BioRePortAP, an electronic clinical record coupled with a database : an example of its use in a single

Aims: To evaluate the efficacy and safety of the treatment of psoriatic arthritis (PsA) patients with tumor necrosis factor (TNF) antagonists in the Rheumatology Department of Hospital de Santa Maria using the BioRePortAP. Methods: The Portuguese Society of Rheumatology (SPR) developed an electronic medical chart coupled with a database for the follow up of PsA patients, the BioRePortAP, which was launched in May 2009. This evaluation was based on all the PsA patients that were on active treatment with TNF antagonists in September 2009 and were registered in the BioRePortAP. All the previous data on these patients were introduced in BioRePortAP using the prospective paper based follow up protocol that this Department was using since 1999. Only patients with more than 9 months of treatment were analyzed. Results: Forty-two patients with PsA, actively treated with anti-TNF agents in September 2009, for at least 9 months, were analyzed in BioRePortAP. Twenty-three patients were male (55%) and nineteen were female (45%). The average age of these patients was 49.8±10.9 years old, the average disease duration was of 10.7±5.6 years and the mean duration of biological therapy was of 37.8±27.8 months. For the 81% of patients with peripheral joint disease there was a mean reduction of more than 80% in the swollen and tender joint counts, and almost 50% in the health assessment questionnaire (HAQ) value. In the 19% of the patients with axial involvement the reduction of BASDAI and BASFI was not statistically significative. On top of that, PASI score suffered a reduction of 64%. Fourteen patients (33.3%) had to switch their TNF antagonist treatment. 58.8% of the switches were due to adverse effects and 41.2% due to therapy failure. Regarding the 56 adverse reactions registered, only one was a severe reaction. The remaining adverse reactions were not severe and 67% of them were due to infections. Discussion: The results of this first report of the use of the BioRePortAP in clinical practice confirm the efficacy and safety of TNF antagonist treatment in PsA. The results shown here elucidate the potential applications of BioRePortAP as a tool for efficacy and safety assessment of PsA patients treated with biotechnological drugs

Surface photochemistry: photodegradation study of pyrene adsorbed onto microcrystalline cellulose and silica

Ground-state diffuse reflectance, time resolved laser-induced luminescence, diffuse reflectance laser flash-photolysis transient absorption and chromatographic techniques were used to elucidate the photodegradation processes of pyrene adsorbed onto microcrystalline cellulose and silica. Ground-state diffuse reflectance showed that on both substrates low concentrations display absorption of pyrene monomers. At high concentrations spectral changes attributed to aggregate formation were observed. Laser induced fluorescence showed that pyrene onto microcrystalline cellulose mainly presents fluorescence from monomers, while for silica, excimer-like emission was observed from low surface loadings (greater than or equal to 0.5 mumol g(-1)). Transient absorption and photodegradation studies were performed at concentrations where mainly monomers exist. On silica, pyrene presents transient absorption from its radical cation. On microcrystalline cellulose both radical cation, radical anion and pyrene triplet-triplet absorption were detected. Irradiation followed by chromatographic analysis showed that pyrene decomposes on both substrates. For pyrene on microcrystalline cellulose 1-hydroxypyrene was the main identified photoproduct since in the absence of oxygen further oxidation of 1-hydroxypyrene was very slow. For pyrene on silica photodegradation was very efficient. Almost no 1-hydroxypyrene was detected since in the presence of oxygen it is quickly oxidized to other photooxidation products. On both substrates, pyrene radical cation is the intermediate leading to photoproducts and oxygen it is not involved in its formation

Microchip electrophoresis with amperometric detection for the study of the generation of nitric oxide by NONOate salts

Microchip electrophoresis (ME) with electrochemical detection was used to monitor nitric oxide (NO) production from diethylammonium (Z)-1-(N,N-diethylamino)diazen-1-ium-1,2-diolate (DEA/NO) and 1-(hydroxyl-NNO-azoxy)-L-proline disodium salt (PROLI/NO). NO was generated through acid hydrolysis of these NONOate salts. The products of acid hydrolysis were introduced into a 5-cm separation channel using gated injection. The separation was accomplished using reverse polarity and a background electrolyte consisting of 10 mM boric acid and 2 mM tetradecyltrimethylammonium bromide, pH 11. Electrochemical detection was performed using an isolated potentiostat in an in-channel configuration. Potentials applied to the working electrode, typically higher than +1.0 V vs. Ag/AgCl, allowed the direct detection of nitrite, NO, DEA/NO, and PROLI/NO. Baseline resolution was achieved for the separation of PROLI/NO and NO while resolution between DEA/NO and NO was poor (1.0±0.2). Nitrite was present in all samples tested

Pyrene-p-tert-butylcalixarenes inclusion complexes formation: a surface photochemistry study

