• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 3
  • 2
  • Tagged with
  • 6
  • 3
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Microbial Pre-treatment of Double Refractory Gold Ores

Afidenyo, JAMES 23 September 2008 (has links)
The use of microorganisms notably bacteria in mineral processing industry is presently one of the leading emerging pre-treatment techniques being employed for the processing of double refractory gold ores and concentrates. Currently numerous studies are in progress to further improve upon the efficiency of the bacterial process and to investigate the potential of other microorganisms. In this study, microbial pre-treatment of double refractory gold ore (sample A) and concentrate (sample B) was investigated using a white-rot fungus, Tramestes versicolor (ATTC 20869). Pulp density, temperature, pH and retention times were the process variables considered. Preliminary studies investigated the amenability of selected pure sulfide sulfur minerals, various types of coal and ore sample A to fungal degradation. Various pre-treatment scenarios were also studied to optimize gold extraction. These were single stage, a two-step and two stage processes involving the well known chemolithotrophic bacteria Acidithiobacillus thiooxidans (ATTC 15494), Acidithiobacillus ferrooxidans (ATTC 19859) and Leptospirillum ferrooxidans (ATTC 53992), the bacterium, Streptomyces setonii (ATTC 39116) and the white-rot fungus, Tramestes versicolor. Preliminary results for sample A indicated that T. versicolor did not degrade sulfides significantly at its optimum growth conditions (pH range of 4.5 – 5.0) and carbonaceous matter was not degraded but rather passivated as preg-robbing decreased significantly. Lignite was inert to passivation by T. versicolor unlike bituminous coal and to lower extent anthracite. Stimulated alkaline conditions (pH range of 9.5 – 10.5) recorded the overall best sulfur oxidation. Results of both the single stage and two-step processes confirmed that carbonaceous matter was passivated by T. versicolor; as preg-robbing decreased significantly from 18.1% to ≤ 1.0%. Gold extraction by cyanidation of the pre-treated sample A was 82.5% for the two-step as against 80.5 % for the single stage and 15.0% for the untreated sample. Application of the two-step and single stage process conditions to sample B resulted in 93.3% and 89.9% gold extraction respectively as against untreated concentrate of 30.5%. For the various two stage pre-treatment processes investigated, the abiotic - S. setonii process recorded the best gold extraction of 81.5% for sample A. S. Setonii degraded carbonaceous matter unlike T. versicolor which passivated it. However, it takes only 3 - 7 days for T. versicolor to effect passivation and eliminate preg-robbing while 14 - 56 days is required for S. setonii to degrade carbonaceous matter significantly. The result of the novel microbial pre-treatment process indicated that sulfide sulfur was degraded under alkaline conditions and carbonaceous matter passivated by T. versicolor at its optimum growth conditions. This led to a significant improvement in gold extraction from the double refractory gold ore and concentrate investigated. / Thesis (Master, Mining Engineering) -- Queen's University, 2008-09-22 16:42:01.272
2

Chemical and Biological Treatment of Acid Mine Drainage for the Removal of Heavy Metals and Acidity

Diz, Harry Richard 16 September 1997 (has links)
