Diimide generated from the hydrazine/hydrogen peroxide/catalyst system can be used to hydrogenate unsaturated polymers in latex form. As an economical and environmentally benign alternative to the commercial processes based on hydrogen/transition metal catalysts, this method is of special interest to industry. This thesis provides a detailed description of the diimide hydrogenation process. Reaction kinetics, catalysts and gel formation mechanism have been investigated. <br /> <br /> Four main reactions and a mass transfer process form three parallel processes in this system: diimide is generated at the interface of the latex particles; diimide diffuses into the organic phase to saturate carbon-carbon double bonds; diimide may be consumed at the interface by hydrogen peroxide, and may also be consumed by the disproportionation reaction in the organic phase. The two side reactions contribute to the low hydrogenation efficiency of hydrogen peroxide. Slowing down hydrogen peroxide addition and using stable interfacial catalysts may totally suppress the side reaction in the aqueous phase. The actual catalytic activity of metal ions in the latex depends on the hydrogen peroxide concentration and the addition procedure of reactants. Cupric ion provides better selectivity for hydrogenation than ferric ion and silver ion do. Boric acid as a promoter provides improved selectivity for hydrogenation and faster diimide generation rate. The side reaction in the rubber phase results in low efficiency and gel formation. The rate constants of the four reactions in this system are estimated. <br /> <br />It is shown that the hydrogenation of nitrile rubber latex with an average particle diameter of 72 nm is mainly a reaction-controlled process. Diimide diffusion presents limitation upon hydrogenation at high hydrogenation degree range. Antioxidants can not effectively inhibit gel formation during hydrogenation. Hydrogenation of a core-shell latex with NBR as the shell layer should be able to achieve a higher efficiency, a higher degree of hydrogenation and a lower level of crosslinking.

ABSTRACT Recent studies have shown that R. rhodochrous DAP 96253 has the ability to delay the ripening of many climacteric fruit, by potentially degrading volatile compounds released by plant cells during the ripening process. Rhodococcus rhodochrous DAP 96253 cells were cultured on YEMEA medium supplemented with inducers, (16mM cobalt and 125mM urea), that over-expressed nitrile hydratase (NHase) and amidase (AMDase) enzymes. Cells were cultured on propylene/ ethylene as sole carbon source to induce alkene monooxygenase (AMO) like activity. Induced R. rhodochrous DAP 96253 cells displayed an 83% increase in final total dry weight compared to cells previously cultured on non-induced medium. Induced R. rhodochrous DAP 96253 cells displayed a 53-85% increase in NHase activity after exposure to propylene/ethylene, and cells displayed a 24-53% increase in NHase activity after exposure to fruit. Non-induced R. rhodochrous DAP 96253 cells displayed a 1-5% increase in NHase activity after propylene/ethylene, and cells displayed an 18-38% increase in NHase activity after exposure to fruit. Propylene/ethylene induced nitrilase activity in non-induced R. rhodochrous DAP 96253cells. Experimental results suggest that R. rhodochrous DAP 96253 may use NHase, amidase, nitrilase, and AMO like activity to delay ripening of climacteric fruit. Rhodococcus rhodochrous 96253 cells cultured on propylene/ethylene and cofactors (16mM cobalt and 125mM urea) displayed improved ability to delay ripening of fruit.