Diffuse reflectance and luminescence techniques were used to study the photophysics and photochemistry of pyrene within p-tert-butylcalix[n]arenes with n = 4, 6, and 8, and to study their ability to form inclusion complexes in heterogeneous media. Evidences for inclusion complex formation were found for the three hosts under study. Ground state diffuse reflectance results have shown the formation of ground state dimers of pyrene inside the cavity of calix[ 6] arene and calix[ 8] arene, with this feature much more evident for calix[ 6] arene. For calix[ 4] arene, only a monomer fits inside the cavity and the presence of pyrene microcrystals outside the cavity was detected. A luminescence lifetime distribution analysis was performed, revealing the presence of prompt emissions from the pyrene microcrystals outside the cavity in the case of calix[ 4] arene and from the constrained dimers inside the cavities of calix[ 6] arene and calix[ 8] arene. Transient absorption results have shown the presence of pyrene radical cation and also of trapped electrons for the three hosts under study. The formation of the phenoxyl radical of the calixarene following the laser pulsed excitation of pyrene at 355 nm is increased for calix[ 6] arene and calix[ 8] arene. This feature is particularly relevant for calix[ 6] arene, suggesting a very favourable situation for the hydrogen atom abstraction to occur. The analysis of the degradation products revealed the presence of hydroxypyrene as a major photodegradation product for the three hosts. Dihydro-hydroxypyrene was also formed in the case of calix[ 6] arene and calix[ 8] arene. The formation of the calixarene's phenoxyl radical and subsequent hydrogen abstraction is consistent with the formation of dihydro-dihydroxypyrene

Avaliação multicritério da acessibilidade em ambiente SIG: o caso de um campus universitário

Ao longo dos últimos anos, o crescimento contínuo das comunidades universitárias atingiu proporções tais que motivaram a expansão e a actualização dos campi universitários. Visando uma melhoria da oferta de instalações e serviços, quer qualitativa quer quantitativa, essa expansão tomou contornos tão expressivos que justificam uma avaliação da acessibilidade interna. O objectivo desta análise é procurar identificar áreas ou, mais especificamente, locais que apresentem um eventual défice de acessibilidade do ponto de vista pedonal (por este ser modo de locomoção predominante). Os resultados servirão de apoio na procura de medidas no sentido de corrigir ou prevenir este tipo de problema. A título de exemplo, apontam-se algumas das causas, a saber, a edificação de novas instalações em zonas de baixa acessibilidade sem que aconteça um reajuste dos acessos ou, simplesmente, a diminuição da acessibilidade global (em relação ao campus remodelado) do espaço inicialmente atribuído a um serviço fundamental, impondo-se assim a sua deslocaçãopara uma zona mais conveniente. Neste trabalhoé apresentado um modelo de avaliação multicritério da acessibilidadeque permite o desenvolvimento de cenários de avaliação baseados na atitude de risco e compensação entre critérios, obtendo-se desta forma um espectro estratégico de avaliação. Inserido num ambiente SIG, é contemplada a componente espacialao apresentar os resultados sob a forma de superfícies contínuas,favorecendo-se a leitura dos níveis de acessibilidade ao longo da área em estudo. A aplicação prática incidiu sobre a avaliação da acessibilidadeinterna de um campus universitário, reflectindo-se o ponto de vista da comunidade utenteatravés da elaboração de um inquérito para a recolha de dados de base. Este exemplo de avaliação de acessibilidade, por se realizarcom recurso à técnica de avaliação multicritério integrada a um SIG vectorial, abre ainda perspectivas de aplicação do modelo proposto para outros problemas de planeamento de transportes

Cidades sustentáveis: um desafio comum para Brasil e Portugal

Como conseqüência dos crescentes problemas ambientais, econômicos e sociais de muitas cidades faz-se necessária a criação de métodos para o acompanhamento e gestão do crescimento urbano, de tal forma que se possa promover os conceitos de desenvolvimento sustentável e qualidade de vida urbana. A implementação de estratégias para este fim deve partir da investigação e análise crítica da condição atual de desenvolvimento das cidades, a partir de indicadores que devem refletir o contexto específico em que se inserem. Desta forma, o presente trabalho tem por objetivo realizar uma discussão acerca da problemática de sustentabilidade urbana dirigida a um contexto particular: cidades de pequeno e médio portes no Brasil e em Portugal. O primeiro passo é a identificação das principais características geopolíticas, nos dois países, daquilo que constitui o objeto de estudo deste trabalho: as cidades. A breve discussão que se segue, baseada neste diagnóstico preliminar e em inúmeros trabalhos já produzidos sobre as cidades dos dois países, aponta para algumas preocupações que devem estar presentes na definição de indicadores de sustentabilidade urbana para o contexto específico de Brasil e Portugal, resumidas em três aspectos principais: o desafio da mobilidade, o desafio ambiental e o desafio da eficiência

Novel laser-induced luminescence resulting from benzophenone/O-propylated p-tert-butylcalix[4]arene complexes. A diffuse reflectance study

