Potential of choline chloride - based natural deep eutectic solvents (NaDES) in the extraction of microalgal metabolites

In a typical chemical process, the solvents are widely used for the dissolution of the reagents, to favor the kinetics and the thermodynamics of a chemical reaction, for the extraction of products, for the separation of mixtures. However most of the currently used organic solvents are characterized by different properties harmful to human health and the environment. Among the principles of Green Chemistry are that solvents should be innocuous to Man and to the Environment (safer solvents) and that the substances used in a chemical process should be chosen to minimize the potential for chemical accidents (intrinsically safe processes). Biorefining, the biomass Era counterpart of oil refining is most likely going to be extraction-based, and thus heavily solvent-dependent, much as the Oil Era was based on distillation and hence heat-dependent. Ionic Liquids (ILS) and eutectic mixtures exploited as solvents (DES) are two major classes of solvents that are making their way in Green Chemistry and, in particular, in biomass processing research. NaDES ('Natural Deep Eutectic Solvents'), i.e. mixtures formed by natural primary metabolites present in all organisms, such as sugars, polyols, amino acids, organic acids, derivatives of choline, form intermolecular hydrogen bonds and, when mixed in a certain ratio, change their state from solid to liquid forming a eutectic system. The most interesting NaDESs are those in which water is one of a ternary system since the degree of dilution with water modifies such physical properties of the NaDES as the density, the viscosity, and the polarity. By modulating the water content the solvation power can be adjusted to specific needs. In this work, the PCH (1,2-propanediol, choline chloride, water 1:1:1) NaDES was used to treat microalgal biomass and carry out the extraction of cellular components, such as lipids, proteins, carbohydrates and photosynthetic pigments (chlorophylls and carotenoids) from the biomass itself. Three sets of experiments were carried out based on different contact time between biomass and PCH: 24 and 72 hours, with and without pre-treatment with ultrasound. Biomass was shaken together with the PCH solvent in the presence of glass beads to promote the extraction efficiency. The analysis of the extract composition was carried out spectrophotometrically for pigments (chlorophylls and carotenoids), with biochemical assays for proteins and carbohydrates and gravimetrically for the determination of lipids. The results showed the ability of PCH, coupled with the mechanical destruction of cell walls, to solubilize a wide range of polar biomolecules at room temperature

Control sustentable poscosecha: extractos de Larrea cuneifolia mediados por nades frente a Botrytis cinerea

Botrytis cinerea es un hongo ubicuo que ocasiona la podredumbre gris, una de las principales enfermedades de fruta en poscosecha, siendo responsable de pérdidas económicas. Debido a la creciente preocupación por los efectos adversos del uso de pesticidas, la búsqueda de alternativas se presenta como una meta prioritaria. En este contexto, los extractos de plantas representan una rica fuente de biocompuestos con atractivas propiedades antimicrobianas. Recientemente, los solventes eutécticos naturales (NADES) se han propuesto como agentes extractantes sustentables de compuestos bioactivos a partir de plantas. En el presente estudio, se evaluó un bioextracto de L. cuneifolia basado en NADES hacia B. cinerea. Para este propósito, se usó un NADES compuesto por ácido láctico, glucosa y agua (LGH) como agente de extracción y se comparó con solventes tradicionales en términos de capacidad antioxidante y contenido fenólico total. Además, la actividad antimicrobiana del bioextracto se evaluó in vitro e in vivo en uvas inoculadas artificialmente. A una concentración del 2% el bioextracto fue capaz de inhibir el crecimiento miceliar de B. cinerea en un 92%. Interesantemente, L. cuneifolia mostró un excelente rendimiento para el control de la podredumbre gris en uvas, demostrando su potencial como alternativa sustentable a los fungicidas sintéticos.Botrytis cinerea is a ubiquitous fungus causing gray mold, the main postharvest disease in fruit, which implies important economic losses in agriculture. With growing concern over health and environmental effects of pesticides, the search for eco-friendly alternatives is a clear priority. Plant extracts represent a rich source of biocompounds with attractive antimicrobial properties. In the last decade, Natural Deep Eutectic Solvents (NADES) has emerged as an auspicious green extraction media to achieve bioextract for a sustainable postharvest control. In the present study, a novel L. cuneifolia NADES-based bioextract was evaluated against B. cinerea. To this purpose, a NADES composed by lactic acid, glucose and water (LGH) was used as extracting agent and compared with traditional solvents in terms of antioxidant capacity and total phenolic content. Furthermore, the bioextract antifungal activity was tested in vitro and also in vivo on artificially inoculated grapes, in order to obtain preliminary data about the efficacy on gray mold development. The antimicrobial activity of the bioextract was assessed using agar diffusion method against B. cinerea, inhibition of 92% was achieved with the bioextract at 2%. Notably, L. cuneifolia bioextract showed an excellent performance for gray mold control on grapes, supporting their potential as alter-native green fungicide.Fil: Boiteux, Joana Jaqueline. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Espino, Magdalena Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Fernández, María de Los Ángeles. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Pizzuolo, Pablo Humberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; ArgentinaFil: Silva, María Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; Argentin