Student Number : 0009756Y - MSc dissertation - School of Molecular and Cell Biology - Faculty of Science / A versatile nitrile-degrading bacterium was isolated through enrichment culturing of soil samples from Johannesburg, South Africa. It was identified as Rhodococcus rhodochrous and submitted to the ATCC culture collection as strain BAA-870. This organism was determined to be a potential biocatalyst in that it contains a two enzyme system with strong nitrile-converting activity comprising nitrile hydratase and amidase. The development of a suitable assay for measuring the activity of the enzymes of interest was explored. A pHsensitive indicator-based assay was found to be suitable only for colorimetrically identifying highly concentrated enzymes with acid-forming activity. An ophthaldialdehyde- based fluorimetric assay was found to be applicable to conversions of select compounds, but the assay could not be used to measure the activity of Rhodoccocus rhodochrous ATCC BAA-870. High performance liquid chromatography was the most suitable method for reliable and quantitative measurement of nitrile hydrolysis, and is applicable to monitoring activities of whole-cell and cell-free extracts. Initial analysis of six compounds, benzonitrile, benzamide, benzoic acid, hydrocinnamonitrile, 3-hydroxy-3- phenylpropionitrile and 3-hydroxy-3-phenylpropionic acid, was performed by HPLC to measure linearly the average retention area, amount and absorbance of the compounds up to 10 mM concentrations. The conversion of the substrates benzonitrile, benzamide and 3- hydroxy-3-phenylpropionitrile were further analysed with respect to time and enzyme concentration. Conversion of benzonitrile to benzamide by the nitrile hydratase was rapid and could be measured in 10 minutes. Conversion of benzamide to benzoic acid by the amidase was considered the rate-limiting step and could be followed for 90 minutes of the reaction at the concentrations tested. Conversion of 3-hydroxy-3-phenylpropionitrile was linearly measured over 20 minutes. Mass spectral analysis was used to confirm, at a structural level, relatively less volatile reactant compounds with a higher thermal stability, including benzamide, 3-hydroxy-3-phenylpropionitrile and 3-hydroxy-3-phenylpropionic acid. Protein concentration studies indicated that activity against benzonitrile was probably due to a nitrile hydratase with potent activity rather than a concentrated enzyme, since formation of benzamide from benzonitrile showed first order reaction kinetics at protein concentrations less than 0.2 mg/ml. Formation of benzoic acid from benzamide was linear up to 1.3 mg total protein and product formation from 3-hydroxy-3-phenylpropionitrile was linear up to 1.4 mg total protein. Overlapping activities against benzonitrile and 3- hydroxy-3-phenylpropionitrile indicate that the nitrile hydratase has differing substrate specificity for the two compounds, with higher activity toward the small aromatic mononitrile, benzonitrile, than the arylaliphatic b-hydroxy nitrile, 3-hydroxy-3- phenylpropionitrile. The nitrile-converting activity of Rhodococcus rhodochrous ATCC BAA-870 would be suitable for biocatalysis as the conversions take place under a wide pH range, require low concentrations of enzyme and reactions are fast. Separation of nitrileconverting activities in Rhodococcus rhodochrous ATCC BAA-870 was undertaken using various chromatography methods to establish a simple, one-step protocol for biocatalytic enzyme preparations. HPLC was not suited to assaying nitrile-converting activity in chromatofocusing fractions, and chromatofocusing Ampholyte buffers were found to interfere with activity measurements. Gel exclusion chromatography of the soluble protein extract from Rhodococcus rhodochrous ATCC BAA-870 indicated the enzyme/s responsible for nitrile hydratase activity are high molecular weight proteins ranging from 40 to 700 kDa in size, while the amidase native enzyme is proposed to be roughly 17 to 25 kDa. SDS-PAGE analysis of gel exclusion and ion exchange chromatography fractions indicated nitrile converting activity in Rhodococcus rhodochrous ATCC BAA-870 is likely due to multimer-forming enzymes made up of 84, 56, 48 and 21 kDa subunits. It is postulated that nitrile hydratase is made up of ab and a2b2 tetramers that may form larger enzyme aggregates. Ion exchange chromatography was used to separate nitrile hydratase with high activity against benzonitrile and 3-hydroxy-3-phenylpropionitrile from amidase activity, and showed that an additional, substrate specific nitrile hydratase may exist in the organism.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação foi estudado um processo de polimerização em emulsão de acrilonitrila, butadieno e ácido carboxílico, em escala piloto, para a produção de látex nitrílico carboxilado com alto teor de sólidos diretamente no processo reacional, sem precisar passar por etapas pós-reação de concentração. Foi estudado o efeito da temperatura, do tipo e quantidade de emulsificante, do tipo e quantidade de iniciador, do tipo de agitador e da velocidade de agitação e das etapas de adição incremental para obtenção de látex com alto teor de sólidos e a sua influência no tamanho e distribuição das partículas. Os polímeros obtidos foram caracterizados por gravimetria, usando forno de microondas para obtenção do teor de sólidos, espalhamento de luz, para determinação de tamanho e distribuição das partículas, e por espectroscopia na região do infravermelho para determinação da composição monomérica. Foi obtido polímero com até 57% de sólidos totais. O tamanho médio de partícula variou de 130 nm a 230 nm. / In this dissertation an emulsion polymerization process of acrylonitrile, butadiene and carboxylic acid was studied, in pilot scale, for the production of carboxylated nitrile latex with high solids content directly from the reaction process, without the need of post-reaction steps of concentration. It was studied the effect of temperature, type and amount of emulsifier, type and amount of initiator, type of stirring system, stirring speed and the steps of incremental additions for the production of high solid latex and its influence in the average particle size and distribution. The obtained copolymers were characterized by gravimetry using a microwave oven to determine total solids content, by light scattering in order to determine the average particle size and its distribution and by infrared spectroscopy to determine monomer composition. A latex up to 57% of total solids was obtained. The average particle size ranged from 130 nm to 230 nm.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação foi estudado um processo de polimerização em emulsão de acrilonitrila, butadieno e ácido carboxílico, em escala piloto, para a produção de látex nitrílico carboxilado com alto teor de sólidos diretamente no processo reacional, sem precisar passar por etapas pós-reação de concentração. Foi estudado o efeito da temperatura, do tipo e quantidade de emulsificante, do tipo e quantidade de iniciador, do tipo de agitador e da velocidade de agitação e das etapas de adição incremental para obtenção de látex com alto teor de sólidos e a sua influência no tamanho e distribuição das partículas. Os polímeros obtidos foram caracterizados por gravimetria, usando forno de microondas para obtenção do teor de sólidos, espalhamento de luz, para determinação de tamanho e distribuição das partículas, e por espectroscopia na região do infravermelho para determinação da composição monomérica. Foi obtido polímero com até 57% de sólidos totais. O tamanho médio de partícula variou de 130 nm a 230 nm. / In this dissertation an emulsion polymerization process of acrylonitrile, butadiene and carboxylic acid was studied, in pilot scale, for the production of carboxylated nitrile latex with high solids content directly from the reaction process, without the need of post-reaction steps of concentration. It was studied the effect of temperature, type and amount of emulsifier, type and amount of initiator, type of stirring system, stirring speed and the steps of incremental additions for the production of high solid latex and its influence in the average particle size and distribution. The obtained copolymers were characterized by gravimetry using a microwave oven to determine total solids content, by light scattering in order to determine the average particle size and its distribution and by infrared spectroscopy to determine monomer composition. A latex up to 57% of total solids was obtained. The average particle size ranged from 130 nm to 230 nm.

