Utilisation du limonène comme synthon agrochimique pour la synthèse et l'extraction de produits naturels

The objective of this study was to transform limonene as an agro-chemical platform for the production of a wide range of added-value compounds for pharmaceutical, cosmetic and food ingredients. This molecule was also evaluated as an alternative solvent for the extraction of several bioactive compounds compared to n-hexane. Limonene was extracted from the essential oils of orange peels through a solvent-free microwave extraction technique. Limonene was successfully transformed into products with industrial interest by catalytic oxidation using three different iron catalysts. The ability of limonene to be used as an alternative solvent was performed using two simulation tools, Hansen solubility parameters (HSPs) and the Conductor-like Screening Model for Real Solvents (COSMO-RS), and via experimentation. The results indicated that limonene could be a promising green solvent and synthon for petroleum substitution in the extraction or synthesis of bioactive compounds.L'objectif de cette étude est de montrer les potentialités du limonène comme une plateforme agrochimique pour la production d'une large gamme de composés à valeur ajoutée pour les industries pharmaceutique, cosmétique et agroalimentaire. Cette molécule a été évaluée en tant que synthon pour la synthèse de molécules bioactives et comme solvant alternatif à l'hexane pour l'extraction de composés bioactifs. Deux outils de simulation solvant--soluté ont été utilisés pour simuler et optimiser les potentialités du limonène : les paramètres de solubilité Hansen (HSP) et le modèle « Conductor-like Screening Model for Real Solvents » (COSMO-RS). Les résultats indiquent que le limonène peut être un solvant vert et un synthon prometteur pour la substitution du pétrole dans l'extraction ou la synthèse de composés bioactifs.This work was supported in part thanks to funding from the fellowship given to Edinson Yara Varón (No. TECSPR14-2-0029) from the People Programme (Marie Curie Actions) of the Seventh Framework Programme of the European Union (FP7/2007-2013) under REA grant agreement no. 600388 (TECNIOspring programme), and from the Agency for Business Competitiveness of the Government of Catalonia, ACCIÓ

Ionic compounds derived from crude glycerol: Thermal energy storage capability evaluation

Ionic liquids (diimidazol-1-ium esters) prepared from wastes, crude glycerol and carboxylic acids are investigated as potential phase change materials (PCM). The ionic liquids (IL) with best thermophysical properties were those with also better production yield (higher than 75%). The chemical composition of those IL was with R1 being (CH3)3CCO, CH3(CH2)14CO or C2H3CO; R2 being BIM+; R3 being BIM+; and X- being 2 Cl‾. Phase change of state (solid-liquid) of this IL was 85 ºC, 264 ºC and 128 ºC, which means potential application in different fields such as domestic hot water, solar cooling and industry, respectively. The measured melting enthalpy 328 kJ/kg, 408 kJ/kg, and 660 kJ/kg is much higher in all cases than the usual found in commercial PCM (100 kJ/kg), therefore, these ILs synthetized in this study are proper candidates to be used as PCM because of the huge amounts of energy that they are able to store and their low cost. Moreover, biobPCM are sustainable materials since its obtaining process is based on oil.The work is partially funded by the Spanish government (ENE2015-64117-C5-1-R (MINECO/FEDER) and CTQ2015-70982-C3-1-R (MINECO/FEDER)). The authors would like to thank the Catalan Government for the quality accreditation given to the research groups GREA (2014 SGR 123), Agricultural Biotechnology (2014 SGR 1296) and DIOPMA (2014 SGR 1543). Dr. Camila Barreneche would like to thank Ministerio de Economia y Competitividad de España for Grant Juan de la Cierva, FJCI-2014-22886.The research leading to these results has received funding from the European Union’s Seventh Framework Program (FP7/2007–2013) under grant agreement n° PIRSES-GA-2013-610692 (INNOSTORAGE) and from the European Union’s Horizon 2020 research and innovation program under grant agreement No 657466 (INPATH-TES)

Sustainable Synthesis of Omega-3 Fatty Acid Ethyl Esters from Monkfish Liver Oil

The search for economic and sustainable sources of polyunsaturated fatty acids (PUFAs) within the framework of the circular economy is encouraged by their proven beneficial effects on health. The extraction of monkfish liver oil (MLO) for the synthesis of omega-3 ethyl esters was performed to evaluate two blending systems and four green solvents in this work. Moreover, the potential solubility of the MLO in green solvents was studied using the predictive simulation software COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS). The production of ethyl esters was performed by one or two-step reactions. Novozym 435, two resting cells (Aspergillus flavus and Rhizopus oryzae) obtained in our laboratory and a mix of them were used as biocatalysts in a solvent-free system. The yields for Novozym 435, R. oryzae and A. flavus in the one-step esterification were 63, 61 and 46%, respectively. The hydrolysis step in the two-step reaction led to 83, 88 and 93% of free fatty acids (FFA) for Novozym 435, R. oryzae and A. flavus, respectively. However, Novozym 435 showed the highest yield in the esterification step (85%), followed by R. oryzae (65%) and A. flavus (41%). Moreover, selectivity of polyunsaturated fatty acids of R. oryzae lipase was evidenced as it slightly esterified docosahexaenoic acid (DHA) in all the esterification reactions tested.This research was funded by Interreg POCTEFA program (EFA253/16 BIOPLAST) and the PhD student aid program “Jade Plus” financed by Banco Santander of which Johanna Aguilera Oviedo is a beneficiary

