Total soluble solids (TSS) is a reliable indicator of melon eating quality, with a minimum standard of 10% recommended. The state of Australian melon production with respect to this quality criterion was considered within seasons, between growing districts and over seasons. It was concluded that improvement in agronomic practice and varietal selection is required to produce sweeter melons. The scientific literature addressing melon physiology and agronomy was summarised, as a background to the work that is required to improve melon production practices in Australia. The effect of source sink manipulation was assessed for commercially grown and glasshouse grown melon plants. The timing of fruit thinning, pollination scheduling, the application of a growth inhibitor and source biomass removal were assessed in relation to fruit growth and sugar accumulation. Results are interpreted against a model in which fruit rapidly increase in weight until about two weeks before harvest, with sugar accumulation continuing as fruit growth ceases. Thus treatment response is very dependant on timing of application. For example, fruit thinning at 25 days before harvest resulted in further fruit set and increased fruit weight but did not impact on fruit TSS (at 9.8%, control 9.3%), while thinning at 5 days before harvest resulted in a significant (Pless than 0.05) increase in fruit TSS (to 10.8%, control 9.3%) and no increase in fruit weight or number. A cost/ benefit analysis is presented, allowing an estimation of the increase in sale price required to sustain the implementation of fruit thinning. The effect of irrigation scheduling was also considered with respect to increasing melon yield and quality. To date, recommended practice has been to cause an irrigation deficit close to fruit harvest, with the intent of 'drying out' or 'stressing' the plant, to 'bring on' maturity and increase sugar accumulation. Irrigation trials showed that keeping plants stress-free close to harvest and during harvest, facilitated the production of sweeter fruit. The maintenance of a TSS grade standard using either batch based (destructive) sampling or (non-invasive) grading of individual fruit is discussed. On-line grading of individual fruit is possible using near infrared spectroscopy (NIR), but the applicability of the technique to melons has received little published attention. Tissue sampling strategy was optimised, in relation to the optical geometry used (in commercial operation in Australia), both in terms of the diameter and depth of sampled tissue. NIR calibration model performance was superior when based on the TSS of outer, rather than inner mesocarp tissue. However the linear relationship between outer and middle tissue TSS was strong (r2 = 0.8) in immature fruit, though less related in maturing fruit (r2 = 0.5). The effect of fruit storage (maturation/senescence) on calibration model performance was assessed. There was a negligible effect of fruit cold storage on calibration performance. Currently, the agronomist lacks a cost-effective tool to rapidly assess fruit TSS in the field. Design parameters for such a tool were established, and several optical front ends compared for rapid, though invasive, analysis. Further, for visualisation of the spatial distribution of tissue TSS within a melon fruit, a two-dimensional, or hyper-spectral NIR imaging system based on a low cost 8-bit charge coupled device (CCD) camera and filter arrangement, was designed and characterised.

Chapter 1.<br />1-Ethynyl-2-phenyltetramethyldisilanes HCºCSiMe2SiMe2C6H4-p-X [X = NMe2(1.1), Me (1.2), H (1.3), Br (1.4), CF3 (1.5)] are accessible from ClSiMe2SiMe2Cl, BrMgC6H4X and HCºCMgBr in a two step Grignard reaction. The crystal structure of 1.1 as determined by single crystal X-ray crystallography exhibits a nearly planar PhNMe2 moiety and an unusual gauche array of the phenyl and the acetylene group with respect to rotation around the Si-Si-bond. Full geometry optimization (B3LYP/6- 31+G**) of the gas phase structures of 1.1 and 1.3 affords minima for the gauche and the trans rotational isomers, both being very close in energy with a rotational barrier of only 3 – 5 kJ/mol. Experimental and calculated (time-dependent DFT B3LYP/TZVP) UV absorption data of 1.1 – 1.5 show pronounced electronic interactions of the HCºC- and the C6H4X p-systems with the central Si-Si bond.<br /><br />Chapter 2.<br />A family of [( 5-Cp*)Ru( 6-arene)]+ (Cp* = C5Me5) sandwich complexes of 1- and 1,4-substituted phenyl and naphthyl systems are described along with the regioselectivities of the reactions under various conditions. Finally, the (h 5-Cp*) Ru+ arenophile was found to act as a gate to the flow of electrons between para-substituted termini. When it is complexed onto the phenyl or A naphthyl ring, the gate is closed. On the contrary, when it is complexed onto the B naphthyl ring, the gate is open.<br /><br />Chapter 3.<br />Regioselective complexation reactions of the organoiron acetylide derivatives (h 2- dppe)(h 5-Cp*)Fe-C C-Ar (Ar = phenyl, 1-naphthyl; dppe = 1,2- bis(diphenylphosphino)ethane) with [(h 5-Cp*Ru(CH3CN)3][PF6] to afford heterobimetallic complexes formulated as [(h 2-dppe)(h 5-Cp*)Fe-C C-{(h 6-Ar)Ru(h 5- Cp*)}][PF6], were achieved. In the case of the FeII-RuII 1-naphthyl derivative, the (h 5-Cp*)Ru+ arenophile was complexed both onto the substituted ring and free rings of the acetylide 1-naphthyl linker. The first redox-driven h 6-h 6 inter-ring haptotropic migration of the (h 5-Cp*)Ru+ moeity was shown to occur. Crystal structures of all of the seven new iron acetylenes were resolved, including both haptotropomers of the naphthyl compound.