Continuous flow reactor based with an immobilized biocatalyst for the continuous enzymatic transesterification of crude coconut oil.

Here, we have assessed the use of one packed bed or two packed bed reactors in series in which Burkholderia cepacia lipase (BCL) was immobilized on protic ionic liquid (PIL)-modified silica and used as a biocatalyst for the transesterification of crude coconut oil. Reaction parameters including volumetric flow, temperature, and molar ratio were evaluated. The conversion of transesterification reaction products (ethyl esters) was determined using gas chromatography and the quantities of intermediate products (diglyceride and monoglyceride [MG]) were assessed using high-performance liquid chromatography. Packed bed reactors in series produced ethyl esters with the greatest efficiency, achieving 65.27% conversion after 96 H at a volumetric flow rate of 0.50 mL Min-1 at 40 °C and a 1:9 molar ratio of oil to ethanol. Further, within the first 24 H of the reaction, increased MG (54.5%) production was observed. Molecular docking analyses were performed to evaluate the catalytic step of coconut oil transesterification in the presence of BCL. Molecular docking analysis showed that triglycerides have a higher affinity energy (-5.7 kcal mol-1 ) than the smallest MG (-6.0 kcal mol-1 ), therefore, BCL catalyzes the conversion of triglycerides rather than MG, which is consistent with experimental results.

Lipase Immobilization on Silica Xerogel Treated with Protic Ionic Liquid and its Application in Biodiesel Production from Different Oils.

Treated silica xerogel with protic ionic liquid (PIL) and bifunctional agents (glutaraldehyde and epichlorohydrin) is a novel support strategy used in the effective immobilization of lipase from Burkholderia cepacia (LBC) by covalent binding. As biocatalysts with the highest activity recovery yields, LBC immobilized by covalent binding with epichlorohydrin without (203%) and with PIL (250%), was assessed by the following the hydrolysis reaction of olive oil and characterized biochemically (Michaelis⁻Menten constant, optimum pH and temperature, and operational stability). Further, the potential transesterification activity for three substrates: sunflower, soybean, and colza oils, was also determined, achieving a conversion of ethyl esters between 70 and 98%. The supports and the immobilized lipase systems were characterized using Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), elemental analysis, and thermogravimetric (TG) analysis.

Effect of Hydrothermal Aging on Damping Properties in Sisal Mat-Reinforced Polyester Composites.

Hydrothermal aging is a matter of considerable concern for natural fiber-reinforced polymers; it can alter dimensional stability and induce microcracks and macro strain on the composite structure. This study applied a sorption kinetic model and examined the effects of water on the damping factor of sisal mat-reinforced polyester composites. The experimental data were fitted well using a Boltzmann sigmoid function, suggesting a promising first step toward kinetic water sorption modeling. Additionally, a damping test was carried out using the impulse excitation technique, highlighting the composite material's dynamic response under varying water absorption conditions. The result showed that damping exhibited sensitivity to water absorption, increasing significantly during the first 24 h of immersion in water, then remained steady over time, inferring a critical time interval. An empirical model proved satisfactory with the correlation coefficient for sorption rates and damping of sisal mat polymeric composites.

Enhanced Antimalarial Activity of Extracts of Artemisia annua L. Achieved with Aqueous Solutions of Salicylate Salts and Ionic Liquids.

Artemisinin, a drug used to treat malaria, can be chemically synthesized or extracted from Artemisia annua L. However, the extraction method for artemisinin from biomass needs to be more sustainable while maintaining or enhancing its bioactivity. This work investigates the use of aqueous solutions of salts and ionic liquids with hydrotropic properties as alternative solvents for artemisinin extraction from Artemisia annua L. Among the investigated solvents, aqueous solutions of cholinium salicylate and sodium salicylate were found to be the most promising. To optimize the extraction process, a response surface method was further applied, in which the extraction time, hydrotrope concentration, and temperature were optimized. The optimized conditions resulted in extraction yields of up to 6.50 and 6.44 mg·g-1, obtained with aqueous solutions of sodium salicylate and cholinium salicylate, respectively. The extracts obtained were tested for their antimalarial activity, showing a higher efficacy against the Plasmodium falciparum strain compared with pure (synthetic) artemisinin or extracts obtained with conventional organic solvents. Characterization of the extracts revealed the presence of artemisinin together with other compounds, such as artemitin, chrysosplenol D, arteannuin B, and arteannuin J. These compounds act synergistically with artemisinin and enhance the antimalarial activity of the obtained extracts. Given the growing concern about artemisinin resistance, the results here obtained pave the way for the development of sustainable and biobased antimalarial drugs.

Dipropyl ammonium ionic liquids to prepare Ti/RuO2-Sb2O4 anodes at different calcination temperatures.

