It was the goal of this work to explore two different synthesis pathways using green chemistry. The first part of this thesis is focusing on the use of the urea-glass route towards single phase manganese nitride and manganese nitride/oxide nano-composites embedded in carbon, while the second part of the thesis is focusing on the use of the “saccharide route” (namely cellulose, sucrose, glucose and lignin) towards metal (Ni0), metal alloy (Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5, Cu0.5Ni0.5 and W0.15Ni0.85) and ternary carbide (Mn0.75Fe2.25C) nanoparticles embedded in carbon. In the interest of battery application, MnN0.43 nanoparticles surrounded by a graphitic shell and embedded in carbon with a high surface area (79 m^2/g) were synthesized, following a previously set route.The comparison of the material characteristics before and after the discharge showed no remarkable difference in terms of composition and just slight differences in the morphological point of view, meaning the particles are stable but agglomerate. The graphitic shell is contributing to the resistance of the material and leads to a fine cyclic stability over 140 cycles of 230 mAh/g after the first charge/discharge and coulombic efficiencies close to 100%. Due to the low voltage towards Li/Li+ and the low polarization, it might be an attractive anode material for lithium ion batteries. However, the capacity is still noticeably lower than the theoretical value for MnN0.43. A mixture of MnN0.43 and MnO nanoparticles embedded in carbon (surface area 93 m^2/g) was able to improve the cyclic stability to over 160 cycles giving a capacity of 811 mAh/g, which is considerably higher than the capacity of the conventional material graphite (372 mAh/g). This nano-composite seems to agglomerate less during the process of discharge. Interestingly, although the capacity is much higher than of the single phase manganese nitride, the nano-composite seems to only contain MnN0.43 nanoparticles after the process of discharge with no oxide phase to be found. Concerning catalysis application, different metal, metal alloy, and metal carbide nanoparticles were synthesized using the saccharide route. At first, systems that were already investigated before, being Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5 and Mn0.75Fe2.25C using cellulose as the carbon source were prepared and tested in an alkylation reaction of toluene with benzylchloride. Unexpectedly, the metal alloys did not show any catalytic activity, but the ternary carbide Mn0.75Fe2.25C showed fine catalytic activity of 98% conversion after 9 hour reaction time (110 °C). In a second step, the saccharide route was modified towards other carbon sources and carbon to metal ratios in order to improve the homogeneity of the samples and accessibility of the particle surfaces. The used carbon sources sucrose and glucose are similar in their basic structure of carbohydrates, but reducing the (polymeric) chain length. Indeed, the cellulose could be successfully replaced by sucrose and glucose. A lower carbon to metal ratio was found to influence the size, homogeneity and accessibility (as evidenced by TEM) of the samples. Since sucrose is an aliment, glucose is the better choice as a carbon source. Using glucose, the synthesis of Cu0.5Ni0.5 and W0.15Ni0.85 nano-composites was also possible, although the later was never obtained as pure phase. These alloy nano-composites were tested, along with nickel0 nanoparticles also prepared with glucose and on their catalytic activity towards the reduction of phenylacetylene. The results obtained let believe that any (poly) saccharide, including lignin, could be used as carbon source. The nickel0 nano-composites prepared with lignin as a carbon source were tested along with those prepared with cellulose and sucrose for their catalytic activity in the transfer hydrogenation of nitrobenzene (results compared with exposed nickel nanoparticles and nickel supported on carbon) leading to very promising results. Based on the urea-glass route and the saccharide route, simple equipment and transition metals, it was possible to have a one-pot synthesize with scale-up possibilities towards new material that can be applied in catalysis and battery systems. / Im Rahmen dieser Arbeit wird sowohl die Synthese von Mangannitrid- und -oxid-Nanopartikeln, als auch die Synthese verschiedener Metall- und Legierungsnanopartikel untersucht. Einen Schwerpunkt stellt dabei die Optimierung der Synthese unter den Gesichtspunkten der Nachhaltigkeit dar, was sich insbesondere in der Verwendung diverser nachwachsender Rohstoffe als Kohlenstoffquelle äußert. Für eine mögliche Anwendung in Akkumulatoren werden mit Graphit ummantelte MnN0.43-Nanopartikel mit einer großen Oberfläche (79 m^2/g) synthetisiert. Diese werden exemplarischen Ladezyklen unterzogen, wobei eine strukturelle und auch elektrochemische Stabilität festgestellt werden kann. Eine Mischung der Mangannitride mit Manganoxiden führt zu einer weiteren Verbesserung der Ladekapazität und einer weiteren Oberflächenvergrößerung (93 m^2/g). Die Langlebigkeit der Strukturen wird durch die Einbettung der Nanopartikel in Kohlenstoff unterstützt und kann zu einer Anwendung als Anodenmaterial in den heutzutage vielfach verwendeten Lithiumionen-Akkus führen. Im Sinne der Nachhaltigkeit ist auch die Entwicklung von Katalysatoren. Dabei soll insbesondere die Verwendung von Lignin, was als Bestandteil vieler Pflanzen zwar leicht verfügbar, aber unglücklicherweise bisher chemisch unverwertbar ist, fokussiert werden. Um sich diesem Ziel zu nähern und entsprechende Mechanismen zur Reduktion des Lignins zu entwickeln, werden in dieser Arbeit zunächst verschiedene Kohlenstoffquellen (wie Cellulose, Sucrose und Glucose) zur Synthese von reduktiven Katalysatoren untersucht. Der Kohlenstoff dient dabei sowohl als preiswertes Reduktionsmittel für Metallsalze zur Gewinnung von Metallnanopartikel als auch zur Stabilisierung ebendieser. Es werden vielfältige Legierungen mit Nickel (z.B. Pd0.9Ni0.1, Pd0.5.Ni0.5, Fe0.5.Ni0.5, und Cu0.5.Ni0.5) aber auch ternäre Carbide (z.B. Mn0.75Fe2.25C) erhalten, die schon in ersten Alkylierungs- und Hydrierungsreaktionen ein großes Potential als Katalysatoren zeigen. Um die erhaltenen Nanopartikel in zukünftigen Anwendungen nutzbar zu machen, ist eine ausführliche Charakterisierung unabdingbar. Auch die Ergebnisse der zahlreichen durchgeführten Analysen werden in dieser Arbeit zusammengestellt und bilden gemeinsam mit den optimierten Syntheserouten einen tiefgreifenden Überblick über dieses Forschungsfeld.