<br /><br />Chapter 4.<br />The diorganoiron [{(h2-dpppe)(h5-Cp*)Fe-CC-}2(1,4-naphthyl)] (4.12) was synthesized in good yield in two steps via the vinylidene, and oxidation led to the mixed valence (MV) and iron(III)-iron(III) species in good to excellent yields. This exhaustive empirical study on the family of complexes 4.12[PF6]n (n = 0,1,2) includes a crystal structure for the case in which n = 2. This work clearly establishes good electronic and magnetic communication between the iron centers across the bis(ethynyl)naphthalene bridge. All empirical measurements of these naphthyl compounds reveal that their properties fall between those of known phenyl and anthracenyl derivatives. In some cases, the naphthyl derivative behaves as an average of the phenyl and anthracenyl complexes. For example, the comproportionation constant of the naphthyl species falls at the midpoint between those for the phenyl and anthracenyl compounds. The same is true for the UV absorption maxima in all three oxidation states (Fe[II]- Fe[II], MV, and Fe[III]- Fe[III]). The large electronic (2043 cm-1) and magnetic (-526 cm-1) coupling constants were determined via NIR spectroscopy and SQUID magnetometry, respectively. As for the heterotrinuclear species, the iron(II) acetylene, 4.14B[PF6] [{Cp*(dppe)Fe-C C}2-(h 6 – [1,4-napthyl])RuCp*](PF6), [Cp* = h 5 - C5Me5; Fe = FeII] was prepared in high yields with an adapted, regioselective synthesis via the trinuclear vinylidene. Complete characterization, including a crystal structure, of this sandwich complex reveals that the arenophile perturbs the organoiron ligand more in the bis(iron) than in the previously reported mono(iron) case.

Cancer is a leading cause of death that affects millions of people across the globe each year. Photodynamic therapy (PDT) is a relatively new treatment approach for cancer in which anticancer drugs are activated by light at an appropriate wavelength to generate highly cytotoxic reactive oxygen species (ROS) and achieve tumor destruction. Compared with conventional chemo- and radiotherapy, PDT can be performed with minimal invasiveness, local targeting and reduced side effects. However, most of the currently available PDT drugs mainly absorb in the visible part of the spectrum, where light penetration depth into human tissues is very limited. Therefore, increasing the treatment depth of PDT has been considered to be an important approach to improve the effectiveness of PDT for treating larger and thicker tumor masses. In this thesis, we present our investigation into the potential of two-photon activated PDT (2-γ PDT), combination therapy of PDT and chemotherapy, and bioluminescence-activated PDT as a means to increase the treatment depth of this modality. In 2-γ PDT, the photosensitizing agents are activated through simultaneous absorption of two photons. This approach allows the use of near-infrared (NIR) light that can penetrate deeper into tissues and thus, has the potential of treating deep-seated tumors and reducing side effects, while the non-linear nature of two-photon excitation (TPE) may improve tumor targeting. We have evaluated the PDT efficacy of a second-generation photosensitizer derived from chlorophyll a, pyropheophorbide a methyl ester (MPPa), through both one- and two-photon activation. We observed that MPPa had high one-photon (1-γ PDT efficacy against both cisplatin-sensitive human cervical (HeLa) and cisplatin-resistant human lung (A549) and ovarian (NIH:OVCAR-3) cancer cells when activated by femtosecond (fs) laser pulses at 674 nm. At a low light dose of 0.06 J cm-2, the MPPa concentration required to produce a 50% cell killing effect (IC50) was determined to be 5.3 ± 0.3, 3.4 ± 0.3 and 3.6 ± 0.4 μM in HeLa, A549 and NIH:OVCAR-3 cells, respectively. More significantly, we also found that MPPa could be effectively activated at the optimal tissue-penetrating wavelength of 800 nm through TPE. At a light dose of 886 J cm-2, where no measurable photodamage was observed in the absence of MPPa, the IC50 values were measured to be 4.1 ± 0.3, 9.6 ± 1.0 and 1.6 ± 0.3 μM in HeLa, A549 and NIH:OVCAR-3 cells, respectively. We obtained corresponding LD50 (the light dose required to produce a 50% killing effect) values of 576 ± 13, 478 ± 18 and 360 ± 16 J cm-2 for 10 μM MPPa, which were approximately 3-5 times lower than the published 2-γ LD50 of Visudyne® and 20-30 times lower than that of Photofrin®. These results indicate that MPPa may serve as a photosensitizer for both 1- and 2-γ activated PDT treatment of difficult-to-treat tumors by conventional therapies. Indocyanine green (ICG), a dye having an absorption maximum near 800 nm, has been considered to be a potential NIR PDT agent. However, the PDT efficacy of ICG has been found to be very limited probably due to the low yield of cytotoxic ROS. In the present work, we have evaluated the combination effects of ICG-mediated PDT with conventional chemotherapy mediated by two types of chemotherapeutic drugs, namely the type II topoisomerase (TOPII) poisons etoposide (VP-16)/teniposide (VM-26) and the platinum-based drugs cisplatin (CDDP)/oxaliplatin (OXP). Synergistic enhancement of cytotoxicity and increased yields of DNA double strand breaks (DSBs) were observed in HeLa, A549 and NIH:OVCAR-3 cancer cells treated with the combination of ICG-PDT and VP-16. The presence of VP-16 during the laser irradiation process was found to be critical for producing a synergistic effect. An electron-transfer-based mechanism, in which ICG could increase the yield of highly cytotoxic VP-16 metabolites, was proposed for the observed synergistic effects, although direct spectroscopic detection of the reaction products