Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

The sound of whiteness: early music vocal performance practice in Britain

American Musicological Society annual meeting, San Francisco, 10 Nov. 2011

Sedimentology of a Middle Jurassic Base-of-Slope environment, Cutri Formation, Mallorca

The Cutri Formation’s, type location, exposed in the NW of Mallorca, Spain has previously been described by Álvaro et al., (1989) and further interpreted by Abbots (1989) unpublished PhD thesis as a base-of-slope carbonate apron. Incorporating new field and laboratory analysis this paper enhances this interpretation. From this analysis, it can be shown without reasonable doubt that the Cutri Formation was deposited in a carbonate base-of-slope environment on the palaeowindward side of a Mid-Jurassic Tethyan platform. Key evidence such as laterally extensive exposures, abundant deposits of calciturbidtes and debris flows amongst hemipelagic deposits strongly support this interpretation.

Juniperus navicularis - a study of Portuguese population structure and fitness

Juniperus navicularis Gand. is a dioecious endemic conifer that constitutes the understory of seaside pine forests in Portugal, areas currently threatened by increasing urban expansion. The aim of this study is to assess the conservation status of previously known populations of this species located on its core area of distribution. The study was performed in south-west coast of Portugal. Three populations varying in size and pine density were analyzed. Number of individuals, population density, spatial distribution and individual characteristics of junipers were estimated. Female cone, seed characteristics and seed viability were also evaluated. Results suggest that J. navicularis populations are vulnerable because seminal recruitment is scarce, what may lead to a reduction of genetic variability due solely to vegetative propagation. This vulnerability seems to be strongly determined by climatic constraints toward increasing aridity. Ratio between male and female shrubs did not differ from 1:1 in any population. Deviations from 1:1 between mature and non-mature plants were found in all populations, denoting population ageing. Very low seed viability was observed. A major part of described Juniperus navicularis populations have disappeared through direct habitat loss to urban development, loss of fitness in drier and warmer locations and low seed viability. This study is the first to address J. navicularis conservation, and represents a valuable first step toward this species preservation. 

Financial sustainability of cooperatives: a case of portuguese olive oil cooperatives

En Portugal, como en otros países, las cooperativas agrícolas tienen un papel económico importante en el sistema alimentario. Similar a otras organizaciones económicas, las cooperativas agrícolas han sido testigos de cambios estructurales en las últimas décadas en términos de modelos de gobernación y gestión. Las cooperativas agrícolas portuguesas se han visto constreñidas por su contexto a adoptar un modelo tradicional de propiedad y control. El objetivo principal de este estudio era analizar cuestiones relacionadas con la estructura de gestión y desempeño financiero de las cooperativas, basada en los datos recogidos de cooperativas de aceite de oliva situadas en la región interior norte de Portugal. La combinación de un análisis cualitativo de la estructura y toma de decisiones, una evaluación financiera y la aplicación de un enfoque en varios criterios (PROMETHEE II), los resultados están en línea con expectativas (por ejemplo, bajos niveles de participación de los miembros, gestión no profesional, ratios de rentabilidad bajos, bajo apalancamiento y una capacidad para cumplir compromisos financieros), excepto la relación entre la gestión profesional y el desempeño financiero. La existencia de gestión profesional no conduce a mejores resultados financieros. Este resultado refuerza la creencia de que las cooperativas que están estructuradas de diferente manera tienen intereses diferentes y contradictorios a las partes interesadas.

Resident’s Perceptions on Impacts of Hosting the Guimaraes 2012 European Capital of Culture: Comparisons of the Pre- and Post Periods

Residents tend to have high expectations regarding the benefits of hosting a mega- event, in particular the creation of new infrastructure, growth in GDP and employ- ment, image enhancement and the spin-offs of attracting tourists and fostering sustainable growth of the cultural supply (Jeong and Faulkner 1996; Deccio and Baloglu 2002; Gursoy and Kendall 2006; Getz 2008; Langen and Garcia 2009; Ritchie et al. 2009; Gursoy et al. 2011; Palonen 2011). Nevertheless, they normally recognise that some costs will be incurred (Kim and Petrick 2005; Kim et al. 2006; Ritchie et al. 2009; Gursoy et al. 2011; Lee et al. 2013). So, it was not surprising that the nomination of Guimaraes, a small city in the northwest of Portugal, as one of the two European Capitals of Culture in 2012 (2012 ECOC), had raised great expectations in the local community vis- a-vis its socio-economic and cultural benefits. Our research was designed to examine the Guimar~aes residents’ perceptions of the impacts of hosting the 2012 ECOC, approached at two different times: before and after the event, to try and capture the evolution of the residents’ assessment of its impacts. From the empirical literature, we know that residents’ perceived impacts tend to change as time goes by (Kim et al. 2006; Ritchie et al. 2009; Gursoy et al. 2011; Lee et al. 2013). The data were gathered via two surveys applied to Guimaraes residents, one in 2011, before the event, and the other afterwards, in 2013. The Guimaraes residents’ assessment was thought to be essential to get an accurate appraisal of the impact of the mega-event as they were a main part of the hosting process. 2012 ECOC impacts were mainly felt by local people who, in most cases, will go on feeling them in the short and long term. The research was thought to be socially pertinent as the opinions collected through the surveys can help to prevent repeating mistakes when similar mega- events are organised in the future, and to increase the positive impacts derived from hosting them. When we talk about the social pertinence of the empirical results, we want to stress that the expertise acquired can be useful to any host city or country.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

