Em países em desenvolvimento, doenças infecciosas se constituem ainda um grave problema de saúde pública. Muitas vezes, essas doenças estão altamente relacionadas a condições urbanas que podem ser encontradas em áreas mais pobres. Nesses casos, o sensoriamento remoto (SR) pode ser utilizado como uma poderosa ferramenta de estudo. Novos produtos de SR se encontram disponíveis no mercado, permitindo o desenvolvimento de análises espaciais cada vez mais profundas e precisas. No entanto, a complexidade que envolve a epidemiologia de doenças, a irregularidade de ocupações urbanas e a heterogeneidade das imagens de alta resolução espacial têm restringido o desenvolvimento de estudos nesse campo científico. O desafio de identificar elementos e tipologias urbanas em imagens de sensoriamento remoto relacionadas à ocorrência da leptospirose justifica-se pela crença de que ferramentas de SR podem ser mais amplamente utilizadas no monitoramento de carências urbanísticas e, consequentemente, na gestão de ações e investimentos públicos. A metodologia contempla uma revisão bibliográfica sistemática, com base na qual foram criados modelos de transmissão da leptospirose e investigadas tipologias urbanas presentes na área de estudo. As variáveis baseadas em dados de SR que formam os indicadores dos modelos e que caracterizam as tipologias foram usadas para definir objetos e atributos, alvos das investigações em imagens de alta resolução espacial. Os procedimentos de SR adotados baseiam-se na segmentação multi-nível, classificação baseada em objeto, e utilizam ortofotografias aéreas, imagem QuickBird e base cartográfica do eixo viário do Subúrbio Ferroviário de Salvador. Para o cálculo das variáveis utilizou-se produtos do processamento da imagem QuickBird. Procedimentos de geoprocessamento foram realizados em sistema de informações geográficas. Por fim, realizaram-se as primeiras análises epidemiológicas que investigam a relação da leptospirose com os elementos e tipologias urbanas identificados por meio de SR, cujos resultados apontam maior influência do percentual de pavimentação das vias, sua largura e qualidade da edificação na possibilidade de ocorrência da leptospirose no Subúrbio. Possíveis fontes de viés são discutidas ao lado de propostas de continuação da pesquisa. Apesar dos problemas e limitações identificados no processo, o estudo mostra que a metodologia desenvolvida baseada em SR se constitui uma poderosa ferramenta de análise do espaço intra-urbano, uma vez que permite a identificação de elementos e tipologias relacionados a situações de risco, apoiando assim, o direcionamento de investimentos públicos que venham refletir na melhoria das condições de saúde da população. / In developing countries, infectious diseases are still a serious public health problem. These diseases are often and highly related to urban conditions found in poor areas, in these cases, remote sensing (RS) can be used as a powerful tool. New RS products are now available allowing the development of more complex and precise spatial analysis. On the other hand, the complexity of epidemiological studies, the lack of regularity of precarious urban settlements and the heterogeneity of high spatial resolution images have been restricting the development of studies in this areas. The challenge of identifying urban elements and typologies related to the leptospirosis using RS products is pursued due the belief that RS can be more used among professionals and researchers in the task of monitoring the urban environment, and directing public investments and actions. The methodology presented consists in a broad literature review, which was used to support leptospirosis transmission risk models and to find urban typologies at the study area. Variables based on RS were identified in the disease models and in the typologies characterization. This models and typologies also defined targets to look for in the high spatial resolution images. RS procedures were based on multi-level segmentation, object-based classification, aerial photography, QuickBird satellite images and street axis vector data of the Railroad Suburb of Salvador. In order to obtain the variable\'s values, results of QuickBird image processing were added to a geographic database and processed using vector and raster over layering techniques. At last, epidemiological analysis were initiated aiming to find its relationship with the urban elements and typologies identified using RS. The results points paved streets, streets wideness and house quality as the RS variables that have more influence on the leptospirosis transmission chance. The dissertation also presents research restrains, potentials, possible sources of bias and future studies proposals. It concludes that the RS based methodology presented is a powerful tool for urban analysis, due to its capabilities for identifying urban targets related to risky situations, and, therefore, for helping direct public investments to improve life conditions an unprivileged city areas.