was found to be very challenging. Moreover, we observed a much lower degree of synergy in the human normal fibroblast GM05757 cells than that in the three cancer cell lines investigated. Synergistic effects were also observed in A549 cells treated with the combination of ICG-PDT and VM-26 (i.e. an analog of VP-16). Furthermore, the combination of low-dose CDDP/OXP and ICG-PDT was demonstrated to produce an additive or synergistic effect in selected cancer cell lines. These preliminary results suggest that the combination of ICG-PDT with VP-16/VM-26 or CDDP/OXP chemotherapy may offer the advantages of enhancing the therapeutic effectiveness of ICG-PDT and lowering the side effects associated with the chemotherapeutic drugs. Bioluminescence, the generation of light in living organisms through chemical reactions, has been explored as an internal light source for PDT in recent years. This approach, in principle, does not suffer from the limited tissue penetration depth of light. In the present project, we have evaluated the effectiveness of luminol bioluminescence in activating the porphyrin photosensitizers meso-tetra(4-sulfonatophenyl)porphine dihydrochloride (TPPS4) and Fe(III) meso-tetra(4-sulfonatophenyl)porphine chloride (FeTPPS). The combination treatment induced significant killing of HeLa cells, while additive effects were observed in two normal human fibroblast cell lines (GM05757 and MRC-5). Our observations indicate that bioluminescence of luminol may generate sufficient light for intracellular activation of PDT sensitizers. Furthermore, the combination treatment may have intrinsic selectivity towards cancerous tissues. In summary, we have demonstrated effective killing of cancer cells by MPPa-mediated 1- and 2-γ PDT, combination of ICG-PDT and VP-16/VM-26 or CDDP/OXP chemotherapy, and bioluminescence of luminol activated PDT mediated by TPPS4/FeTPPS. These positive preliminary results indicate that all these three approaches have the potential of increasing the treatment depth of PDT and facilitating the development of more effective PDT treatment strategies.

Este trabalho de pesquisa descreve três estudos de utilização de métodos quimiométricos para a classificação e caracterização de óleos comestíveis vegetais e seus parâmetros de qualidade através das técnicas de espectrometria de absorção molecular no infravermelho médio com transformada de Fourier e de espectrometria no infravermelho próximo, e o monitoramento da qualidade e estabilidade oxidativa do iogurte usando espectrometria de fluorescência molecular. O primeiro e segundo estudos visam à classificação e caracterização de parâmetros de qualidade de óleos comestíveis vegetais utilizando espectrometria no infravermelho médio com transformada de Fourier (FT-MIR) e no infravermelho próximo (NIR). O algoritmo de Kennard-Stone foi usado para a seleção do conjunto de validação após análise de componentes principais (PCA). A discriminação entre os óleos de canola, girassol, milho e soja foi investigada usando SVM-DA, SIMCA e PLS-DA. A predição dos parâmetros de qualidade, índice de refração e densidade relativa dos óleos, foi investigada usando os métodos de calibração multivariada dos mínimos quadrados parciais (PLS), iPLS e SVM para os dados de FT-MIR e NIR. Vários tipos de pré-processamentos, primeira derivada, correção do sinal multiplicativo (MSC), dados centrados na média, correção do sinal ortogonal (OSC) e variação normal padrão (SNV) foram utilizados, usando a raiz quadrada do erro médio quadrático de validação cruzada (RMSECV) e de predição (RMSEP) como parâmetros de avaliação. A metodologia desenvolvida para determinação de índice de refração e densidade relativa e classificação dos óleos vegetais é rápida e direta. O terceiro estudo visa à avaliação da estabilidade oxidativa e qualidade do iogurte armazenado a 4C submetido à luz direta e mantido no escuro, usando a análise dos fatores paralelos (PARAFAC) na luminescência exibida por três fluoróforos presentes no iogurte, onde pelo menos um deles está fortemente relacionado com as condições de armazenamento. O sinal fluorescente foi identificado pelo espectro de emissão e excitação das substâncias fluorescentes puras, que foram sugeridas serem vitamina A, triptofano e riboflavina. Modelos de regressão baseados nos escores do PARAFAC para a riboflavina foram desenvolvidos usando os escores obtidos no primeiro dia como variável dependente e os escores obtidos durante o armazenamento como variável independente. Foi visível o decaimento da curva analítica com o decurso do tempo da experimentação. Portanto, o teor de riboflavina pode ser considerado um bom indicador para a estabilidade do iogurte. Assim, é possível concluir que a espectroscopia de fluorescência combinada com métodos quimiométricos é um método rápido para monitorar a estabilidade oxidativa e a qualidade do iogurte / This research work describes three studies of chemometric methods employed for the classification and characterization of edible oils and its quality parameters through Fourier Transform mid infrared spectroscopy and near infrared spectroscopy, and for the monitoring the oxidative stability and quality of yogurt using fluorescence spectroscopy . The first and second studies aimed the classification and characterization of edible oil and its quality parameters using Fourier Transform mid infrared spectroscopy (FT-MIR) and near infrared spectroscopy (NIR) measurements, respectively. Kennard-Stone algorithm was used for selecting the training set, after a principal component analysis (PCA) was applied. The discrimination of canola oils from sunflower, corn and soybean was investigated using SVM-DA, SIMCA and