Orientador: Jonas Contiero / Resumo: A contaminação ambiental causada por compostos orgânicos é um importante problema que afeta solos e água superficiais. Para reduzir ou remover esses poluentes, os locais contaminados são geralmente tratados com métodos físicos e químicos. No entanto, a maioria dessas técnicas de remediação é custosa e geralmente leva à remoção incompleta e à produção de resíduos secundários. A nanotecnologia consiste na produção e aplicação de estruturas extremamente pequenas, cujas dimensões estão na faixa de 1 a 100 nm, neste cenário a nanopartícula de ferro zero valente representa uma nova geração de tecnologias de remediação ambiental. É não tóxica, abundante, barata, fácil de produzir, e seu processo de produção é simples. No entanto, a fim de diminuir a tendência de agregação, a nanopartícula de ferro zero é frequentemente revestida com surfactantes. A maioria dos surfactantes é quimicamente sintetizado a partir de fontes petroquímicas, eles são persistentes ou parcialmente biodegradáveis, enquanto oferecem baixos riscos à saúde humana, esses compostos podem prejudicar plantas e animais. Para diminuir o uso de métodos químicos, a síntese e estabilização verde de nanomateriais metálicos apresentam-se como uma opção menos perigosa ao meio ambiente. Os biossurfactantes podem potencialmente substituir qualquer surfactante sintético, eles são compostos extracelulares produzidos por microrganismos, como bactérias, e cultivados em diferentes fontes de carbono, podendo ser substratoshidrofílico... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Environmental contamination caused by organic compounds is the most important challenge that affects a huge number of soils and water surfaces. To reduce or remove these pollutants, contaminated sites are usually treated using physical and chemical methods. However, most of these remediation techniques are expensive and commonly lead to incomplete removal and to the production of secondary wastes. Nanotechnology is the production and application of extremely small structures, whose dimensions are in the range of 1 to 100 nm and Nanoscale zero-valent iron represents a new generation of environmental remediation technologies, is non-toxic, abundant, cheap, easy to produce, and its reduction process requires little maintenance. Nonetheless, in order to diminish the tendency of aggregation, nanoscale zero-valent iron is often coated with surfactants. Most surfactants are chemically synthesized from petrochemical sources, they are slowly or partially biodegradable, while offer low harm to humans, such compounds can influence plants and animals. To decrease the use of chemical methods green synthesis and stabilization of metallic nanomaterials viable option. Biosurfactants can potentially replace virtually any synthetic they are extracellular compounds produced by microbes such as by bacteria and grown on different carbon sources containing hydrophobic/hydrophilic substrates. The biosurfactants have a wide variety of chemical structures and surface properties and among them is the ... (Complete abstract click electronic access below) / Doutor

[pt] Corrosão é um fenômeno natural que afeta basicamente todo tipo de material, consome bilhões de dólares anualmente em todo o mundo e pode ter resultados catastróficos. Revestimentos são a técnica de prevenção de corrosão mais utilizada de todas. Nesse sentido, resinas epóxi são amplamente utilizadas em todos os setores da indústria. Apesar de serem polímeros de alta performance, resinas epóxi apresentam problemas, como a necessidade do uso de endurecedores normalmente tóxicos e longos tempos de cura. Benzoxazinas são uma classe emergente de monômeros termofixos de alta performance e auto-cura. Enquanto monômeros mono- e bifuncionais são tipicamente explorados, benzoxazinas de funcionalidade mais alta e sintetizados em procedimento sem solvente e purificados por solventes mais seguros, são um caminho mais desejável em direção à síntese de PBZ para aplicações de alta performance. Nesse trabalho nós descrevemos uma abordagem sustentável para a síntese de benzoxazina trifuncional a partir de melamina, fenol e paraformaldeído. A estrutura química do monômero sintetizado foi confirmada por análises espectroscópicas, enquanto o processo de polimerização foi monitorado por análise calorimétrica. O monômero de benzoxazina foi, então, copolimerizado com uma resina epóxi bifuncional comercial. Nós investimgamos o efeito sinergístico no aumento das propriedades térmicas por meio de DSC e TGA. Resultados revelaram temperatura de transição vítrea de até 268 Graus C. Alta estabilidade térmica também foi obtida, com início de degradação próximo a 400 Graus C e