Les composés à commutation électronique constituent une large famille de systèmes particulièrement prometteuse, notamment pour le stockage de l’information à l’échelle moléculaire. Parmi ces composés, les analogues du bleu de Prusse cobalt-fer (ABP AxCoFe) sont des polymères inorganiques formés d’enchaînements Co-N≡C-Fe pouvant présenter deux états électroniques CoII(HS)-N≡C-FeIII(BS) et CoIII(BS)-N≡C-FeII(BS) (HS : haut spin ; BS : bas spin) aux propriétés structurales et électroniques bien distinctes. La transition électronique entre ces deux états peut être contrôlée de manière réversible par une grande variété de paramètres chimique (insertion de cations alcalins) et physiques (température, pression, irradiation). Ces propriétés de photo-commutation sont particulièrement intéressantes pour le développement de mémoires optiques à l’échelle moléculaire.Afin de comprendre les propriétés électroniques des ABP AxCoFe, nous nous sommes intéressés à l’interaction entre les centres métalliques via le pont cyanure dans l’enchaînement Co-N≡C-Fe, aussi bien sur un plan expérimental (mise en œuvre de techniques d’analyse reposant sur l’utilisation du rayonnement synchrotron) que théorique (modélisation ab initio de type post-Hartree-Fock). Nous avons également étudié la nature de l’interaction, démontrée expérimentalement, entre les cations alcalins et le réseau bimétallique formé par les enchaînements Co-N≡C-Fe. Finalement, la pertinence du modèle à deux états, habituellement utilisé pour rendre compte des propriétés électroniques des systèmes commutables, est discutée, avec la mise en évidence de multistabilités au sein des ABP AxCoFe. Ce travail propose ainsi une étude la plus complète possible des phénomènes électroniques rencontrés dans ces systèmes. / Electronically switchable compounds constitute a wide family of very promising systems, especially in the field of data storage at a molecular scale. Amongst these compounds, cobalt-iron Prussian blue analogues (AxCoFe PBAs) are inorganic polymers based on Co-N≡C-Fe linkages that may exhibit two CoII(HS)-N≡C-FeIII(LS) and CoIII(LS)-N≡C-FeII(LS) (HS: high spin; LS: low spin) electronic states with very different structural and electronic properties. Electronic transition in between these two states can be reversibly controlled by a large variety of both chemical (insertion of alkali cations) and physical (temperature, pressure, irradiation) parameters. These photo switching properties are extremely appealing for the development of optical memory devices at the molecular scale.In order to understand the electronic properties of AxCoFe PBAs, the interaction occurring between the metallic centres through the cyanide bridge in the Co-N≡C-Fe linkages was investigated both at an experimental (use of synchrotron-radiation-based analytic techniques) and a theoretical (post-Hartree-Fock ab initio modelling) levels. The nature of the experimentally-demonstrated interaction between the alkali cations and the bimetallic network, made of the Co-N≡C-Fe linkages, was also studied. Finally, the relevance of the two-state model, usually invoked to account for the electronic properties of switchable systems, is discussed, as multistabilities are evidenced in PBAs. This work therefore offers study of the electronic phenomena occurring in such systems as comprehensive as possible.

A presente tese de doutorado defende a aplicação da técnica de modulação de efeitos das decisões na jurisdição infraconstitucional exercida pelo Superior Tribunal de Justiça e, consequentemente, sua utilização para relativizar efeitos precedentes processuais. A modulação de precedentes ou jurisprudência é uma técnica adotada pelos tribunais para evitar que a (nova) interpretação do direito por eles elaborada tenha efeitos retroativos e, assim, atinja situações consolidadas ou casos judiciais pendentes. Essa flexibilização é comumente utilizada para evitar que uma reviravolta jurisprudencial (i.e., um overruling) cause efeitos danosos àqueles cidadãos que depositaram confiança no precedente revogado, por ele pautando suas vidas e negócios. A modulação serve também para conservar situações jurídicas perpetradas com base em uma lei que veio ser, apenas posteriormente, declarada inconstitucional ou ilegal por um tribunal superior. A tese inicia demonstrando o desenvolvimento histórico da reestruturação de efeitos decisórios no Brasil, a partir de sua implementação na jurisdição constitucional sob controle do Supremo Tribunal Federal (analisa-se, dentro do contexto, o art. 27 da Lei 9.868/99). Passa-se, então, o trabalho a defender a modulação de precedentes também na jurisdição infraconstitucional praticada pelo Superior Tribunal de Justiça, fazendo, em primeiro lugar, um paralelo com o direito estrangeiro. Na sequência, o estudo traz fundamentos para comprovar a tese, explicando que a jurisprudência equivale, em certos casos, à norma legal (função criativa da decisão judicial) e, portanto, merece