PLS-DA. The quality parameters refraction index and relative density of edible oil was investigated using partial least squares (PLS), iPLS, LS- SVM multivariate calibration of FT-MIR and NIR data were evaluated. Several preprocessing alternatives (first derivative, multiplicative scatter correction, mean centering, orthogonal signal correction and standard normal variate) were investigated by using the root mean square error of validation cross validation (RMSECV) and prediction (RMSEP), as control parameters. In fact, the methodology developed is proposed for direct relative density and refraction index in edible oils and their classification, requiring a few minutes per sample without any previous treatment. The third study aimed to evaluate the oxidative stability and quality of yogurt stored at 40C with light or dark using the combined parallel factor (PARAFAC) analysis and fluorescence spectroscopy. PARAFAC analysis of the fluorescence landscapes exhibited three fluorophores present in the yogurt, where, at least one of them was strongly related to the storage conditions. The fluorescence signal was resolved into excitation and emission profiles of the pure fluorescent compounds, which are suggested to be vitamin A, tryptophan and riboflavin. Regression model based on PARAFAC scores for riboflavin were built using the scores obtained in the first day as dependent variable and the scores obtained during the storage as independent variable. It was clear demonstrated that the slope of the analytical curve has become smaller throughout the experiment. Therefore, riboflavin level could be considered a good indicator for the yogurt stability. Thus, it is concluded that fluorescence spectroscopy in combination with chemometrics has a potential as a fast method for monitoring the oxidative stability and quality of yogurt

Este trabalho de pesquisa descreve três estudos de utilização de métodos quimiométricos para a classificação e caracterização de óleos comestíveis vegetais e seus parâmetros de qualidade através das técnicas de espectrometria de absorção molecular no infravermelho médio com transformada de Fourier e de espectrometria no infravermelho próximo, e o monitoramento da qualidade e estabilidade oxidativa do iogurte usando espectrometria de fluorescência molecular. O primeiro e segundo estudos visam à classificação e caracterização de parâmetros de qualidade de óleos comestíveis vegetais utilizando espectrometria no infravermelho médio com transformada de Fourier (FT-MIR) e no infravermelho próximo (NIR). O algoritmo de Kennard-Stone foi usado para a seleção do conjunto de validação após análise de componentes principais (PCA). A discriminação entre os óleos de canola, girassol, milho e soja foi investigada usando SVM-DA, SIMCA e PLS-DA. A predição dos parâmetros de qualidade, índice de refração e densidade relativa dos óleos, foi investigada usando os métodos de calibração multivariada dos mínimos quadrados parciais (PLS), iPLS e SVM para os dados de FT-MIR e NIR. Vários tipos de pré-processamentos, primeira derivada, correção do sinal multiplicativo (MSC), dados centrados na média, correção do sinal ortogonal (OSC) e variação normal padrão (SNV) foram utilizados, usando a raiz quadrada do erro médio quadrático de validação cruzada (RMSECV) e de predição (RMSEP) como parâmetros de avaliação. A metodologia desenvolvida para determinação de índice de refração e densidade relativa e classificação dos óleos vegetais é rápida e direta. O terceiro estudo visa à avaliação da estabilidade oxidativa e qualidade do iogurte armazenado a 4C submetido à luz direta e mantido no escuro, usando a análise dos fatores paralelos (PARAFAC) na luminescência exibida por três fluoróforos presentes no iogurte, onde pelo menos um deles está fortemente relacionado com as condições de armazenamento. O sinal fluorescente foi identificado pelo espectro de emissão e excitação das substâncias fluorescentes puras, que foram sugeridas serem vitamina A, triptofano e riboflavina. Modelos de regressão baseados nos escores do PARAFAC para a riboflavina foram desenvolvidos usando os escores obtidos no primeiro dia como variável dependente e os escores obtidos durante o armazenamento como variável independente. Foi visível o decaimento da curva analítica com o decurso do tempo da experimentação. Portanto, o teor de riboflavina pode ser considerado um bom indicador para a estabilidade do iogurte. Assim, é possível concluir que a espectroscopia de fluorescência combinada com métodos quimiométricos é um método rápido para monitorar a estabilidade oxidativa e a qualidade do iogurte / This research work describes three studies of chemometric methods employed for the classification and characterization of edible oils and its quality parameters through Fourier Transform mid infrared spectroscopy and near infrared spectroscopy, and for the monitoring the oxidative stability and quality of yogurt using fluorescence spectroscopy . The first and second studies aimed the classification and characterization of edible oil and its quality parameters using Fourier Transform mid infrared spectroscopy (FT-MIR) and near infrared spectroscopy (NIR) measurements, respectively. Kennard-Stone algorithm was used for selecting the training set, after a principal component analysis (PCA) was applied. The discrimination of canola oils from sunflower, corn and soybean was investigated using SVM-DA, SIMCA and PLS-DA. The quality parameters refraction index and relative density of edible oil was investigated using partial least squares (PLS), iPLS, LS- SVM multivariate calibration of FT-MIR and NIR data were evaluated. Several preprocessing alternatives (first