Laser-induced room temperature luminescence of air-equilibrated benzophenone/O-propylated p-tert-butylcalix[ 4] arene solid powdered samples revealed the existence of a novel emission, in contrast with benzophenone/p-tertbutylcalix[ 4] arene complexes, where only benzophenone emits. This novel emission was identified as phosphorescence of 1-phenyl-1,2-propanedione, which is formed as the result of an hydrogen atom abstraction reaction of the triplet excited benzophenone from the propoxy substituents of the calixarene. Room temperature phosphorescence was obtained in air-equilibrated samples in all propylated hosts. The decay times of the benzophenone emission vary greatly with the degree of propylation, the shortest lifetimes being obtained in the tri- and tetrapropylated calixarenes. Triplet - triplet absorption of benzophenone was detected in all cases, and is the predominant absorption in the p-tert-butylcalix[ 4] arene case, where an endo-calix complex is formed. Benzophenone ketyl radical formation occurs with the O-propylated p-tert-butylcalix[ 4] arenes hosts, suggesting a different type of host/guest molecular arrangement. Diffuse reflectance laser. ash photolysis and gas chromatography - mass spectrometry techniques provided complementary information, the former about transient species and the latter regarding the final products formed after light absorption. Product analysis and identification clearly show that the two main degradation photoproducts following laser excitation in the propylated substrates are 1-phenyl-1,2- propanedione and 2- hydroxybenzophenone, although several other minor photodegradation products were identified. A detailed mechanistic analysis is proposed. While the solution photochemistry of benzophenone is dominated by the hydrogen abstraction reaction from suitable hydrogen donors, in these solid powdered samples, the alpha-cleavage reaction also plays an important role. This finding occurs even with one single laser pulse which lasts only a few nanoseconds, and is apparently related to the fact that scattered radiation exists, due to multiple internal reflections possibly trapping light within non-absorbing microcrystals in the sample, and is detected until at least 20 mus after the laser pulse. This could explain how photoproducts thus formed could also be excited with only one laser pulse

Elemental mapping of Portuguese ceramic pieces with a full-field XRF scanner based on a 2D-THCOBRA detector

UID/FIS/04559/2020In this work, we present a novel application of the full-field energy-dispersive X-ray fluorescence (EDXRF) imaging system based on a MicroPattern Gaseous Detector (2D-THCOBRA) in the cultural heritage field. The detector has an intrinsic imaging capability with spatial resolution of 400μmFWHM, and is energy sensitive, presenting an energy resolution of approximately 1keVFWHM at 5.9keV. The full-field XRF scanner based on the 2D-THCOBRA detector allows mapping the distribution of elements in large area samples with high detection efficiency (75 % at 5.9keV), being a very promising choice for elemental mapping analysis of large area cultural heritage samples. In this work, we have demonstrated the imaging capabilities of the full-field XRF scanner and used it to assess the restoration of a Portuguese faience piece.publishersversionpublishe

Polyoxometalate/laccase-mediated oxidative polymerization of catechol for textile dyeing

The synergistic effect between polyoxometalates (POMs), namely K5[SiW11VVO40]·11H2O and H5[PMo10 VV2O40]·13H2O and laccase from ascomycete Myceliophthora thermophila has been employed for the first time in oxidative polymerization of catechol. Such a laccase-mediator system allowed the formation of a relatively high molecular weight polycatechol as confirmed by size exclusion chromatography and electrospray ionization mass spectrometry (ESI-MS) (3990 Da when using K5[SiW11VVO40]·11H2O and 3600 Da with H5[PMo10VV 2O40]·13H2O). The synthesized polymers were applied as dyes for the dyeing of flax fabrics. The color intensity of flax fabrics colored with polymer solutions was evaluated by diffuse reflectance spectrophotometry via k/s measurements (+10% of fixation ratio). A new synthetic process allowed a dyeing polymer, provided upon flax coloration, better color fixation and color resistance when compared to that obtained by conventional synthesis with laccase solely or with addition of organic mediator (1-hydroxybenzotriazole)

Contribuição ao Estudo Anatômico do Lenho de 7 Espécies de Dimorphandra (Leguminosae - Caesalpinioideae)

Os autores apresentam neste trabalho o estudo dos caracteres anatômicos das madeiras de 7 espécies do gênero Dimorphandra(leguminosae - Caesalpinioideae) e para cada uma delas são apresentadas ainda informações sobre: a) daárvore.:descrição botânica, distribuição geográfica e nomes vulgares; b) da madeira:características gerais, descrição macro e microscópica, 7 macro e 14 microfotografias estruturais do lenho. As espécies estudadas foram: Dimon.phandAa conjugata(Splitgerber) Sandw., D.gardnerianaTut., V. giganteaDucke, D. mollísBenth., D.multifloraDucke, D. palleiAmsh. e D, unijagaTul. Um quadro sinótico com as principais características anatômicas diferenciais das, espécies é também apresentado