ter sua eficácia prospectada no tempo, tal como ocorre com a lei ordinária (aplicação pro futuro, cf. art. 5º, inc. XXXVI, CF e art. 6º, LICC), a fim de preservar a segurança jurídica e outros tantos relevantes princípios constitucionais (no ensejo dessa análise, critica-se pontualmente julgado da 1ª Seção do STJ). O trabalho, entretanto, destaca a excepcionalidade do (re)ajustamento da eficácia decisória, pois o precedente, geralmente, deve abarcar situações pendentes e passadas, observados determinados fundamentos técnico-jurídicos explicitados no trabalho. De lege ferenda, aborda-se o Projeto do Novo Código de Processo Civil, cujo art. 882, inc. V, objetiva instituir a prospecção de efeitos decisórios em todo o contexto jurisdicional brasileiro, especialmente no overruling. O capítulo final da tese analisa casos de modulação de decisões processuais, sugerindo sua adoção como técnica (processual) adicional para efetivação dos escopos do processo e de outros tantos princípios processuais. / This doctoral thesis advocates the application of the technique of modulation of the effects of decisions on infra-constitutional jurisdiction (prospective overruling) exercised by the Superior Court of Justice and hence its use in order to relativize precedent procedural effects. Modulation of precedents or case law is a technique used by courts to prevent retroactive effects of the (new) interpretation of law as prepared by them, thus striking consolidated situations or pending court cases. Such flexibility is commonly used to preclude a reversal of jurisprudence (i.e., an overruling) from causing harmful effects to those citizens who put their trust in the revoked precedent, using it to guide their lives and businesses. The modulation also serves to retain legal situations perpetrated based on a law that was only later declared unconstitutional or illegal by a higher court. The thesis starts showing the historical development of the restructuring effects of decision-making in Brazil, from its implementation on constitutional jurisdiction under the control of the Supreme Court (as analyzed within the context of the art. 27 of Law 9.868/99). Afterwards, it comes to defend the modulation of precedents also in infraconstitutional jurisdiction, as practiced by the Superior Court of Justice, drawing initially a parallel with foreign law. It continues by providing groundings to prove the thesis, explaining that, in some cases, judge-made law is equal to the legal norm (creative function of the judicial decision) and therefore deserves its effectiveness prospected in time, as occurs with the ordinary law (application pro futuro, cf. art. 5th, inc. XXXVI, CF and art. 6, LICC) in order to preserve legal certainty and so many other relevant constitutional principles (on occasion of this analysis, criticism is exemplarily made on o judgment by the 1st Section of the STJ). The paper, however, highlights the uniqueness of the (re)adjustment of effectiveness, because the precedent should generally encompass situations pending and past, technical legal grounds observed. De lege ferenda, the thesis addresses the design of the New Code of Civil Procedure, whose art. 882, inc. V, aims to establish the prospection of decisionmaking effects throughout the whole Brazilian judicial context, especially in overruling. The final chapter of the thesis is devoted to analyze cases of modulation of procedural decisions and to suggest its adoption as additional (procedural) technique in order to implement the scopes of the process as well as many other procedural principles.

Lanthanide elements display many remarkable and exciting properties which explain their widespread use in a number of very important biomedical tools like efficient MRI contrast agents or luminescent probes for highly sensitive assays of bioanalytes amongst other fields of application. In this context, the aim of the present work was to prepare and characterize lanthanide complexes of two ligands that feature a linear or a macrocyclic chelating unit compactly grafted onto a 1,10-phenanthroline derived moiety (phenDTPA and PhenHDO3A). The ditopic nature of the ligands allows the selective incorporation of a d6 metal ion and a lanthanide one in close proximity. The resulting rigid heterobimetallic supramolecular species show useful properties and constitute potential MRI contrast agents or new luminescent compounds depending on the type of the lanthanide and transition metal ions employed: for example, the selfassembly process of gadolinium(III) chelates around an iron(II) ion brings a remarkable increase of their relaxivity, a key parameter for use in MRI. On the other hand, association of a ruthenium and and a near infrared emitting 4f ion like ytterbium(III) gives mixed d-f structures able to harvest visible light and convert it into near infra-red signal. Visible light luminescent pH probes were also obtained with Eu3+ or Tb3+ phenHDO3A complexes.

