Chemical reaction network of flavylium ions in heterogeneous media

Dissertação apresentada para a obtenção do Grau de Doutor em Química, especialidade em Química-Física, pela Universidade Nova de Lisboa, Faculdade de Ciências e TecnologiaFlavylium compounds (2-phenyl 1-benzopyrylium) constitute a versatile family of molecules that illustrates the concept of multistate system, since different forms exhibiting diverse properties can be obtained by means of external inputs such as pH and light. Dramatic changes in the properties of the flavylium network can be observed in heterogeneous media due to specific interactions of some of the states with different chemical microenvironments. In this thesis, the effects of CTAB micelles (chapters 2 and 3), Pluronic micelles and gels (chapter 4)and encapsulation in molecular clips (chapter 5) and zeolite L (chapter 6) on the chemical reaction network of flavylium ions are reported. Positively charged CTAB micelles, stabilizing trans-chalcone species, Ct, can be used to achieve efficient photochromism of flavylium compounds. 2-styryl 1-benzopyrylium salts, obtained by the introduction of a double bond between the benzopyrylium and the phenyl units, exhibit red shifted absorption maxima compared with flavylium analogues (up to 90 nm). This new family of compounds allows the design of photochromic systems based on CTAB micelles; in particular, switching from yellow to light blue using these derivatives of natural anthocyanins is possible. Flash photolysis experiments provided evidence for a singlet state isomerization process. In Pluronic media, photochromic gels based on the flavylium network can be obtained. In chapter 4, the Ct photochromic mechanism was analyzed, using mainly fluorescence techniques such as steady-state, time-resolved and anisotropy. Evidences for Ct distribution among different sites within the Pluronic aggregate and for selective Ct photochemistry were found. Finally, our approach focused on the encapsulation of flavylium salts. The association between a sulphate molecular clip and the several species from the network of a flavylium salt afforded water soluble host-guest complexes that were thoroughly studied. It was demonstrated that hydrophobic interactions between the molecular clips and the flavylium guest molecules are dominant; the other potential interactions, which certainly determine the structures of these host-guest complexes to a large extent, seem to be of minor importance for their stability. The hydration of the flavylium cation was found to be retarded in the presence of clip and the photochemically induced trans-cis isomerization seems essentially unaffected by the sulphate molecular clip. Spectroscopic studies on flavylium compounds encapsulated into the one-dimensional channels of zeolite L revealed drastic changes on fluorescence behavior and it was shown thatCt can isomerize inside the channels of zeolite L

Polarized light emission by deposition of aligned semiconductor nanorods

The ability to control the position and orientation of nanorods in a device is interesting both from a scientific and a technological point of view. Because semiconductor nanorods exhibit anisotropic absorption, and spontaneous and stimulated emission, aligning individual NRs to a preferred axis is attractive for many applications in photonics such as solar cells, light-emitting devices, optical sensors, switches, etc. Electric-field-driven deposition from colloidal suspensions has proven to be an efficient method for the controlled positioning and alignment of anisotropic particles. In this work, we present a novel technique for the homogeneous deposition and alignment of CdSe/CdS NRs on a glass substrate patterned with transparent indium tin oxide interdigitated electrodes, with a spacing of a few micrometers. This method is based on applying a strong AC electric field over the electrodes during a dip-coating procedure and subsequent evaporation of the solvent. The reproducible and homogeneous deposition on large substrates is required for large size applications such as solar cells or OLEDs. The accumulation, alignment, and polarized fluorescence of the nanorods as a function of the electrical field during deposition are investigated. A preferential alignment with an order parameter of 0.92 has been achieved

Direct determination of absorption anisotropy in colloidal quantum rods

We propose a direct method to determine absorption anisotropy of colloidal quantum rods. In this method, the rods are aligned in solution by using an alternating electric field and we measure simultaneously the resulting average change in absorption. We show that a frequency window for the electric field exists in which the change in absorbance as a function of field strength can be analyzed in terms of the quantum-rod dipole moment and the absorption coefficient for light that is polarized parallel or perpendicular to the long axis of the rod. The approach is verified by measuring the absorbance change of CdSe rods at 400 nm as a function of field strength, where we demonstrate excellent agreement between experiment and theory. This enables us to propose improved values for the CdSe quantum-rod extinction coefficient. Next, we analyze CdSe/CdS dot-in-rods and find that the absorption of the first exciton transition is fully anisotropic, with a vanishing absorption coefficient for light that is polarized perpendicularly to the long axis of the rod

Patient-physician discordance in assessment of adherence to inhaled controller medication: a cross-sectional analysis of two cohorts