derivative, multiplicative scatter correction, mean centering, orthogonal signal correction and standard normal variate) were investigated by using the root mean square error of validation cross validation (RMSECV) and prediction (RMSEP), as control parameters. In fact, the methodology developed is proposed for direct relative density and refraction index in edible oils and their classification, requiring a few minutes per sample without any previous treatment. The third study aimed to evaluate the oxidative stability and quality of yogurt stored at 40C with light or dark using the combined parallel factor (PARAFAC) analysis and fluorescence spectroscopy. PARAFAC analysis of the fluorescence landscapes exhibited three fluorophores present in the yogurt, where, at least one of them was strongly related to the storage conditions. The fluorescence signal was resolved into excitation and emission profiles of the pure fluorescent compounds, which are suggested to be vitamin A, tryptophan and riboflavin. Regression model based on PARAFAC scores for riboflavin were built using the scores obtained in the first day as dependent variable and the scores obtained during the storage as independent variable. It was clear demonstrated that the slope of the analytical curve has become smaller throughout the experiment. Therefore, riboflavin level could be considered a good indicator for the yogurt stability. Thus, it is concluded that fluorescence spectroscopy in combination with chemometrics has a potential as a fast method for monitoring the oxidative stability and quality of yogurt

O grande desafio da Implantodontia é alcançar resultados a longo prazo com maior preservação dos tecidos ósseos, resposta adequada dos tecidos conjuntivos e manutenção da estabilidade secundária adequada para a retenção de próteses. Estes fatores evitam a perda indesejável tanto do tratamento reabilitador quanto dos tecidos ósseos de suporte. A região extraoral apresenta menores espessuras ósseas em comparação às regiões de maxila e mandíbula, especialmente no osso temporal. Portanto, os seguintes aspectos foram investigados: (i) Análise pelo Método dos Elementos Finitos (FEA) de 16 modelos virtuais, com aplicação de forças estáticas de tensão e compressão nos pontos médios entre os implantes. Três implantes maxilofaciais extraorais foram posicionados no osso temporal, onde um deles foi posicionado sobre o processo mastóide. Este estudo foi totalmente realizado em ambiente computacional. Foram empregados dois tipos de conexões protéticas e intermediários retos de conicidades 20º e 45º, posicionados virtualmente no modelo de osso temporal, com paralelismo entre eles. Foi desenhada uma barra virtual para retenção protética do tipo barra-clipe da prótese auricular. Foram consideradas as melhores configurações aquelas apresentando distribuição uniforme e branda das tensões de von Mises sobre o tecido ósseo adjacente aos implantes. (ii) Confecção de corpos de prova com graus variáveis de pigmentação para (a) melhorar a reprodutibilidade da coloração (b) entender e reduzir o processo de descoloração para melhorar a longevidade das próteses. Um elastômero maxilofacial tipo A foi pigmentado intrinsecamente de acordo com os seis tons da Escala de Fitzpatrick. Uma técnica de pigmentação foi desenvolvida a partir dos resultados obtidos a partir de uma Escala de Fitzpatrick impressa em papel e dos pigmentos intrínsecos de cores primárias. Este dimetil-metilvinil-siloxano reforçado por platina A 223-30 (Factor II, Inc., Lakeside, AZ, USA) apresenta dureza \"Shore-A\" 30. As amostras foram expostas a fotoenvelhecimento acelerado, e sua degradação mapeada com Espectroscopia UV/Vis/NIR. Concluiu-se que: (i) Os implantes com conexão cone Morse plataforma 3.7 tem melhor comportamento biomecânico com intermediários de 45o e altura de 2mm. Sugere-se planejamento cirúrgico visando a instalação a 3 horas para o temporal esquerdo e 9 horas para o temporal direito, mais 6 horas (mastóide). Implantes com conexão cone Morse plataforma 4.0 apresentaram comportamento biomecânico desejável com intermediários de 20o e alturas de 2mm or 4mm. Para implantes com conexão cone Morse plataforma 4.0, sugere-se a instalação a 6-9-12 horas para o temporal direito, e 12-6-3 para o esquerdo, visando comportamento biomecânico adequado. Sugere-se que os implantes extraorais Brånemark hexágono externo com plataforma 4.1 regular ou expandida sejam preferencialmente empregados com intermediários de 20o. (ii) O SiO2 5% pode ser adicionado à preparação do silicone para retardar o desbotamento da prótese maxilofacial. O TiO2 traz mudanças visuais significativas e pode ser considerado como opacificador. / Major challenges in Implantology include: achieving longevity of implants, bone tissue preservation, connective tissue suitable answer and maintenance of secondary stability in order to retain prosthesis. These factors avoid the undesirable loss of both rehabilitation treatment and supporting bone tissues. The extraoral region has less bone depth compared to the maxilla and mandible regions, especially for the temporal bone. Therefore, the following aspects were investigated: (i) Finite Elements Analysis (FEA) of 16 virtual models, with static application of tension and compression forces in medium points between implants. Three extraoral maxillofacial implants were placed on the temporal bone, which one of them was placed on the mastoid process. This study was made entirely in a computational environment. Two prosthetic connection types and straight Intermediários were employed, with conicities of 20º and 45º, placed virtually on the temporal bone model, mutually parallel. A virtual bar