María Luján Ferreira

The effect of pH in the adsorption of Alizarin and Eriochrome Blue Black R onto iron oxides.

The adsorption process of two dyes as a function of pH on three different adsorbents (goethite, Co-goethite, and magnetite) has been analyzed. Typical anionic adsorption behavior was observed for both dyes onto goethite and Co-goethite. The adsorption level was practically constant in the range of pH studied when the adsorbent was magnetite. The constant capacitance model (CCM) was employed to fit the experimental results. The surface complexes proposed from the adsorption data were in agreement with the patterns obtained from FTIR spectroscopy and a molecular mechanics calculation. Goethite has very good performance as adsorbent of Alizarin and Eriochrome Blue Black R. The presence of a foreign cation in Co-goethite does not improve the adsorption abilities of goethite. At low pH, the amounts of Alizarin and Eriochrome Blue Black R adsorbed on goethite and Co-goethite are similar. However, a higher dependence with the increase of pH is observed by Eriochrome Blue Black R. On magnetite, the dye adsorption shows less affinity for both dyes. Electronic and steric considerations can explain the trends found in the adsorption of the two dyes on the three iron oxides studied in this work.

Cross-linked enzyme aggregates (CLEAs) of selected lipases: a procedure for the proper calculation of their recovered activity

In the last few years, synthesis of carrier-free immobilized biocatalysts by cross-linking of enzyme aggregates has appeared as a promising technique. Cross-linked enzyme aggregates (CLEAs) present several interesting advantages over carrier-bound immobilized enzymes, such as highly concentrated enzymatic activity, high stability of the produced superstructure, important production costs savings by the absence of a support, and the fact that no previous purification of the enzyme is needed. However, the published literature evidences that a) much specific non-systematic exploratory work is being done and, b) recovered activity calculations in CLEAs still need to be optimized. In this context, this contribution presents results of an optimized procedure for the calculation of the activity retained by CLEAs, based on the comparison of their specific activity relative to their free enzyme counterparts. The protocol implies determination of precipitable protein content in commercial enzyme preparations through precipitation with ammonium sulphate and a protein co-feeder. The identification of linear ranges of activity versus concentration/amount of protein in the test reaction is also required for proper specific activity determinations. By use of mass balances that involve the protein initially added to the synthesis medium, and the protein remaining in the supernatant and washing solutions (these last derived from activity measurements), the precipitable protein present in CLEAs is obtained, and their specific activity can be calculated. In the current contribution the described protocol was applied to CLEAs of Thermomyces lanuginosa lipase, which showed a recovered specific activity of 11.1% relative to native lipase. The approach described is simple and can easily be extended to other CLEAs and also to carrier-bound immobilized enzymes for accurate determination of their retained activity.

The Co-adsorption of tetramethylpiperidine and TiCl4 on β-MgCl2. A theoretical study of a Ziegler-Natta pre-catalyst

Abstract An extended Huckel method (ICONC), which includes core-core repulsion energy terms, was used to characterise the MgCl 2 2,2,6,6-tetramethylpiperidine (TMPiP) TiCl 4 system by modelling the TMPiP and TiCl4 adsorption on the (100)–(101) and (110) faces of MgCl2. The results show how the amine modifies the chemical and electronic states of adsorbed TiCl4. The appearance of complexes at the surface, previously studied by infrared spectroscopy is supported by our calculation. The geometrical and structural factors governing the formation of precursors of active sites for propylene polymerisation were also studied.

Nanosized magnetite in low cost materials for remediation of water polluted with toxic metals, azo- and antraquinonic dyes

Nanosized magnetite has emerged as an adsorbent of pollutants in water remediation. Nanoadsorbents include magnetic iron oxide and its modifiers/stabilizers, such as carbon, silica, clay, organic moieties (polymers, aminoacids, and fatty acids) and other inorganic oxides. This review is focused on the recent developments on the synthesis and use of magnetic nanoparticles and nanocomposites in the treatment of contaminated water. The emphasis is on the influence of the iron oxide modifiers on some properties of interest such as size, BETarea, and magnetization. The characteristics of these nanomaterials are related to their ability to eliminate heavy metal ions and dyes from wastewater. Comparative analysis of the actual literature was performed aiming to present the magnetic material, its preparation methodology and performance in the elimination of the selected pollutants. Vast information has been properly summarized according to the materials, their properties and preferential affinity for selected contaminants. The mechanisms governing nanomaterial’s formation as well as the interactions with heavy metals and dyes have been carefully analyzed and associated to their efficiency.

Lipase-catalyzed acidolysis of tripalmitin with capric acid in organic solvent medium: Analysis of the effect of experimental conditions through factorial design and analysis of multiple responses

The acidolysis of tripalmitin with capric acid catalyzed by an immobilized form of a 1,3-positionally selective lipase (Rhizomucor miehei) showed to be effective for the synthesis of structured lipids of the MLL and MLM type. The effects that reaction parameters such as substrate molar ratio (N), biocatalyst load (E), and reaction temperature (T) have on selected responses variables (i.e. total conversion of tripalmitin, selectivity and yield of the desired structured lipid, hydrolysis yield, and acyl migration importance), were evaluated by use of an experimental factorial design of three factors and three levels with two central points and with a confidence level of 95%. The range of each parameter was selected as follows: N=3-9, E=5-15wt%, T=50-70°C. The statistical analysis of results was addressed by use of both simple linear models and more complicated quadratic models using specific commercial software. The results obtained showed that a proper selection of reaction conditions is needed in order to maximize not only the yield of the desired structured lipid, but also to minimize the generation of hydrolysis and acyl migration by-products.