rendimento residual de 22 wt (porcentagem) a 800 Graus C. Posteriormente, o copolímero foi combinado com sílica para produzir revestimentos anti-corrosão. Resultados revelaram superfícies superhidrofóbicas com ótimas resistência a risco e adesão ao substrato de aço. Teste eletroquímico provou alta efetividade dos revestimentos como barreira anti-corrosão, com performance aumentada pela incorporação de sílica. / [en] Corrosion is a natural phenomenon that affects virtually every material, consumes billions of dollars annually worldwide and may result in catastrophic events. Coating is the most utilized technique to prevent corrosion. In this sense, epoxies are widely applied in all sectors of industry. Despite being high performance polymers, epoxies present issues, such as the use of toxic crosslinkers and long curing time. Benzoxazines are an emerging class of high performance self-curing thermosets. While typical monomers are based on mono- and difunctional derivatives, higher functional benzoxazines, prepared without using solvents, but purified with nontoxic solvents, are more desirable towards a greener synthesis of PBZ for high performance applications. Herein, we describe an environment-friendly approach to synthesizing a trifunctional benzoxazine from melamine, phenol, and paraformaldehyde. The chemical structure of the synthesized benzoxazine was confirmed by spectroscopic analyses, while the polymerization was monitored by thermal analysis. The synthesized benzoxazine monomer is, then, copolymerized with a commercial difunctional epoxy resin. We investigate the synergistic effect on improved thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Results showed that a glass transition temperature of up to 268 Degrees C was obtained. A higher thermal stability was also achieved with an onset degradation of nearly 400 Degrees C and char yield of 22 wt (percentage) at 800 degrees C. Later, the copolymer was combined with silica to produce anticorrosion coatings. Results revealed superhydrophobic surfaces with great scratch resistance and adhesion to steel substrate. Electrochemical test proved high effectiveness of the coatings as anti-corrosion barrier, with increasing performance with the incorporation of silica.

This study was carried out at the Department of Nanotechnology and Functional Materials,Uppsala University, one of several places where the interest of lignin in cosmetics is constantly growing. The functionalities of lignin have been studied to a great extent revealing its potential as a natural biopolymer to serve as a replacement for environmentally hazardous components in cosmetic formulations, namely UV-filters in sunscreens. Using ethnographic methods and qualitative interviews the lignin-cosmetic industry was observed and analyzed in order to discern how concerned the industry is with ecological andaesthetic value. Ecological value is a hallmark of the value proposition in the cosmetic industry, and leaders of the industry indeed share this view. The analysis further revealed that the actors of the lignin-cosmetic industry are at different stages of development and that as of this year we can expect the first product to be launched. Furthermore, the value chain of the lignin actors was identified and for the first time mapped out in detail from the qualitative analysis that was carried out targeting lignin actors within the lignin-cosmetic industry. Mapping the value chain revealed the actors included in the entire chain identified as biorefinery, manufacturer, modifier, formulator, distributor and retailer which together compose the lignin-cosmetic value chain. A qualitative, semi structured interview approach was used and adapted as we met with eleven actors interviewing them about ecological and aesthetic values in the lignin based product value proposition. The grounded theory was applied to analyze the data, generating eight categories representing the concepts comprising ecological and aesthetic values of the value proposition. The kernel category, Green Profile, explains the most important concepts valued by lignin actors in terms of what ecological and aesthetic value could be offered to be appealing to customers. The findings of this study reveals the current situation of lignin in the cosmetic market as of today, and discerns where the value of lignin lies. The understanding of lignin actors' values contributes to the current gray-area in biopolymer research, lacking information on the value chain of lignin in cosmetics. The findings therefore foster the advancement of sustainable innovative solutions for cosmetics and personal care.

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No description available.

