Edinson Yara-Varón

Is it possible to substitute hexane with green solvents for extraction of carotenoids? A theoretical versus experimental solubility study

The present study was designed to evaluate five green solvents, i.e. 2-methyltetrahydrofuran (2-MeTHF), dimethyl carbonate (DMC), cyclopentyl methyl ether (CPME), isopropyl alcohol (IPA) and ethyl acetate, for the substitution of n-hexane in the extraction of carotenoids from carrots. Initially, solvent selection was made through the theoretical physicochemical solvent properties and solubility results obtained using two simulation programs, Hansen Solubility Parameters (HSPs) and Conductor-like Screening Model for Realistic Solvation (COSMO-RS) which use a statistical thermodynamics approach based on the result of quantum chemical calculation, for comprehension of the dissolving mechanism. On the basis of the HSPs analysis, non-polar or slightly polar solvents were the most suitable solvents for extraction of carotenoids. COSMO-RS analysis showed a higher probability of solubility for all the carotenoids from carrot in CPME, 2-MeTHF and ethyl acetate compared with n-hexane. The experimental results using a conventional solid–liquid extraction by maceration showed that the best green solvents were CPME, 2-MeTHF and ethyl acetate in accordance with the predictive results from COSMO-RS. The highest carotenoid content (78.4 mg 100 g−1 DM) was observed in CPME where 66% was represented by β-carotene and 34% was α-carotene. These results support the potential of CPME and 2-MeTHF as alternative green solvents for extraction of carotenoids.

Vegetable Oils as Alternative Solvents for Green Oleo-Extraction, Purification and Formulation of Food and Natural Products

Since solvents of petroleum origin are now strictly regulated worldwide, there is a growing demand for using greener, bio-based and renewable solvents for extraction, purification and formulation of natural and food products. The ideal alternative solvents are non-volatile organic compounds (VOCs) that have high dissolving power and flash point, together with low toxicity and less environmental impact. They should be obtained from renewable resources at a reasonable price and be easy to recycle. Based on the principles of Green Chemistry and Green Engineering, vegetable oils could become an ideal alternative solvent to extract compounds for purification, enrichment, or even pollution remediation. This review presents an overview of vegetable oils as solvents enriched with various bioactive compounds from natural resources, as well as the relationship between dissolving power of non-polar and polar bioactive components with the function of fatty acids and/or lipid classes in vegetable oils, and other minor components. A focus on simulation of solvent-solute interactions and a discussion of polar paradox theory propose a mechanism explaining the phenomena of dissolving polar and non-polar bioactive components in vegetable oils as green solvents with variable polarity.

Solvent from forestry biomass. Pinane a stable terpene derived from pine tree byproducts to substitute n-hexane for the extraction of bioactive compounds

The ability to be used as an alternative solvent of a cis-rich pinane (cis/trans: 7/3), which was obtained for the first time at the multigram scale through an environmentally friendly catalytic hydrogenation of α/β-pinenes or turpentine oil under neat conditions over a Pd/C catalyst, was investigated and compared to n-hexane for the extraction of several bioactive compounds. Experimental evaluation as well as a simulation of the cis-rich pinane extraction capacity have been undertaken. The predictive approach was performed using the simulation software COSMO-RS (conductor like screening model for realistic solvents), which uses a statistical thermodynamics approach based on the result of quantum chemical calculation, for the understanding of dissolving mechanism. COSMO-RS simulation showed that the bio-based solvent is a good solvent to solubilize carotenoids, oil from rapeseed and aromas from caraway seeds. The experimental results indicated that the highest carotenoid yield was obtained with the cis-rich pinane with 95.4% of the maximum carotenoid content in carrots while n-hexane was only able to extract 78.1% of them. With respect to the extraction of oil from rapeseeds, both solvents showed similar extraction yields and no differences were observed in the fatty acid profiles. In relation to the aromas, the characterization of the essential oil extracted by the two solvents showed a similar composition, where carvone (64%) was the main component followed by limonene (34%). No selectivity of the solvents was observed for any of the two major compounds. The results indicate that the bio-based solvent could be a promising solvent for n-hexane substitution.

Entrapment in polymeric material of resting cells of Aspergillus flavus with lipase activity. Application to the synthesis of ethyl laurate

The lipase activity of resting cells of Aspergillus flavus was improved by entrapment in various polymeric acrylates (PAAFs). Commercially available ethyl acrylate, butyl acrylate and ethyl methacrylate, and acrylates synthesized from 1,3-dichloropropan-2-ol were used as monomers for the in situ polymerization. The cells were physically entrapped via free-radical-polymerization in aqueous medium or by bulk polymerization. The percentage of resting cells immobilized in the polymers was assessed by analysing the ergosterol content. Bulk polymerization with ethyl methacrylate allowed the greatest incorporation ratio, with 85% of entrapped biocatalyst. Entrapped resting cells were used to prepare ethyl laurate, achieving yields of up to 98%. The specific activity (r) of PAAFs was determined using a batch reactor and a packed-bed reactor (PBR). The highest r was observed for the resting cells entrapped in poly(ethyl methacrylate) using PBR. These results demonstrate that entrapped resting cells of A. flavus can be used to prepare commercial products.