No description available.

Content: As it is known in the tanning sector, in recent times, the so-called wet-white and/or metal-free concepts have had a certain increase. For example, in the automotive sector, the wet-white tanning system, carried out with glutaraldehyde and tannins, has been widely diffused. In fact, car manufacturers offer, for interior furnishings, leather not only for high-end cars but increasingly also in the lower segments. The components on which the leather upholstery is applied are mainly steering wheel, seats, dashboard and panels. Therefore, the use of leather also in this context must be able to meet both the aesthetic/performance criteria and the environmental ones; environmental criteria should also consider the air quality of the interior of a motor vehicle. In practice, the interior furniture consisting of finished leather must be able to release a few volatile substances and, at the same time, provide a typical smell of leather. Considering, therefore, the diffusion of alternative chrome tanning systems for the different uses, in this work, wet-white (glutaraldehyde and tannins) will be investigated, both from the point of view of the performance characteristics and from the ecotoxicological ones. and leathers deriving from the latest generation of metal-free tanning. For the characterization of Volatile Organic Compounds (VOC) the GC-MS will be used coupled with the 'Purge and Trap' technique with the aim of obtaining information on the new substances used in the wetwhite / metal free production process and then avoiding undesired effects during use (eg bad smell, SVHC substances, etc.) Take-Away: metal-free automotive VOC

Aromatic rings are universal motifs in natural products, pharmaceuticals, agrochemicals, and wide variety of organic materials. Aromatic halides are widely used as synthetic precursors in all these applications. Therefore, tremendous effort has been devoted to activate aryl halides in the past decades. The common methods to activate aryl halides require the use of transition-metals either in the form of Grignard reagents or through the use of transition-metal catalysis. <br>Over the past decade, photoredox catalysis has attracted significant attention as a cogent tool to develop greener synthetic processes and enable new molecular activation pathways under mild conditions. The most common of these approaches uses a photoredox/nickel dual catalytic cycle.<br>While this technology has greatly expanded the toolbox of organic chemists, this method still requires expensive rare-metal-based catalyts. Herein, we present a series of visible light-induced methods that are transition-metal-free. These new base-promoted transformations and their mechanistic work will be discussed in the following order:<br>We will first present our discovery that the dimsyl anion enables visible-light-promoted charge transfer in cross-coupling reactions of aryl halides. This work was applied to the synthesis of unsymmetrical diaryl chalcogenides. This method has a broad scope and functional group tolerance. An electron-donor-acceptor (EDA) complex between a dimsyl anion and the aryl halide is formed during the reaction and explains the observed aryl radical reactivity observed.<br>Then, a visible-light-induced borylation and phosphorylation of aryl halides under mild conditions was developed. Inspired by the mechanistic breakthroughs observed in the previous work. The mechanism of this reaction also involves an aryl radical that is presumed to be formed also via an EDA complex. In other work, a photo-induced phosphonation of ArI using N,N-diisopropylethylamine (DIPEA) and trialkyl phosphites was developed. This method uses very mild conditions, which allowed the preparation a wide variety of functionalized aromatic phosphonates derivatives, including natural products and medicinal compounds. Finally, a photochemical amination of amides was developed via a C(sp 3 )–H bond functionalization<br>process under visible light irradiation. This reaction showed good functional group compatibility without the use of external radical initiators, strong oxidants, or heat source. An EDA complex between N-bromophthalimide and LiOtBu is formed during the reaction.

No description available.

No description available.