[pt] O objetivo desta pesquisa foi a substituição de técnicas convencionais de extração de amostras para análise hidrocarbonetos policíclicos aromáticos (HPAs) em amostras de tecido para um procedimento confiável, rápido e ambientalmente mais sustentáveis. O novo método foi desenvolvido usando um método de extração com solvente pressurizado, avaliando dois materiais de referência padrão (peixe e mexilhão) e amostras de sardinhas fortificadas (Sardinella sp.). Cinco procedimentos de extração diferentes foram avaliados e o melhor desempenho obtido foi pela extração de 1 g de tecido liofilizado em conjunto com 5 g de sílica desativada (5 por cento), mistura de diclorometano: metanol (4: 1 v / v), temperatura de 80 graus C, três ciclos, 10 min de tempo estático e 90 s de tempo de purga. Este método foi ainda validado pela análise de nove réplicas do material de referência número 2974a(Orgânicos em Tecido de Mexilhão Liofilizado) do National Institute of Standard and Technology (NIST), resultando em uma recuperação média de 85 mais ou menos 14 por cento. As médias e as incertezas obtidos para cada HPA foram equivalentes aos do material de referência, corroborando a confiabilidade do método desenvolvido. Um tempo de processamento mais curto, menos uso de solventes e reagentes e menor manipulação do extrato resultou em um método eficaz e alinhado às diretrizes da química verde. / [en] The aim of this research was the replacement of conventional sample extraction techniques for polycyclic aromatic hydrocarbons (PAH) in tissue samples for a reliable, fast and environmentally more sustainable. The methodwas developed using a pressurized solvent extraction method and assessing two different standard reference materials (fish and mussel) and freeze-dried and fortified sardine samples (Sardinella sp.). Five different extraction procedures were evaluated and the best performance comprised 1 g of lyophilized tissue, 5 g of deactivated (5 percent) silica, a dichloromethane:methanol (4:1 v/v) mixture, a temperature of 80 C degrees, three cycles, 10 min of static time and 90 s of purge time. The method selected following these tests was further validated through the analysis of nine replicates of the National Institute of Standard and Technology (NIST) reference material No. 2974a (Organics in Freeze-Dried Mussel Tissue), resulting in an effective recovery of 85 more or less 14 percent. The means and uncertainties attained for each PAH were equivalent to those of the reference material, corroborating the reliability of the developed method. A shorter processing time, less use of solvents and reagents and lower extract manipulation resulted in an effective method aligned with green-chemistry guidelines.

Le 21e siècle est le berceau d’une conscientisation grandissante sur les impacts environnementaux des processus utilisés pour synthétiser des molécules cibles. Parmi les avancées qui ont marqué ces dernières décennies, il est également question de réduction de déchets, de conservation de l’énergie et de durabilité des innovations. Ces aspects constituent les lignes directrices de la chimie verte. De ce fait, il est impératif de développer des stratégies de synthèse dont les impacts environnementaux sont bénins. Dans ce mémoire nous présentons la synthèse, la caractérisation et l’étude des propriétés catalytiques en milieu aqueux d’un ligand composé d’une unité -cyclodextrine native, d’une unité imidazolium et d’une chaine alkyle à 12 carbones. Ce ligand hybride s’auto-assemble dans l’eau sous forme de micelles, permettant ainsi d’effectuer en sa présence des couplages de Suzuki-Miyaura dans l’eau, avec de bons rendements. La fonctionnalisation de la face primaire de la -cyclodextrine par un noyau alkyl-imidazolium, précurseur de ligand de type carbène N-hétérocyclique, a permis le développement d’un système catalytique vert et hautement recyclable. Dans un deuxième temps, nous présentons l’utilisation du même ligand hybride dans des couplages de Heck dans l’eau, démontrant ainsi la versatilité du ligand. / Chemistry keeps evolving in new directions. Research has provided improved methodologies for the design and synthesis of targeted molecules. At the same time, the 21st century is witnessing increasing concern about the environmental impacts of chemical wastes. A new philosophy of chemical research and engineering has emerged, known as «Green chemistry». This concept encourages the design of products, processes and technologies that minimize the use and generation of hazardous substances. Therefore, there is an urge to develop environmentally friendly process to convert molecules into product of interest. In the present thesis, we describe the synthesis, characterization and catalytic properties of a novel alkylimidazolium-modified β-cyclodextrin (-CD). Our strategy was to construct a single amphiphilic bimodal ligand by the combination of a mass transfer unit (-CD), covalently bound to a ligand moiety (alkylimidazolium, an N-heterocyclic carbene (NHC) precursor) for aqueous catalysis. First, we demonstrated that the introduction of a dodecyl chain on the imidazolium moiety attached to the primary face of a native β-CD allows the formation of a highly active micellar self-assembled catalytic system in neat water with remarkable recyclable properties for the Suzuki–Miyaura coupling. In addition, we studied the versatility of this self-assembled bimodal system by performing Heck coupling in neat water.

