Polycyclic aromatic hydrocarbons (PAHs) are an important environmental issue and the identification of new biocatalysts for an efficient biodegradation of these compounds is essential for bioremediation. Therefore, fungi strains isolated for the first time from a tropical peat at Santo Amaro das Brotas (Brazil) were studied for fluoranthene biodegradation. Fusarium sp. AC-7, Penicillium sp. AC-1 and Penicillium sp. AC-6 were isolated using fluoranthene as sole carbon source. All strains were tested for biodegradation of 100 mg L−1 fluoranthene during 14 and 28 days. After 28 days of biodegradation, 64 ± 3, 60 ± 4 and 51 ± 2% biodegradation was observed for Penicillium sp. AC-1, Penicillium sp. AC-6 and Fusarium sp. AC-7, respectively. Analysis of the obtained compounds enabled the identification of four metabolites, which were common to the three employed strains: anthrone, anthraquinone, 9-methoxyanthracene and cyclopropa[1]phenanthrene. It is important to note that control experiments were performed. The obtained results clearly demonstrated the efficiency of tropical peat fungi in the transformation of fluoranthene. These findings showed the potential of tropical peats for isolation of fungi and indicated that these strains can be applied for bioremediation processes of areas contaminated with fluoranthene and other PAHs.

New biocatalysts for bioremediation techniques are necessary nowadays. Therefore, a bacterial consortium isolated from Brazilian Savannah was employed for biodegradation of 100 mg L-1 esfenvalerate in liquid culture medium. The bacterial consortium (Lysinibacillus xylanilyticus CBMAI2085, Bacillus cereus CBMAI2067, Lysinibacillus sp. CBMAI2051 and Bacillus sp. CBMAI2052) biodegraded this pyrethroid efficiently. The assays were conducted in triplicate, and after 12 days, 90% of the pesticide was degraded producing 3-phenoxybenzoic acid (35.0 ± 3.1 mg L-1) and 2-(4-chlorophenyl)-3-methylbutanoic acid (34.0 ± 2.8 mg L-1). The bacterial consortium (52 ± 5% biodegradation) was more efficient in the biodegradation than the average of the same strains solely employed (40 ± 7% biodegradation), showing that the use of consortia is an interesting approach. However, the strain Bacillus cereus CBMAI2067 (67 ± 3% biodegradation) was more efficient than the bacterial consortium, showing its potential as source of carboxylesterases and proving that, in this case, the use of a unique efficient strain is more adequate.

In this study, whole cells of marine-derived fungi were used to reduce isatin (1H-indole-2,3-dione) to dioxindole (3-hydroxyindolin-2-one) for 7 days at 32 °C. The screening showed that several strains could reduce isatin and produce the enantioenriched dioxindole. The best conversions were obtained by Cladosporium sp. CBMAI 1237 and Westerdykella sp. CBMAI 1679, however, the best enantiomeric excess was obtained only by Aspergillus sydowii CBMAI 935 (66% ee). In conclusion, marine-derived fungi show potential for asymmetric and chemoselective reduction of isatin (1H-indole-2,3-dione).

This manuscript describes the biooxidation of rac-camphor using whole cells of marine-derived fungus Botryosphaeria sp. CBMAI 1197. The main biotransformation products of this monoterpene were achieved via a hydroxylation reaction and occurred with 5 days of rac-camphor incubation. Products were identified by means of gas chromatography mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) data. The major hydroxylated products were 6-endo-hydroxycamphor, 6-exo-hydroxycamphor, 5-exo-hydroxycamphor, 5-endo-hydroxycamphor, 3-exo-hydroxycamphor and 8-hydroxycamphor. The 6-exo-hydroxycamphor was obtained through a retro-aldol reaction when 6-endo-hydroxycamphor was maintained in presence of CDCl3; this isomerization was confirmed by 1H NMR and GC-MS data.

<p>Enzymatic kinetic resolution (EKR) of (±)-cyanohydrins was performed by using immobilized lipase from <italic>Candida antarctica</italic> (CALB) under conventional ordinary conditions (orbital shaking) and under microwave radiation (MW). The use of microwave radiation contributed very expressively on the reduction of the reaction time from 24 to 2 h. Most importantly, high selectivity (up to 92% <italic>ee</italic>_p) as well as conversion was achieved under MW radiation (50-56%).</p>

Este trabalho descreve a síntese e caracterização de um novo adsorvente mesoporoso que consiste o MCM-41 funcionalizado com o ácido p-aminobenzóico modificado (PABA-Si). A síntese foi realizada pelo método hidrotermal/co-condensação. O PABA-MCM-41 foi caracterizado usando FTIR, SAXS, adsorção/desorção de N2, MEV e TG. Os experimentos em batelada foram utilizados para determinar os efeitos da concentração inicial do adsorbato, tempo de contato e temperatura. A adsorção do benzo[a]pireno (B[a]P) alcançou o equilíbrio depois de 90 min (q e = 27,2 µg g-1) e concentrações mais altas do adsorbato foram associadas com o aumento, em ambos, da percentagem de remoção (71,0-95,7%) e no valor de q e (20,1-27,1 µg g-1). A adsorção seguiu o modelo cinético de pseudo-segunda ordem, e se ajustou ao modelo de isoterma de Langmuir. Foi verificado em temperaturas mais altas um aumento na taxa inicial de adsorção e na constante cinética. Os parâmetros termodinâmicos indicaram que o processo foi espontâneo, endotérmico e com uma tendência para desordem.