This dissertation reports the design of a process (patent pending) to remove iron from acid mine drainage (AMD) without the formation of metal hydroxide sludge. The system includes the oxidation of ferrous iron in a packed bed bioreactor, the precipitation of iron within a fluidized bed, the removal of manganese and heavy metals (Cu, Ni, Zn) in a trickling filter at high (>9) pH, with final neutralization in a carbonate bed. The technique avoided the generation of iron oxyhydroxide sludge. In the packed bed bioreactor, maximum substrate oxidation rate (R<sub>,max</sub>) was 1500 mg L⁻¹ h⁻¹ at dilution rates of 2 h⁻¹, with oxidation efficiency at 98%. The half-saturation constant (similar to a Ks) was 6 mg L⁻¹. The oxidation rate was affected by dissolved oxygen below 2 mg L⁻¹, with a Monod-type Ko for DO of 0.33 mg L⁻¹. Temperature had a significant effect on oxidation rate, but pH (2.0 to 3.25) and supplemental CO₂ did not affect oxidation rates. Iron hydroxide precipitation was not instantaneous when base was added at a OH/Fe ratio of less than 3. Induction time was found to be a function of pH, sulfate concentration and iron concentration, with a multiple R² of 0.84. Aqueous [Al (III)] and [Mn (II)] did not significantly (α = 0.05) affect induction time over the range of concentrations investigated. When specific loading to the fluidized bed reactor exceeded 0.20 mg Fe m⁻² h⁻¹, dispersed iron particulates formed leading to a turbid effluent. Reactor pH determined the minimum iron concentration in the effluent, with an optimal at pH 3.5. Total iron removals of 98% were achieved in the fluidized bed with effluent [Fe] below 10 mg L⁻¹. Further iron removal occurred within the calcium carbonate bed. Heavy metals were removed both in the fluidized bed reactor as well as in the trickling filter. Oxidation at pH >9 caused manganese to precipitate (96% removal); removals of copper, nickel, and zinc were due primarily to sorption onto oxide surfaces. Removals averaged 97% for copper, 70% for nickel and 94% for zinc. The treatment strategy produced an effluent relatively free of iron (< 3 mg/L), without the formation of iron sludge and may be suitable for AMD seeps, drainage from acidic tailings ponds, active mine effluent, and acidic iron-rich industrial wastewater. / Ph. D.
3

Resolução cinética de haloidrinas racêmicas com a lipase B de Candida antarctica e biotransformação de produtos naturais por micro-organismos / Kinetic resolution of racemic halohydrins by lipase B from Candida antarctica and biotransformation of natural products by microrganisms

Martins, Mariana Provedel 22 November 2012 (has links)
Neste trabalho foram realizadas as resoluções cinéticas das haloidrinas racêmicas (RS)-1-benziloxi-3-cloropropan-2-ol (4a), (RS)-1-benziloxi-3-bromopropan-2-ol (4b), (RS)-1-cloro-3-(4-metoxifenoxi)propan-2-ol (5a), (RS)-1-bromo-3-(4-metoxifenoxi)propan-2-ol (5b), (RS)-1-aliloxi-3-cloro-propan-2-ol (6a) e (RS)-1-aliloxi-3-bromo-propan-2-ol (6b) empregando-se a lipase comercial de Candida antarctica CALB como catalisador e acetato de vinila como agente acilante. As razões enantioméricas das resoluções cinéticas foram determinadas com o intuito de avaliar a influência dos grupos substituintes halogênios presentes nas haloidrinas na eficiência das resoluções cinéticas desses substratos. Os valores de razão enantiomérica obtidos foram: E = 5,6, 4a; E = 4,3, 4b; E = 98, 5a; E = 6,6, 5b; E = 20, 6a; E = 5,8, 6b. Assim, somente as resoluções cinéticas das cloroidrinas 5a e 6a apresentaram valores de E característicos de resoluções eficientes, fornecendo os produtos (R)-1-cloro-3-(4-metoxifenoxi)propan-2-ol 5a com rendimento de 46% e ee = 40%; (S)-acetato de 1-cloro-3-(4-metoxifenoxi)propan-2-ila 8a com rendimento de 40% e ee = 97%; (R)-1-aliloxi-3-cloro-propan-2-ol (R)-6a com rendimento de 45% e ee = 72% e (S)-acetato de 1-aliloxi-3-cloro-propan-2-ila (S)-9a com rendimento de 41% e ee = 81%. Realizou-se também uma triagem com os fungos de origem marinha Bostryospharia sp. Br09, Eutypella sp. Br23, Hidropisphaera sp. Br27, Xylaria sp. Br61, Aspergillus sydowii Ce19, Aspergillus sydowii Ce15, Penicillium raistriicki Ce16, Penicillium oxalicum F30 e Penicillium citrinum F53 frente aos produtos naturais sclareol, ambrox e sclareolide, a fim de selecionar os micro-organismos capazes de promover reações de bio-oxidação nesses substratos. Os metabólitos hidroxilados obtidos nas