Tout au long du siècle dernier, l’électronique s’est révélé être un progrès technologique majeur, et ses applications sont tellement nombreuses qu’elles ont envahi notre vie de tous les jours. De par leurs propriétés bien spécifiques, les semi-conducteurs organiques représentent une remarquable alternative aux matériaux inorganiques utilisés actuellement. Cependant, leurs propriétés électriques peuvent être limitées, et l’efficacité des dispositifs composés de tels matériaux ne permet pas encore de rivaliser avec ceux basés sur des matériaux inorganiques. Dans ce contexte, ce travail de thèse a pour objectif de synthétiser et caractériser de nouveaux polymères conjugués et d’étudier leurs propriétés, dans le but d’ajouter de nouveaux matériaux au déjà riche catalogue de polymères semi-conducteurs disponibles, ainsi que de permettre une meilleure compréhension de la relation structure-propriétés dans les systèmes conjugués. Des copolymères alternés composés de motifs carbazole, benzothiadiazole ou encore squaraine ont été synthétisés et caractérisés. De plus, des polymérisations originales et sans catalyseurs métalliques ont été développées. / Within the last century, electronics have become a major technological breakthrough and the resulting applications are so numerous that it has invaded our every-day life. Due to their properties, organic semiconductors have attracted much attention and represent a great alternative to the nowadays used inorganic materials. However, their electrical properties can be limited, and the efficiencies of the resulting devices are still not completely competitive against the inorganic-based ones. In this context, this PhD goal was to synthesize novel conjugated polymers (CPs) and investigate their properties, in order to add novel materials to the already wide catalogue of semiconducting polymers and allow a better comprehension of the structure-properties relationship in conjugated systems. Alternated copolymers based on carbazole, benzothiadiazole, or squaraine were synthesized and characterized. Furthermore, original and metal catalyst-free polymerizations were successfully developed.

A estética tornou-se de fundamental importância nas últimas décadas, fazendo com que houvesse uma grande evolução nos materiais dentários e técnicas restauradoras para atender a esta exigência. As cerâmicas odontológicas são materiais estéticos e biocompatíveis, podendo ser uma ótima alternativa quando aplicadas a casos apropriadamente selecionados. O sucesso estético de uma restauração de cerâmica depende da caracterização de superfície, da integridade marginal, da forma anatômica e da coloração. O presente estudo teve o objetivo de avaliar a estabilidade de cor de dois tipos de restaurações em cerâmica odontológica, metalocerâmica e livre de metal, submetidas a múltiplos ciclos de queimas. Foram realizados 60 corpos-de-prova, sendo 30 na forma de metalocerâmicas e 30 livres de metal que foram divididas em três grupos de 10 amostras cada, sendo confeccionadas em duas, três e quatro queimas respectivamente. As leituras de cor foram realizadas em espectrofotômetro PCB 6807 BYK GARDNER antes e após envelhecimento artificial acelerado (Comexim Matérias Primas). Analisando-se inicialmente a influência do número de queimas sobre a cor da cerâmica odontológica, houve diferenças estatisticamente significantes para as coordenadas L* nas amostras metalocerâmicas, sendo que o grupo de 3 queimas foi o que apresentou diferenças em relação aos outros dois grupos. Para as amostras livres de metal, houve diferenças nas coordenadas L*, a* e b*, com comportamentos heterogêneos para as 3 coordenadas. Os resultados indicaram diferenças estatisticamente significantes na variação total de cor (&#8710;E) para as amostras de 3 e 4 queimas, comparando-se os tipos de restauração. Quando analisada a interferência do número de queimas de um mesmo tipo de restauração, não houve diferença estatisticamente significante para a amostra livre de metal. Para a amostra metalocerâmica, houve apenas diferença estatisticamente significante entre as amostras que receberam 2 e 3 queimas. Para a variação total nas coordenadas L*, a* e b* também houve variação de valores para os dois tipos de amostras e em relação aos ciclos de queimas. Concluiu-se que as pequenas diferenças estatisticamente significantes encontradas em alguns grupos não foram visíveis ao olho humano e portanto sem qualquer significado clínico (&#8710;E < 3,3). Além disso, os múltiplos ciclos de queima e o envelhecimento acelerado não modificaram de forma significativa a estabilidade de cor da cerâmica nas formas em que foi empregada (&#8710; < 1). / Esthetics has become essential over the past few decades, causing dental materials and restorative techniques to evolve significantly. Dental ceramics are esthetic and biocompatible materials which may be an excellent alternative for properly selected cases. The esthetic success of a ceramic’s restoration depends on surface characterization, marginal integrity, anatomic form, and color. This study aimed to assess the color stability of two types of dental ceramic restorations, metalloceramic and metal-free, submitted to multiple burn cycles. Sixty specimens were fabricated: 30 metalloceramic and 30 metal-free. The specimens were divided into 3 groups (n= 10) according to the number of burns (2, 3, and 4 burns). Color readings were performed using a PCB 6807 BYK GARDNER spectrophotometer before and after artificial accelerated aging (Comexim Raw Materials). By analyzing the influence of the number of burns over the dental ceramic’s color, statistically significant differences were found for the coordinate L* for the metalloceramic specimens, in the group of 3 burns, in relation to the other 2 groups. For the metal-free specimens, there were differences for the coordinates L*, a*, and b*, with heterogeneous compartments for the 3 coordinates. The results revealed statistically significant differences for total color variation (&#8710;E) for the 3 burns group, in comparison to the other types of restoration. When analyzing the specimens of a single type of material, in terms of the interference of the number of burns, the metal-free samples showed no statistically significant differences, whereas the metalloceramic samples showed difference only between those that received 2 and 3 burns. For the total variation of coordinates L*, a*, and b*, both materials showed a variation in those values and in relation to burn cycles. The small statistically significant differences found in some groups are invisible and present no clinical meaning (&#8710;E<3.3). In addition, the multiple burn cycles and accelerated aging did not modify significantly the ceramic’s color stability (&#8710;<1).