Ce travail de thèse vise à comprendre les propriétés thermodynamiques et les mécanismes réactionnels engendrés dans les réactions de cycloaddition d'époxydes en milieu CO2 supercritique catalysées par des liquides ioniques pour la synthèse de carbonates cycliques. Les propriétés thermodynamiques (solubilité, gonflement, diagramme de phase) des mélanges binaires époxyde/CO2 ont été déterminées pour des époxydes modèles et des époxydes dérivées d'huiles végétales. Des suivis cinétiques in-situ par spectroscopie IR-TF et Raman ont été effectués pour déterminer l'influence de la nature des liquides ioniques étudiés et des paramètres température-pression sur les cinétiques de réaction. Des modélisations moléculaires de type DFT nous ont permis de proposer un mécanisme réactionnel en accord avec les résultats expérimentaux et de bien comprendre quels sont les rôles respectifs de l'anion et du cation du liquide ionique dans la réaction. / This thesis aims to understand the thermodynamic properties and reaction mechanisms generated in the cycloaddition reaction of epoxides in supercritical CO2 medium catalyzed by ionic liquids for the green synthesis of cyclic carbonates. Thermodynamic properties (solubility, swelling, phase diagram) of epoxide/CO2 binary mixtures were determined for commercial mono-epoxides and vegetable based epoxidized oils. Kinetics study in-situ by FTIR and Raman spectroscopy were performed to determine the influence of the nature of the ionic liquids studied and of different parameters such as temperature and pressure on the reaction. Molecular modeling using DFT method has helped us to propose a reaction mechanism consistent with the experimental results and to understand what are the respective roles of the anion and cation of the ionic liquid in the reaction.

L'oxydation de Baeyer-Villiger (BV) par voie enzymatique est une méthode efficace pour obtenir de lactones sous forme énantiomériquement pure. Les Baeyer-Villiger Monooxygénases (BVMO) sont ainsi capables d'oxyder de nombreux substrats avec une stéréospécificité remarquable.Nous avons recherché de nouvelles enzymes dans le génome de deux souches appartenant au genre Acinetobacter, A. baylyi ADP1 et A. baumannii AYE. Six gènes ont été clonés dans E. coli. Leur profil de substrat a été étudié en utilisant des cellules entières de ce microorganisme recombinant comme biocatalyseur. Quatre enzymes ont montré une spécificité de substrat similaire, avec une préférence pour les petites cétones cycliques et pour les substituants aryliques. Une de ces enzymes a permis le Dédoublement Cinétique Parallèle Régiodivergent d'une bicyclohepténone et la désymétrisation de cyclobutanones benzyliques avec, dans chaque cas, une énantiosélectivité intéressante car conduisant à des énantiomères rarement obtenus par réaction de BV enzymatique.Dans une seconde partie, des Dédoublements Cinétiques Dynamiques, associant réaction de BV enzymatique et racémisation in situ ont été réalisés avec des cellules entières d'E. coli produisant la Cyclohexanone Monooxygenase (CHMO) issue d'A. calcoaceticus. La racémisation de cyclohexanones α-substituées, habituellement difficilement racémisables, a été assurée par l'emploi de solutions tampons à base de sels de phosphate ou de glycine. Les -caprolactones correspondantes ont été isolées sous forme d'esters méthyliques hydroxylés quasi énantiopurs avec des rendements compris entre 70 et 80%. / Enzyme-mediated Baeyer-Villiger oxidation is nowadays largely recognized as an efficient method to obtain highly optically active lactones. An increasing number of Baeyer-Villiger Monooxygenases from various sources has been found to oxidize a large range of substrates with a good to excellent stereospecificity.Firstly, in order to enlarge the scope of these biotransformations, the genome of two strains of the Acinetobacter genus, A.baylyi ADP1 and A.baumannii AYE was explored. Six genes were expressed in E. coli and the substrate profile of each enzyme was studied using whole cell biotransformations. Four enzymes showed close substrate specificity with a preference for small cyclic ketones and for arylic substituents. Interestingly, one enzyme led to a Kinetic Parallel Regiodivergent Resolution of a bicycloheptenone and desymmetrisation of benzylic cyclobutanones in an enantiocomplementary manner when compared to the most of already known enzymes.The second part of this work describes the implementation of Dynamic Kinetic Resolution processes combining enzymatic BV oxidation and in situ racemization of α-substituted cyclohexanones to afford corresponding lactones in more than 50% yield. Cyclohexanone Monooxygenase (CHMO) from another Acinetobacter strain, A. calcoaceticus, was selected and the reactions were carried out with whole cells of producing CHMO E. coli strain. The racemization of α-substituted cyclohexanones, usually slowly racemized under basic conditions, was ensured by the use of containing phosphate salts or glycine buffer solutions. Several corresponding -caprolactones were isolated after methylation as enantiopure hydroxy methyl esters in 70-80% yield.