reações de biotransformação foram: 3&beta;-hidroxi-ambrox 10a (rendimentos de 17% e 11%, com os fungos Br09 e Br23, respectivamente); 1&beta;-hidroxi-ambrox 10b (rendimento de 14% com o fungo Ce19); 3&beta;-hidroxi-sclareol 11a (rendimentos de 31%, 69% e 55%, com os fungos Br61, Br09 e Br23, respectivamente); 18-hidroxi-sclareol 11b (rendimento de 10% com o fungo Br61); 3&beta;-hidroxi-sclareolide 12a (rendimentos de 34% e 7%, com os fungos Br09 e Br23, respectivamente). Realizou-se também um estudo utilizando-se três meios de cultura líquidos (meio sintético, meio YM e meio PDB) para a reação de biotransformação do sclareol 11 no composto ambradiol 13 com a levedura Hyphozyma roseonigra. Observou-se que a reação com o meio de cultura líquido PDB apresentou os melhores resultados, com uma grande eficiência na conversão do substrato no produto de interesse, o qual foi obtido com um rendimento de 82%. Esta reação foi realizada também através de um processo fermentativo conduzido em biorreator, apresentando bons resultados quanto à conversão da reação, porém com a desvantagem do alto custo do meio de cultura PDB, o que dificulta a realização deste processo fermentativo em larga escala. / In this work we performed kinetic resolutions of the racemic halohydrins (RS)-1-benzyloxy-3-chloropropan-2-ol (4a), (RS)-1-benzyloxy-3-bromopropan-2-ol (4b), (RS)-1-chloro-3-(4-methoxyphenoxy)propan-2-ol (5a), (RS)-1-bromo-3-(4-methoxyphenoxy)propan-2-ol (5b), (RS)-1-allyloxy-3-chloro-propan-2-ol (6a) and (RS)-1-allyloxy-3-bromo-propan-2-ol (6b) using the lipase from Candida antarctica CALB as catalyst and vinyl acetate as acylating agent. The enantiomeric ratios of the kinetic resolutions were determined in order to evaluate the influence of the halogen substituents present in halohydrins in the efficiency of the kinetic resolutions of these substrates. The enantiomeric ratio values obtained were: E = 5.6, 4a; E = 4.3, 4b; E = 98, 5a; E = 6.6, 5b; E = 20, 6a; E = 5.8, 6b. Thus, only the kinetic resolutions of the chlorohydrins 5a and 6a showed characteristic values of E of efficient resolutions, providing the products (R)-1-chloro-3-(4-methoxyphenoxy)propan-2-ol 5a with 46% yield and ee = 40%; (S)-1-chloro-3-(4-methoxyphenoxy)propan-2-yl acetate 8a with 40% yield and ee = 97%; (R)-1-allyloxy-3-chloro-propan-2-ol (R)-6a with 45% yield and ee = 72% and (S)-1-allyloxy-3-chloro-propan-2-yl acetate (S)-9a with 41% yield and ee = 81%. We also performed a screening with the marine fungi Bostryospharia sp. Br09, Eutypella sp. Br23, Hidropisphaera sp. Br27, Xylaria sp. Br61, Aspergillus sydowii Ce19, Aspergillus sydowii Ce15, Penicillium raistriicki Ce16, Penicillium oxalicum F30 and Penicillium citrinum F53 using the natural products ambrox, sclareol and sclareolide in order to select the microorganisms capable of promoting bio-oxidation reactions of these substrates. The hydroxylated metabolites obtained from the biotransformation reactions were: 3&beta;-hydroxy-ambrox 10a (17% and 11% yield with Br09 and Br23, respectively); 1&beta;-hydroxy-ambrox 10b (14% yield with Ce19); 3&beta;-hydroxy-sclareol 11a (31%, 69% and 55% yield with Br61, Br23 and Br09, respectively); 18-hydroxy-sclareol 11b (10% yield with Br61); 3&beta;-hydroxy-sclareolide 12a (34% and 7% yields with Br09 Br23, respectively). We also performed a study employing three liquid culture media (synthetic, YM and PDB media) for the biotransformation reaction of sclareol 11 into ambradiol 13 using Hyphozyma roseonigra as catalyst. The reaction with the liquid culture media PDB showed the best results, with a high efficiency in the conversion of the substrate into the desired product, which was obtained in 82% yield. This reaction was also performed using a fermentation process conducted in a bioreactor, with good results, however with the disadvantage of the high cost of culture media PDB, which hinders the performance of this large-scale fermentation.
