fonológicas criada por Silva (2008), a fim de averiguar a consciência fonológica das crianças, e realizámos um ditado ao aluno, apenas como instrumento de verificação da componente ortográfica. Os participantes do nosso estudo foram as crianças de três turmas existentes do 1.º ano do 1.º ciclo do Ensino Básico, numa escola situada no concelho e no distrito de Aveiro, durante o 3.º período do ano letivo de 2013/2014. Com os resultados obtidos com os instrumentos aplicados conseguimos verificar que existe uma relação positiva entre as duas competências e que a) as crianças com maiores níveis de consciência fonológica apresentam menos erros de orto-grafia, assim como b) as crianças que têm mais representações sobre o escrito e sobre a escrita apresentam menos erros de ortografia.This report deals with the phonological awareness and orthographic ability of children from year 1, with the main goal of studying the relationship between these skills. From the point of view of several authors in the area, we tried to approach the concept of phonological awareness, the access into the world of writing and the difficulties that the child faces in the beginning of literacy, in order to study how children develop their spelling ability and relate this capacity with phonological awareness. To establish this relationship, we applied the phonological tests battery created by Silva (2008), in order to verify the phonological awareness of children, and we performed a spelling test to the student, only as a checking instrument spell com-ponent. The participants in our study were children from three existing classes of the year 1 of the 1st cycle of basic education in a school in the county and in the district of Aveiro, during the 3rd period of the school year 2013/2014. With the results with the applied tools, we can verify that there is a positive rela-tionship between the two skills and a) children with higher levels of phonological awareness have fewer spelling errors, and b) children who have more represen-tations about writing and the writing have less misspellings

Apoio a idosos em territórios envelhecidos: o papel das IPSSS

O aumento do número de idosos na estrutura demográfica nacional marca o contexto social contemporâneo. A ampliação do número de idosos na estrutura da população é frequentemente entendido como um problema. No entanto, e tal como defende Capucha (2005), este é antes um sinal de desenvolvimento social, que reflecte a melhoria das condições de vida das populações. A velhice ganha visibilidade enquanto problema social não só pelo aumento do número de idosos, mas também devido às transformações emergentes dos processos de individualização. Nos contextos de modernidade “tardia” ou “reflexiva” (Beck 1992; Giddens, 2000), marcados pela perda dos suportes tradicionais, particularmente dos familiares, os idosos afirmam-se como um grupo particularmente vulnerável à exclusão social. A velhice transita do âmbito restritamente familiar para o domínio da responsabilidade colectiva, sendo enquadrada nos sistemas de protecção social do Estado. Em Portugal, os sistemas de protecção social, embora com algum desfasamento temporal, seguem o modelo de outras sociedades industrializadas, em que o Estado assume um papel central na protecção social dos cidadãos. É neste âmbito que é instituído um conjunto de direitos sociais que visa garantir a qualidade de vida dos cidadãos. As políticas sociais para os idosos incluem uma série de direitos, dos quais se destaca o direito a uma prestação pecuniária após um determinado patamar etário e socioprofissional – a reforma. Este direito social, que ganhou um carácter universal com a emergência do Estado Providência português, traduziu-se numa “independência” intergeracional que passa a marcar as relações familiares (Fernandes, 1997a). [...

Quality in Hospital Administrative Databases

The clinical content of administrative databases includes, among others, patient demographic characteristics, and codes for diagnoses and procedures. The data in these databases is standardized, clearly defined, readily available, less expensive than collected by other means, and normally covers hospitalizations in entire geographic areas. Although with some limitations, this data is often used to evaluate the quality of healthcare. Under these circumstances, the quality of the data, for instance, errors, or it completeness, is of central importance and should never be ignored. Both the minimization of data quality problems and a deep knowledge about this data (e.g., how to select a patient group) are important for users in order to trust and to correctly interpret results. In this paper we present, discuss and give some recommendations for some problems found in these administrative databases. We also present a simple tool that can be used to screen the quality of data through the use of domain specific data quality indicators. These indicators can significantly contribute to better data, to give steps towards a continuous increase of data quality and, certainly, to better informed decision-making