Tamizaje fitoquimico y actividad antioxidante de extractos acuoso y orgánicos de justicia pectoralis jacq. (amansa toros) y de volátiles y no volátiles de lippia alba mill. (pronto alivio) cultivadas en diferentes pisos térmicos

El uso de Justicia pectoralis Jacq. y Lippia alba Mill en la cultura popular colombiana en el tratamiento de diferentes enfermedades y su escaso conocimiento y aplicabilidad en la región tolimense, motivó el estudio de estas especies vegetales a fin de determinar el efecto del cambio altitudinal en la actividad antioxidante de los extractos acuoso y orgánicos de J. pectoralis y de los volátiles y no volátiles de L. alba. Las diferencias de altitud no modifican la proporción relativa de los constituyentes químicos, lo que a su vez no influye en la actividad antioxidante de estas especies

Tamizaje fitoquimico y actividad antioxidante de extractos acuoso y orgánicos de justicia pectoralis jacq. (amansa toros) y de volátiles y no volátiles de lippia alba mill. (pronto alivio) cultivadas en diferentes pisos térmicos

El uso de Justicia pectoralis Jacq. y Lippia alba Mill en la cultura popular colombiana en el tratamiento de diferentes enfermedades y su escaso conocimiento y aplicabilidad en la región tolimense, motivó el estudio de estas especies vegetales a fin de determinar el efecto del cambio altitudinal en la actividad antioxidante de los extractos acuoso y orgánicos de J. pectoralis y de los volátiles y no volátiles de L. alba. Las diferencias de altitud no modifican la proporción relativa de los constituyentes químicos, lo que a su vez no influye en la actividad antioxidante de estas especies

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.Edinson Yara Varón thanks to fellowship funding (No. TECSPR14-2-0029) from the People Programme (Marie Curie Actions) of the Seventh Framework Programme of the European Union (FP7/2007-2013) under REA grant agreement No. 600388 (TECNIOspring programme), and from the Agency for Business Competitiveness of the Government of Catalonia, ACCIÓ. Ying Li would like to thank the National Natural Science Foundation of China (Grant 31701633) and the Fundamental Research Funds for the Central Universities (Grant 17817028), as well as special funds from “SanWu Talent 2014” and sixth “100-Talent” Programs

Síntesis y aplicaciones de acrilatos polimerizables mediante interesterificación quimioenzimática

Es presenta una modalitat de reacció d'interesterificació que aporta nous avenços en l'ús de biocatalitzadors en síntesi orgànica. Els biocatalitzadors, tant enzims aïllats com resting cells fúngiques, són eficaços catalitzadors de processos químics. Així mateix, els biocatalitzadors poden ser utilitzats en sistemes de flux continu connectats a reactors de llit empaquetat (PBR). L'acrilat d'al·lil va ser sintetitzat en un reactor tipus batch i en un reactor PBR, utilitzant diferents lipases. La lipasa B de Candida antarctica (CALB) va ser l'enzim amb major activitat. El producte obtingut va ser utilitzat per preparar un copolímer. També es va dur a terme la síntesi d'acrilat de dicloropropil. CALB novament, va ser la lipasa amb major activitat. El producte obtingut va ser polimeritzat. Finalment, es van immobilitzar les resting cells d'Aspergillus flavus en diferents materials polimèrics. Les resting cells immobilitzades van mostrar una activitat específica major a l'obtinguda amb el miceli fúngic sense immobilitzar.Se presenta una modalidad de reacción de interesterificación que aporta nuevos avances en el empleo de biocatalizadores en síntesis orgánica. Los biocatalizadores, tanto enzimas aisladas como resting cells fúngicas, son eficaces catalizadores de procesos químicos. Asimismo, los biocatalizadores pueden ser usados en sistemas de flujo continuo conectados a reactores de lecho empaquetado (PBR). El acrilato de alilo fue sintetizado en un reactor tipo batch y en un reactor PBR, usando diferentes lipasas. La lipasa B de Candida antarctica (CALB) fue la enzima con mayor actividad. El producto obtenido fue usado para preparar un copolímero. También se llevó a cabo la síntesis de acrilato de dicloropropilo. CALB nuevamente, fue la lipasa con mayor actividad. El producto obtenido fue polimerizado. Finalmente, se inmovilizaron las resting cells de Aspergillus flavus en diferentes materiales poliméricos. Las resting cells inmovilizadas mostraron una actividad específica mayor a la obtenida con el micelio fúngico sin inmovilizar.We present an interesterification reaction mode that brings new advances in the use of biocatalysts in the organic synthesis. Biocatalysts, both isolated enzymes and fungal resting cells are effective catalysts for chemical processes. Also, the biocatalysts may be used in continuous flow connected to packed beds reactors (PBR). Allyl acrylate was synthesized in a batch type reactor and a PBR reactor using different lipases. Lipase B from Candida antarctica (CALB) was the most active enzyme. The obtained product was used to prepare a copolymer. Also it was performed the synthesis of dichloropropyl acrylate. CALB again, was the lipase with the highest activity. The obtained product was polymerized. Finally, resting cells from Aspergillus flavus were immobilized in different polymeric materials. Immobilized resting cells showed a higher specific activity than the fungal mycelium without immobilization