for bar-clip prosthetic retention of auricular prosthesis was designed. The best configurations were considered to be the ones presenting uniform and mild von Mises tension distribution over the bone tissue around the implants. (ii) Generation of samples with varying degree of pigmentation to (a) improve the reproducibility of the colouration (b) understand and minimise the discolouration process to improve prosthetics longevity. A maxillofacial elastomer type A was intrinsically pigmented according to the six tones of the Fitzpatrick Scale. A pigmentation technique was developed from spectroscopy outcomes of paper printed Fitzpatrick Scale and the primary colors pigments. This platinum reinforced dimethyl methylvinyl siloxane A 223-30 (Factor II, Inc., Lakeside, AZ, USA) presents \"Shore-A\" hardness 30. The samples were exposed to accelerated photo aging, and their degradation mapped with UV/Vis/NIR Spectroscopy. The effects of exclusion of oxygen and inclusion of nanoparticle fillers during prosthetic formulation were investigated. It was concluded that: (i) Morse taper prosthetic connection 3.7 platform implants, should be employed with 45o abutments with 2mm height. The surgical planning shall be for placement 3 hours for the left temporal bone and 9 hours for the right, and in 6 hours (mastoid). Morse taper prosthetic connection 4.0 platform implants behaved biomechanically desirably with 20o abutments in 2mm or 4mm heights. For the Morse taper connection 4.0 platform implants, their placement shall be in 6-9-12 hours, for the right temporal, and 12-3-6, for the left temporal, in order to achieve proper biomechanical behaviour. The Brånemark extraoral external hexagon implant, with 4.1 platform (normal or expanded) should preferrably be used with 20o abutments. (ii) The SiO2 5% may be added to the silicone preparation in order to slow maxillofacial prosthesis colour fading. The TiO2 brings visually significant changes and may be considered as an opacifier.

The present thesis deals with different aspects of the chemistry of oxovanadium(IV) complexes, their interaction with double stranded DNA, photo-induced DNA cleavage, photo-enhanced cytotoxicity in visible light and red light and localisation and cellular uptake to understand the mechanism of cell death. Chapter I presents a general introduction on potential of transition metal complexes as photochemotherapeutic agents. A brief introduction about Photodynamic Therapy (PDT) as a new alternative to chemotherapy for treating cancer has been made. Various modes of interaction of small molecules with duplex DNA are described. Recent reports on metal-based photocytotoxicity, photo-induced DNA cleavage activity and cellular localization are presented in detail. Objective of the present investigation is also dealt in this Chapter. Chapter II of the thesis deals with the synthesis, characterization, DNA binding and photo-induced DNA cleavage activity of ternary oxovanadium(IV) complexes of ONO-donor 2-(2-hydroxybenzylideneamino)phenol (salamp) and phenanthroline bases to explore the photo-induced DNA cleavage activity in UV-A light of 365 nm and photocytotoxicity in visible light. Chapter III deals with the photo-induced DNA cleavage and photocytotoxicity of ternary oxovanadium(IV) complexes containing ONN-donor N-2-pyridylmethylidine-2-hydroxyphenylamine (Hpyamp) Schiff bases and phenanthroline bases. The objective of this work is to investigate the photo-induced DNA cleavage activity in near-IR light. Photocytotoxicity and cell cycle arrest have been studied in HeLa cancer cells. Chapter IV deals serendipitous discovery of planar triazinuim cationic species by vanadyl-assisted novel ring cyclization reaction. The compounds are synthesised, characterized and their DNA binding and anaerobic photoinduced DNA cleavage activity are presented. The importance of the thiazole moiety in the triazinuim species in cellular uptake has been investigated. Photocytotoxicity, localization and cell death mechanism have been studied in HeLa and MCF-7 cells. Chapter V describes the synthesis, characterization, DNA binding, photo-induced DNA cleavage activity and photocytotoxicity of oxovanadium(IV) complexes containing 2-(1H-benzimidazol-2-yl)-N-(pyridin-2-ylmethylene)ethaneamine (Hpy-aebmz) and curcumin as photosensitizer. The effect of conjugating naphthalimide on Hpy-aebmz on photoinduced DNA cleavage and photocytotoxicity has been studied. Cellular uptake, localization and mechanism of cell death induced by complexes have been investigated. Chapter VI presents ternary oxovanadium(IV) complexes having, 2-((1H-benzimidazol-2-yl)methylimino-methyl)phenol (Hsal-ambmz) and phenanthroline bases. The complexes were synthesized, characterized and their DNA binding property studied. Photo-induced DNA cleavage activity and photocytotoxicity in red light has been discussed. Anthracene has been conjugated to a tridentate ligand to investigate cellular uptake, localization and cell death mechanism. Mitochondria targeting property of the complexes having dipeptide has been studied and compared with clinically used drug Photofrin®. The references have been compiled at the end of each chapter and indicated as superscript numbers in the text. The complexes presented in this thesis are represented by bold-faced numbers. Crystallographic data of the complexes, characterized structurally by single crystal X-ray crystallography, are given in CIF format in the enclosed CD (Appendix-I). Due acknowledgements have been made wherever the work described is based on the findings of other investigators. Any unintentional omission that might have happened due to oversight or mistake is regretted.