Removal of Fluorescein using different iron oxides as adsorbents: effect of pH.

In this work the adsorption process of Fluorescein (dye with aril-methane group) as a function of pH on three different adsorbents: goethite, Co-goethite, and magnetite has been studied experimentally and theoretically. FTIR and Raman spectroscopy have been performed in an attempt to confirm the structure of surface complexes formed by sorption of the Fluorescein to different iron oxides. Typical anionic adsorption behaviour was observed for this dye onto goethite and Co-goethite whereas the adsorption level was practically constant in the range of pH studied when the adsorbent was magnetite. The diffuse layer model was employed to fit the experimental results. The surface complexes proposed from the adsorption data were in agreement with the patterns obtained from FTIR and Raman spectroscopy. The surface structure of the oxides affects the adsorption process and the final adsorbed amount at the equilibrium. Our model of diffuse double layer with the addendum of the effect of hydrophobic forces fits well the adsorption data of Fluorescein on iron oxides at different pH in the studied range. At lower pH electrostatic forces by ligand-exchange are predominant. In the range of pH 9-11 hydrophobic forces are managing the Fluorescein adsorption on the iron oxides, with the formation of outer-sphere complexes through van der Waals/hydrophobic forces. It is interesting that in the three iron oxides studied, the adsorbed amount in this range is similar.

An insight on acyl migration in solvent-free ethanolysis of model triglycerides using Novozym 435.

In this work, the ethanolysis of triglycerides catalyzed by immobilized lipase was studied, focusing on the secondary reaction of acyl migration. The catalytic tests were performed in a solvent-free reaction medium using Novozym 435 as biocatalyst. The selected experimental variables were biocatalyst loading (5-20mg), reaction time (30-90min), and chain length of the fatty acids in triglycerides with and without unsaturation (short (triacetin), medium (tricaprylin) and long (tripalmitin/triolein)). The formation of 2-monoglyceride by ethanolysis of triglycerides was favored by long reaction times and large biocatalyst loading with saturated short- to medium-chain triglycerides. In the case of long-chain triglycerides, the formation of this monoglyceride was widely limited by acyl migration. In turn, acyl migration increased the yield of ethyl esters and minimized the content of monoglycerides and diglycerides. Thus, the enzymatic synthesis of biodiesel was favored by long-chain triglycerides (which favor the acyl migration), long reaction times and large biocatalyst loading. The conversion of acylglycerides made from long-chain fatty acids with unsaturation was relatively low due to limitations in their access to the active site of the lipase.

Molecular recognition of an acyl–enzyme intermediate on the lipase B from Candida antarctica

This investigation provides evidence of the acyl enzyme species involved in the interaction of R/S-ketoprofen with the lipase B from Candida antarctica. The interaction between the profen and the enzyme was studied by in situ time-resolved ATR-FTIR under both static and transient conditions. Particularly, modulation excitation spectroscopy (MES) with phase sensitive detection (PSD) allowed us to univocally distinguish the signals belonging to the interaction between ketoprofen and the enzyme from the strong background signals. These experimental tools coupled with theoretical DFT analysis allowed us to propose various species derived from the interaction of ketoprofen with serine through H bonding (without reaction) and the acyl enzyme species (ester bond formation) which are the intermediates in the biocatalytic assisted esterification and hydrolysis using lipases.

Influencia del Recubrimiento de las Fibras de Vidrio sobre la Efectividad de la Reacción de Copolimerización Propileno-Vidrio

The influence of fiber coatings on the effectiveness of the propylene-glass copolymerization reaction has been analyzed. The mechanical properties of fiber reinforced composites depend on the effective stress transfer fiber-matrix, which is possible if the adhesion between them is strong. An alternative method to improve the adhesion is the establishment of chemical links between matrix-fiber such as in situ polymerization. The study was carried out on sandwich composite of polypropylene and fiber glass, with and without acrylic coating. Adhesion is analyzed through its influence on the mechanical properties of the composites. The copolymerization reaction acts as an effective bonding agent, when it is carried out on uncoated fibers, making this proposal technological attractive.

Influence of the nature of the support on the catalytic performance of CALB: experimental and theoretical evidence

The immobilization of the lipase B of Candida antarctica (CALB) was carried out on various hydrophilic and hydrophobic supports through adsorption and covalent bond interactions. The catalytic performance of the biocatalysts was evaluated in the enantioselective esterification of R/S-ibuprofen with ethanol without co-solvents added. The present investigation demonstrates that the biocatalysts based on CALB immobilized by adsorption on hydrophobic supports (acrylic resin, polymethylmethacrylate, polystyrene, epoxy resin and polypropylene) exhibit higher conversion of ibuprofen and enantiomeric excess towards the S-enantiomer than CALB immobilized on hydrophilic materials. Additionally, the enzyme loading is a key factor influencing the conversion of the substrate regardless of the nature of the support material. A high enzyme loading is detrimental to the specific activity of the biocatalysts. Experimental and molecular modeling investigations provided evidence for the influence of water activity in the stereospecificity of the lipase.