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This paper reports the enantioseparation of ß-hydroxy-1,2,3-triazole derivatives, which present a broad range of biological properties, by supercritical fluid chromatography (SFC) and high-performance liquid chromatography techniques (HPLC). Polysaccharide-based chiral columns (cellulose and amylose) were used to evaluate the separation in SFC and HPLC. Time of analyses, consumption of solvent, and parameter optimization were reduced using SFC technique. The columns based on cellulose chiral stationary phase using 2-propanol and ethanol as modifiers showed the best results for the enantioresolution of the (±)-ß-hydroxy-1,2,3-triazoles by SFC analyses. These techniques were applied to evaluate the selectivity of biocatalytic reduction of ß-keto-1,2,3-triazoles by marine-derived fungus Penicillium citrinum CBMAI 1186 to obtain the (±)-ß-hydroxy-1,2,3-triazoles.

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The contamination of agricultural lands by pesticides is a serious environmental issue. Consequently, the development of bioremediation methods for different active ingredients, such as pyrethroids, is essential. In this study, the enantioselective biodegradation of (±)-lambda-cyhalothrin ((±)-LC) by marine-derived fungi was studied. Experiments were performed with different fungi strains (Aspergillus sp. CBMAI 1829, Acremonium sp. CBMAI 1676, Microsphaeropsis sp. CBMAI 1675 and Westerdykella sp. CBMAI 1679) in 3% malt liquid medium with 100 mg L-1 of (±)-LC. All strains biodegraded this insecticide and the residual concentrations of (±)-LC (79.2-55.2 mg L-1, i.e., 20.8-44.8% biodegradation), their enantiomeric excesses (2-42% ee) and the 3-phenoxybenzoic acid (PBAc) concentrations (0.0-4.1 mg L-1) were determined. In experiments for 28 days of biodegradation in the absence and presence of artificial seawater (ASW) with the most efficient strain Aspergillus sp. CBMAI 1829, increasing concentrations of PBAc with (0.0-4.8 mg L-1) and without ASW (0.0-15.3 mg L-1) were observed. In addition, a partial biodegradation pathway was proposed. All the evaluated strains biodegraded preferentially the (1R,3R,αS)-gamma-cyhalothrin enantiomer. Therefore, marine-derived fungi enantioselectively biodegraded (±)-LC and can be applied in future studies for bioremediation of contaminated areas. This enantioselective biodegradation indicates that the employment of the most active enantiomer GC as insecticide not only enable the use of a lower amount of pesticide, but also a more easily biodegradable product, reducing the possibility of environmental contamination.

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The biodegradation of polycyclic aromatic hydrocarbons (PAHs) by marine-derived fungi was reported in this work. Marine-derived fungi (Trichoderma harzianum CBMAI 1677, Cladosporium sp. CBMAI 1237, Aspergillus sydowii CBMAI 935, Penicillium citrinum CBMAI 1186 and Mucor racemosus CBMAI 847) biodegraded anthracene (14days, 130rpm, 50mgmL-1 initial concentration in malt 2% medium). Cladosporium sp. CBMAI 1237 was the most efficient strain and biodegraded more anthracene in the presence (42% biodegradation) than in the absence (26%) of artificial seawater, suggesting that the biodegradation of PAHs may be faster in seawater than in non-saline environment. After 21days, Cladosporium sp. CBMAI 1237 biodegraded anthracene (71% biodegradation), anthrone (100%), anthraquinone (32%), acenaphthene (78%), fluorene (70%), phenanthrene (47%), fluoranthene (52%), pyrene (62%) and nitropyrene (64%). Previous undocumented metabolites were identified and, anthraquinone was a common product of different PAHs biodegradation. The marine-derived fungus Cladosporium sp. CBMAI 1237 showed potential for bioremediation of PAHs.

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Esfenvalerate biodegradation by marine-derived fungi is reported here. Esfenvalerate (S,S-fenvalerate) and its main metabolites [3-phenoxybenzaldehyde (PBAld), 3-phenoxybenzoic acid (PBAc), 3-phenoxybenzyl alcohol (PBAlc), and 2-(4-chlorophenyl)-3-methylbutyric acid (CLAc)] were quantitatively analyzed by a validated method in triplicate experiments. All the strains (Penicillium raistrickii CBMAI 931, Aspergillus sydowii CBMAI 935, Cladosporium sp. CBMAI 1237, Microsphaeropsis sp. CBMAI 1675, Acremonium sp. CBMAI 1676, Westerdykella sp. CBMAI 1679, and Cladosporium sp. CBMAI 1678) were able to degrade esfenvalerate, however, with different efficiencies. Initially, 100 mg L(-1) esfenvalerate (Sumidan 150SC) was added to each culture in 3 % malt liquid medium. Residual esfenvalerate (64.8-95.2 mg L(-1)) and the concentrations of PBAc (0.5-7.4 mg L(-1)), ClAc (0.1-7.5 mg L(-1)), and PBAlc (0.2 mg L(-1)) were determined after 14 days. In experiments after 7, 14, 21, and 28 days of biodegradation with the three most efficient strains, increasing concentrations of the toxic compounds PBAc (2.7-16.6 mg L(-1), after 28 days) and CLAc (6.6-13.4 mg L(-1), after 28 days) were observed. A biodegradation pathway was proposed, based on HPLC-ToF results. The biodegradation pathway includes PBAld, PBAc, PBAlc, ClAc, 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile, 3-(hydroxyphenoxy)benzoic acid, and methyl 3-phenoxy benzoate. Marine-derived fungi were able to biodegrade esfenvalerate in a commercial formulation and showed their potential for future bioremediation studies in contaminated soils and water bodies.

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This review presents the recent research in biocatalysis and biotransformation in Brazil. Several substrates were biotransformed by fungi, bacteria and plants. Biocatalytic deracemization of secondary alcohols, oxidation of sulfides, sp(3) CH hydroxylation and epoxidation of alkenes were described. Chemo-enzymatic resolution of racemic alcohols and amines were carried out with lipases using several substrates containing heteroatoms such as silicon, boron, selenium and tellurium. Biotransformation of nitriles by marine fungi, hydrolysis of epoxides by microorganisms of Brazilian origin and biooxidation of natural products were described. Enzymatic reactions under microwave irradiation, continuous flow, and enzymatic assays using fluorescent probes were reported.

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RESUMO

Seven marine fungi strains (Aspergillus sydowii CBMAI 934, A. sydowii CBMAI 935, A. sydowii CBMAI 1241, Penicillium decaturense CBMAI 1234, Penicillium raistrickii CBMAI 931, P. raistrickii CBMAI 1235, and Trichoderma sp. CBMAI 932) were screened by their growth in the presence of methyl parathion (MP) in a solid culture medium. The strains with best growth were A. sydowii CBMAI 935 and P. decaturense CBMAI 1234. Biodegradation reactions were performed in 10, 20 and 30d in a malt extract liquid medium containing commercial MP and whole cells of A. sydowii CBMAI 935 and P. decaturense CBMAI 1234. In 20d, A. sydowii CBMAI 935 was able to degrade all pesticide, whereas P. decaturense CBMAI 1234 promoted a complete degradation in 30d. A. sydowii CBMAI 935 and P. decaturense CBMAI 1234 could degrade the product of the MP enzymatic hydrolysis, p-nitrophenol, on average of 51 and 40% respectively. Both strains used MP as a sole source of carbon and provided satisfactory results. Metabolites detected in the medium showed that the presumable reaction pathway occurred through the activation of MP to its more toxic form, methyl paraoxon, which was further degraded to p-nitrophenol.

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