Die vorliegende Dissertation beschäftigt sich mit dem elektrochemischen Verhalten verschiedener Ferrocenyl-substituierter Thiophene. Dabei wird sich zunächst mit dem elektrochemischen Verhalten der Serie der Ferrocenylthiophene beschäftigt, die Anzahl der Ferrocenyleinheiten variiert von n = 1 – 4. Die Abhängigkeit der elektronischen Eigenschaften von numerischen und konstitutionellen Veränderungen der redox-aktiven Gruppen wird evaluiert. Daraus resultierend wird sich einer eingehenderen Untersuchung und Modifikation des 2,5-Diferrocenylthiophen-Motivs zugewandt. Diese Modifikationen werden im Kontext möglicher Ladungstransferprozesse zwischen den Ferrocenyleinheiten in den verschiedenen Redoxzuständen und unter Beeinflussung durch den Thiophen-Brückenliganden diskutiert. Es folgen des Weiteren Ausführungen zu Substitutionen an den Ferrocenylen (Einführung elektronen-ziehender Funktionalitäten) sowie der Vergleich zwischen einer Thiophen- und der Ethylendioxythiophen-Brückeneinheit. Anschließend wird sich mit der elektronischen Variation des Brückenliganden durch die Einführung von N-haltigen Substituenten befasst. In den abschließenden Kapiteln wird der Einfluss zusätzlicher σ- (Fischercarben-Komplexe) oder π-gebundener ([Ru(η5-C5H5)]+/[Ru(η5-C5Me5)]+) Übergangsmetallkomplexfragmente auf Ladungstransferwechselwirkungen im 2,5-Diferrocenylthiophen in verschiedenen Redoxzuständen beleuchtet.

<p>To apply Industry 4.0 technologies and accelerate the modernization of continuous pharmaceutical manufacturing, digital twin (DT) and advanced process control (APC) strategies are indispensable. The DT serves as a virtual representation that mirrors the behavior of the physical process system, enabling real-time monitoring and predictive capabilities. Consequently, this facilitates the feasibility of real-time release testing (RTRT) and enhances drug product development and manufacturing efficiency by reducing the need for extensive sampling and testing. Moreover, APC strategies are required to address variations in raw material properties and process uncertainties while ensuring that desired critical quality attributes (CQAs) of in-process materials and final products are maintained. When deviations from quality targets are detected, APC must provide optimal real-time corrective actions, offering better control performance than the traditional open loop-control method. The progress in DT and APC is beneficial in shifting from the paradigm of Quality-by-Test (QbT) to that of Quality-by-Design (QbD) and Quality-by-Control (QbC), which emphasize the importance of process knowledge and real-time information to ensure product quality.</p> <p><br></p> <p>This study focuses on four key elements and their applications in a continuous dry granulation tableting process, including feeding, blending, roll compaction, ribbon milling and tableting unit operations. Firstly, the necessity of a digital infrastructure for data collection and integration is emphasized. An ISA-95-based hierarchical automation framework is implemented for continuous pharmaceutical manufacturing, with each level serving specific purposes related to production, sensing, process control, manufacturing operations, and business planning. Secondly, investigation of process analytical technology (PAT) tools for real-time measurements is highlighted as a prerequisite for effective real-time process management. For instance, the measurement of mass flow rate, a critical process parameter (CPP) in continuous manufacturing, was previously limited to loss-in-weight (LIW) feeders. To overcome this limitation, a novel capacitance-based mass flow sensor, the ECVT sensor, has been integrated into the continuous direct compaction process to capture real-time powder flow rates downstream of the LIW feeders. Additionally, the use of near-infrared (NIR)-based sensor for real-time measurement of ribbon solid fraction in dry granulation processes is explored. Proper spectra selection and pre-processing techniques are employed to transform the spectra into useful real-time information. Thirdly, the development of quantitative models that establish a link between CPPs and CQAs is addressed, enabling effective product design and process control. Mechanistic models and hybrid models are employed to describe the continuous direct compaction (DC) and dry granulation (DG) processes. Finally, applying APC strategies becomes feasible with the aid of real-time measurements and model predictions. Real-time optimization techniques are used to combine measurements and model predictions to infer unmeasured states or mitigate the impact of measurement noise. In this work, the moving horizon estimation-based nonlinear model predictive control (MHE-NMPC) framework is utilized. It leverages the capabilities of MHE for parameter updates and state estimation to enable adaptive models using data from the past time window. Simultaneously, NMPC ensures satisfactory setpoint tracking and disturbance rejection by minimizing the error between the model predictions and setpoint in the future time window. The MHE-NMPC framework has been implemented in the tableting process and demonstrated satisfactory control performance even when plant model mismatch exists. In addition, the application of MHE enables the sensor fusion framework, where at-line measurements and online measurements can be integrated if the past time window length is sufficient. The sensor fusion framework proves to be beneficial in extending the at-line measurement application from just validation to real-time decision-making.</p>