4

Biooxidation of sulphide under denitrifying conditions in an immobilized cell bioreactor

Tang, Kimberley Marie Gar Wei 26 June 2008
Hydrogen sulphide (H2S) is a serious problem for many industries, including oil production and processing, pulp and paper, and wastewater treatment. In addition, H2S is usually present in natural gas and biogas. It is necessary to control the generation and release of H2S into the environment because H2S is corrosive, toxic, and has an unpleasant odour. In addition, the removal of H2S from natural gas and biogas is essential for preventing the emission of SO2 upon combustion of these gases. Physicochemical processes have been developed for the removal of H2S. These processes employ techniques such as chemical or physical absorption, thermal and catalytic conversion, and liquid phase oxidation. In comparison, biological processes for the removal of sulphide typically operate at ambient temperature and pressure, with the feasibility for the treatment of smaller streams, and the absence of expensive catalysts. The objective of the present work was to study the biooxidation of sulphide under denitrifying conditions in batch system and a continuous immobilized cell bioreactor using a mixed microbial culture enriched from the produced water of a Canadian oil reservoir. <p>In the batch experiments conducted at various initial sulphide concentrations, an increase in the sulphide oxidation and nitrate reduction rates was observed as the initial sulphide concentration was increased in the range 1.7 to 5.5 mM. An extended lag phase of approximately 10 days was observed when sulphide concentrations around or higher than 14 mM were used. This, when considered with the fact that the microbial culture was not able to oxidize sulphide at an initial concentration of 20 mM, indicates the inhibitory effects of sulphide at high concentrations.<p>The effect of the initial sulphide to nitrate concentrations ratio (ranging from 0.3 to 4.0) was also studied. As the initial sulphide to nitrate ratio decreased, the sulphide oxidation rates increased. The increasing trend was observed for initial nitrate concentrations in the range of 1.3 to 7.3 mM, corresponding to ratios of 4.08 to 0.83. The increase in nitrate reduction rates was more pronounced than that of the sulphide oxidation rates. However at nitrate concentrations higher than 7.3 mM (ratios lower than 0.83) the nitrate reduction rate remained constant. The percentage of sulphide that was oxidized to sulphate increased from 2.4% to 100% as the initial sulphide to nitrate ratio decreased from 4.08 to 0.42. This indicated that at ratios lower than 0.42, nitrate would be in excess and at ratios exceeding 4.08, nitrate would be limiting. In the continuous bioreactor systems, at sulphide loading rates ranging from 0.26 to 30.30 mM/h, sulphide conversion remained in the range of 97.6% to 99.7%. A linear increase in the volumetric oxidation rate of sulphide was observed as the sulphide loading rate was increased with the maximum rate being 30.30 mM/h (98.5% conversion). Application of immobilized cells led to a significant increase in oxidation rate of sulphide when compared with the rates obtained in a bioreactor with freely suspended cells. At nitrate loading rates ranging from 0.19 to 24.44 mM/h, the nitrate conversion ranged from 97.2% to 100% and a linear increase in volumetric reduction rate was observed as the nitrate loading rate was increased, with the maximum rate being 24.44 mM/h (99.7% conversion). <p>A second bioreactor experiment was conducted to investigate the effects of sulphide to nitrate concentrations ratio on the performance of the system. Sulphide conversion was complete at sulphide to nitrate ratios of 1.1 and 1.3, but decreased to 90.5% at the ratio of 3.1 and 65.0% at the ratio of 5.0, indicating nitrate was limiting for sulphide to nitrate ratios of 3.1 and 5.0. The increase in the sulphide to nitrate ratio (and the resulting limitation of nitrate) caused a decrease in the volumetric reaction rate of sulphide.<p>Nitrate conversion was complete at sulphide to nitrate ratios of 1.3, 3.1, and 5.0; however, at a ratio of 1.1, the conversion of nitrate dropped to 59.6%, indicating that nitrate was in excess, and sulphide was limiting. The volumetric reaction rate of nitrate decreased as the sulphide to nitrate ratio increased for ratios of 1.3, 3.1, and 5.0; this was due to the decrease in the nitrate loading rate. For sulphide to nitrate ratios of 1.1 and 1.3, 7.2% and 19.6% of the sulphide was converted to sulphate, respectively. At ratios of 3.1 and 5.0, no sulphate was generated. For ratios between 1.3 and 5.0, an increase in the ratio caused a decrease in the generation of sulphate.