Em países em desenvolvimento, doenças infecciosas se constituem ainda um grave problema de saúde pública. Muitas vezes, essas doenças estão altamente relacionadas a condições urbanas que podem ser encontradas em áreas mais pobres. Nesses casos, o sensoriamento remoto (SR) pode ser utilizado como uma poderosa ferramenta de estudo. Novos produtos de SR se encontram disponíveis no mercado, permitindo o desenvolvimento de análises espaciais cada vez mais profundas e precisas. No entanto, a complexidade que envolve a epidemiologia de doenças, a irregularidade de ocupações urbanas e a heterogeneidade das imagens de alta resolução espacial têm restringido o desenvolvimento de estudos nesse campo científico. O desafio de identificar elementos e tipologias urbanas em imagens de sensoriamento remoto relacionadas à ocorrência da leptospirose justifica-se pela crença de que ferramentas de SR podem ser mais amplamente utilizadas no monitoramento de carências urbanísticas e, consequentemente, na gestão de ações e investimentos públicos. A metodologia contempla uma revisão bibliográfica sistemática, com base na qual foram criados modelos de transmissão da leptospirose e investigadas tipologias urbanas presentes na área de estudo. As variáveis baseadas em dados de SR que formam os indicadores dos modelos e que caracterizam as tipologias foram usadas para definir objetos e atributos, alvos das investigações em imagens de alta resolução espacial. Os procedimentos de SR adotados baseiam-se na segmentação multi-nível, classificação baseada em objeto, e utilizam ortofotografias aéreas, imagem QuickBird e base cartográfica do eixo viário do Subúrbio Ferroviário de Salvador. Para o cálculo das variáveis utilizou-se produtos do processamento da imagem QuickBird. Procedimentos de geoprocessamento foram realizados em sistema de informações geográficas. Por fim, realizaram-se as primeiras análises epidemiológicas que investigam a relação da leptospirose com os elementos e tipologias urbanas identificados por meio de SR, cujos resultados apontam maior influência do percentual de pavimentação das vias, sua largura e qualidade da edificação na possibilidade de ocorrência da leptospirose no Subúrbio. Possíveis fontes de viés são discutidas ao lado de propostas de continuação da pesquisa. Apesar dos problemas e limitações identificados no processo, o estudo mostra que a metodologia desenvolvida baseada em SR se constitui uma poderosa ferramenta de análise do espaço intra-urbano, uma vez que permite a identificação de elementos e tipologias relacionados a situações de risco, apoiando assim, o direcionamento de investimentos públicos que venham refletir na melhoria das condições de saúde da população. / In developing countries, infectious diseases are still a serious public health problem. These diseases are often and highly related to urban conditions found in poor areas, in these cases, remote sensing (RS) can be used as a powerful tool. New RS products are now available allowing the development of more complex and precise spatial analysis. On the other hand, the complexity of epidemiological studies, the lack of regularity of precarious urban settlements and the heterogeneity of high spatial resolution images have been restricting the development of studies in this areas. The challenge of identifying urban elements and typologies related to the leptospirosis using RS products is pursued due the belief that RS can be more used among professionals and researchers in the task of monitoring the urban environment, and directing public investments and actions. The methodology presented consists in a broad literature review, which was used to support leptospirosis transmission risk models and to find urban typologies at the study area. Variables based on RS were identified in the disease models and in the typologies characterization. This models and typologies also defined targets to look for in the high spatial resolution images. RS procedures were based on multi-level segmentation, object-based classification, aerial photography, QuickBird satellite images and street axis vector data of the Railroad Suburb of Salvador. In order to obtain the variable\'s values, results of QuickBird image processing were added to a geographic database and processed using vector and raster over layering techniques. At last, epidemiological analysis were initiated aiming to find its relationship with the urban elements and typologies identified using RS. The results points paved streets, streets wideness and house quality as the RS variables that have more influence on the leptospirosis transmission chance. The dissertation also presents research restrains, potentials, possible sources of bias and future studies proposals. It concludes that the RS based methodology presented is a powerful tool for urban analysis, due to its capabilities for identifying urban targets related to risky situations, and, therefore, for helping direct public investments to improve life conditions an unprivileged city areas.