Grasslands are one of the most important ecosystems on Earth, covering approximately one-third of the Earth’s surface. Grassland biodiversity is important as many services provided by such ecosystems are crucial for the human economy and well-being. Given the importance of grasslands ecosystems, in recent years research has been carried out on the potential to monitor them with novel remote sensing techniques. Improved detectors technology and novel sensors providing fine-scale hyperspectral imagery have been enabling new methods to monitor plant traits (PTs) and biodiversity. The aims of the work were to study different approaches to monitor key grassland PTs such as Leaf Area Index (LAI) and biodiversity-related traits. The thesis consists of 3 parts: 1) Evaluating the performance of remote sensing methods to estimate LAI in grassland ecosystems, 2) Estimating plant biodiversity by using the optical diversity approach in grassland ecosystems, and 3) Investigating the relationship between PTs variability with alpha and beta diversity for the applicability of the optical diversity approach in a subalpine grassland of the Italian Alps To evaluate the performance of remote sensing methods to estimate LAI, temporal and spatial observations of hyperspectral reflectance and LAI were analyzed at a grassland site in Monte Bondone, Italy (IT-MBo). In 2018, ground temporal observations of hyperspectral reflectance and LAI were carried out at a grassland site in Neustift, Austria (AT-NEU). To estimate biodiversity, in 2018 and 2019 a floristics survey was conducted to determine species composition and hyperspectral data were acquired at two grassland sites: IT-MBo and University of Padova’s Experimental Farm, Legnaro, Padua, Italy (IT-PD) respectively. Furthermore, in 2018, biochemistry analysis of the biomass samples collected from the grassland site IT-MBo was carried out to determine the foliar biochemical PTs variability. The results of the thesis demonstrated that the grassland spectral response across different spectral regions (Visible: VIS, red-edge: RE, Near-infrared: NIR) showed to be both site-specific and scale-dependent. In the first part of the thesis, the performance of spectral vegetation indices (SVIs) based on visible, red-edge (RE), and NIR bands alongside SVIs solely based or NIR-shoulder bands (wavelengths 750 - 900 nm) was evaluated. A strong correlation (R2 &gt; 0.8) was observed between grassland LAI and both RE and NIR-shoulder SVIs on a temporal basis, but not on a spatial basis. Using the PROSAIL Radiative Transfer Model (RTM), it was demonstrated that grassland structural heterogeneity strongly affects the ability to retrieve LAI, with high uncertainties due to structural and biochemical PTs co-variation. In the second part, the applicability of the spectral variability hypothesis (SVH) was questioned and highlighted the challenges to use high-resolution hyperspectral images to estimate biodiversity in complex grassland ecosystems. It was reported that the relationship between biodiversity (Shannon, Richness, Simpson, and Evenness) and optical diversity metrics (Coefficient of variation (CV) and Standard deviation (SD)) is not consistent across plant communities. The results of the second part suggested that biodiversity in terms of species richness could be estimated by optical diversity metrics with an R2 = 0.4 at the IT-PD site where the grassland plots were artificially established and are showing a lower structure and complexity from the natural grassland plant communities. On the other hand, in the natural ecosystems at IT-MBo, it was more difficult to estimate biodiversity indices, probably due to structural and biochemical PTs co-variation. The effects of canopy non-vegetative elements (flowers and dead material), shadow pixels, and overexposed pixels on the relationship between optical diversity metrics and biodiversity indices were highlighted. In the third part, we examined the relationship between PTs variability (at both local and community scales, measured by standard deviation and by the Euclidean distances of the biochemical and biophysical PTs respectively) and taxonomic diversity (both α-diversity and β-diversity, measured by Shannon’s index and by Jaccard dissimilarity index of the species, families, and functional groups percent cover respectively) in Monte Bondone, Trentino province, Italy. The results of the study showed that the PTs variability metrics at alpha scale were not correlated with α-diversity. However, the results at the community scale (β-diversity) showed that some of the investigated biochemical and biophysical PTs variations metrics were associated with β-diversity. The SVH approach was also tested to estimate β-diversity and we found that spectral diversity calculated by spectral angular mapper (SAM) showed to be a better proxy of biodiversity in the same ecosystem where the spectral diversity failed to estimate alpha diversity, this leading to the conclusion that the link between functional and species diversity may be an indicator of the applicability of optical sampling methods to estimate biodiversity. The findings of the thesis highlighted that grassland structural heterogeneity strongly affects the ability to retrieve both LAI and biodiversity, with high uncertainties due to structural and biochemical PTs co-variation at complex grassland ecosystems. In this context, the uncertainties of satellite-based products (e.g., LAI) in monitoring grassland canopies characterized by either spatially or temporally varying structure need to be carefully taken into account. The results of the study highlighted that the poor performance of optical diversity proxies in estimating biodiversity in structurally heterogeneous grasslands might be due to the complex relationships between functional diversity and biodiversity, rather than the impossibility to detect functional diversity with spectral proxies.