The application of deep eutectic solvent ionic liquids for environmentally-friendly dissolution and recovery of precious metals

publisher: Elsevier articletitle: The application of deep eutectic solvent ionic liquids for environmentally-friendly dissolution and recovery of precious metals journaltitle: Minerals Engineering articlelink: http://dx.doi.org/10.1016/j.mineng.2015.09.026 content_type: article copyright: Copyright © 2015 The Authors. Published by Elsevier Ltd.© 2015 Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

Natural Deep Eutectic Solvents (NADES) as a Tool for Bioavailability Improvement: Pharmacokinetics of Rutin Dissolved in Proline/Glycine after Oral Administration in Rats: Possible Application in Nutraceuticals

There is a need for innovation in plant-derived pharmaceuticals, food supplements and nutraceutical products regarding the use of more eco-sustainable solvents for their extraction. Furthermore, the poor oral bioavailability of several phytochemicals with health promoting effects stimulates the research in the field of pharmaceutical formulations. Natural Deep Eutectic Solvents (NADES) are formed by natural compounds, and can be considered as future solvents being especially useful for the preparation of nutraceuticals and food-grade extracts. In this paper various NADES were prepared using sugars, aminoacids and organic acids. Rutin (quercetin-3-O-\u3b1-l-rhamnopyranosyl-(1\u21926))-\u3b2-d-glucopyranose) was used as a model compound to study NADES. Moreover, the effect of various eutectic mixtures on rutin\u2019s water solubility was studied. Proline/glutamic acid (2:1) and proline/choline chloride (1:1) mixtures have a solubility comparable to ethanol. The proline/glutamic acid (2:1) eutectic containing rutin was used in a pharmacokinetic study in Balb/c mice while bioavailability was compared to oral dosing of water suspension. Plasmatic levels of rutin were measured by HPLC-MS/MS showing increased levels and longer period of rutin permanence in plasma of NADES treated animals. This paper reports the possible use of non-toxic NADES for pharmaceutical and nutraceutical preparations

Green solvents for enhanced impregnation processes in biomedicine

Supercritical carbon dioxide has been used as a green solvent due to their well-known potential in biomaterials impregnation. The versatility of this technique enables the loading of implants with Active Pharmaceutical Ingredients which present several benefits when compared with traditional techniques to impregnate active compounds. In this review, we have summarized the recent progress achieved in supercritical CO2assisted impregnation of active compounds and therapeutic deep eutectic systems for biomedical applications.The research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement number REGPOT-CT2012-316331-POLARIS and from the project “Novel smart and biomimetic materials for innovative regenerative medicine approaches” RL1 - ABMR - NORTE-01-0124-FEDER-000016) cofinanced by North Portugal Regional Operational Programme (ON.2 – O Novo Norte), under the National Strategic Reference Framework (NSRF), through the European Regional Development Fund (ERDF). The authors would also like to acknowledge the financial support of the Associate Laboratory, Life and Health Sciences Research Institute / Biomaterials LA ICVS-3Bs (2015-2017). The authors would like also to thank to the financial support from the Portuguese Foundation for Science and Technology (FCT) for the fellowship grant of LAQV/BPD/037/2016, and to “Fundo Social Europeu”- FSE and “Programa Diferencial de Potencial Humano POPH”. Alexandre Barros acknowledges his FCT PhD grant SFRH/BD/97203/2013. J.M.S acknowledges the project PTDC/CTM-BIO/4706/2014 for funding via an BPD grant.info:eu-repo/semantics/publishedVersio

Are emerging deep eutectic solvents (DES) relevant for lipase-catalyzed lipophilizations?