Infliximab-Induced Lupus: A Case Report

We report the case of a 48-year-old, leukodermic female diagnosed with ulcerative proctitis for 4 years and latent tuberculosis. She was allergic to salicylates and had a minor allergic reaction to infliximab (rash, vertigo, and headache). Thereafter, she started azathioprine (2.5 mg/kg/day). She maintained intravenous infliximab, together with prophylaxis with clemastine and hydrocortisone, due to the steroid-dependent proctitis. The therapy was continued every 8 weeks with anti-tumor necrosis factor for about 3 years. The analytical evaluation when she was diagnosed with ulcerative proctitis (February 2011) showed negative antinuclear antibodies (ANA), double-stranded-DNA antibodies (anti-dsDNA), antineutrophil cytoplasmic antibodies and anti-Saccharomyces cerevisiae antibodies, and a positive outer membrane protein antibody. About 2 years and 6 months after starting infliximab (November 2013), the patient complained of inflammatory symmetrical polyarthralgia (knee, shoulder, elbow, and wrist) without synovitis, which started every week before the administration of infliximab. Resolution of symptoms was observed after each infliximab infusion. In July 2014, the autoantibody re-evaluation showed positive ANA with a homogeneous pattern with a titer of 1:640, weak positive anti-dsDNA (30.2), and positive anti-histone with C3 decreased (80.3). She was then diagnosed with lupus induced by infliximab and initiated hydroxychloroquine 400 mg. Infliximab was suspended. On re-evaluation, the erythrocyte sedimentation rate was 25 mm/h (1st hour), C-reactive protein 0.5 mg/dL (previously erythrocyte sedimentation rate 15 mm/h and C-reactive protein 1.2 mg/dL), and endoscopically, the mucosa was scarred, with some atrophy and scarce mucus in the lower rectum. About 10 months after discontinuation of infliximab, repeated autoantibodies proved all negative, keeping only low C3 (87). The patient also reported complete resolution of the arthralgia.Relato do caso de uma mulher, 48 anos, leucodérmica, com o diagnóstico de proctite ulcerosa com 4 anos de evolução e tuberculose latente. Alérgica aos salicilatos e com reacção alérgica minor ao infliximab (rash, cefaleia e vertigem), iniciou azatioprina (2,5 mg/kg/dia) apenas após a reacção alérgica. Manteve infliximab com profilaxia endovenosa com clemastina e hidrocortisona dada a cortico-depedência da proctite. A terapêutica com antiTNF foi mantida de 8 em 8 semanas durante cerca de 3 anos. Na avaliação analítica aquando o diagnóstico da doença inflamatória intestinal (Fev 2011) apresentava ANA, anti-dsDNA, ANCAs e ASCA negativos com antiOMP positivo. Cerca de 2 anos e meio após o início de infliximab (Nov 2013), iniciou quadro de poliartralgia inflamatória simétrica (joelhos, ombros, cotovelos e punhos) sem sinovite com início regular na semana prévia à admnistração programada de infliximab e resolução após a infusão endovenosa. Em Julho de 2014, apresenta ANA positivos com padrão homogéneo com título de 1/640, anti-dsDNA equívoco (30.2), anti-histonas positivo com C3 diminuído (80.3). Foi diagnosticada com lupus eritematoso sistémico induzido por infliximab e iniciou hidroxicloroquina 400 mg. O infliximab foi suspenso. Na reavaliação da doença, destaca-se VS 25 mm/h (1ª hora), PCR 0,5 mg/dL (previamente VS 15 e PCR 0.6) e endoscopicamente mucosa cicatrizada, com alguma atrofia e escasso muco no recto baixo. Cerca de 10 meses após a suspensão do infliximab, repetiu auto-anticorpos que se revelaram todos negativos, mantendo apenas o C3 baixo (87). Verificou-se ainda resolução completa das queixas articulares.info:eu-repo/semantics/publishedVersio