The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide. The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism.

No description available.

Bioprocessing applications are gaining importance in the traditional chemical industries. With environmental, political, and economical concerns growing, research efforts have recently focused on the substitution of petroleum-derived transportation fuels and materials. As possible products and feedstocks are being investigated, it is important to ensure the new processes are also sustainable. There are several aspects to developing sustainable processes: minimize waste, use environmentally-benign chemicals, find renewable feedstocks, and limit the number of processing steps. This thesis examines ways to enhance the sustainability of bioprocesses. Novel, alternative solvent systems are studied and applied to a variety of bioprocesses. Downstream processing steps and waste can be minimized by designing systems that combine reactions and separations into one process unit. This is accomplished by designing new reactor systems and by replacing currently used solvents. Additional studies, involving analytical techniques that reduce the use of organic solvents, are tested and applied to industrial problems. Finally, new solvent systems are examined for potential processes using renewable carbohydrate feedstock.

The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide. The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism.

Computational chemistry employs mathematical algorithms, statistics, and large databases to integrate chemical theory with experimental observations. Computational modeling allows us to make predictions concerning molecular properties and reactivity that ultimately lead to accurate assessment of the most important fundamental properties of chemical systems. Advances in theoretical techniques and computer power have dramatically increased the usefulness and importance of computational chemistry as a complement to experimental studies. This is especially relevant to catalytic reactions of industrial importance as well as the analysis of structural properties and the resulting spectroscopic phenomena in what are often otherwise counterintuitive models. This dissertation is a representation of the research I performed during my years as a graduate student in the Chemistry Department at the University of North Texas. My research has examined novel carbenes as efficient organocatalysts, structure-based design and optimization of small molecule drugs, and surveying methods to accurately describe structure and bonding and catalytic abilities of inorganic and organometallic systems. The works presented herein have been published or are awaiting submission to peer-reviewed scientific journals. A variety of computational techniques were employed in studying metal-mediated catalysis and organocatalysis as well as the structural and photophysical properties of systems containing closed-shell transition metal ions.

