Anamaria Todea

Selectivity of lipases for estolides synthesis

Abstract Lipase-catalyzed synthesis of estolides starting from different saturated (C16 16OH, C18 12OH) and unsaturated (C18:1 9 cis 12-OH) hydroxy-fatty acids was investigated. For this reason, the catalytic efficiency of several native and immobilized lipases in different organic reaction media at temperatures up to 75 °C was studied. The formation of mono- and di-lactone as well as estolide’s chain elongation depends on the type and source of lipase. The lipase from Pseudomonas stutzeri immobilized by cross-linking as cross-linked enzymes aggregates (CLEAs) was the best biocatalyst in terms of chain elongation. Estolides with polymerization degree up to 10 were obtained at substrate conversions higher than 80 %.

Decontamination of colored wastewater using synthetic sorbents

Abstract In the recent years, the adsorption capacities of synthetic polymeric adsorbents have been intensively studied due to their diversity in surface and porosity, physicochemical stability and the regeneration potentiality. In this study four synthetic polymers have been used as alternative adsorbent for the removal of two azo dyes from aqueous solutions. The effects of dye concentration, adsorbent nature, temperature, and pH of the solution onto the kinetics of the adsorption process were in detail investigated. With the increase in the initial concentration from 5.10–5 to 1.10–3 mol/L the amount of dye adsorbed increased, while the removal percentage decreased. The increase of the temperature (298–338 K) induced a positive effect on the adsorption indicating that the process is endothermic, and the increase of pH induced a decrease in removal percentage. The maximum dye removal percentage obtained was found to be up to 99 %. The experimental data were well correlated by the Sips adsorption model, and the results were applied for obtaining the equilibrium parameters.

Optimization of enzymatic ring-opening copolymerizations involving δ-gluconolactone as monomer by experimental design

Abstract Enzymatic incorporation of carbohydrate-derived monomer units into hydrophobic polyester backbones represents a promising alternative to obtain new biodegradable oligomers and polymers. Immobilized lipases are efficient biocatalysts for copolymerization of β-butyrolactone and δ-gluconolactone, but only a systematic optimization study was able to highlight the influence of the main reaction parameters on the polymerization degree and on the relative copolymer content of the product. Therefore, experimental design was employed for determination of the optimal ring-opening copolymerization conditions in solventless reaction systems, at temperatures up to 80 °C. The obtained products, cyclic and linear polyesters, have been characterized by FT-IR, MALDI-TOF MS, NMR, and TG analysis, demonstrating the incorporation of gluconolactone unit(s) into the hydrophobic backbone of the polyester and the formation of new bio-based products.

Synthesis, characterization and enzymatic degradation of copolymers of ε-caprolactone and hydroxy-fatty acids

Abstract New copolymers of ε-caprolactone with three hydroxy-fatty acids, 12-hydroxy stearic acid, 16-hydroxyhexadecanoic acid and ricinoleic acid, were synthesized by catalytic polyesterification. The reactions were carried out in solvent-free systems and in organic solvents as well, using tin(II) 2-ethylhexanoate as catalyst, at different temperatures and molar ratios of the comonomers. Cyclic and linear polymeric products with medium molar weight of about 2000 Da have been synthesized and their chemical structures were confirmed by FT-IR, NMR and MALDI-TOF MS analysis. The synthesis parameters were optimized and the ε-caprolactone/hydroxy acid molar ratio was set as 5:1, according to mass spectrometry results. The biodegradability of the newly synthesized polymers was studied in the presence of Candida antarctica B lipase in phosphate buffer solutions (pH=7.4), at 37°C. The weight-loss profile emphasized the degradation of the 16-hydroxyhexadecanoic acid based polymer samples at more than 50% of their initial weight in 18 days of incubation in the presence of the lipase. The composition of the degradation products was assessed using the GC-MS technique and displayed residues of the comonomers moieties.

Removal of Colored Organic Pollutants from Wastewaters by Magnetite/Carbon Nanocomposites: Single and Binary Systems

This work develops a methodology for selective removal of industrial dyes from wastewaters using adsorption technology based on magnetic adsorbents. The magnetic nanoparticles embedded within a matrix of activated carbon were tested as adsorbents for removal of industrial dyes from aqueous solutions. The effects of four independent variables, solution pH, initial concentration of pollutant, adsorbent dose, contact time, and their interactions on the adsorption capacity of the nanocomposite were investigated in order to optimize the process. The removal efficiency of pollutants depends on solution pH and increases with increasing the carbon content, with initial concentration of the pollutants, the temperature, and the dose of magnetite/carbon nanocomposites. Pseudo-second-order kinetic model was fitted to the kinetic data, and adsorption isotherm analysis and thermodynamics were used to elucidate the adsorption mechanism. The maximum adsorption capacities were 223.82 mg g−1 for Nylosan Blue, 114.68 mg g−1 for Chromazurol S, and 286.91 mg g−1 for Basic Red 2. The regeneration and reuse of the sorbent were evaluated in seven adsorption/desorption cycles. The optimum conditions obtained for individual adsorption were selected as starting conditions for simultaneous adsorption of dyes. In binary systems, in normal conditions, selectivity decreases in the order: Red Basic 2 > Nylosan Blue > Chromazurol S.

Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

Developments of past years placed the bio-based polyesters as competitive substitutes for fossil-based polymers. Moreover, enzymatic polymerization using lipase catalysts has become an important green alternative to chemical polymerization for the synthesis of polyesters with biomedical applications, as several drawbacks related to the presence of traces of metal catalysts, toxicity and higher temperatures could be avoided. Copolymerization of ϵ-caprolactone (CL) with four hydroxy-fatty acids (HFA) from renewable sources, 10-hydroxystearic acid, 12-hydroxystearic acid, ricinoleic acid, and 16-hydroxyhexadecanoic acid, was carried out using commercially available immobilized lipases from Candida antarctica B, Thermomyces lanuginosus, and Pseudomonas stutzeri, as well as a native lipase. MALDI-TOF-MS and 2D-NMR analysis confirmed the formation of linear/branched and cyclic oligomers with average molecular weight around 1200 and polymerization degree up to 15. The appropriate selection of the biocatalyst and reaction temperature allowed the tailoring of the non-cyclic/cyclic copolymer ratio and increase of the total copolymer content in the reaction product above 80%. The catalytic efficiency of the best performing biocatalyst (Lipozyme TL) is evaluated during four reaction cycles, showing excellent operational stability. The thermal stability of the reaction products is assessed based on TG and DSC analysis. This new synthetic route for biobased oligomers with novel functionalities and properties could have promising biomedical applications.