The mol­ecular structure of ruthenocenecarbo­nitrile, [Ru([eta]5-C5H4C[triple bond]N)([eta]5-C5H5)], exhibits point group symmetry m, with the mirror plane bis­ecting the mol­ecule through the C[triple bond]N substituent. The RuII atom is slightly shifted from the [eta]5-C5H4 centroid towards the C[triple bond]N substituent. In the crystal, mol­ecules are arranged in columns parallel to [100]. One-dimensional inter­molecular [pi]-[pi] inter­actions [3.363 (3) Å] between the C[triple bond]N carbon atom and one carbon of the cyclo­penta­dienyl ring of the overlaying mol­ecule are present.

The mol­ecular structure of ruthenocenecarbo­nitrile, [Ru([eta]5-C5H4C[triple bond]N)([eta]5-C5H5)], exhibits point group symmetry m, with the mirror plane bis­ecting the mol­ecule through the C[triple bond]N substituent. The RuII atom is slightly shifted from the [eta]5-C5H4 centroid towards the C[triple bond]N substituent. In the crystal, mol­ecules are arranged in columns parallel to [100]. One-dimensional inter­molecular [pi]-[pi] inter­actions [3.363 (3) Å] between the C[triple bond]N carbon atom and one carbon of the cyclo­penta­dienyl ring of the overlaying mol­ecule are present.

