RESUMO
Whole cells of the marine fungi Aspergillus sydowii Gc12, Penicillium raistrickii Ce16, P. miczynskii Gc5, and Trichoderma sp. Gc1, isolated from marine sponges of the South Atlantic Ocean (Brazil), have been screened for the enzymatic resolution of (±)-2-(benzyloxymethyl)oxirane (benzyl glycidyl ether; 1). Whole cells of A. sydowii Gc12 catalyzed the enzymatic hydrolysis of (R,S)-1 to yield (R)-1 with an enantiomeric excess (ee) of 24-46% and 3-(benzyloxy)propane-1,2-diol (2) with ee values <10%. In contrast, whole cells of Trichoderma sp. Gc1 afforded (S)-1 with ee values up to 60% and yields up to 39%, together with (R)-2 in 25% yield and an ee of 32%. This is the first published example of the hydrolysis of 1 by whole cells of marine fungi isolated from the South Atlantic Ocean. The hydrolases from the two studied fungi exhibited complementary regioselectivity in opening the epoxide ring of racemic 1, with those of A. sydowii Gc12 showing an (S) preference and those of Trichoderma sp. Gc1 presenting an (R) preference for the substrate.
Assuntos
Aspergillus/metabolismo , Desinfetantes/metabolismo , Óxido de Etileno/metabolismo , Trichoderma/metabolismo , Poluentes Químicos da Água/metabolismo , Acetofenonas/química , Acetofenonas/metabolismo , Aspergillus/isolamento & purificação , Biotransformação , Desinfetantes/química , Óxido de Etileno/química , Hidrólise , Trichoderma/isolamento & purificação , Microbiologia da Água , Poluentes Químicos da Água/químicaRESUMO
5,6-Epoxycholestan-3beta-ol derivatives were hydrolyzed in a diastereoconvergent manner by growing and resting cells of several strains of Aspergillus niger, particularly A. niger ATCC 11394. These strains displayed opposite regioselectivity toward each isomer in an alpha and beta epoxide mixture, thus, the nucleophilic attack took place at the less substituted and the most substituted carbon atom on each diasteromer, respectively. These biocatalysts opened trisubstituted oxiranes but were unable to hydrolyze the disubstituted oxiranes in the tested sterol derivatives. These findings suggest that A. niger strains possess another hydrolytic ability different from the commercial A. niger epoxide hydrolase (EH) that did not accept this kind of steroidal oxiranes as substrates.
Assuntos
Aspergillus niger/metabolismo , Epóxido Hidrolases/metabolismo , Compostos de Epóxi/química , Óxido de Etileno/química , Biotransformação , Óxido de Etileno/metabolismo , Hidrólise , Cinética , Modelos Moleculares , Estrutura Molecular , EstereoisomerismoRESUMO
Ethylene oxide (EtO) is an important intermediate industrial chemical which is also used for sterilizing medical products and hospital equipment. In the present study we have evaluated some biological markers, such as chromosomal aberrations, micronuclei and EtO-hemoglobin adducts in the peripheral blood cells, and micronuclei in buccal exfoliated cells of 22 controls and 75 workers employed in an industry in Brazil using EtO as an intermediate. Measurements of EtO in the general area showed that workers were exposed to 2-5 ppm time-weighted average (TWA) for an 8-h working day, during the 3-month sampling. Our results indicate that exposure to EtO resulted in a statistically significant enhancement of chromosomal aberrations (P = 0.01) and of micronuclei in binucleated lymphocytes (P < 0.001). For the frequencies of micronucleated cells in buccal mucosa there was no statistically significant difference between exposed and control groups. The mean values of hemoglobin adduct (HOEtVal) measurements obtained from a selected group of exposed and unexposed donors were statistically different.