With the recent interest on green chemistry, the scientists have focused on developing new and more efficiient solvents to carry out enzymatic-catalyzed reactions with emphasis on reduced costs, risks and toxicity while improving biodegradability. Among the new available solvents, the multimolecular-based liquids (such as ionic liquids and eutectic solvents) have been the subject of most recent studies. Currently, and mainly due to its environmental and economic features, DES are arousing much interest and curiosity. Regarding the biotransformations with lipases, the so-called “lipophilization” reactions are of major interest. However, they are complex to implement mainly because it is difficult to find a suitable reaction medium. Thus, this review aimed at providing a presentation of these multimolecular- based solvents with general overview of the recent studies dealing with lipase-catalyzed reactions in DES. In addition, emphasis was placed on their strengths and weaknesses, especially with the perspective to be use as efficient and green medium to implement complex and valuable biotransformation such as lipase-catalyzed lipophilizations. (Résumé d'auteur

Deep Eutectic Solvents (DESs) and their applications [forthcoming]

Deep Eutectic Solvents (DESs) and Their Application

Deep Eutectic Solvents: The Organic Reaction Medium of the Century

This microreview summarizes the use of deep eutectic solvents (DESs) and related melts in organic synthesis. Solvents of this type combine the great advantages of other proposed environmentally benign alternative solvents, such as low toxicity, high availability, low inflammability, high recyclability, low volatility, and low price, avoiding many disadvantages of the more modern media. The fact that many of the components of these mixtures come directly from nature assures their biodegradability and renewability. The classification and distribution of the reactions into different sections in this microreview, as well as the emphasis paid to their scope, easily allow a general reader to understand the actual state of the art and the great opportunities opened, not only for academic purposes but also for industry.This work was supported by the University of Alicante, Spain (VIGROB-173 and UAUSTI13-09)

Synthesis of 3,5-Disubstituted Isoxazoles and Isoxazolines in Deep Eutectic Solvents

The synthesis of different 3,5-disubstituted isoxazoles and related isoxazolines using choline chloride:urea as deep eutectic solvent (DES) in a one-pot three step reaction has been accomplished successfully. The use of highly nucleophilic functionalized DES did not affect the process where highly electrophilic reagents or intermediates are involved. The presence of DES showed to be essential since the reaction in absence of this media did not proceed. The DES media could be reused up to five times without a detrimental effect on the yield of the reaction. To exemplify the synthetic potential of this methodology, the reaction was scaled up to the gram scale without any noticeable problem. Finally, different isoxazoles were easily transformed into β-aminoenones.This work was supported by the Spanish Ministerio de Economía y Competitividad (MICINN; Grant CTQ2011-24151) and University of Alicante. J.M.P. thanks the MICINN (FPI program) for her fellowship

Measurement and PC-SAFT modeling of solid-liquid equilibrium of deep eutectic solvents of quaternary ammonium chlorides and carboxylic acids

In this study the solid-liquid equilibria (SLE) of 15 binary mixtures composed of one of three different symmetrical quaternary ammonium chlorides and one of five different fatty acids were measured. The experimental data obtained showed extreme negative deviations to ideality causing large melting-temperature depressions (up to 300 K) that are characteristic for deep eutectic systems. The experimental data revealed that cross-interactions between quaternary ammonium salt and fatty acid increase with increasing alkyl chain length of the quaternary ammonium chloride and with increasing chain length of the carboxylic acid. The pronounced decrease of melting temperatures in these deep eutectic systems is mainly caused by strong hydrogen-bonding interactions, and thermodynamic modeling required an approach that takes hydrogen bonding into account. Thus, the measured phase diagrams were modeled with perturbed-chain statistical associating fluid theory based on the classical molecular homonuclear approach. The model showed very good agreement with the experimental data using a semi-predictive modeling approach, in which binary interaction parameters between quaternary ammonium chloride and carboxylic acid correlated with chain length of the components. This supports the experimental findings on the phase behavior and interactions present in these systems and it allows estimating eutectic points of such highly non-ideal mixtures.This work was developed in the scope of the project CICECO e Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (Ref. FCT UID/CTM/50011/2013) and LSRE-LCM, POCI-01-0145- FEDER-006984jUID/EQU/50020/2013, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. M.A.R.M acknowledges FCT for her PhD grant (SFRH/BD/87084/2012). FCT is also acknowledged for funding the project DeepBiorefinery (PTDC/AGRTEC/ 1191/2014). P.V.A.P., G.J.M., M.D.H. and E.A.C.B thank the national funding agencies CNPq (National Council for Scientific and Technological Development) (305870/2014-9, 309780/2014, 406856/2013-3), FAPESP (Research Support Foundation of the State of S~ao Paulo) (2014/21252-0, 2016/08566-1), FAEPEX/UNICAMP (Fund for Research, Teaching, and Extension) (0125/16) and CAPES (Coordination of Improvement of Higher Level Personnel) for financial support and scholarships. E.A.C thanks Erasmusþ program of the European Union for co-funding.info:eu-repo/semantics/publishedVersio