Villa Aroca, Rocío

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Villa Aroca, Rocío

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Villa Aroca, Rocío

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Bioquímica y Biología Molecular "B" e Inmunología

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Open Access
Ionic liquids as an enabling tool to integrate reaction and separation processes
(RSC, 2019-10-22) Alvarez, Elena; Porcar, Raul; Garcia-Verdugo, Eduardo; V Luis, Santiago; Lozano Rodríguez, Pedro; Villa Aroca, Rocío; Bioquímica y Biología Molecular B e Inmunología
The development of advanced processes able to directly provide pure products by integrating chemical transformations, product separation and recovery and reuse of the solvent and the catalytic phases by straightforward and smart approaches, is a key feature to build green chemical processes. The unique properties of ILs, one of the key enabling technologies, can lead, when combined with (bio)catalysts, to amazing synergies not only improving the catalytic efficiency (i.e. improved activity and enantioselectivity, enhanced stability, etc.), but also allowing the design of smarts approaches for product separation (e.g. IL/scCO2 biphasic reactors, membrane reactors, nanodrop systems, microfluidic devices, supported ionic liquid phases, sponge-like ionic liquids, etc.), incorporating the full recovery and reuse of the catalyst and the ILs phase. This tutorial review highlights representative examples of ILs-based systems integrating reaction/separation as a tool for the development of sustainable chemical processes leading to clean and pure chemical products.
Open Access
Sistemas (bio) catalíticos verdes para el desarrollo de procesos químicos sostenibles de interés industrial
(Universidad de Murcia, 2021-07-27) Villa Aroca, Rocío; Lozano Rodríguez, Pedro; Escuela Internacional de Doctorado
El diseño de nuevos procesos químicos sostenibles, basados en el desarrollo de procesos catalíticos eficientes con la adecuada combinación de protocolos de reacción y / o separación, son elementos fundamentales para el desarrollo de la industria química sostenible, ya que suponen importantes ahorros en la producción, así como la minimización de los impactos ambientales. En este sentido, se deben reemplazar los disolventes orgánicos volátiles por disolventes no volátiles y totalmente recuperables (p. ej., líquidos iónicos, scCO2, DES, etc.), así como fomentar el uso de (bio)catalizadores eficientes, que permitan su reutilización, y que son capaces de proporcionar una alta selectividad en los procesos con la mínima generación de subproductos. La Química Verde es una filosofía científica que se centra en el diseño de procesos y reacciones químicas que reduzcan o eliminen la generación de productos nocivos para el ser humano y el medioambiente en su conjunto. Desde el punto de vista del sector químico, la idea fundamental es minimizar o erradicar el uso de sustancias peligrosas y transformar las que ya se pueden generar en compuestos no tóxicos. Claramente, se trata de un objetivo que no se puede lograr fácilmente. En este sentido, los procesos químicos incluyen etapas en las que las sustancias se transforman progresivamente para obtener el producto deseado. Sin embargo, la mayoría de procesos requieren el uso de solventes orgánicos tradicionales. Generalmente, los disolventes se utilizan como materiales auxiliares en síntesis química, ya que actúan como medio de reacción y mejoran el transporte y la separación de los productos. Sin embargo, la gran mayoría de los disolventes que se utilizan en los laboratorios son líquidos moleculares, que pertenecen al grupo de los compuestos orgánicos volátiles, y su recuperación nunca puede ser total y, además, está asociada a procesos de destilación que requieren un alto gasto energético. Por este principal motivo, su sustitución y / o eliminación no es tarea fácil, ya que por su funcionalidad resultan ser elementos clave en la mayoría de los procesos químicos. En los últimos años, con el objetivo principal de crear una industria química más respetuosa con el medioambiente, centrándose en el uso de medios de reacción alternativos y estrategias sintéticas más sostenibles. Estos disolventes alternativos (p. ej., LIs o dióxido de carbono supercríticos), ofrecen la posibilidad de ser recuperados y reutilizados en su totalidad, por lo que su explotación como alternativa a los disolventes orgánicos está hoy a la vanguardia. Esta Tesis Doctoral se ha llevado a cabo en el campo conceptual de la Química Sostenible, con aportes directos de aplicaciones de interés para diversos sectores industriales. En este sentido, esta Tesis Doctoral presenta con éxito el desarrollo y diseño de procesos químicos que integran la síntesis y separación de productos puros de gran interés industrial con alto valor agregado en los sectores farmacéutico, alimentario y cosmético, así como en la industria de los polímeros. Los enfoques de protocolo desarrollados ofrecen las ventajas sinérgicas que brindan los diferentes elementos sostenibles, como LI, DES, scCO2 y enzimas, y su correcta combinación, para obtener los productos de manera eficiente y segura. Además, se han implementado protocolos para la separación de productos, de fácil extrapolación para un posible escalado a nivel industrial, en diversos productos sintéticos como ésteres de aromas, monoacilglicéridos de ácidos grasos omega-3 o carbonatos cíclicos. Adicionalmente, se ha podido demostrar la idoneidad de los sistemas de reacción libres de solventes, incluso basados en mezclas de sustratos sólidos a temperatura ambiente, para la verificación de biotransformaciones mediante la formación de DES, o la asistencia con ultrasonidos, obteniendo productos de interés para la industria cosmética (p. ej. monoésteres de pantenol, monoésteres de xilitol).