La limitation optique (LO) est un processus de protection des détecteurs optiques (yeux, caméras…) vis-à-vis des agressions laser. Le développement rapide de ces derniers aux fréquences des télécommunications a encouragé l’ingénierie moléculaire pour la LO dans cette fenêtre spectrale, en particulier à 1500 nm. Un des principaux mécanismes de la LO est l’absorption multiphotonique et plus particulièrement l’absorption à deux photons (ADP). Il s’agit d’un phénomène d’optique non-linéaire du troisième ordre au cours duquel un électron est promu de l’état fondamental vers l’état excité par absorption simultanée de deux photons. De plus, des travaux récents ont mis en évidence que le phénomène de LO peut être exalté par des processus d’absorption à l’état excité (AEE) induits par ADP. Dans ce contexte, cette thèse décrit la synthèse d’une nouvelle famille de chromophores de type aza-dipyrrométhène de bore (Aza-Bodipy), fonctionnalisés par des groupements donneur ou accepteur d’électrons. Ces molécules ont un comportement de limiteur optique sur toute la gamme spectrale voulue, avec un maximum d’efficacité vers 1300 nm. Les résultats ont été interprétés sur la base de deux phénomènes : l’ADP, suivie de l’AEE pour un procédé d’absorption globale à trois photons. Ces deux processus ont été mesurés séparément et des relations structure-activité ont été établies, afin de rationnaliser les données de LO. L’importance du transfert de charge et la superposition spectrale des deux phénomènes sont alors apparues comme les paramètres clefs à optimiser. En vue d’une application dans un dispositif optique réel, il est nécessaire que les chromophores soient incorporés dans un matériau solide, qui peut être poli et transformé. Ainsi, les composés synthétisés ont été insérés avec succès dans une matrice sol-gel. Pour la première fois, des matériaux de qualité optique ont été réalisés, possédant des propriétés de LO dans l’infra-rouge très performantes et meilleures qu’en solution. / The optical power limiting (OPL) is a protection process of detectors (eyes, cameras…) against laser aggression. The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths led to the design of new materials for nonlinear absorption in this spectral range, in particular at 1500 nm. Mutiphotonic absorption, such as the two-photon absorption (TPA) is one of the mechanisms involved in the OPL. TPA is a third order nonlinear phenomenon that promotes a molecule to an excited state by the simultaneous absorption of two photons. Moreover, the overall OPL efficiency can be enhanced by excited state absorption (ESA). In this context, this thesis describes the synthesis of a new family of versatile near infra-red dyes, namely aza-borondipyrromethene (Aza-Bodipy) featuring several sites of functionalization by electro-donating or electro-withdrawing moieties. These molecules present the typical behavior of optical limiters at telecommunication wavelengths, with a maximal efficiency around 1300 nm. OPL curves were interpreted on the basis of two phenomena: TPA, followed by ESA for an overall 2+1 photons absorption. These two processes have been measured independently and structure-activity relationships have been established in order to rationalize OPL experiments. The charge transfer effect and the spectral overlap between TPA and ESA are therefore the key parameters. For practical use of OPL functions, it is required for the chromophores to be introduced into a solid material, which enables polishing and other post-processing. Therefore, Aza-Bodipy dyes have been successfully incorporated to a solid matrix using the sol-gel technique. For the first time, optical quality materials have been prepared featuring OPL properties in the infra-red, which are better than the ones in solution.

No description available.