No presente trabalho foram investigados vários sistemas moleculares contendo o dióxido de enxofre (SO2) como espécie elétron aceptora e diversas espécies elétron doadoras como aminas (alifáticas e aromáticas), complexos inorgânicos e líquidos iônicos. Estes compostos são chamados de complexos do tipo doador-aceptor, que no caso do SO2 são caracterizados por apresentarem baixas energias de ligação entre as espécies se comparada à maioria dos complexos desta categoria. A caracterização vibracional dos complexos e adutos de SO2, assim como do processo de transferência de carga (CT) intermolecular e da estabilidade destes sistemas consistem nos principais objetivos deste trabalho, tendo sido para tanto utilizadas as técnicas de espectroscopia eletrônica (UV-Vis), espectroscopia vibracional (Raman e infravermelho), cálculos de química quântica (DFT) e cálculos de dinâmica molecular clássica (MD). No caso de complexos entre aminas e SO2 foi observado que além da basicidade das aminas, o efeito estérico consiste em um fator crucial para a estabilidade. No caso de aminas aromáticas, complexos coloridos foram formados permitindo a obtenção de espectros Raman ressonante. No caso de um complexo inorgânico, com utilidade potencial como sensor de SO2foi observada a aplicação da espectroscopia Raman ressonante na caracterização do complexo de estequiometria 2:1. Já no caso da interação de SO2 e líquidos iônicos (LI) foi observada a capacidade de absorção de SO2 por LI e a conseqüente mudança das propriedades físico-químicas destes líquidos, o que abre a possibilidade, além de sua potencial utilização no contexto ambiental, de sintonizar propriedades de líquidos iônicos através da adição controlada de SO2. / In the present work molecular systems bearing the sulfur dioxide (SO2) as an electron acceptor species and several electron donor species as amines (aliphatic and aromatic), inorganic complexes and ionic liquids were investigated. Such complexes are commonly known as donor-acceptor complexes, and in particular, in the case of SO2 complexes are characterized by low binding energies when compared with the majority of charge transfer (CT) complexes. The vibrational characterization of the SO2 complexes, as well as of the intermolecular charge transfer (CT) process and of their stabilities are the main subjects of this work, and for such, electronic spectroscopy (UV-Vis), vibrational spectroscopy (Raman and infrared), quantum chemical (DFT) calculations and molecular dynamics (MD) simulations were used. In the case of complexes formed by amines and SO2 it was observed that besides the amine basicities, the steric effect plays a crucial role in their stabilities. In the case of aromatic amines, colored complexes were formed allowing the resonance Raman study. The use of Raman spectroscopy in the characterization of an inorganic complex (SO2 sensor) indicates the potential use of the resonance Raman effect for SO2 monitoring. In the case of the interaction between SO2 and ionic liquids it was observed the great capability of ionic liquids as SO2 absorbers, and the consequent change in the physical-chemical properties of these liquids, what opens the possibility, in addition to its potential use in the environmental context, for tuning the ionic liquids properties via the controlled addition of SO2.