Toxicity and larvicidal activity on Aedes aegypti of citronella essential oil submitted to enzymatic esterification

The essential oil of citronella (Cymbopogon winterianus) has several biological activities, among them the insect repellent action. Some studies showed that cinnamic acid esters can be applied as natural pesticides, insecticides and fungicides. In this context, the objective of the present work was to evaluate the production of esters from citronella essential oil with cinnamic acid via enzymatic esterification. Besides, the essential oil toxicity before and after esterification against Artemia salina and larvicidal action on Aedes aegypti was investigated. Esters were produced using cinnamic acid as the acylating agent and citronella essential oil (3:1) in heptane and 15 wt% NS 88011 enzyme as biocatalysts, at 70 °C and 150 rpm. Conversion rates of citronellyl and geranyl cinnamates were 58.7 and 69.0% for NS 88011, respectively. For the toxicity to Artemia salina LC50 results of 5.29 μg mL-1 were obtained for the essential oil and 4.36 μg mL-1 for the esterified oils obtained with NS 88011. In the insecticidal activity against Aedes aegypti larvae, was obtained LC50 of 111.84 μg mL-1 for the essential oil of citronella and 86.30 μg mL-1 for the esterified oils obtained with the enzyme NS 88011, indicating high toxicity of the esters. The results demonstrated that the evaluated samples present potential of application as bioinsecticide.

Simplified Method to Optimize Enzymatic Esters Syntheses in Solvent-Free Systems: Validation Using Literature and Experimental Data

The adoption of biocatalysis in solvent-free systems is an alternative to establish a greener esters production. An interesting correlation between the acid:alcohol molar ratio and biocatalyst (immobilized lipase) loading in the optimization of ester syntheses in solvent-free systems had been observed and explored. A simple mathematical tool named Substrate-Enzyme Relation (SER) has been developed, indicating a range of reaction conditions that resulted in high conversions. Here, SER utility has been validated using data from the literature and experimental assays, totalizing 39 different examples of solvent-free enzymatic esterifications. We found a good correlation between the SER trends and reaction conditions that promoted high conversions on the syntheses of short, mid, or long-chain esters. Moreover, the predictions obtained with SER are coherent with thermodynamic and kinetics aspects of enzymatic esterification in solvent-free systems. SER is an easy-to-handle tool to predict the reaction behavior, allowing obtaining optimum reaction conditions with a reduced number of experiments, including the adoption of reduced biocatalysts loadings.

A Parameter Study of Ultrasound Assisted Enzymatic Esterification

This work is focused on the study of esterification parameters for the ultrasound assisted synthesis of isoamyl acetate catalyzed by lipase Lipozyme 435 in a continuous loop reactor. Investigating the influence of different parameters shows that a higher concentration of ester (462 mg/gmixture) can be obtained at temperature 50 °C, flow rate 0.16 mL/min. The best ultrasonication conditions are: continuously applied sonication for a short time (20 minutes), ultrasound power 32 mW, and amplitude 20 %. The enzyme can be successfully reused tree times without loss of enzyme activity. Reaction kinetics for isoamyl acetate ultrasound assisted production showed that satisfactory reaction concentration (close to the equilibrium concentrations) could be reached in short reaction times (2 h). Ultrasound assisted enzymatic esterification is consequently a cleaner and a faster process.

Glyceric Prodrug of Ursodeoxycholic Acid (UDCA): Novozym 435-Catalyzed Synthesis of UDCA-Monoglyceride

Bile acids (BAs) are a family of steroids synthesized from cholesterol in the liver. Among bile acids, ursodeoxycholic acid (UDCA) is the drug of choice for treating primary biliary cirrhosis and dissolving cholesterol gallstones. The clinical effectiveness of UDCA includes its choleretic activity, the capability to inhibit hydrophobic bile acid absorption by the intestine under cholestatic conditions, reducing cholangiocyte injury, stimulation of impaired biliary output, and inhibition of hepatocyte apoptosis. Despite its clinical effectiveness, UDCA is poorly soluble in the gastro-duodeno-jejunal contents, and pharmacological doses of UDCA are not readily soluble in the stomach and intestine, resulting in incomplete absorption. Indeed, the solubility of 20 mg/L greatly limits the bioavailability of UDCA. Since the bioavailability of drug products plays a critical role in the design of oral administration dosages, we investigated the enzymatic esterification of UDCA as a strategy of hydrophilization. Therefore, we decided to enzymatically synthesize a glyceric ester of UDCA bile acid to produce a more water-soluble molecule. The esterification reactions between UDCA and glycerol were performed with an immobilized lipase B from Candida antarctica (Novozym 435) in solvent-free and solvent-assisted systems. The characterization of the UDCA-monoglyceride, enzymatically synthesized, has been performed by 1H-NMR, 13C-NMR, COSY, HSQC, HMBC, IR, and MS spectroscopy.