Plastskräp har blivit ett global problem på grund av nedskräpning och otillräcklig avfallshantering. Användning av biologiskt nedbrytbart material kan underlätta problemet, även om det inte är en universallösning. Produkter gjorda av biologiskt nedbrytbart material skall ändå till avfallshantering eftersom nedbrytningen kan vara långvarig och variera mycket beroende av omgivningen. Därmed är användningen av biologiskt nedbrytbart material endast berättigat då det är svårt att samla in materialet eller avskilja det från organiskt material. Studiens mål var att undersöka biologiskt nedbrytbara material som kan användas i produkter som fungerar under många olika driftsförhållanden och inte kan återställas efter användning. I den litterära delen av denna studie definieras nedbrytning genom egenskaper och förhållanden som påverkar nedbrytningsprocessen. Nedbrytning av polyestrar och cellulosa och de standardprocessarna som används i nedbrytningsexperimenten betraktades. Standardprocesserna för nedbrytning studerades för att få en klarare inblick i den eftertraktade nedbrytningsgraden och de standardiserade förhållandena för nedbrytningen i olika miljöer. En sammanfattning av olika nedbrytningsexperiment och analysmetoder är också inkluderade för att försäkra att experimenten som utfördes är både giltiga och jämförbara med andra forskningsresultat inom fältet. I detta forskningsprojekt utfördes nedbrytningsexperiment i färskvatten- och hemkompostmiljöer. Målet med projektet var att bedöma ifall materialen kunde brytas ned i ett brett spektrum av miljöer, ifall de var mindre skadliga för naturen än konventionella material som används av dagens industri och för att uppskatta nedbrytningstakten. Nedbrytningstiden var 140 dagar och experimentet utfördes med 10 olika material: betecknade som A-J. Materialen analyserades 8 gånger under nedbrytningsperioden förutom materialen I och J som analyserades en gång efter 140 dagar. Materialen analyserades mekaniskt, strukturellt och termiskt med hjälp av dragprovning, FTIR och DSC. Provernas viktförändring bestämdes också. Nedbrytning observerades visuellt från provernas yta och genom mekaniska prover. Materialen som placerades i hemkomposten visade klara tecken på nedbrytning då färgen hade förändrats och förstärkningsfibrerna hade blivit synliga. Materialen som placerats i hemkompostmiljö visade också klara tecken på tillväxt av mikroorganismer och biomassa som uppstått på ytan av materialen. Sammanfattningsvist, visade materialen B, C och G de mest lovande resultaten med klara tecken på biologisk nedbrytning och de hade en snabbare nedbrytningstakt än de andra materialen som undersöktes. Material D visade klara tecken på biologisk nedbrytning på ytan men dess nedbrytningstakt var uppskattad att vara mycket långsammare. Därmed rekommenderas det att använda material A, B, D och G istället för konventionella icke biologiskt nedbrytbara material. Dessa material har potential att sänka den negativa inverkan och de långsiktiga riskerna av plastskräp för miljön. / Plastic debris has become a global crisis due to littering and misplaced waste management. The use of biodegradable materials can ease the problem, but it is not always the answer. Products made of biodegradable materials are still to be waste managed since biodegradation can be a long process and is highly dependent on the environment conditions. Hence, the use of biodegradable materials is justified only when retrieving the product after use is impossible or prohibitively expensive or separating it from organic matter is difficult. This study was made to investigate biodegradable materials that can be used in products that are operating in broad range of operational conditions and cannot be retrieved back after use in most cases. In the literature part of this study the biodegradation is defined along with properties and conditions that affect the biodegradation process. Biodegradation of polyesters and cellulose, and standards used in the biodegradation experiments were reviewed. Biodegradation standards were studied in order to have a clearer picture of the pursued degree of biodegradation and standardized properties in the biodegradation experiments. Review of different biodegradation tests and analysis methods are included as well to ensure that the experiments performed in this work are valid and comparable with other biodegradation studies.  In this study, the biodegradation experiment was conducted in freshwater and home compost environments. The aim was to determine if the materials were able to biodegrade in wide range of environments, to make sure they are less harmful than the conventional materials used in the industry and to estimate the rate of biodegradation. The duration of the experiments were 140 days with 10 different materials: A – J. The materials were analyzed 8 times during the aging period, except materials I and J, which were analyzed only once after 140 days. The samples were analyzed mechanically, structurally, and thermally using tensile test, FTIR and DSC measurements, respectively. Also, the samples weight changes were analyzed.  The degradation was visually observed from the surfaces of the samples and from mechanical testing in both experimental environments. Home compost environment showed clear signs of biodegradation where reinforcement fibers became visible and changed the color of some of the samples. Also, home compost samples had microorganisms growing on them, and biomass was developing around them. To conclude, material B, C and G had the most promising results with clear signs of biodegradation and had faster estimated biodegradation rate compared with the other studied materials. Material D had signs of biodegradation on the surface as well. However, the biodegradation rate was estimated to be much slower. In conclusion, it is recommended to use the studied materials A, B, D and G instead of the conventional non-biodegradable polymers. These materials have potential to lower the negative impact and long-term risks of plastic debris to the environment.

