Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta no. 4-12, 030018 Bucharest 030016, Romania
Prof. Simona Coman
Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta no. 4-12, 030018 Bucharest 030016, Romania
A biocatalytic synthesis of glycerol carbonate (GlyC), as an added-value product of renewable glycerol, has been developed using a catalytic route in which glycerol (Gly) was reacting with dimethyl carbonate (DMC) in the presence of lipase under solvent-free conditions. The enzyme screening indicated lipase from Aspergillus niger as the most efficient biocatalyst for the GlyC synthesis. After the optimization of the reaction conditions it was established that the best results corresponded to 12% (w/w) Aspergillus nigerlipase, to a glycerol : DMC molar ratio of 1 : 10, to an incubation time of 4 h and to an incubation temperature of 60 °C. Consequently, the glycerol conversion was around 74%, the yield in GlyC of 59.3% and the selectivity to GlyC of 80.3%. Recycling experiments demonstrated that the biocatalyst can be successfully used for several reaction cycles (at least 4 times) and confirmed its very high stability under the reaction conditions.
4 November 2003 in Angewandte Chemie International Edition
Beta zeolites, impregnated with Ir, catalyze the one-pot full conversion of citronellal to menthol by consecutive acid-catalyzed cyclization and Ir-catalyzed hydrogenation, with 95% selectivity for the menthol isomers, of which 75% is the desired (−)-menthol.
A new strategy for the preparation of biocatalysts based on enzyme immobilization was explored, leading to cross-linked enzyme aggregate onto magnetic particles (CLEMPA). Lipase enzyme from Aspergillus niger was precipitated from aqueous solution followed by cross-linking of the enzyme aggregates onto magnetic particles using glutaraldehyde as cross-linker. An optimization study has been carried out for the CLEMPA approach to determine the best experimental conditions for both preparation steps (i.e. enzyme precipitation and cross-linking of the enzyme aggregates onto magnetic particles). Type and concentration of the precipitation agent, type and size of magnetic particles, ratio of lipase to magnetic particles, concentration of the cross-linker and growth time of CLEMPA clusters were the experimental factors taken under investigation. Characterization of CLEMPA biocatalyst considering the cluster size and lipase loading was performed using light scattering detection and UV-vis spectrophotometric techniques. The catalytic capacity of CLEMPA biocatalyst was tested with the “green” alternative of glycerol carbonate (GlyC) synthesis. CLEMPA catalyzed the conversion of glycerol to GlyC with an excess of dimethyl carbonate (DMC) providing solvent-free conditions for the reaction. These experiments resulted in encouraging biocatalytic performance with 61% glycerol conversion, 55% GlyC yield and 90% selectivity in GlyC. CLEMPA biocatalyst was also tested in the reaction of “crude” glycerol extracted from the biodiesel process, with similar performance results. Recycling experiments for 20 successive reaction cycles demonstrated the robustness of the prepared CLEMPA structure.
Currently, carbon quantum dots (CQDs) have been widely investigated as an enhancing photocatalytic component of various nanocomposites. In this study, hetero-structures containing carbon quantum dots (CQDs) associated to zinc oxide were prepared following two one-pot procedures: (i) a hydrothermal approach in which commercial ZnO was used as carrier for CQDs; and (ii) an approach in which the ZnO/CQDs samples were produced in situ by adding zinc acetate to an aqueous suspension of CQDs. CQDs were prepared in advance by a low-temperature hydrothermal (LHT) treatment of useless humins wastes produced by the glucose dehydration in an acidic medium. These samples were characterized by several techniques such asadsorption-desorption isotherms of liquid nitrogen at 77K, X-ray diffraction (XRD), infrared diffuse reflectance with Fourier transform (DRIFT) and UV-vis spectroscopy. The photocatalytic behavior of these materials was investigated in the degradation of methylene blue (MB). The obtained results revealed electronic interactions between CQDs and ZnO which have as an effect an enhancement of the charge separation and diminution of the charge recombination. In accordance, a correlation between the photocatalytic activity and the intrinsic properties of ZnO/CQDs has been evidenced. The highest photocatalytic activity corresponded to the heterostructure containing highly dispersed narrow sized CQDs onto ZnO. Under visible light irradiation and after 180 min of irradiation, MB was degraded by as much as 97.6%.