The disappearing of palheiros in Aveiro lagoon

Palheiros are traditional timber constructions existing in the littoral centre region of Portugal. This is particularly the case of the Aveiro lagoon region where for many years many such constructions have existed. They were originally built to store working tools related with lagoon activity (fishing and sea salt extraction) and to give shelter for the fishermen during the fishing season. These constructions were built with superimposed veneers in vertical or horizontal directions. Since they are mostly located near the sea, they have started to be used as holiday houses and are often painted in vivid colours. Most of these buildings are being replaced by concrete constructions, since their preservation state is rather unsatisfactory or simply because there is a need to increase their size. Additionally, little knowledge about the possibilities of maintenance and building in timber structures exists. In some cases, although the structures were changed from timber to concrete, the exterior appearance of the palheiros remains the same, which might be interesting from the pictorial point of view but it isn’t certainly from a heritage preservation perspective. However in many other situations, they are being substituted by “modern” constructions that were not valuable in any of the previous viewpoints. Fortunately, there are also cases where palheiros have been preserved and remain in good condition. For how long these examples will remain is certainly the major question that must be answered since these are only on the dependence of owner’s will and not based on local authorities concern. A consciousness of local authorities and citizens is mandatory in order to preserve this heritage because it is perfectly possible to preserve the traditional constructions offering all the comfort of modern houses. Keywords: timber construction, vernacular construction, preservation.

Chemical characterization and evaluation of biological activity of Cynara cardunculus extractable compounds