The development of technologies capable of producing efficient and economically viable anodes is essential for the electrochemical treatment of water contaminated with complex organic pollutants. In this context, the use of ionic liquids as solvents to prepare mixed metal oxide (MMO) anodes has proven to be an up-and-coming alternative. Here, we analyze the influence of the temperature of calcination (300, 350, and 400 ºC) on the production of Ti(RuO2)0.8-(Sb2O4)0.2 anodes made using the thermal decomposition method using three ionic liquids (IL) as solvents: dipropyl ammonium acetate (DPA-Ac), dipropyl ammonium propionate (DPA-Pr), and dipropyl ammonium butyrate (DPA-Bu). The decomposition temperature for all IL, accessed by thermogravimetry, is below 200 ºC. Physical and electrochemical analyses demonstrate that the calcination temperature of the anodes is decisive for their durability and electrochemical properties. Anodes prepared with DPA-Bu at 350 ºC show higher stability (around 35 h) than those made with other ILs at temperatures of 300 and 400 ºC and improved results in terms of 4-NP mineralization, where 97% of TOC removal was achieved in 120 min. It could be verified that the calcination temperature and IL employed had a decisive influence on the characteristics of the presented anodes. Therefore, the anode prepared with DPA-Bu at 350 ºC is promising for application in the degradation of organic compounds.

Toxicity of oleate-based amino protic ionic liquids towards Escherichia coli, Danio rerio embryos and human skin cells.

Protic ionic liquids (PILs) have been widely employed with the label of "green solvents'' in different sectors of technology and industry. The studied PILs are promising for corrosion inhibition and lubrication applications in industry. Industrial use of the PILs can transform them in wastes, due to accidental spill or drag in water due to washing, that can reach water bodies. In addition, the handling of the product by the workers can expose them to accidental contact. Thus, the aim of this work is to evaluate the toxicity of PILs 2-hydroxyethylammonium oleate (2-HEAOl), N-methyl-2-hydroxyethylammonium oleate (m-2HEAOl) and bis-2-hydroxyethylammonium oleate (BHEAOl) towards Escherichia coli, zebrafish embryos, model organisms that can be present in water, and human skin cells. This is the first work reporting toxicity results for these PILs, which constitutes its novelty. Results showed that the studied PILs did not inhibit E. coli bacterial growth but could cause human skin cells death at the concentrations of use. LC50 values for zebrafish eggs were 40.21 mg/L for 2HEAOl, 12.92 mg/L for BHEAOl and 32.74 mg/L for m-2HEAOl, with sublethal effects at lower concentrations, such as hatching retarding, low heart rate and absence of free swimming.

Remediation of petroleum contaminated saline water using value-added adsorbents derived from waste coconut fibres.

Oil spill from petrochemical industries into marine areas has resulted in severe environmental pollution. The use of natural sorbents to clean marine areas affected by petroleum contaminants is a promising approach to alleviate this problem. Therefore, this study aims at developing an technique that uses waste coconut fibres (Cocos nucifera L.) pre-treated with a "green" solvent, viz. protic ionic liquid (PIL) [2-HEA][Ac], for the remediation of oil in saline water. Conventional chemical pre-treatments (mercerisation/acetylation) and the innovative treatment (using PIL), chemical characterisation, Scanning Electron Microscope, Fourier-transform infrared spectroscopy, and oil sorption tests in hydrodynamic simulation on a laboratory scale were conducted. The fibres treated with PIL[2-HEA][Ac] possessed more pores and hydrophobic content than the mercerised/acetylated coconut fibres, indicating the efficiency of sorption. The average sorption of the PIL[2-HEA][Ac] fibre was 1.40 ± 0.06 g/g and that of the mercerised/acetylated fibre was 1.32 ± 0.12 g/g. Although the difference in sorption results is not significant, according to the Tukey test, fibre pre-treatment with PIL[2-HEA][Ac] is more advantageous than conventional treatments because it exhibits better average sorption results; furthermore, the synthesis procedure for PIL[2-HEA][Ac] is simple, reusable and non-toxic. Therefore, the use of these petroleum biosorbents is a technology with environmental benefits, such as the availability of the biosorbent in the form of biodegradable waste and treated with a "green" solvent, both of which can be reused. Thus, it adds value for its use in industries with a circular economy product; that are environment-friendly and economical.

Determination of Cu, Ni, Mn and Zn in diesel oil samples using energy dispersive X-ray fluorescence spectrometry after solid phase extraction using sisal fiber.

As a natural adsorbent, sisal (agave sisalana) fibers were used to extract Cu, Ni, Mn, and Zn from diesel oil samples for posterior determination (i.e., direct analytical measurements on the solid support) of the analytes by energy dispersive X-ray fluorescence spectrometry (EDXRF). In the proposed procedure, 0.2 g of sisal fiber was directly added to 5.0 mL of diesel oil contained in a glass tube. After 5 min of contact time, the mixture was filtered, and the collected fibers were oven-dried for 30 min at 70 °C. After drying, the analytes were quantified directly by EDXRF using the sisal fibers as a solid support. The calibration curves showed linear concentration ranges of 0.09-1.00, 0.12-1.00, 0.09-1.00, 0.06-1.0 µg g-1 for Cu, Ni, Mn, and Zn, respectively. The limits of detection (LOD) for Cu, Ni, Mn, and Zn were 0.03, 0.04, 0.03, and 0.02 µg g-1, respectively. The repeatability, evaluated by performing ten measurements at a concentration of 0.50 µg g-1 for each metal, with the results expressed in terms of the relative standard deviation (RSD), was 3.2, 6.5, 6.8, and 6.1% for Cu, Ni, Mn, and Zn, respectively. The results obtained by the proposed method were compared with the results obtained by a comparative method using inductively coupled plasma optical emission spectrometry, and both results showed good agreement. The proposed method was applied for Ni, Cu, Mn, and Zn determination in diesel oil samples collected from different gas stations.

