Browsing by Author "Pires, João"
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- Avaliação da área avascular da fóvea: deferenças entre dois protocolos de aquisiçãoPublication . Anacleto, Inês; Tarracha, Catarina; Pires, João; Santos, Verónica; Varandas, Teresa; Camacho, Pedro; Pereira, BrunoIntrodução - O OCT-A é um MCDT não invasivo, que permite a visualização da vascularização da retina e da coroide. Este exame permite a visualização tridimensional dos plexos vasculares em diferentes profundidades, fornecendo informação funcional sobre o fluxo sanguíneo nos vasos, zonas de não perfusão ou neovascularização. É possível ainda a avaliação de diversas patologias retinianas, entre elas aquelas que afetam a rede vascular macular, em particular a FAZ. A área da FAZ varia entre olhos saudáveis e verifica-se que existe o seu aumento com a progressão da idade. A RD como microangiopatia afeta os capilares sanguíneos, sobretudo a rede venosa, que são suscetíveis a danos devido à hiperglicemia constante e constitui uma das causas para um aumento patológico da área da FAZ. Ao realizar um exame de OCT-A são vários os parâmetros de aquisição que podem ser escolhidos, entre eles a dimensão da área examinada e a velocidade de aquisição, que afetam a resolução do exame. Pergunta de partida - Existem diferenças de medição da área da FAZ entre dois protocolos diferentes de aquisição de OCT-A?
- Copper Bis(oxazoline) Encapsulated in Zeolites and Its Application as Heterogeneous Catalysts for the Cyclopropanation of StyrenePublication . Silva, Ana Rosa; Albuquerque, Hélio; Fontes, Andre; Borges, Susana; Martins, Angela; Carvalho, Ana Paula; Pires, JoãoA copper C(2)-symmetric bis(oxazoline), CuBox, was introduced in two forms of commercial Y zeolite: a sodium form (NaY) and an ultrastable form (NaUSY). CuBox was introduced by first partially exchanging the sodium cations of both zeolites for copper and then by refluxing the obtained materials with a solution of bis(oxazoline) (Box). Two different loadings were prepared for each form of zeolite. The materials were characterized by copper ICP-AES, elemental analysis, XPS, FTIR, TG, and nitrogen adsorption isotherms at -196 degrees C. Evidence for Box ligand location in the supercages of NaY and NaUSY zeolites and its coordination to the exchanged copper(II) was obtained by the several techniques used. The materials were all active in the cyclopropanation of styrene with ethyldiazoacetate at room temperature and diastereoselective toward trans cydopropanes. Although the materials containing Box showed low enantioselectivities, their catalytic activities were higher than the parent copper exchanged zeolites, and did not decrease with reuse, at least during three consecutive cycles.
- Diabetic foveal avascular zone: differences between high speed and high resolution scansPublication . Pereira, Bruno; Anacleto, Inês; Pires, João; Santos, Verónica; Tarracha, Catarina; Varandas, Teresa; Camacho, PedroDiabetic retinopathy is one of the causes of the pathological increase of the Foveal Avascular Zone (FAZ) area and is assessable by optical coherence tomography angiography (OCTA). Even using the same equipment, different acquisition protocols may lead to different results. Aim of the study: To evaluate the differences in manual FAZ area measurements comparing two different OCTA acquisition protocols, High Speed (HS) versus High Resolution (HS).
- Effective zinc-substituted keggin composite to catalyze the removal of sulfur from real diesels under a solvent-free systemPublication . Ribeiro, Susana; Granadeiro, Carlos; Almeida, Pedro L.; Pires, João; Valença, Rita; Campos-Martin, J. M.; Ribeiro, Jorge C.; De Castro, Baltazar; Balula, SaleteThe Keggin phosphotungstate (PW12) and its zinc derivative (PW11Zn) were tested as oxidative catalysts for desulfurization processes using simulated and real diesels. These compounds were used as homogeneous catalysts, while the corresponding SBA-15 composites were used as heterogeneous catalysts. The comparison of their catalytic performance demonstrated that the zinc-substituted polyoxometalate is more efficient than the plenary PW12 structure. Additionally, using the heterogeneous PW11Zn@aptesSBA-15, the sustainability and catalytic efficiency was largely improved, allowing the total sulfur removal from model diesel after 1 h using a small amount of oxidant (H2O2/S = 4) under an oxidative solvent-free system. The desulfurization of real diesels was performed under similar conditions, achieving 87.8% of efficiency using the PW11Zn@aptesSBA-15 catalyst. Furthermore, the catalyst maintained its activity over consecutive desulfurization cycles. The cost-effective operational conditions achieved with PW11Zn@aptesSBA-15 turn this into a promising material to be used in an industrial scale to treat diesel.