Open Access
Chemo-enzymatic production of omega-3 monoacylglycerides using sponge-like ionic liquids and supercritical carbon dioxide
(2020-07-22) Alvarez, Elena; Donaire González, Antonio; Garcia-Verdugo, Eduardo; Luis, Santiago V; Lozano Rodríguez, Pedro; Nieto Cerón, Susana; Villa Aroca, Rocío; Bioquímica y Biología Molecular B e Inmunología
A clean chemo-enzymatic synthesis of omega-3 monoacylglycerides was carried out by two consecutive catalytic steps, the enzymatic transesterification of raw fish or linseed oil with solketal for producing fatty acid solketyl esters, followed by the hydrolysis of these solketal moieties catalysed by solid acids (e.g. zeolites) in either supercritical carbon dioxide (scCO2) or sponge-like ionic liquids (SLILs). By using scCO2 as reaction/extraction medium, an excellent performance of both coupled catalytic steps was observed when t-butanol was used as a co-solvent, resulting in a 100% monoacylglyceride yield for seven days under continuous operation and without any loss in catalytic activity. For discontunuous operation, the process involved two separated steps in SLIL and water, respectively, leading to 100% product yield and IL-free monoacylglyceride product by following a cooling and centrifugation protocol, which allow for the full recovery of the enzyme / SLIL / zeolite components of the reaction system that could be reused for at least 6 cycles with unchanged catalytic performance.
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Clean enzymatic production of flavor esters in Spongelike Ionic Liquids
(American Chemical Society, 2019-07-02) Alvarez, Elena; Rodríguez, José; Villa Aroca, Rocío; Gómez, Celia; Donaire, Antonio; Villa Aroca, Rocío; Lozano Rodríguez, Pedro; Nieto Cerón, Susana; Bioquímica y Biología Molecular B e Inmunología
The biocatalytic synthesis of 16 flavor esters was carried out by the direct esterification of aliphatic acids (e.g., acetic, propionic, etc.) with an alcohol (e.g., cinnamyl alcohol, benzyl alcohol, anisyl alcohol, rac-1-phenylethanol, or rac-sulcatol) using hydrophobic ionic liquids (ILs) based on ammonium or imidazolium cations containing a long alkyl side chain (e.g., hexadecyltrimethylammonium bistriflimide, [C16tma][NTf2]) as the reaction medium. As temperature-switchable liquid/solid phases, these ILs behave as spongelike systems (so-called spongelike ionic liquids (SLILs)), which act as excellent monophasic reaction media for the lipase-catalyzed synthesis of flavor esters. Under appropriate selected reaction conditions (e.g., enzyme, substrate molar ratio, nature of the SLIL, etc.), product yields near 100% were obtained for all of the synthesized flavor esters. Because of the unique spongelike properties of these ILs, a separation protocol based on the centrifugation of the solid IL/flavor ester through nylon membranes was successfully used. By means of this approach, the clean separation of all flavor products from the solid reaction media was easily achieved, while the recovered SLIL/biocatalyst system was reused for six consecutive operation cycles with unchanged catalytic performance.
Open Access
A green chemo-enzymatic approach for CO2 capture and transformation into bis(cyclic carbonate) esters in solvent-free media
(American Chemical Society, 2024-10-02) Ruiz, Francisco J.; Velasco, Francisco; Porcar, Raul; Garcia Verdugo, Eduardo; Villa Aroca, Rocío; Lozano Rodríguez, Pedro; Nieto Cerón, Susana; Bioquímica y Biología Molecular B e Inmunología
A sustainable approach for CO2 capture and chemo-enzymatic transformation into bis(cyclic carbonate) esters from CO2, glycidol and organic anhydrides under solvent-free conditions has been demonstrated. The chemo-enzymatic process is based in two consecutive catalytic steps, which can be executed through separated operations, or within a one-pot combo system, taking advantage of the synergic effects that emerge from integrating ionic liquid (ILs) technologies and biocatalysts. In a first step, lipase-catalyzed transesterification and esterification reactions of different diacyl donors (e.g. glutaric anhydride, succinic anhydride, dimethyl succinate, etc.) with glycidol in solvent-free under mild reaction conditions (70 °C, 6 h), producing the corresponding diglycidyl esters derivatives up to 41% yield. By a second step, the synthesis of bis(cyclic carbonate) esters was carried out as results of the cycloaddition reaction of CO2 (from an exhausted gas source, 15% CO2 purity) on these diglycidyl esters, catalyzed by the covalently attached 1-decyl-2-methylimidazolium IL (Supported Ionic Liquid-Like Phase, SILLP), in solvent-free, leading up to 65% yield after 8 h at 50 °C and 1MPa CO2 pressure. Both key elements of the reaction system (biocatalyst and SILLP) were successfully recovered and reused for at least 5 operational cycles. Finally, different metrics have been applied to assess the greenness of the solvent-free chemo-enzymatic synthesis of bis(cyclic carbonate) esters here reported.