The synthesis of high value acrylic monomers is currently done industrially via cyanohydrin hydration using concentrated acids, resulting in large quantities of useless byproducts. This current process is energy intensive and lacks atom economy; therefore, alternative cyanohydrin hydration strategies are under investigation. Ideally, cyanohydrin hydration would be done using organometallic nitrile hydration catalysts. Cyanohydrin hydration with these catalysts is challenging, because it needs to be done at low temperatures and under acidic conditions to reduce cyanohydrin degradation and catalyst poisoning with cyanide. This dissertation describes the reactivity of [Ru(#951; / 10000-01-01

Acrylic monomers are important materials that represent a large portion of the economy. The current industrial synthesis hydrates cyanohydrins with sulfuric acid, a process which results in large amounts of waste and significant energy costs. A transition metal catalyzed, acid free hydration of cyanohydrins would be beneficial from both economic and environmental standpoints. However, this reaction is challenging, as many catalysts are poisoned by the cyanide released when cyanohydrins degrade. Therefore the development of a catalyst that is resistant to cyanide poisoning is the ideal method to circumvent these difficulties. This dissertation describes several cyanohydrin hydration catalysts, with an emphasis on nanoparticle catalysts. These are at the interface between the homogeneous and heterogeneous catalysts that have been explored previously for this reaction. Chapter I surveys previous studies on nanoparticle catalysts for nitrile hydration and their implications for the hydration of cyanohydrins. Chapter II reports on the homogeneous platinum catalysts [PtHCl(P(NMe2)3)2] and [PtH2(P(NMe2)3)2], exploring secondary coordination sphere effects to enhance nitrile hydration. Chapter III describes another example of this type of complex, [PtH2(P(OMe)3)2], that forms catalytically active nanoparticles under reaction conditions. Explorations of the reactivity of this catalyst with nitriles and cyanohydrins are also described in this chapter. Chapter IV investigates a silver nanoparticle catalyst with a water soluble phosphine (1,3,5-triaza-7-phosphaadamantane) ligand for its activity towards the hydration of nitriles and cyanohydrins. The results of the degradation of the nanoparticles in the presence of cyanide are also described. Chapter V reports on the preparation and examination of a solid supported nickel catalyst for cyanohydrin hydration. Finally, Chapter VI describes how these investigations have made progress towards the development of a cyanide resistant nitrile hydration catalyst. This dissertation includes previously published and unpublished co-authored material. / 2015-09-29

Three new tetrakis [Rh2(PhNCOCH3)4·xNCR] (R = {2-CH3}C6H4 (x=2), R = {3-CH3}C6H4 (x=1), R = (3-CN)C6H4∞ (x=1)) complexes have been synthesized and characterized. These complexes were characterized by IR and 1H NMR spectroscopies and X-ray crystallography which solved with R1<0.05. [Rh2(PhNCOCH3)4·2NC{2-CH3}C6H4] was triclinic (a=9.79Å, b=14.79Å, c=16.36Å, α=103.84⁰, β=99.17⁰, γ=99.77⁰, P-1(#2), μCN=2227.78cm-1, Rh-Rh=2.42Å, N-C=1.13Å, 1.14Å, Rh-N=2.34Å, 2.35Å, Rh-N-C=151.6⁰, 152.5⁰, Rh-Rh-N=173.0⁰, 174.6⁰). [Rh2(PhNCOCH3)4·NC{3-CH3}C6H4] was triclinic (a=11.71Å, b=13.02Å, c=13.40Å, α=72.34⁰, β=66.78⁰, γ=82.74⁰, P-1(#2), μCN=2241.28cm-1, Rh-Rh=2.40Å, N-C=1.14Å, Rh-N=2.16Å, Rh-N-C=166.3⁰, Rh-Rh-N=175.9⁰). [Rh2(PhNCOCH3)4·2NC{3-CN}C6H4]∞ was triclinic (a=11.88Å, b=13.30Å, c=14.88Å, α=77.98⁰, β=74.61⁰, γ=65.48⁰, P-1(#2), μCN=2233.57cm-1, Rh-Rh=2.41Å, N-C=1.13Å, 1.13Å, Rh-N=2.18Å, 2.38Å, Rh-N-C=166.8⁰, 127.7⁰, Rh-Rh-N=178.4⁰, 175.4⁰). The bond distances, bond angles and bonding interactions (σ and π) are similar to the metal-carbene bond formed during carbenoid transformations catalyzed by dirhodium(II) compounds.