- Oxidative desulfurization strategies using Keggin-type polyoxometalate catalysts: Biphasic versus solvent-free systemsPublication . Ribeiro, Susana; Granadeiro, Carlos; Almeida, Pedro L.; Pires, João; Capel-Sanchez, Maria C.; Campos-Martin, J. M.; Gago, S.; De Castro, Baltazar; Balula, SaleteStrategic polyoxometalate Keggin-type structural modification was performed to increase the oxidative catalytic performance to desulfurize model and real diesels. The most active lacunar structure [PW11O39](7-) (PW11) showed to complete desulfurize a simulated diesel after 60 min at 70 degrees C. Its application as homogeneous catalyst using a biphasic system 1: 1 diesel/acetonitrile needed to use an excess of oxidant (ratio H2O2/S = 8). The immobilization of the PW11 on amine-functionalized SBA-15 supports originated two heterogeneous catalysts PW11@aptesSBA-15 and PW11@tbaSBA-15. The best results were attained with the PW11@aptesSBA-15 catalyst showing identical oxidative desulfurization performance as the homogeneous analogue. As advantage, this heterogeneous catalyst promotes the complete desulfurization of simulated diesel using a solvent-free system, i.e. without the need of acetonitrile use. On the other hand, the same desulfurization efficiency could be achieved using half the amount of oxidant (H2O2/S = 4). The oxidative desulfurization of the real diesel achieved a remarkable 83.4% of efficiency after just 2 h. The recycling capacity of PW11@aptesSBA-15 catalyst was confirmed for eight consecutive cycles using the biphasic and the solvent-free systems. Its stability investigation demonstrates to be higher under the solvent-free system than the biphasic system, without practically any occurrence of PW11 leaching in the first case. On the other hand, the Venturello peroxocomplex [PO4{W(O-2)(2)}(4)](3-), recognized as active intermediate in the homogeneous biphasic system, was not identified in the heterogeneous catalytic systems.
- Polyoxometalate@Periodic mesoporous organosilicas as active materials for oxidative desulfurization of dieselsPublication . Ribeiro, Susana; Almeida, Pedro L.; Pires, João; De Castro, Baltazar; Balula, SaleteNovel material catalysts based in the active zinc-substituted polyoxotungstate ([PW11Zn(H2O)(39)](5-), abbreviated as PW11Zn) were efficiently used in the oxidative desulfurization of real and model diesels. These active catalytic center was strategically immobilized in a less hydrophilic periodic mesoporous organosilicas (PMOs), containing ethane-bridge (PMOE) and benzene-bridge (PMOB) walls, functionalized with (3-aminopropyl)triethoxysilane (aptes). The efficiency of the novel catalytic composites (PW11Zn@aptesPMOE and PM11Zn@aptesPMOB) was studied under oxidative desulfurization system (CODS) without the presence of an extraction solvent and also using a biphasic (diesel/extraction solvent) oxidative desulfurization system (ECODS). Both composites presented higher desulfurization efficiency under the solvent-free system, reaching ultra-low levels of sulfur compounds after only 1 h and using low ratio of H2O2/S = 4. The catalysts could be recycled without loss of activity for ten consecutive cycles. However, after the first desulfurization cycle complete desulfurization was achieved within only 30 min using PW11Zn@aptesPMOE composite. Also, the structure of PW it Zn@aptesPMOE demonstrated to be more stable than PW11Zn@aptesPMOB, probably due to the occurrence of some PW11Zn leaching from the PMOB surface, probably caused by the lower interaction of PW11Zn with the benzene-bridge PMOB wall. The most robust catalyst PW11Zn@aptesPMOE was used to desulfurize a real diesel achieving 75.9% of desulfurization after 2 h. The catalyst was further recycled with success to treat real diesel.
- Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerizationPublication . Fernandes, Sara; Andrade, Marta; Ania, Conchi O.; Martins, Angela; Pires, João; Carvalho, Ana P.The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.