Potential applications of spent adsorbents and catalysts: Re-valorization of waste.

Water pollution has increased with the growth of human population and its industrial activities. Textile effluents constitute a particular threat due to the presence of heavy metals and dyes. Adsorption is one of the most applied technologies in contaminant removal owing to its high efficiency, low cost, practical implementation and possibility to operate in several experimental conditions. However, this process implies the generation of spent materials, representing a limitation to scale-up. Although the applications of exhausted solids in effluent treatments have not been extensively reviewed before, their reutilization appears to be an environmentally and economically attainable alternative. This work summarizes the potential value of solids post-use. The open literature reports that spent adsorbents based on polysaccharides with iron oxides may adsorb up to 1 g g-1 of organic pollutants and up to near 100% of metallic ions from wastewater (Cu2+, Cd2+, Zn2+, Pb2+). The studied conditions vary from 30 to 60 °C, 0,05 to 6 g L-1 of adsorbent, 10 mg L-1 to 250 mg L-1 of organic pollutants (dyes) and pH between 2 and 8. Spent adsorbents in dye removal have proven to have near 95% efficiency in metallic ion adsorption. Otherwise, the spent solids could be applied to remove Ca2+ and Mg2+ to decrease the hardness of water. Furthermore, at the end-of-life, these materials could be used in cement and ceramic production. To achieve these aims, it is necessary to design the bioadsorbents and biocatalysts considering not only their primary uses (as adsorbent of organic pollutants), but also secondary applications (as toxic metal or hardness removal) and even their final destination (as additive in ceramic or cement production). Finally, further studies are required on the composition, properties, stability at long-term and the life-cycle cost of these materials when they are applied in the construction industry.

Immobilization and bioimprinting strategies to enhance the performance in organic medium of the metagenomic lipase LipC12.

The present work evaluates the immobilization of LipC12 on different supports in tandem with bioimprinting technique, in order to improve its activity and stability in organic medium. Oleic acid was selected as the bioimprinting molecule. The immobilized LipC12 was applied in the synthesis of pentyl oleate by esterification reaction and in the production of fatty acids, mono, and diglycerides via hydrolysis of triacylglycerols, in n-heptane reaction media. For all immobilized lipase preparations, an increase in the conversion of oleic acid to pentyl oleate was observed when immobilization in tandem with bioimprinting treatment was carried out versus immobilization without bioimprinting. The highest conversions were achieved using LipC12 immobilized on hydrophobic supports. The reuse potential of the immobilized preparations was evaluated. The preparations were used in eight successive cycles of esterification reactions and the best results were obtained for LipC12 immobilized on Immobead 150 and chitosan. The activity for the hydrolysis of soybean oil was improved by bioimprinting treatment only for LipC12 immobilized on commercial polypropylene and Accurel MP-1000. LipC12 immobilized on hydrophilic supports or on Immobead150 could be used to hydrolyze tricaprylin to obtain diglycerides with a high proportion of 1,2-diglycerides in reaction times as short as 30 min.

Rationale of an Advanced Integrative Approach Applied to Autism Spectrum Disorder: Review, Discussion and Proposal.

The rationale of an Advanced Integrative Model and an Advanced Integrative Approach is presented. In the context of Allopathic Medicine, this model introduces the evaluation, clinical exploration, diagnosis, and treatment of concomitant medical problems to the diagnosis of Autism Spectrum Disorder. These may be outside or inside the brain. The concepts of static or chronic, dynamic encephalopathy and condition for Autism Spectrum Disorder are defined in this model, which looks at the response to the treatments of concomitant medical problemsto the diagnosis of Autism Spectrum Disorder. (1) Background: Antecedents and rationale of an Advanced Integrative Model and of an Advanced Integrative Approach are presented; (2) Methods: Concomitant medical problems to the diagnosis of Autism Spectrum Disorder and a discussion of the known responses of their treatments are presented; (3) Results: Groups in Autism are defined and explained, related to the responses of the treatments of the concomitant medical problems to ASD and (4) Conclusions: The analysis in the framework of an Advanced Integrative Model of three groups including the concepts of static encephalopathy; chronic, dynamic encephalopathy and condition for Autism Spectrum Disorder explains findings in the field, previously not understood.

Low-cost nanoparticulate oxidation catalysts for the removal of azo and anthraquinic dyes.