5

Biooxidation of sulphide under denitrifying conditions in an immobilized cell bioreactor

Tang, Kimberley Marie Gar Wei 26 June 2008 (has links)
Hydrogen sulphide (H2S) is a serious problem for many industries, including oil production and processing, pulp and paper, and wastewater treatment. In addition, H2S is usually present in natural gas and biogas. It is necessary to control the generation and release of H2S into the environment because H2S is corrosive, toxic, and has an unpleasant odour. In addition, the removal of H2S from natural gas and biogas is essential for preventing the emission of SO2 upon combustion of these gases. Physicochemical processes have been developed for the removal of H2S. These processes employ techniques such as chemical or physical absorption, thermal and catalytic conversion, and liquid phase oxidation. In comparison, biological processes for the removal of sulphide typically operate at ambient temperature and pressure, with the feasibility for the treatment of smaller streams, and the absence of expensive catalysts. The objective of the present work was to study the biooxidation of sulphide under denitrifying conditions in batch system and a continuous immobilized cell bioreactor using a mixed microbial culture enriched from the produced water of a Canadian oil reservoir. <p>In the batch experiments conducted at various initial sulphide concentrations, an increase in the sulphide oxidation and nitrate reduction rates was observed as the initial sulphide concentration was increased in the range 1.7 to 5.5 mM. An extended lag phase of approximately 10 days was observed when sulphide concentrations around or higher than 14 mM were used. This, when considered with the fact that the microbial culture was not able to oxidize sulphide at an initial concentration of 20 mM, indicates the inhibitory effects of sulphide at high concentrations.<p>The effect of the initial sulphide to nitrate concentrations ratio (ranging from 0.3 to 4.0) was also studied. As the initial sulphide to nitrate ratio decreased, the sulphide oxidation rates increased. The increasing trend was observed for initial nitrate concentrations in the range of 1.3 to 7.3 mM, corresponding to ratios of 4.08 to 0.83. The increase in nitrate reduction rates was more pronounced than that of the sulphide oxidation rates. However at nitrate concentrations higher than 7.3 mM (ratios lower than 0.83) the nitrate reduction rate remained constant. The percentage of sulphide that was oxidized to sulphate increased from 2.4% to 100% as the initial sulphide to nitrate ratio decreased from 4.08 to 0.42. This indicated that at ratios lower than 0.42, nitrate would be in excess and at ratios exceeding 4.08, nitrate would be limiting. In the continuous bioreactor systems, at sulphide loading rates ranging from 0.26 to 30.30 mM/h, sulphide conversion remained in the range of 97.6% to 99.7%. A linear increase in the volumetric oxidation rate of sulphide was observed as the sulphide loading rate was increased with the maximum rate being 30.30 mM/h (98.5% conversion). Application of immobilized cells led to a significant increase in oxidation rate of sulphide when compared with the rates obtained in a bioreactor with freely suspended cells. At nitrate loading rates ranging from 0.19 to 24.44 mM/h, the nitrate conversion ranged from 97.2% to 100% and a linear increase in volumetric reduction rate was observed as the nitrate loading rate was increased, with the maximum rate being 24.44 mM/h (99.7% conversion). <p>A second bioreactor experiment was conducted to investigate the effects of sulphide to nitrate concentrations ratio on the performance of the system. Sulphide conversion was complete at sulphide to nitrate ratios of 1.1 and 1.3, but decreased to 90.5% at the ratio of 3.1 and 65.0% at the ratio of 5.0, indicating nitrate was limiting for sulphide to nitrate ratios of 3.1 and 5.0. The increase in the sulphide to nitrate ratio (and the resulting limitation of nitrate) caused a decrease in the volumetric reaction rate of sulphide.<p>Nitrate conversion was complete at sulphide to nitrate ratios of 1.3, 3.1, and 5.0; however, at a ratio of 1.1, the conversion of nitrate dropped to 59.6%, indicating that nitrate was in excess, and sulphide was limiting. The volumetric reaction rate of nitrate decreased as the sulphide to nitrate ratio increased for ratios of 1.3, 3.1, and 5.0; this was due to the decrease in the nitrate loading rate. For sulphide to nitrate ratios of 1.1 and 1.3, 7.2% and 19.6% of the sulphide was converted to sulphate, respectively. At ratios of 3.1 and 5.0, no sulphate was generated. For ratios between 1.3 and 5.0, an increase in the ratio caused a decrease in the generation of sulphate.