Thesis (PhD(Agric) (Horticulture))--University of Stellenbosch, 2011. / Includes bibliography. / ENGLISH ABSTRACT: Plums with good taste, aroma and eating quality lead to repeat purchases and sustained demand. Taste includes non-volatile compounds, e.g. sugars and acids, and has been well researched to meet the consumers’ preferences. Plum aroma, however, has not enjoyed the same attention. Limited literature is available on the aroma of Japanese plums and none could be found on the effects of relatively long cold storage on the profiles. The main aim of this study is to investigate the changes in aroma compounds of Japanese plums throughout maturation and ripening and the effects of commercial cold storage regimes. Near infra-red (NIR) spectroscopy was also evaluated as a non-destructive method to determine plum quality parameters aimed at minimising sample variability. In Paper 1, NIR spectroscopy was used to develop prediction models for total soluble solid (TSS), total acidity (TA), sugar-to-acid ratio, firmness and weight in three cultivars (Pioneer, Laetitia and Angeleno) and a multi-cultivar model. Samples were collected for seven consecutive weeks and repeated over two seasons. TSS results showed excellent predictability (R2 = 0.817-0.955; RMSEP= 0.453-0.610 % Brix) but the TA models did not perform well. The sugar-to-acid ratio models had results comparable to that of TSS. Both the firmness and weight models had acceptable results. The models of ‘Pioneer’ and ‘Laetitia’ had a better predictability capacity than the ‘Angeleno’ model. Although the multi-cultivar models outperformed the single cultivar models on R2 values it had higher prediction errors. The robustness of all the TSS, TA and firmness models is high in terms of seasonality, range and cultivar. Papers 2 and 3, the main focus of the study, are concerned with the aroma profile dynamics of Japanese plums. HS-SPME was used in both papers to extract the aroma compounds followed by GC-TOFMS for separation and identification. In Paper 2, the aroma volatile compounds of three cultivars (Pioneer, Laetitia and Angeleno) were determined for a seven week period including samples from three maturity stages (immature, harvest and tree-ripe). A total of 35 compounds were identified of which ten were generic. Each cultivar had five unique compounds resulting in different aroma profiles for each of the maturity stages and distinct separation patterns using discriminant analysis. The study was extended in Paper 3 where the aroma volatile compounds of six cultivars (Pioneer, Sapphire, Laetitia, Songold, Larry Anne and Angeleno) and one plumcot (Flavor King) were determined at three functional stages (commercial harvest, tree-ripe fruit and cold stored fruit). A total of 62 compounds were identified and classified into three groups (‘unique’ (31), ‘generic’ (11) and ‘frequent’ (20)) based on their frequency of occurrence. The aroma profiles of ‘Larry Anne’ and ‘Flavor King’ are the most affected by cold storage conditions and ‘Pioneer’ appears to be the least affected. All the cultivars have significantly different aroma profiles at all three of the functional stages with ‘Sapphire’, ‘Larry Anne’ and ‘Flavor King’ showing the largest differences. ‘Flavor King’, a plumcot, presented a ripe aroma profile that was much diverged from that of the true plums. / AFRIKAANSE OPSOMMING: Pruime met ‘n goeie smaak, aroma en eetkwaliteit lei tot herhaalde verkope en volhoubare aanvraag. Smaak sluit die nie-vlugtige stowwe (suikers en sure) in en is goed nagevors om die verbruikersvoorkeure te bevredig. Pruim aroma het egter nie dieselfde aandag geniet nie. Daar is beperkte literatuur beskikbaar wat handel oor die aroma van Japanese pruime en geen kon gevind word oor die effekte van lang koelopberging op die aromaprofiele nie. Die hoof doel van hierdie studie is om die veranderinge in die aromatiese komponente van Japanese pruime te ondersoek tydens die volwassewording- en rypwordingsprosesse asook die effekte van kommersiele koelopberging. Naby infrarooi (NIR) spektroskopie is ook geevalueer as ‘n nie-destruktiewe manier om pruim kwaliteitsparameters te bepaal met die doel om monstervariasie te beperk. In Artikel 1 is NIR spektroskopie gebruik om voorspellingsmodelle vir totale oplosbare suikers (TOS), totale suur (TS), suiker-tot-suur verhouding, fermheid en gewig te bepaal in drie kultivars (Pioneer, Laetitia en Angeleno) asook ‘n