PURPOSE: This study aimed to test the activity of Mn ferrite, hematin-Mn ferrite and colloidal maghemite in decomposition of Orange II (O-II) and Alizarin Red S (ARS) in model aqueous solutions. METHODS: Color removal was explored at room temperature using magnetic stirring with and without a magnetic bar, taking advantage of the solids' magnetism. Decomposition of H2O2 was also studied separately and as radicals provider in dye decomposition. Catalyst/dye solution was fixed at 10 mg/4 mL. pH and dye concentration were variable. Absorbance was measured during 120 min by UV-Vis. Reuse of catalysts was also performed. RESULTS: Azo dyes such as O-II are more resistant to oxidative removal using hydrogen peroxide than anthraquinone-like ARS. CITMD5 reduced ARS absorbance up to 71.9% when dye was less than 250 mg/L. HEM-Mn-MAG completely decolorized a 62.5 mg/L O-II solution at pH 11 while CITMD5 reached half of that conversion under the same conditions. The highest color removal in O-II/ARS mixtures was obtained with HEM-Mn-MAG, 40% absorbance reduction in 2 h. Mn-MAG is not active to remove O-II in presence of hydrogen peroxide in the 3-9 pH range at rt. CONCLUSIONS: The high activity of Mn-MAG in hydrogen peroxide decomposition may be assigned to the combination of Mn+2/Mn+3 and Fe+2/Fe+3, because the MnOx is active in the decomposition of hydrogen peroxide. Mn-MAG can be reused, preserving high activity in this reaction. Mn-based magnetic nanoparticles should be considered as inexpensive materials to treat textile wastewaters. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40201-021-00640-x.

Magnetic nanotechnology for diclofenac remediation: molecular basis of drug adsorption and neurobehavioral toxicology as a preliminary study for safe application.

Diclofenac is a commercial non-steroidal anti-inflammatory drug commonly present as a pollutant in naturally occurring water sources and wastewaters. In this work, the adsorption of diclofenac onto chitosan-coated magnetic nanosystems is proposed as a possible tool for remediation. Experimental and theoretical studies have been carried out to reveal the mechanisms associated with diclofenac interactions among all the components of the nanosystem. Mechanisms are presented, analyzed and discussed. A toxicological study in mice was carried out to evaluate the parameters associated with neurotoxicity of the nanodevice. The elucidation of the mechanisms implied in the adsorption process of diclofenac onto magnetic chitosan nanocomposites suggests that diclofenac remediation from water is possible by adsorption onto chitosan. The strategy innovates the commonly used methodologies for diclofenac remediation from pharmaceutical wastes. This magnetic nanotechnology would not induce damage on the nervous system in a murine model, in case of traces remaining in water sources.

Immobilization of CALB on lysine-modified magnetic nanoparticles: influence of the immobilization protocol.

Magnetic biocatalysts offer enormous advantages over traditional ones. Their ability to be isolated by means of a magnet, in combination with their extensive reuse possibilities, makes them highly attractive and competitive from the commercial point of view. In this work, magnetic biocatalysts were prepared by immobilization of Candida antarctica Lipase B (E.C. 3.1.1.3, CALB) on magnetite-lysine nanoparticles. Two methodologies were explored tending to find the optimal biocatalyst in terms of its practical implementation: I-physical adsorption of CALB followed by cross-linking, and II-covalent coupling of the lipase on the nanoparticles surface. Both procedures involved the use of glutaraldehyde (GLUT) as cross-linker or coupling agent, respectively. A range of GLUT concentrations was evaluated in method I and the optimum one, in terms of efficiency and operational stability, was chosen to induce the covalent linkage CALB-support in method II. The chosen test reaction was solvent-free ethyl oleate synthesis. Method I produced operationally unstable catalysts that deactivated totally in four to six cycles. On the other hand, covalently attached CALB (method II) preserved 60% of its initial activity after eight cycles and also retained 90% of its initial activity along 6 weeks in storage. CALB immobilization by covalent linkage using controlled GLUT concentration appears as the optimum methodology to asses efficient and stable biocatalysts. The materials prepared within this work may be competitive with commercially available biocatalysts.

Screening of Lipases with Unusual High Activity in the sn-2 Esterification of 1,3-Dicaprin under Mild Operating Conditions.

In this work, the synthesis of acylglycerides with high nutritional value was carried out by enzymatic esterification at sn-2 position of 1,3-dicaprin with palmitic acid. A comparative study of the performance of several biocatalysts according to the obtained products was carried out. The results obtained with several of the biocatalysts evaluated are very interesting, and it would be possible to use them to obtain a mixture of acylglycerides to act as a fat substitute. The final product was composed of about 90% of nutritionally attractive glycerides. These glycerides were medium-chain length triglycerides, medium-long chain triglycerides (mainly triglycerides with medium chain fatty acids at sn-1 and sn-3 positions and long chain fatty acid at sn-2 position), and 1,3-diglycerides. Pseudomonas fluorescens lipase and Burkholderia cepacia lipase immobilized on chitosan demonstrated unusual high activity in the sn-2 esterification of 1,3-dicaprin with palmitic acid at 45 °C and 12 h with 33% yield to 1,3-dicaproyl-2-palmitoyl glycerol. Burkholderia cepacia lipase has the advantage of being immobilized; however, BCL/chitosan has the advantages of being immobilized and therefore its easy recovery from the reaction media.

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.

Development of a magnetic biocatalyst useful for the synthesis of ethyloleate.