6

Resolução cinética de haloidrinas racêmicas com a lipase B de Candida antarctica e biotransformação de produtos naturais por micro-organismos / Kinetic resolution of racemic halohydrins by lipase B from Candida antarctica and biotransformation of natural products by microrganisms

Mariana Provedel Martins 22 November 2012 (has links)
Neste trabalho foram realizadas as resoluções cinéticas das haloidrinas racêmicas (RS)-1-benziloxi-3-cloropropan-2-ol (4a), (RS)-1-benziloxi-3-bromopropan-2-ol (4b), (RS)-1-cloro-3-(4-metoxifenoxi)propan-2-ol (5a), (RS)-1-bromo-3-(4-metoxifenoxi)propan-2-ol (5b), (RS)-1-aliloxi-3-cloro-propan-2-ol (6a) e (RS)-1-aliloxi-3-bromo-propan-2-ol (6b) empregando-se a lipase comercial de Candida antarctica CALB como catalisador e acetato de vinila como agente acilante. As razões enantioméricas das resoluções cinéticas foram determinadas com o intuito de avaliar a influência dos grupos substituintes halogênios presentes nas haloidrinas na eficiência das resoluções cinéticas desses substratos. Os valores de razão enantiomérica obtidos foram: E = 5,6, 4a; E = 4,3, 4b; E = 98, 5a; E = 6,6, 5b; E = 20, 6a; E = 5,8, 6b. Assim, somente as resoluções cinéticas das cloroidrinas 5a e 6a apresentaram valores de E característicos de resoluções eficientes, fornecendo os produtos (R)-1-cloro-3-(4-metoxifenoxi)propan-2-ol 5a com rendimento de 46% e ee = 40%; (S)-acetato de 1-cloro-3-(4-metoxifenoxi)propan-2-ila 8a com rendimento de 40% e ee = 97%; (R)-1-aliloxi-3-cloro-propan-2-ol (R)-6a com rendimento de 45% e ee = 72% e (S)-acetato de 1-aliloxi-3-cloro-propan-2-ila (S)-9a com rendimento de 41% e ee = 81%. Realizou-se também uma triagem com os fungos de origem marinha Bostryospharia sp. Br09, Eutypella sp. Br23, Hidropisphaera sp. Br27, Xylaria sp. Br61, Aspergillus sydowii Ce19, Aspergillus sydowii Ce15, Penicillium raistriicki Ce16, Penicillium oxalicum F30 e Penicillium citrinum F53 frente aos produtos naturais sclareol, ambrox e sclareolide, a fim de selecionar os micro-organismos capazes de promover reações de bio-oxidação nesses substratos. Os metabólitos hidroxilados obtidos nas reações de biotransformação foram: 3&beta;-hidroxi-ambrox 10a (rendimentos de 17% e 11%, com os fungos Br09 e Br23, respectivamente); 1&beta;-hidroxi-ambrox 10b (rendimento de 14% com o fungo Ce19); 3&beta;-hidroxi-sclareol 11a (rendimentos de 31%, 69% e 55%, com os fungos Br61, Br09 e Br23, respectivamente); 18-hidroxi-sclareol 11b (rendimento de 10% com o fungo Br61); 3&beta;-hidroxi-sclareolide 12a (rendimentos de 34% e 7%, com os fungos Br09 e Br23, respectivamente). Realizou-se também um estudo utilizando-se três meios de cultura líquidos (meio sintético, meio YM e meio PDB) para a reação de biotransformação do sclareol 11 no composto ambradiol 13 com a levedura Hyphozyma roseonigra. Observou-se que a reação com o meio de cultura líquido PDB apresentou os melhores resultados, com uma grande eficiência na conversão do substrato no produto de interesse, o qual foi obtido com um rendimento de 82%. Esta reação foi