A estética tornou-se de fundamental importância nas últimas décadas, fazendo com que houvesse uma grande evolução nos materiais dentários e técnicas restauradoras para atender a esta exigência. As cerâmicas odontológicas são materiais estéticos e biocompatíveis, podendo ser uma ótima alternativa quando aplicadas a casos apropriadamente selecionados. O sucesso estético de uma restauração de cerâmica depende da caracterização de superfície, da integridade marginal, da forma anatômica e da coloração. O presente estudo teve o objetivo de avaliar a estabilidade de cor de dois tipos de restaurações em cerâmica odontológica, metalocerâmica e livre de metal, submetidas a múltiplos ciclos de queimas. Foram realizados 60 corpos-de-prova, sendo 30 na forma de metalocerâmicas e 30 livres de metal que foram divididas em três grupos de 10 amostras cada, sendo confeccionadas em duas, três e quatro queimas respectivamente. As leituras de cor foram realizadas em espectrofotômetro PCB 6807 BYK GARDNER antes e após envelhecimento artificial acelerado (Comexim Matérias Primas). Analisando-se inicialmente a influência do número de queimas sobre a cor da cerâmica odontológica, houve diferenças estatisticamente significantes para as coordenadas L* nas amostras metalocerâmicas, sendo que o grupo de 3 queimas foi o que apresentou diferenças em relação aos outros dois grupos. Para as amostras livres de metal, houve diferenças nas coordenadas L*, a* e b*, com comportamentos heterogêneos para as 3 coordenadas. Os resultados indicaram diferenças estatisticamente significantes na variação total de cor (&#8710;E) para as amostras de 3 e 4 queimas, comparando-se os tipos de restauração. Quando analisada a interferência do número de queimas de um mesmo tipo de restauração, não houve diferença estatisticamente significante para a amostra livre de metal. Para a amostra metalocerâmica, houve apenas diferença estatisticamente significante entre as amostras que receberam 2 e 3 queimas. Para a variação total nas coordenadas L*, a* e b* também houve variação de valores para os dois tipos de amostras e em relação aos ciclos de queimas. Concluiu-se que as pequenas diferenças estatisticamente significantes encontradas em alguns grupos não foram visíveis ao olho humano e portanto sem qualquer significado clínico (&#8710;E < 3,3). Além disso, os múltiplos ciclos de queima e o envelhecimento acelerado não modificaram de forma significativa a estabilidade de cor da cerâmica nas formas em que foi empregada (&#8710; < 1). / Esthetics has become essential over the past few decades, causing dental materials and restorative techniques to evolve significantly. Dental ceramics are esthetic and biocompatible materials which may be an excellent alternative for properly selected cases. The esthetic success of a ceramic’s restoration depends on surface characterization, marginal integrity, anatomic form, and color. This study aimed to assess the color stability of two types of dental ceramic restorations, metalloceramic and metal-free, submitted to multiple burn cycles. Sixty specimens were fabricated: 30 metalloceramic and 30 metal-free. The specimens were divided into 3 groups (n= 10) according to the number of burns (2, 3, and 4 burns). Color readings were performed using a PCB 6807 BYK GARDNER spectrophotometer before and after artificial accelerated aging (Comexim Raw Materials). By analyzing the influence of the number of burns over the dental ceramic’s color, statistically significant differences were found for the coordinate L* for the metalloceramic specimens, in the group of 3 burns, in relation to the other 2 groups. For the metal-free specimens, there were differences for the coordinates L*, a*, and b*, with heterogeneous compartments for the 3 coordinates. The results revealed statistically significant differences for total color variation (&#8710;E) for the 3 burns group, in comparison to the other types of restoration. When analyzing the specimens of a single type of material, in terms of the interference of the number of burns, the metal-free samples showed no statistically significant differences, whereas the metalloceramic samples showed difference only between those that received 2 and 3 burns. For the total variation of coordinates L*, a*, and b*, both materials showed a variation in those values and in relation to burn cycles. The small statistically significant differences found in some groups are invisible and present no clinical meaning (&#8710;E<3.3). In addition, the multiple burn cycles and accelerated aging did not modify significantly the ceramic’s color stability (&#8710;<1).