Pineapple crown delignification using low-cost ionic liquid based on ethanolamine and organic acids.

Pineapple fibre was treated with protic ionic liquids (PILs) and the effects on the structure, composition, and properties of the fibres were evaluated. Treatment with PILs efficiently exposed the fibre surface, as confirmed by scanning electron microscopy. The chemical composition analysis revealed reductions in the lignin and hemicellulose contents in the treated fibres, promoting exposure of cellulose. The results correlated with the crystallinity index, which was greater in the treated fibres compared with that in the untreated fibres. The generated residue from the treatment of fibres with PIL (1%, v/v) showed lower levels of toxic compounds, demonstrating the advantages of this treatment over conventional biomass treatments.

(Eco)toxicity and biodegradability of protic ionic liquids.

Ionic liquids (ILs) are often claimed to be "environmentally friendly" compounds however, the knowledge of their potential toxicity towards different organisms and trophic levels is still limited, in particular when protic ionic liquids (PILs) are addressed. This study aims to evaluate the toxicity against various microorganisms and the biodegradability of four PILs namely, N-methyl-2-hydroxyethylammonium acetate, m-2-HEAA; N-methyl-2-hydroxyethylammonium propionate, m-2-HEAPr; N-methyl-2-hydroxyethylammonium butyrate, m-2-HEAB; and N-methyl-2-hydroxyethylammonium pentanoate, m-2-HEAP. The antimicrobial activity was determined against the two bacteria, Sthaplylococcus aureus ATCC-6533 and Escherichia coli CCT-0355; the yeast Candida albicans ATCC-76645; and the fungi Fusarium sp. LM03. The toxicity of all PILs was tested against the aquatic luminescent marine bacterium Vibrio fischeri using the Microtox(®) test. The impact of the PILs was also studied regarding their effect on lettuce seeds (Lactuta sativa). The biodegradability of these PILs was evaluated using the ratio between the biochemical oxygen demand (BOD) and the chemical oxygen demand (COD). The results show that, in general, the elongation of the alkyl chain tends to increase the negative impact of the PILs towards the organisms and biological systems under study. According to these results, m-2-HEAA and m-2-HEAP are the less and most toxic PILs studied in this work, respectively. Additionally, all the PILs have demonstrated low biodegradability.

Protic ionic liquid as additive on lipase immobilization using silica sol-gel.

Ionic liquids (ILs) have evolved as a new type of non-aqueous solvents for biocatalysis, mainly due to their unique and tunable physical properties. A number of recent review papers have described a variety of enzymatic reactions conducted in IL solutions, on the other hand, to improve the enzyme's activity and stability in ILs; major methods being explored include the enzyme immobilization (on solid support, sol-gel, etc.), protic ionic liquids used as an additive process. The immobilization of the lipase from Burkholderia cepacia by the sol-gel technique using protic ionic liquids (PIL) as additives to protect against inactivation of the lipase due to release of alcohol and shrinkage of the gel during the sol-gel process was investigated in this study. The influence of various factors such as the length of the alkyl chain of protic ionic liquids (monoethanolamine-based) and a concentration range between 0.5 and 3.0% (w/v) were evaluated. The resulting hydrophobic matrices and immobilized lipases were characterised with regard to specific surface area, adsorption-desorption isotherms, pore volume (V(p)) and size (d(p)) according to nitrogen adsorption and scanning electron microscopy (SEM), physico-chemical properties (thermogravimetric - TG, differential scanning calorimetry - DSC and Fourier transform infrared spectroscopy - FTIR) and the potential for ethyl ester and emulsifier production. The total activity yields (Y(a)) for matrices of immobilized lipase employing protic ionic liquids as additives always resulted in higher values compared with the sample absent the protic ionic liquids, which represents 35-fold increase in recovery of enzymatic activity using the more hydrophobic protic ionic liquids. Compared with arrays of the immobilized biocatalyst without additive, in general, the immobilized biocatalyst in the presence of protic ionic liquids showed increased values of surface area (143-245 m(2) g(-1)) and pore size (19-38 Å). Immobilization with protic ionic liquids also favoured reduced mass loss according to TG curves (always less than 42.9%) when compared to the immobilized matrix without protic ionic liquids (45.1%), except for the sample containing 3.0% protic ionic liquids (46.5%), verified by thermogravimetric analysis. Ionic liquids containing a more hydrophobic alkyl group in the cationic moiety were beneficial for recovery of the activity of the immobilized lipase. The physico-chemical characterization confirmed the presence of the enzyme and its immobilized derivatives obtained in this study by identifying the presence of amino groups, and profiling enthalpy changes of mass loss.