realizada também através de um processo fermentativo conduzido em biorreator, apresentando bons resultados quanto à conversão da reação, porém com a desvantagem do alto custo do meio de cultura PDB, o que dificulta a realização deste processo fermentativo em larga escala. / In this work we performed kinetic resolutions of the racemic halohydrins (RS)-1-benzyloxy-3-chloropropan-2-ol (4a), (RS)-1-benzyloxy-3-bromopropan-2-ol (4b), (RS)-1-chloro-3-(4-methoxyphenoxy)propan-2-ol (5a), (RS)-1-bromo-3-(4-methoxyphenoxy)propan-2-ol (5b), (RS)-1-allyloxy-3-chloro-propan-2-ol (6a) and (RS)-1-allyloxy-3-bromo-propan-2-ol (6b) using the lipase from Candida antarctica CALB as catalyst and vinyl acetate as acylating agent. The enantiomeric ratios of the kinetic resolutions were determined in order to evaluate the influence of the halogen substituents present in halohydrins in the efficiency of the kinetic resolutions of these substrates. The enantiomeric ratio values obtained were: E = 5.6, 4a; E = 4.3, 4b; E = 98, 5a; E = 6.6, 5b; E = 20, 6a; E = 5.8, 6b. Thus, only the kinetic resolutions of the chlorohydrins 5a and 6a showed characteristic values of E of efficient resolutions, providing the products (R)-1-chloro-3-(4-methoxyphenoxy)propan-2-ol 5a with 46% yield and ee = 40%; (S)-1-chloro-3-(4-methoxyphenoxy)propan-2-yl acetate 8a with 40% yield and ee = 97%; (R)-1-allyloxy-3-chloro-propan-2-ol (R)-6a with 45% yield and ee = 72% and (S)-1-allyloxy-3-chloro-propan-2-yl acetate (S)-9a with 41% yield and ee = 81%. We also performed a screening with the marine fungi Bostryospharia sp. Br09, Eutypella sp. Br23, Hidropisphaera sp. Br27, Xylaria sp. Br61, Aspergillus sydowii Ce19, Aspergillus sydowii Ce15, Penicillium raistriicki Ce16, Penicillium oxalicum F30 and Penicillium citrinum F53 using the natural products ambrox, sclareol and sclareolide in order to select the microorganisms capable of promoting bio-oxidation reactions of these substrates. The hydroxylated metabolites obtained from the biotransformation reactions were: 3&beta;-hydroxy-ambrox 10a (17% and 11% yield with Br09 and Br23, respectively); 1&beta;-hydroxy-ambrox 10b (14% yield with Ce19); 3&beta;-hydroxy-sclareol 11a (31%, 69% and 55% yield with Br61, Br23 and Br09, respectively); 18-hydroxy-sclareol 11b (10% yield with Br61); 3&beta;-hydroxy-sclareolide 12a (34% and 7% yields with Br09 Br23, respectively). We also performed a study employing three liquid culture media (synthetic, YM and PDB media) for the biotransformation reaction of sclareol 11 into ambradiol 13 using Hyphozyma roseonigra as catalyst. The reaction with the liquid culture media PDB showed the best results, with a high efficiency in the conversion of the substrate into the desired product, which was obtained in 82% yield. This reaction was also performed using a fermentation process conducted in a bioreactor, with good results, however with the disadvantage of the high cost of culture media PDB, which hinders the performance of this large-scale fermentation.

Page generated in 0.174 seconds