Adsorption of monolayers and multilayers of metal-free and metal phthalocyanines molecules on metal surfaces has been investigated using complementary microscopic and synchrotron-based spectroscopic techniques. It was observed by STM measurements that at monolayer coverage the adsorption direction of the metal-free phthalocyanine molecules with respect to the gold surface vary as a function of temperature, i.e. at room temperature (RT) and low temperature (LT). It was explained by the difference in strength of intermolecular and adsorbate-substrate interactions at room and low temperatures. Nature of the interaction between adsorbed species and the surfaces as a function of coverage has been further characterized by XPS measurements. Binding energy shifts as a function of coverage have been attributed to initial- and final-state effects, the latter being due to different core-hole screening for the different molecular coverage. The alignment of molecular films at both monolayer and multilayer coverages, which has been determined by XAS measurements in several cases, is also dependent upon the relative strength of molecule-molecule versus molecule-substrate interaction. Parallel alignment of the molecular film with respect to the surface is the result of significant interaction between the adsorbate and the substrate, whilst standing geometry of the molecular film is due to more significant intermolecular interactions. DFT simulations have provided further information on the nature of the adsorbate-substrate interaction as well as contribution of different molecular orbitals in XPS and XAS spectra. Moreover, investigation of alkali interaction with the phthalocyanine films revealed a significant modification in their geometric and electronic structures due to charge transfer from the alkali metal to the molecular film. However, no sign of metallization of the molecules has been observed by spectroscopic and microscopic studies.

Aliphatic polyesters such as polycaprolactone and polylactide have received more attention in recent years for their use in biomedical applications because of their biodegradable nature. These polymers are often synthesized using homogeneous metal complexes. Unfortunately, using homogeneous metals as catalysts leads to metal contamination in the product polymer, a result which is highly undesirable in a polymer intended for biomedical use. More recent work has shown that these polymers can be synthesized using homogeneous metal-free complexes. These catatlysts are generally less active than metal catalysts, and although they do not contaminate the polymer with metal residue, they are still difficult to recover and hence recycle for further use. In this work, we attempted to create a metal-free, silica-supported catalyst for use in the synthesis of polycaprolactone or polylactide. Ultimately, n-propylsulfonic acid-functionalized porous and nonporous silica materials are evaluated in the ring-opening polymerization of epsilon-caprolactone. All catalysts allow for the controlled polymerization of the monomer, producing polymers with controlled molecular weights and narrow polydispersities. Polymerization rates are low, with site-time-yields generally one to three orders of magnitude lower than metal-based systems. The catalysts are easily recovered from the polymerization solution after use and are shown to contain significant residual adsorbed polymer. Solvent extraction techniques are useful for removing most of the polymer, although the extracted solids are not effective catalysts in recycle experiments. These new materials represent a green alternative to traditional metal-based catalysts, as they are recoverable and leave no metal residues in the polymer.