The Mediterranean species Cynara cardunculus L. is recognized in the traditional medicine, for their hepatoprotective and choleretic effects. Biomass of C. cardunculus L. var. altilis (DC), or cultivated cardoon, may be explored not only for the production of energy and pulp fibers, but also for the extraction of bioactive compounds. The chemical characterization of extractable components, namely terpenic and phenolic compounds, may valorize the cultivated cardoon plantation, due to their antioxidant, antitumoral and antimicrobial activities. In this study, the chemical composition of lipophilic and phenolic fractions of C. cardunculus L. var. altilis (DC), cultivated in the south of Portugal (Baixo Alentejo region) was characterized in detail, intending the integral valorization of its biomass. The biological activity of cultivated cardoon extracts was evaluated in terms of antioxidant, human tumor cell antiproliferative and antibacterial effects. Gas chromatography-mass spectrometry (GC-MS) was used for the chemical analysis of lipophilic compounds. Sixty-five lipophilic compounds were identified, from which 1 sesquiterpene lactone and 4 pentacyclic triterpenes were described, for the first time, as cultivated cardoon components, such as: deacylcynaropicrin, acetates of β- and α-amyrin, lupenyl acetate and ψ-taraxasteryl acetate. Sesquiterpene lactones were the major family of lipophilic components of leaves (≈94.5 g/kg), mostly represented by cynaropicrin (≈87.4 g/kg). Pentacyclic triterpenes were also detected, in considerably high contents, in the remaining parts of cultivated cardoon, especially in the florets (≈27.5 g/kg). Taraxasteryl acetate was the main pentacyclic triterpene (≈8.9 g/kg in florets). High pressure liquid chromatography-mass spectrometry (HPLC-MS) was utilized for the chemical analysis of phenolic compounds. Among the identified 28 phenolic compounds, eriodictyol hexoside was reported for the first time as C. cardunculus L. component, and 6 as cultivated cardoon components, namely 1,4-di-O-caffeoylquinic acid, naringenin 7-O-glucoside, naringenin rutinoside, naringenin, luteolin acetylhexoside and apigenin acetylhexoside. The highest content of the identified phenolic compounds was observed in the florets (≈12.6 g/kg). Stalks outer part contained the highest hydroxycinnamic acids abundance (≈10.3 g/kg), and florets presented the highest flavonoids content (≈10.3 g/kg). The antioxidant activity of phenolic fraction was examined through 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging assay. Stalks outer part, and receptacles and bracts extracts demonstrated the highest antioxidant effect on DPPH (IC50 of 34.35 μg/mL and 35.25 μg/mL, respectively). (cont.) abstract (cont.) The DPPH scavenging effect was linearly correlated with the total contents of hydroxycinnamic acids (r = -0.990). The in vitro antiproliferative activity of cultivated cardoon lipophilic and phenolic extracts was evaluated on a human tumor cells line of triple-negative breast cancer (MDA-MB-231), one of the most refractory human cancers to conventional therapeutics. After 48 h of exposition, leaves lipophilic extract showed higher inhibitory effect (IC50 = 10.39 μg/mL) than florets lipophilic extract (IC50 = 315.22 μg/mL), upon MDA-MB-231 cellular viability. Pure compound of cynaropicrin, representative of the main compound identified in leaves lipophilic extract, also prevented the cell proliferation of MDA-MB-231 (IC50 = 17.86 μM). MDA-MB-231 cells were much more resistant to the 48 h- treatment with phenolic extracts of stalks outer part (IC50 = 3341.20 μg/mL) and florets (IC50 > 4500 μg/mL), and also with the pure compound of 1,5-di-O-caffeoylquinic acid (IC50 = 1741.69 μM). MDA-MB-231 cells were exposed, for 48 h, to the respective IC50 concentrations of leaves lipophilic extract and pure compound of cynaropicrin, in order to understand their ability in modelling cellular responses, and consequently important potentially signaling pathways for the cellular viability decrease. Leaves lipophilic extract increased the caspase-3 enzymatic activity, contrarily to pure compound of cynaropicrin. Additionally, leaves lipophilic extract and pure compound of cynaropicrin caused G2 cell cycle arrest, possibly by upregulating the p21Waf1/Cip1 and the accumulation of phospho-Tyr15-CDK1 and cyclin B1. The inhibitory effects of leaves lipophilic extract and cynaropicrin pure compound, against the MDA-MB-231 cell proliferation, may also be related to the downregulation of phospho-Ser473-Akt. The antibacterial activity of cultivated cardoon lipophilic and phenolic extracts was assessed, for the first time, on two multidrug-resistant bacteria, such as the Gram-negative Pseudomonas aeruginosa PAO1 and the Gram-positive methicillin-resistant Staphylococcus aureus (MRSA), two of the main bacteria responsible for health care-associated infections. Accordingly, the minimum inhibitory concentrations (MIC) were determined. Lipophilic and phenolic extracts of florets did not have antibacterial activity on P. aeruginosa PAO1 and MRSA (MIC > 2048 μg/mL). Leaves lipophilic extract did not prevent the P. aeruginosa PAO1 growth, but pure compound of cynaropicrin was slightly active (MIC = 2048 μg/mL). Leaves lipophilic extract and pure compound of cynaropicrin blocked MRSA growth (MIC of 1024 and 256 μg/mL, respectively). The scientific knowledge revealed in this thesis, either by the chemical viewpoint, or by the biological viewpoint, contributes for the valorization of C. cardunculus L. var. altilis (DC) biomass. Cultivated cardoon has potential to be exploited as source of bioactive compounds, in conciliation with other valorization pathways, and Portuguese traditional cheeses manufacturing.

A imagem percebida e projetada de Portugal como destino turístico

O caráter competitivo dos mercados na área do turismo tem-se acentuado nas últimas décadas e, por conseguinte, cada vez mais os destinos têm de conseguir demonstrar a sua diferenciação. Ao desempenhar um papel fundamental no comportamento dos consumidores e, em particular, na tomada de decisão sobre os destinos a visitar, a imagem do destino na mente dos consumidores finais e dos intermediários que os comercializam é fundamental para o sucesso dos destinos. Desta forma, a imagem dos destinos turísticos tem sido alvo de extensa investigação, uma vez que a compreensão da imagem percebida dos destinos e também da imagem projetada através dos diversos canais de promoção poderá permitir a identificação de aspetos a melhorar nas suas estratégias de marketing, uma maior eficiência dos recursos financeiros investidos no estímulo da procura turística e uma maior eficácia na atração dos turistas que, consecutivamente, avaliam potenciais novos destinos a visitar. A presente dissertação tem como objeto de estudo o destino turístico Portugal e debruça-se sobre a análise da imagem percebida, na perspetiva dos intermediários turísticos dos cinco países que mais enviam turistas para Portugal, e da imagem projetada no portal oficial de promoção deste destino. Os seus objetivos centrais prendem-se com a comparação destas duas vertentes da imagem, no sentido de apurar as suas diferenças e semelhanças e, assim, apurar contributos relevantes para as estratégias de promoção do destino Portugal, e ainda a identificação dos fatores determinantes da imagem percebida de Portugal pelos intermediários turísticos analisados e das suas consequências ao nível da lealdade atitudinal. De uma forma global, conclui-se que a imagem percebida e a imagem projetada de Portugal como destino turístico apresentam semelhanças em alguns aspetos e diferenças noutros. Além disso, verifica-se que um conjunto de fatores determinantes exerce influência sobre a imagem percebida de Portugal como destino turístico e que esta tem efeito sobre a lealdade atitudinal dos intermediários turísticos, traduzida nas intenções de recomendação do destino.