Valorization of olive tree leaves: Extraction of oleanolic acid using aqueous solutions of surface-active ionic liquids.

The global olive oil industry annually generates approximately 750,000-1,500,000 tons of Olea europaea leaves as waste that are typically burned for energy production. Yet, this agricultural by-product is a rich source of oleanolic acid, a high value triterpenic acid with outstanding pharmaceutical and nutraceutical activities. The present study focuses on the extraction of oleanolic acid from dried O. europaea leaves using aqueous solutions of surface-active ionic liquids as alternative solvents. A number of imidazolium-based ionic liquids with variable chain length, different anions and optional side-chain functionalization was synthesized and employed in the extraction of oleanolic acid. Ionic liquids with long alkyl chains remarkably enhance the solubility of oleanolic acid in water, thus being able to compete with the solubilities afforded by molecular organic solvents, such as chloroform. Consequently, they are suitable alternatives for the solid-liquid extraction of triterpenic acids from natural matrices and provide improved extraction yields of up to 2.5 wt% oleanolic acid extracted from olive tree leaves.

Extraction and recovery processes for cynaropicrin from Cynara cardunculus L. using aqueous solutions of surface-active ionic liquids.

Due to the wide range of relevant biological activities and high commercial value of cynaropicrin, and aiming at developing cost-effective processes, aqueous solutions of ionic liquids (ILs) were investigated for the extraction and recovery of cynaropicrin from the leaves of Cynara cardunculus L. Both cationic (1-alkyl-3-methylimidazolium chloride) and anionic (cholinium carboxylate) surface-active ILs were investigated, as well as a wide range of conventional surfactants and molecular organic solvents, allowing us to conclude that aqueous solutions of cationic surface-active ILs display a better performance for the extraction of cynaropicrin. Operational conditions were optimized, leading to a cynaropicrin extraction yield of 3.73 wt%. The recycling of both the biomass and the solvent were further investigated to appraise the extraction media saturation and to achieve a higher cynaropicrin extraction yield (6.47 wt%). Finally, it was demonstrated that 65 wt% of the extracted cynaropicrin can be efficiently recovered by precipitation from the IL aqueous extract through the addition of water as anti-solvent, allowing us to put forward both the extraction and recovery processes of the target value-added compound from biomass followed by solvent recycling. This approach opens the door to the development of more sustainable processes using aqueous solutions of ILs instead of the volatile organic solvents commonly used in biomass processing.

Deep Eutectic Solvents as Efficient Media for the Extraction and Recovery of Cynaropicrin from Cynara cardunculus L. Leaves.

In recent years a high demand for natural ingredients with nutraceutical properties has been witnessed, for which the development of more environmentally-friendly and cost-efficient extraction solvents and methods play a primary role. In this perspective, in this work, the application of deep eutectic solvents (DES), composed of quaternary ammonium salts and organic acids, as alternative solvents for the extraction of cynaropicrin from Cynara cardunculus L. leaves was studied. After selecting the most promising DES, their aqueous solutions were investigated, allowing to obtain a maximum cynaropicrin extraction yield of 6.20 wt %, using 70 wt % of water. The sustainability of the extraction process was further optimized by carrying out several extraction cycles, reusing either the biomass or the aqueous solutions of DES. A maximum cynaropicrin extraction yield of 7.76 wt % by reusing the solvent, and of 8.96 wt % by reusing the biomass, have been obtained. Taking advantage of the cynaropicrin solubility limit in aqueous solutions, water was added as an anti-solvent, allowing to recover 73.6 wt % of the extracted cynaropicrin. This work demonstrates the potential of aqueous solutions of DES for the extraction of value-added compounds from biomass and the possible recovery of both the target compounds and solvents.

Aqueous solutions of surface-active ionic liquids: remarkable alternative solvents to improve the solubility of triterpenic acids and their extraction from biomass.

Triterpenic acids (TTAs) are well known for their relevant biological properties and have been facing an increasing interest for nutraceutical and pharmaceutical applications. To overcome the concerns associated to the commonly used volatile organic solvents for their extraction from biomass, here we investigate the potential of aqueous solutions of ionic liquids (ILs) as alternative solvents. The solubility of ursolic acid (UA) was firstly determined in several aqueous solutions of ILs (hydrotropes or surface-active) at 30°C to appraise the dissolution phenomenon. Conventional surfactants were also investigated for comparison purposes. The collected data reveal a remarkable enhancement in the solubility of UA (8 orders of magnitude) in surface-active ILs aqueous solutions when compared to pure water. Afterwards, the potential of these ILs aqueous solutions was confirmed by their use in the extraction of TTAs from apple peels. Total extractions yield of TTAs of 2.62 wt.% were obtained using aqueous solutions of surface-active ILs at moderate conditions, overwhelming the extraction yields of 2.48 wt.% obtained with chloroform and 1.37 wt.% with acetone using similar conditions.