Candida antarctica Lipase B was successfully immobilized on magnetite (Fe3O4) nanoparticles functionalized with chitosan and glutaraldehyde. The obtained magnetic catalyst was characterized and its performance was evaluated in solvent-free synthesis of ethyl oleate at room temperature. The performance of this biocatalyst was compared with the commercial Novozym 435, as a tool to estimate the efficiency of immobilization. It was found that using 33 mg of the biocatalyst it was possible to reach almost the same activity that was obtained using 12 mg of Novozym 435. Furthermore, this new biocatalyst presents the advantages of not being degraded by short alcohols, being easily recovered from the reaction media by magnetic decantation, and low fabrication cost. The possibility of reutilization was also studied, keeping a significant activity up to eight cycles. A special sampling protocol was also developed for the multiphasic reaction system, to assure accurate results. This novel biocatalyst is an interesting alternative for potential industrial applications, considering the above-mentioned advantages.

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.

Preparation of iron oxide nanoparticles stabilized with biomolecules: experimental and mechanistic issues.

Nanoparticles (NPs) with magnetic properties based on magnetite (Fe(3)O(4), MAG) modified with oleic acid (OA), chitosan (CS) and bovine serum albumin (BSA) have been prepared. A versatile method of synthesis was employed, involving two steps: (i) co-precipitation of MAG; and (ii) nanoprecipitation of macromolecules on as-formed MAG NPs. Experimental variables have been explored to determine the set of conditions that ensure suitable properties of NPs in terms of their size, functionality and magnetic properties. It was found that the presence of OA in Fe(+2)/Fe(+3) solutions yields MAG NPs with lower aggregation levels, while increasing initial amounts of OA may change the capability of NPs to disperse in aqueous or organic media by modifying the stabilization mechanism. Incorporation of CS was verified through Fourier transform IR spectroscopy. This biopolymer stabilizes NPs by electrostatic repulsions leading to stable ferrofluids and minimal fraction of recoverable solid NPs. BSA was successfully added to NP formulations, increasing their functionality and probably their biocompatibility. In this case too stable ferrofluids were obtained, where BSA acts as a polyelectrolyte. From the proposed methodology it is possible to achieve a wide range of NPs magnetically active intended for several applications. The required properties may be obtained by varying experimental conditions.

Explanation of experimental results of mixed micelles of homologous surfactants through a MM2 bidimensional modeling.

A computational modeling (in gas phase) to study the disposition of the homologous surfactants in a bidimensional simple model of mixed and homogeneous micelles was performed for the case of R-trimethylammonium bromide surfactants with different linear R lengths from R = C(5) to C(17). First, the bidimensional homogeneous (one component) micelle was modeled, and as a second step, heterogeneous (two components) bidimensional micelles were modeled. The difference in the number of carbon atoms between hydrocarbon chains of the surfactants in the heterogeneous micelles, Δn(C), ranged from 2 to 8. Results were contrasted with experimental data obtained at our own laboratory. The exothermic values of the steric energy changes showed strong attraction between components of homologous surfactants mixture, especially when one of the surfactants has a long chain. It may be argued that the inclusion of a shorter surfactant in the mixture and the twisting of the longer surfactant makes the bidimensional arrangement formation more exothermic. All predictions were in agreement with previous experimental results.

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.

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.

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.

Lipase-catalyzed copolymerization of lactic and glycolic acid with potential as drug delivery devices.

The copolymerization of lactic and glycolic acid (PLGA) using Candida antarctica lipase B as biocatalyst has been achieved with the aim to generate useful biomedical materials. The influence of the reaction conditions, such as solvent and temperature, on the enzyme's catalytic activity was studied to optimize the synthetic procedure. The evaluated parameters were the conversion, the isolated PLGA and the number average molecular weight (M(n)). The identification and purity of the products were assessed by FTIR and NMR. The conversion was determined using analytical titration and the M(n) through end-group analysis. It was found that PLGA oligomers were obtained with satisfactory conversion levels when isopropyl ether was employed as solvent. The use of toluene increased the M(n) but decreased the isolated polyester. Higher percentages of recovered PLGA were reached increasing the temperature from 60 to 80 degrees C using toluene, while a reduction in the M(n) was evidenced under these conditions.

PLA nano- and microparticles for drug delivery: an overview of the methods of preparation.

The controlled release of medicaments remains the most convenient way of drug delivery. Therefore, a wide variety of reports can be found in the open literature dealing with drug delivery systems. In particular, the use of nano- and microparticles devices has received special attention during the past two decades. PLA and its copolymers with GA and/or PEG appear as the preferred substrates to fabricate these devices. The methods of fabrication of these particles will be reviewed in this article, describing in detail the experimental variables associated with each one with regard to the influence of them on the performance of the particles as drug carriers. An analysis of the relationship between the method of preparation and the kind of drug to encapsulate is also included. Furthermore, certain issues involved in the addition of other monomeric substrates than lactic acid to the particles formulation as well as novel devices, other than nano- and microparticles, will be discussed in the present work considering the published literature available.