This work describes the synthesis and characterization of a new mesoporous adsorbent consisting of MCM-41 functionalized with modified p-aminobenzoic acid (PABA-Si). The synthesis was performed by a hydrothermal/co-condensation method. The PABA-MCM-41 was characterized using FTIR, SAXS, N2 adsorption/desorption, SEM, and TG. Batch experiments were employed to determine the effects of initial adsorbate concentration, contact time, and temperature. The adsorption of benzo[a]pyrene (B[a]P) reached equilibrium after ca. 90 min (q e = 27.2 µg g-1), and higher adsorbate concentrations were associated with increases in both the percentage removal (71.0-95.7%) and the value of q e (20.1-27.1 µg g-1). The adsorption followed pseudo-second order kinetics, and was fitted using the Langmuir isotherm model. At higher temperatures, there were increases in the initial rate of adsorption and the kinetic constant. The thermodynamic parameters indicated that the process was spontaneous, endothermic, and with a tendency to disorder.

As resoluções cinéticas de (±)-β-azidofeniletanóis foram realizadas usando a lipase de Candida antarctica fornecendo os compostos enantiomericamente enriquecidos, (R)-β-azidofeniletanóis e acetato de (S)-β-azidofeniletila em bons excessos enantioméricos (até > 99%). Os (R)-β-azidofeniletanóis enantiomericamente enriquecidos foram submetidos à reação de ciclização com o triflato de 2-(trimetilsilil)fenila e CsF resultando em 1,2,3-benzotriazóis em bons rendimentos (75-86%) pela reação de cicloadição [3 + 2], a qual envolve a formação in situ de benzino.

The kinetic resolutions of (±)-β-azidophenylethanols were carried out using lipase from Candida antarctica, and enantiomerically enriched (R)-β-azidophenylethanols and their corresponding (S)-β-azidophenylethyl acetates were obtained in good enantiomeric excesses (up to > 99%). The enantiomerically enriched (R)-β-azidophenylethanols were subjected to cyclization reaction with 2-(trimethylsilyl)phenyl triflate and CsF producing chiral 1,2,3-benzotriazole compounds in good yields (75-86%) by a [3 + 2] cycloaddition, which involves the benzyne formation.

A resolução cinética da (±)-mandelonitrila foi realizada utilizando a lipase de Candida antarctica sob condição convencional (agitação orbital) e irradiação de micro-ondas em tolueno, produzindo o acetato de (S)-mandelonitrila com elevada seletividade (92-98% ee, excesso enantiomérico). O álcool remanescente da (R)-mandelonitrila sob irradiação de micro-ondas e agitação orbital foi parcialmente convertido em benzaldeído via equilíbrio químico espontâneo. O acetato de (S)-mandelonitrila foi produzido com 92% ee e rendimento de 35% em 8 h de reação sobre irradiação de micro-ondas. A transesterificação da (±)-mandelonitrila em agitador orbital produziu a (R)-mandelonitrila (51% ee) remanescente e o acetato da (S)-mandelonitrila (98% ee) de acordo com a regra Kazlauskas com 184 h de reação.

The kinetic resolution of (±)-mandelonitrile was carried out using lipase from Candida antarctica under conventional condition (orbital shaker) and microwave irradiation in toluene, producing the (S)-mandelonitrile acetate with high selectivity (up to > 98% ee, enantiomeric excess). The unreacted (R)-mandelonitrile under microwave irradiation and conventional condition was partially converted into benzaldehyde by spontaneous chemical equilibrium. The (S)-mandelonitrile acetate under microwave irradiation was produced with 92% ee and 35% yield for 8 h of reaction. Conventional transesterification of (±)-mandelonitrile in an orbital shaker produced unreacted (R)-mandelonitrile (51% ee) and (S)-mandelonitrile acetate (98% ee) in accordance with Kazlauskas rule for 184 h of reaction.

The bioreduction of a series of substituted a-tetralones, carried out using Daucus carota root (carrot), afforded the corresponding homochiral a-tetralols in variable conversions (9 to 90%) and excellent enantiomeric excesses. Two of the assayed a-tetralones were resistant to the bioreduction conditions. The absolute configurations of four a-tetralols were assigned as being (S), by comparison to the (S)-enantiomers obtained by kinetic resolution promoted by CALB-catalysed acetylation. Additionally, the new 5-methoxy-6-methyl-1-tetralone was synthesized in seven steps from 3-methylsalicylic acid.