Pelos trilhos da inclusão : voando sobre horizontes de transformação

O presente trabalho corresponde a uma dissertação académica conducente ao grau de doutoramento em Ciências da Educação, na vertente de Aprofundamento em Administração e Organização Escolar, onde tentamos perceber o percurso de construção de uma Escola inclusiva que denominamos AE. Para responder aos objetivos de investigação optamos por um enquadramento teórico, recorrendo a um processo de revisão bibliográfica, enquadrado nas Ciências da Educação, mais especificamente na evolução histórica do atendimento à diferença – da exclusão à inclusão - e na concetualização da Educação Inclusiva convocando modelos convergentes e componentes de construção da Escola Para Todos, nomeadamente o papel das lideranças, da formação de professores e do trabalho colaborativo, correspondendo à primeira parte do nosso estudo. Do ponto de vista empírico, a segunda parte integra a justificação metodológica, a contextualização da pesquisa, com especial enfoque no programa (Especial)idades da Casa, na sua cronologia e nas suas potencialidades de alinhamento com a educação inclusiva, bem como a análise dos dados e discussão de resultados recolhidos no âmbito do estudo empírico. Por último, apresentam-se as considerações finais, respeitantes a todo o percurso investigativo Destacamos que se trata de um estudo de caso intrínseco, de cariz quali-quanti, que contou com a participação de vários elementos representativos do contexto de investigação. Desta forma pretendemos, ainda que de forma modesta, contribuir para o debate que se vem fazendo em torno da construção da escola inclusiva desenvolvendo este estudo que reúne, para além da curiosidade científica da investigadora, a crença relativamente à utilidade que, eventualmente poderá ter, para todos os atores envolvidos, um maior conhecimento e aprofundamento desta temática para responder, efetivamente, aos enormes desafios colocados à Escola pra Todos.This work corresponds to an academic dissertation leading to a doctoral degree in Educational Sciences, in the field of Deepening in School Administration and Organization, where we try to understand the way of building an inclusive School that we call AE. To respond to the research objectives, we opted for a theoretical framework, using a bibliographic review process, framed in Educational Sciences, more specifically in the historical evolution of attending to the difference - from exclusion to inclusion - and in the conceptualization of Inclusive Education summoning convergent models and components of the construction of School for All, namely the role of leaders, teacher training and collaborative work, corresponding to the first part of our study. From an empirical point of view, the second part integrates the methodological justification, the contextualization of the research, with a special focus on the Specialities of the House program, its chronology and its potential for alignment with inclusive education, as well as the analysis of data and discussion of the results collected in the context of the empirical study. Finally, we present the final considerations, concerning the entire investigative path. We emphasize that this is an intrinsic case study, of a quali-quanti nature, which included the participation of several representative elements of the research context. In this way, we intend, in a modest way, to contribute to the debate that has been taking place around the building of inclusive school by developing this study that brings together, in addition to the researcher's scientific curiosity, the belief regarding the usefulness that it may eventually have for everyone. the actors involved, greater knowledge and deepening of this theme to effectively respond to the enormous challenges posed to School for All

Coupling gold nanoparticles to Dye-Sensitized Solar Cells for an increased efficiency

New approaches for coupling Au NPs to the photoanode of dye sensitized solar cells (DSSCs) were proposed herein, aiming to improve the typical energy conversion efficiency of these cells. For this purpose, colloidal Au NPs with different particles sizes, ∼5 nm and ∼22 nm, were chemically synthesized and attached (i) directly to titanium dioxide (TiO2) or (ii) to TiO2 surface modified with siliceous shells enriched in dithiocarbamate moieties (SiO2/SiDTC). Photoanodes composed by films of TiO2 anatase, TiO2@Au NPs (∼5 nm and ∼22 nm), or TiO2 functionalized with SiO2/SiDTC, loaded with colloidal Au NPs, were made. DSSCs were set-up in a typical sandwich configuration, using the photoanode, a Pt counter electrode, and an iodide electrolyte solution (I−/I3−). In general, a relevant contribution in the plasmonic DSSC performance was evidenced by using Au NPs of ∼22 nm loaded in different amounts 23.9 wt%, 31.0 wt% and 44.0 wt%. Photoanodes composed by 23.9% of Au yielded an increment of 14.40% in photocurrent and of 11.21% in the overall power conversion efficiency (PCE), when compared to the conventional one. In turn, the new strategy used in the chemical modification of the conventional photoanodes with dithiocarbamate groups showed also a significant improvement of the DSSC parameters.publishe

High yielding synthesis of oxazole-4-carboxylates from dehydroamino acid derivatives : application as fluorescent markers for peptides

This work was funded by Foundation for Science and Technology (FCT) and FEDER through CQ-UM, National NMR Network (Bruker 400), research project PTDC/QUI/81238/2006 and PhD grant of G.P. SFRH/BD/38766/2007