We aimed to compare patient's and physician's ratings of inhaled medication adherence and to identify predictors of patient-physician discordance.(SFRH/BPD/115169/2016) funded by Fundação para a Ciência e Tecnologia (FCT); ERDF (European Regional Development Fund) through the operations: POCI-01-0145-FEDER-029130 ('mINSPIRERS—mHealth to measure and improve adherence to medication in chronic obstructive respiratory diseases—generalisation and evaluation of gamification, peer support and advanced image processing technologies') cofunded by the COMPETE2020 (Programa Operacional Competitividade e Internacionalização), Portugal 2020 and by Portuguese Funds through FCT (Fundação para a Ciência e a Tecnologia).info:eu-repo/semantics/publishedVersio

Identification of clusters of asthma control: A preliminary analysis of the inspirers studies

This work was funded by ERDF (European Regional Development Fund) through the operations: POCI- -01-0145-FEDER-029130 (“mINSPIRERS—mHealth to measure and improve adherence to medication in chronic obstructive respiratory diseases - generalisation and evaluation of gamification, peer support and advanced image processing technologies”) co-funded by the COMPETE2020 (Programa Operacional Competitividade e Internacionalização), Portugal 2020 and by Portuguese Funds through FCT (Fundação para a Ciência e a Tecnologia).© 2020, Sociedade Portuguesa de Alergologia e Imunologia Clinica. All rights reserved. Aims: To identify distinct asthma control clusters based on Control of Allergic Rhinitis and Asthma Test (CARAT) and to compare patients’ characteristics among these clusters. Methods: Adults and adolescents (≥13 years) with persistent asthma were recruited at 29 Portuguese hospital outpatient clinics, in the context of two observational studies of the INSPIRERS project. Demographic and clinical characteristics, adherence to inhaled medication, beliefs about inhaled medication, anxiety and depression, quality of life, and asthma control (CARAT, >24 good control) were collected. Hierarchical cluster analysis was performed using CARAT total score (CARAT-T). Results: 410 patients (68% adults), with a median (percentile 25–percentile 75) age of 28 (16-46) years, were analysed. Three clusters were identified [mean CARAT-T (min-max)]: cluster 1 [27(24-30)], cluster 2 [19(14-23)] and cluster 3 [10(2-13)]. Patients in cluster 1 (34%) were characterised by better asthma control, better quality of life, higher inhaler adherence and use of a single inhaler. Patients in clusters 2 (50%) and 3 (16%) had uncontrolled asthma, lower inhaler adherence, more symptoms of anxiety and depression and more than half had at least one exacerbation in the previous year. Further-more, patients in cluster 3 were predominantly female, had more unscheduled medical visits and more anxiety symp-toms, perceived a higher necessity of their prescribed inhalers but also higher levels of concern about taking these inhalers. There were no differences in age, body mass index, lung function, smoking status, hospital admissions or specialist physician follow-up time among the three clusters. Conclusion: An unsupervised method based on CARAT--T, identified 3 clusters of patients with distinct, clinically meaningful characteristics. The cluster with better asthma control had a cut-off similar to the established in the validation study of CARAT and an additional cut-off seems to distinguish more severe disease. Further research is necessary to validate the asthma control clusters identified.publishersversionpublishe

práticas artísticas no ensino básico e secundário

Educação Artística: integrar a inovação. A educação artística apresenta-se como um território a re-cartografar, numa atualização tão rápida quanto aquela que ocorre no campo artístico. As propostas publicadas neste número 11 da Revista Matéria-Prima trazem essa diversidade de abordagens, com novidades conceptuais que estabelecem as devidas relações entre educação e cidadania, participação, sustentabilidade, cultura visual, e também com alguma atenção sobre os debates pós-coloniais e as questões de género. Os 16 artigos reunidos neste 11º número da Revista Matéria-Prima trazem a realidade operativa quer na formação de professores e quer na formulação dos discursos pedagógicos, suas justificações e suas propostas alternativas.As propostas apresentadas devolvem o debate ao terreno, e alargam-no. Provocam as periferias, convocam abordagens diferenciadas sobre o tema da arte e da educação. Em todas elas a proposta de crescimento através da arte, que hoje implica cada vez mais cidadania, crítica, criatividade, interligação, comprometimento, participação.info:eu-repo/semantics/publishedVersio

MAMMALS IN PORTUGAL : A data set of terrestrial, volant, and marine mammal occurrences in P ortugal