multi-kultivar model. Monsters is vir sewe opeenvolgende weke versamel en herhaal oor twee seisoene. TOS resultate toon uitstekende voorspelbaarheid (R2 = 0.817-0.955; RMSEP= 0.453-0.610 % Brix) maar TS modelle het egter nie so goed gevaar nie. Die suiker-tot-suur verhoudingsmodelle se resultate was vergelykbaar met die van TOS. Beide die fermheid- en gewigsmodelle het aanvaarbare resultate opgelewer. Die modelle vir ‘Pioneer’ en ‘Laetitia’ het ‘n beter voorspelbaarheidskapasiteit getoon as die van ‘Angeleno’. Alhoewel die multi-kultivar model beter presteer het as die enkel kultivar modelle op die R2-waardes was daar meer voorspellingsfoute. Hoe robuustheid is gevind i.t.v. seisoene, datagrense en kultivar vir al die TOS, TA en fermheidsmodelle. Artikels 2 en 3, die fokuspunt van die studie, handel oor die dinamika van die aromaprofiel van Japanese pruime. HS-SPME is in beide artikels gebruik on die aromatiese verbindings te ekstraeer gevolg deur GCTOFMS vir skeiding en identifikasie. In Artikel 2 is die aromatiese stowwe van drie kultivars (Pioneer, Laetitia en Angeleno) bepaal vir sewe opeenvolgende weke en sluit monsters van drie volwassenheidsstadiums in (onvolwasse, oes en boom-rypgemaakte pruime). ‘n Totaal van 35 verbindings is geidentifiseer waarvan tien as generies beskou kan word. Elke kultivar het vyf unieke komponente gehad en het gelei tot verskillende aromaprofiele vir elk van die volwassenheidsstadiums en diverse skeidingspatrone tydens die gebruik van diskriminant analise. Die studie is uitgebrei in Artikel 3 waartydens die aromatiese vlugtige stowwe van ses kultivars (Pioneer, Sapphire, Laetitia, Songold, Larry Anne en Angeleno) en een plumcot (Flavor King) bepaal is tydens drie funksionele stadiums (oes, boom-rypgemaak en koelopgebergde pruime). ‘n Totaal van 62 verbindings is geidentifiseer en in drie groepe geklassifiseer (‘uniek’ (31), ‘generies’(11) en ‘gereeld’ (20)) gebaseer op voorkomsfrekwensie. Die aromaprofiele van ‘Larry Anne’ en ‘Flavor King’ is die meeste deur die koelopberging geaffekteer en ‘Pioneer’ die minste. Al die kultivars het kenmerkend verskil t.o.v. hul aromaprofiele in al drie die funksionele groepe en ‘Sapphire’, ‘Larry Anne’ en ‘Flavor King’ het die grootste verskille getoon. ‘Flavor King’, die plumcot, het ook ‘n ryp aromaprofiel gehad wat baie van die van die egte pruime verskil het.

La conception de récepteurs artificiels pour la reconnaissance moléculaire est un domaine très développé de la chimie supramoléculaire. Ce manuscript renferme les premières études réalisées sur une nouvelle classe de récepteurs supramoléculaires: les Discopus. Le Discopus offre un potentiel d’interactions via un cœur polyaromatique triphénylène (interactions p, effet hydrophobe) et une périphérie fonctionnelle flexible (Liaisons hydrogènes, interactions ioniques, hydrosolubilité) qui peut agir en coopérativité. Ces systèmes de reconnaissance peu préorganisés ont montré leur capacité de reconnaissance et leur aptitude à être sélectivif. Plusieurs familles de ces récepteurs ont été élaborées. Une famille de récepteurs phosphorylés reconnaît sélectivement les dérivés catéchol en milieu organique par liaisons Hydrogène et interactions p. Une seconde famille de Discopus carboxylés ont permis la reconnaissance, en milieu aqueux tamponné, de l’acétylcholine et les catécholamines par interactions ioniques et désolvatation de cibles. La préparation de cages à base triphénylène est en cours de réalisation afin d’amplifier le phénomène de reconnaissance. / The conception of artificial receptors is an intense field of research. This manuscript contains the first studies of a new class of receptors named discopus. The discopus can interact through a triphenylene core (p interactions, hydrophobic effect) and their flexible functional arms (hydrogen bonds, ionic interaction) which may cooperatively interact. These binding systems are just a little bit pre-organized and possess selective recognition properties. Several families of receptors have been prepared. Phosphorylated receptors showed a selective for catechol derivatives in organic media, through Hydrogen bond and p- interactions. In buffered media, carboxylated discopus allowed the recognition of acetylcholine and catecholamines through ionic interactions and desolvatation of the targets. The preparation of cages, based on triphenylene moieties, is in progress to increase the phenomenon of recognition.