Valorization of Agro-Industrial Residues: Bioprocessing of Animal Fats to Reduce Their Acidity

Adding value to agro-industrial residues is becoming increasingly important, satisfying needs to promote resources’ use efficiency and a more sustainable and circular economy. This work performs a parametric and kinetic study of enzymatic esterification of lard and tallow with high acidity, obtained by the rendering of slaughter by-products, allowing their use as a feed ingredient and increasing their market value. After an initial analysis of potential enzyme candidates, a Candida antarctica lipase B was selected as a biocatalyst for converting free fatty acids (FFA) to esters, using excess ethanol as the reagent. Results show that the fat acidity can be reduced by at least 67% in up to 3 h of reaction time at 45 °C, using the mass ratios of 3.25 ethanol/FFA and 0.0060 enzyme/fat. Kinetic modelling shows an irreversible second-order rate law, function of FFA, and ethanol concentration better fitting the experimental results. Activation energy is 54.7 kJ/mol and pre-exponential factor is 4.6 × 106 L mol−1 min−1.

Physical and chemical study of coated Candida cylindracea with sorbitan esters

A new effective biocatalyst was prepared by coating lipase from Candida cylindracea with sorbitan esters such as span 60 and 65. This biocatalyst was characterized by employing the Scanning Electron Microscopy, X-Ray diffraction patterns and a lipase assay. The type of surfactant used during the lipase modification process has shown significant effect in the lipase activity and the protein content of the modified lipase complex. It was found that catalytic behavior of modified lipase was greatly affected by the source of the used span. Span 65-coated Candida cylindracea lipase showed the highest conversion of 50% in enzymatic esterification of glucose and lauric acid.

Synthesis and Characterization of 2-Di-methyl Amino Ethyl Laurate Betaine Surfactant

The growing need for sustainable natural-based surfactants from green chemistry has led to syntheses of surfactants without the use of solvents and without the generation of by-products when milder manufacturing processes are used. The zwitterionic betaine ester surfactants are derived from natural renewable sources and are biodegradable. In this research, the betaine ester surfactant 2-di-methylaminoethyllaurate betaine was synthesized from 2-di-methylaminoehanol and lauric acid derived from coconut oil in a three-step chemo-enzymatic esterification reaction. The enzymatic process was optimized in terms of operating parameters such as temperature, time, molar ratio and enzyme concentration, resulting in a yield of 87.91%. Structural analysis of the intermediate 2-di-methylaminoethyl laurate as well as the final product 2-di-methylaminoethyl laurate betaine was carried out with FTIR and 1H NMR. The surfactant properties of the betaine were also determined and showed that the betaine can be used as a co-surfactant in many cosmetic and personal care products.

Biocatalytic Approach for Direct Esterification of Ibuprofen with Sorbitol in Biphasic Media

Ibuprofen is a nonsteroidal anti-inflammatory drug (NSAID) introduced in the 1960s and widely used as an analgesic, anti-inflammatory, and antipyretic. In its acid form, the solubility of 21 mg/L greatly limits its bioavailability. Since the bioavailability of a drug product plays a critical role in the design of oral administration dosage, this study investigated the enzymatic esterification of ibuprofen as a strategy for hydrophilization. This work proposes an enzymatic strategy for the covalent attack of highly hydrophilic molecules using acidic functions of commercially available bioactive compounds. The poorly water-soluble drug ibuprofen was esterified in a hexane/water biphasic system by direct esterification with sorbitol using the cheap biocatalyst porcine pancreas lipase (PPL), which demonstrated itself to be a suitable enzyme for the effective production of the IBU-sorbitol ester. This work reports the optimization of the esterification reaction.