Mammals are threatened worldwide, with 26% of all species being includedin the IUCN threatened categories. This overall pattern is primarily associatedwith habitat loss or degradation, and human persecution for terrestrial mam-mals, and pollution, open net fishing, climate change, and prey depletion formarine mammals. Mammals play a key role in maintaining ecosystems func-tionality and resilience, and therefore information on their distribution is cru-cial to delineate and support conservation actions. MAMMALS INPORTUGAL is a publicly available data set compiling unpublishedgeoreferenced occurrence records of 92 terrestrial, volant, and marine mam-mals in mainland Portugal and archipelagos of the Azores and Madeira thatincludes 105,026 data entries between 1873 and 2021 (72% of the data occur-ring in 2000 and 2021). The methods used to collect the data were: live obser-vations/captures (43%), sign surveys (35%), camera trapping (16%),bioacoustics surveys (4%) and radiotracking, and inquiries that represent lessthan 1% of the records. The data set includes 13 types of records: (1) burrowsjsoil moundsjtunnel, (2) capture, (3) colony, (4) dead animaljhairjskullsjjaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8),observation in shelters, (9) photo trappingjvideo, (10) predators dietjpelletsjpine cones/nuts, (11) scatjtrackjditch, (12) telemetry and (13) vocalizationjecholocation. The spatial uncertainty of most records ranges between 0 and100 m (76%). Rodentia (n=31,573) has the highest number of records followedby Chiroptera (n=18,857), Carnivora (n=18,594), Lagomorpha (n=17,496),Cetartiodactyla (n=11,568) and Eulipotyphla (n=7008). The data setincludes records of species classified by the IUCN as threatened(e.g.,Oryctolagus cuniculus[n=12,159],Monachus monachus[n=1,512],andLynx pardinus[n=197]). We believe that this data set may stimulate thepublication of other European countries data sets that would certainly contrib-ute to ecology and conservation-related research, and therefore assisting onthe development of more accurate and tailored conservation managementstrategies for each species. There are no copyright restrictions; please cite thisdata paper when the data are used in publications.info:eu-repo/semantics/publishedVersio

Mammals in Portugal: a data set of terrestrial, volant, and marine mammal occurrences in Portugal

Mammals are threatened worldwide, with ~26% of all species being included in the IUCN threatened categories. This overall pattern is primarily associated with habitat loss or degradation, and human persecution for terrestrial mammals, and pollution, open net fishing, climate change, and prey depletion for marine mammals. Mammals play a key role in maintaining ecosystems functionality and resilience, and therefore information on their distribution is crucial to delineate and support conservation actions. MAMMALS IN PORTUGAL is a publicly available data set compiling unpublished georeferenced occurrence records of 92 terrestrial, volant, and marine mammals in mainland Portugal and archipelagos of the Azores and Madeira that includes 105,026 data entries between 1873 and 2021 (72% of the data occurring in 2000 and 2021). The methods used to collect the data were: live observations/captures (43%), sign surveys (35%), camera trapping (16%), bioacoustics surveys (4%) and radiotracking, and inquiries that represent less than 1% of the records. The data set includes 13 types of records: (1) burrows | soil mounds | tunnel, (2) capture, (3) colony, (4) dead animal | hair | skulls | jaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8), observation in shelters, (9) photo trapping | video, (10) predators diet | pellets | pine cones/nuts, (11) scat | track | ditch, (12) telemetry and (13) vocalization | echolocation. The spatial uncertainty of most records ranges between 0 and 100 m (76%). Rodentia (n =31,573) has the highest number of records followed by Chiroptera (n = 18,857), Carnivora (n = 18,594), Lagomorpha (n = 17,496), Cetartiodactyla (n = 11,568) and Eulipotyphla (n = 7008). The data set includes records of species classified by the IUCN as threatened (e.g., Oryctolagus cuniculus [n = 12,159], Monachus monachus [n = 1,512], and Lynx pardinus [n = 197]). We believe that this data set may stimulate the publication of other European countries data sets that would certainly contribute to ecology and conservation-related research, and therefore assisting on the development of more accurate and tailored conservation management strategies for each species. There are no copyright restrictions; please cite this data paper when the data are used in publications

Tuning energy splitting and recombination dynamics of dark and bright excitons in CdSe/CdS dot-in-rod colloidal nanostructures

We report on a time-resolved study of the photoluminescence of core/shell CdSe/CdS dot-in-rod colloidal nanocrystals having various geometries. By studying the exciton recombination dynamics, we unveil a quadratic dependence of the bright dark exciton energy splitting and the dark exciton radiative recombination rate on the inverse CdS rod width, regardless of the CdSe core size. We also evidence a strong dependence of the spin-flip rate between bright and dark exciton states on the shell thickness that suggests an acoustic phonon bottleneck. This work highlights the possibility to fully control and tune the optical properties of colloidal nano crystals by shape engineering of the CdS shell