Orientador: Cristiano Soleo de Funari / Resumo: Aproximadamente 3,7 x 109 toneladas de resíduos agrícolas são produzidos anualmente no mundo. Por ser uma das grandes potências agrícolas atualmente, grandes quantidades de resíduos agrícolas são geradas constantemente no Brasil. Uma das principais culturas produzidas no país é a soja. Além de seu uso na pecuária, utilizada na alimentação animal, assim como para alimentação humana, a soja desperta grande interesse do ponto de vista farmacológico, por ser uma das principais fontes de isoflavonas, uma forma de fitoestrogênio, sendo umas das espécies listadas na RENISUS. Este trabalho teve como objetivo investigar o perfil químico dos resíduos provenientes da cultura da soja (caules, folhas e vagens) por meio de uma abordagem analítica verde. Os extratos foram obtidos em triplicata por maceração dinâmica a 30 °C, com acetona e etanol, com e sem adição de ácido. O solvente acetonitrila foi utilizado como solvente de referência, pois é comumente empregado tanto para a extração como para a separação de isoflavonas presentes em grãos de soja. Os extratos foram analisados por cromatografia líquida de alta eficiência acoplada a um espectrofotômetro de untravioleta/visível (HPLC-PAD/UV) e a comparação da eficiência de extração entre os solventes testados foi feita com base em número total de picos, área total sob os picos e rendimento da extração. Os solventes verdes etanol e acetona mostraram-se mais eficientes do que o solvente de referência acetonitrila. Posteriormente, uma estratég... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Approximately 3.7 x 109 tonnes of agricultural waste is produced annually in the world. Because it is one of the great agricultural powers today, large amounts of agricultural residues are constantly generated in Brazil. One of the main crops produced in the country is soy. In addition to its use in livestock and human nutrition, the soybean awakes great interest from the pharmacological point of view, being one of the main sources of isoflavones, a form of phytoestrogen, being one of the species listed in RENISUS. The objective of this work was to investigate the chemical profile of residues from soybean (shoots, leaves and pods) using a green analytical approach. The extracts were obtained in triplicate by dynamic maceration at 30 ° C, with acetone and ethanol, with and without acid addition. The solvent acetonitrile was used as reference solvent, since it is commonly used both for the extraction and the separation of isoflavones present in soybean grains. The extracts were analyzed by high performance liquid chromatography coupled to an untraviolet/visible spectrophotometer (HPLC-PAD/UV) and the comparison of the extraction efficiency among the solvents tested was done based on total number of peaks, total area under peaks and extraction yield. The green solvents ethanol and acetone were more efficient than the reference solvent acetonitrile. Subsequently, a strategy for the identification of compounds in mixture, based on data obtained by high performance liquid chromatog... (Complete abstract click electronic access below) / Mestre

Orientador: Leonardo Pezza / Co-orientador: Helena Redigolo Pezza / Banca: Edilene Cristina Ferreira / Banca: Sebastião de Paula Eiras / Resumo: A presença de elevadas concentrações de íons cobre(II) na aguardente a torna prejudicial à saúde humana e também é uma das causas que têm impedido o Brasil de atingir níveis maiores de exportação do produto. No Brasil, o limite máximo de cobre permitido em aguardente pelo MAPA (Ministério da Agricultura, Pecuária e Abastecimento) é de 5,00 mg.L-1, sendo que em países da União Européia e Estados Unidos esses limites são mais rigorosos, não permitindo mais que 1,00 e 2,00 mg.L-1, respectivamente. Assim, o presente trabalho propõe um novo método analítico simples, rápido, seguro, sensível, econômico, portátil, com baixo consumo de reagentes, geração de mínima quantidade de resíduos e ambientalmente mais amigável para determinação de íons cobre(II) em aguardente de cana-de-açúcar. Para processar a reação utilizou-se o agente cromogênico 1-(2-piridilazo)-2-naftol (PAN) e detecção por espectroscopia de reflectância difusa combinada com spot test. A reação de formação do complexo bis[1-(2-piridilazo)-2-naftalato]cobre(II) (Cu(PAN)2) foi realizada em papel de filtro, por meio da adição de 30 μL da solução do reagente cromogênico, com posterior secagem do papel e em seguida a adição de 30 μL da solução do analito. A máxima formação do produto ocorreu com concentração do agente cromogênico PAN de 0,12% m/v em etanol, concentração alcoólica de 40,0% v/v em pH 5,00 e 5 minutos de tempo de reação com detecção a 559 nm. Verificou-se que íons cádmio(II), cobalto(II), chumbo(II), ferro(III), manganês(II), níquel(II) e zinco(II) são interferentes na reação. Desta forma, empregou-se ácido malônico e tripolifosfato pentassódico (trifosfato de sódio) como agentes mascarantes a uma concentração de 0,25% m/v, reduzindo os efeitos de interferência para aproximadamente 2,0% e o deixando dentro dos limites toleráveis. Nas condições otimizadas de... / Abstract: The presence of high concentrations of copper(II) ions in sugarcane spirits become harmful to human health and is also one of the causes that have prevented Brazil from achieving higher levels of exports of the product. The maximum limit of copper in spirit allowed by MAPA (Ministry of Agriculture, Livestock and Supply) is 5.00 mg.L-1, and in European Union countries and the United States these limits are more stringent, not allowing more than 1.00 e 2.00 mg.L-1 respectively. In light of the above, this work proposes a new analytical method that is simpler, fast, safe, sensitive, economical, portable, with low reagent consumption, generating minimal waste and environmentally more friendly for the determination of copper(II) ions in Brazilian sugarcane spirits. To process the reaction, the methodology used involved chromogenic agent 1-(2-pyridylazo)-2-naphthol (PAN) and detection by diffuse reflectance spectroscopy combined with spot test. The reaction of complex formation bis[1-(2-pyridylazo)-2-naphthalate]copper(II) (Cu(PAN)2) was carried out on a filter paper through the addition of 30 μL solution of the chromogenic reagent with subsequent drying of the paper, and 30 μL of analyte solution was added thereafter. The maximum product formation occurred at 559 nm with PAN chromogenic agent concentration of 0.12% m/v in ethanol, alcohol concentration of 40.0% v/v at pH 5.0 and 5 minute reaction time. Cadmium(II) ions, cobalt(II), lead(II), iron(III), manganese(II), nickel(II) and zinc(II) were found to interfere in the reaction. By virtue of that, malonic acid and pentasodium tripolyphosphate (sodium triphosphate) were used as masking agents at a concentration of 0.25% m/v, reducing the effects of interference at about 2.0% and leaving it within tolerable limits. In order to optimize the determination of copper(II) ions, an analytical curve was constructed and its equation is described by... / Mestre

Compte tenu du développement continu de nouveaux complexes organométalliques, il est impératif de trouver des alternatives aux méthodes de synthèses classiques qui utilisent des solvants toxiques, des températures de réaction élevées et qui ne conduisent pas toujours aux complexes souhaités avec de bons rendements. L’utilisation de broyeurs billes pour la synthèse de complexes NHC-métal (argent et cuivre tout particulièrement) et de leurs précurseurs a permis le développement de méthodes efficaces, générales, rapides et présentant un impact environnemental plus faible que les méthodes classiques en solution. Ces méthodes permettent aussi de donner accès à des molécules d’intérêts, difficilement synthétisables par voie classique. De nombreux complexes jusqu’alors jamais reportés dans la littérature ont ainsi pu être formés. Ces complexes ont démontré leur efficacité en tant que catalyseur dans la réaction de A3 pour la formation d’amines propargyliques. / Due to the constant increase of publications reporting new organometallic complexes, it becomes urgent to develop alternative synthetic methods to the classical ones that use toxic solvents, high reaction temperatures and that do not always lead to the desired complexes in good yields. The use of ball-mills for the synthesis of NHC-metal complexes (silver and copper in particular) and their precursors has enabled the development of efficient, general, quick and more sustainable methods. These methods give an access to interesting compounds, difficult to synthesize using another pathway. Numerous complexes never reported in the literature were also formed. These complexes have demonstrated their efficiency as catalysts in the A3 reaction to form the propargylamines.

L’originalité de ce travail est d’utiliser de la lignine, une macromolécule aromatique extraite de la biomasse lignocellulosique, en remplacement de résines pétrosourcées pour la formulation d’encres à destination de l’emballage alimentaire. Différentes modifications chimiques ont été réalisées sur des lignines commerciales afin de les rendre compatibles avec les composants utilisés dans la formulation des encres. Les réactifs et les procédés mis en place ont été choisis afin de limiter l’impact environnemental sur l’ensemble de la chaîne de valeur. Les modifications chimiques ont été mesurées par différentes techniques analytiques telles que la GPC SEC pour la distribution des masses molaires et la spectrométrie RMN et FTIR pour la mesure des groupements fonctionnels de la lignine. Les propriétés des encres obtenues ont été caractérisées par des mesures rhéologiques et colorimétriques (système CIE L*a*b*) sur des essais d’impression. Parmi les résultats notables, des changements au niveau de l’équilibre hydrophile/hydrophobe ont été particulièrement remarqués. Qui plus est, les encres à base de lignines modifiées chimiquement ont permis une amélioration du gamut de couleur par rapport à celles contenant de la lignine brute. A l’issue de ces travaux, deux applications ont été proposées Des encres biosourcées à base de lignine qui répondent à la majorité des exigences industrielles ont été formulées. De plus, une formule d’enduction à base de lignine modifiée améliorant les propriétés barrières des papiers recyclés a été développée avec succès. / The originality of this work is to use lignin, an aromatic macromolecule from lignocellulosic biomass, in replacement of petroleum-based resins for the formulation of inks for food contact packaging applications. Different chemical modifications were carried out on commercial lignins, in order to make them compatible with the ink components. Used reagents and processes were chosen in order to limit the environmental impact of the whole value chain. Chemical modifications were monitored by several analytical techniques such as GPC SEC for the molar mass distribution and NMR and FTIR spectrometry for the monitoring of lignin functional groups. Ink properties were characterized by rheological and colorimetric (CIE L*a*b* system) measurements on printed samples. Among the significant results, changes in hydrophilic/hydrophobic balance were particularly noticed. Furthermore, the colour gamut of modified lignin-based inks was enhanced, compared to the one of unmodified lignin-based inks. Two applications emerged from this work: (1) formulation of lignin-based bio-sourced inks, which meet most of the industrial requirements, and (2), development of a modified lignin-based coating which improved barrier properties of recycled paperboard.