Open Access
Biocatalytic synthesis of panthenyl monoacyl esters in ionic liquids and deep eutectic solvents
(Royal Society of Chemistry, 2019-05-21) Álvarez, Elena; Bernal, Juana M.; Donaire González, Antonio; Villa Aroca, Rocío; Lozano Rodríguez, Pedro; Nieto Cerón, Susana; Bioquímica y Biología Molecular B e Inmunología
The enzymatic synthesis of six panthenyl monoacyl esters (PMEs) was carried out by the direct esterification of fatty acids (i.e. capric, lauric, myristic, palmitic, oleic and linoleic acids, respectively) with panthenol in different ionic liquids (ILs) based on cations with a long alkyl side-chain (e.g. 1-dodecyl-3-methylimidazolium tetrafluoroborate [C12mim][BF4], etc.). All the assayed ILs were seen to be suitable reaction media for Novozym 435-catalyzed synthesis of PMEs (i.e. up to 90% conversion and 100% selectivity), enabling easy recovery and the reuse of both biocatalyst and IL. Alternatively, mixtures of panthenol with free fatty acids were seen to act as deep eutectic solvents (DES), that were excellent reaction media for the biocatalytic synthesis of PMEs (i.e. up to 83% conversion and 98% selectivity in the case of the panthenyl monolaurate), the enzymatic activity remaining unchanged for seven consecutive cycles of reuse. The enzymatic synthesis of PMEs by direct esterification using the DES approach can be considered as a clean and useful process for the sustainable industrial scaling up of panthenyl acyl ester production.
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Sustainable chemo-enzymatic synthesis of glycerol carbonate (meth)acrylate from glycidol and carbon dioxide enabled by ionic liquid technologies
(Royal Society of Chemistry, 2021-05-06) Villa Aroca, Rocío; Porcar, Raul; Nieto Cerón, Susana; Donaire González, Antonio; García-Verdugo, Eduardo; Luis, Santiago V.; Lozano Rodríguez, Pedro; Bioquímica y Biología Molecular B e Inmunología; Facultad de Química
A sustainable chemo-enzymatic process for producing both glycerol carbonate acrylate (GCA) and glycerol carbonate methacrylate (GCMA), as useful monomers for the preparation of biodegradable plastic materials, has been carried out by taking advantage of ionic liquid (IL) technologies. The process consiste of two consecutive catalytic steps, which can be carried out by either sequential or one-pot experimental approaches. Glycidyl (meth)acrylate was firstly synthesized by enzymatic transesterification of (meth)acrylate vinyl ester with glycidol in Sponge Like Ionic Liquids (SLILs) as the reaction medium (100% yield after 6 h at 60 °C). SLILs not only provided a suitable reaction medium, but also allowed the simple isolation of the resulting glycidyl esters as an IL-free pure fraction through a straightforward cooling/centrifugation protocol. The second step consisted of the synthesis of GCA, or GCMA, as the outcome of the cycloaddition of CO2 to the obtained glycidyl acrylate or glycidyl methacrylate, respectively, catalysed by a covalently attached 1-decyl-2-methylimidazolium moiety (Supported Ionic Liquid-Like Phase, SILLP) in a solvent-free system and under mild conditions (60 °C, 1–10 bar), leading to up to 100% yield after 6 h. The components of the reaction system (biocatalyst/SLIL/SILLP) can be fully recovered and reused for atleast 6 cycles with unchanged catalytic performance.
Open Access
Ultrasound-assisted enzymatic synthesis of xylitol fatty acid esters in solvent-free conditions
(Elsevier, 2021-07) Donaire, Antonio; Villa Aroca, Rocío; Lozano Rodríguez, Pedro; Nieto Cerón, Susana; Bioquímica y Biología Molecular B e Inmunología
A commercial immobilized lipase was successfully used for the synthesis of five xylityl acyl esters by means of the esterification of free fatty acids (caprylic, capric, lauric and myristic, respectively) with xylitol under solvent-free conditions. Ultrasound-assistance was shown to be a key tool to overcome the handicap imposed by both the mutual immiscibility of fatty acids and xylitol substrates, and the semisolid character of the initial reaction mixtures. In such semisolid systems, ultrasonic irradiation may enable the transport of substrate molecules to the enzyme catalytic-site, leading to the efficient synthesis of xylityl fatty ester (e.g. up to 95% yield after 90 min at 40ºC), with xylityl monoacyl ester and xylitol diacyl ester appearing as the main products (>96%), assessed by HPLC and NMR analyses. The separation of products was carried out by heating and simple centrifugation of the reaction medium, which was possible due to different densities of the resulting fractions.
Open Access
Sustainable set-ups for the biocatalytic production and scale-up of panthenyl monoacyl esters under solvent-free conditions
(American Chemical Society, 2023-03-22) Nieto Cerón, Susana; Bernal Palazón, Juana María; García Verdugo, Eduardo; Donaire González, Antonio; Lozano Rodríguez, Pedro; Villa Aroca, Rocío; Química Inorgánica; Facultades de la UMU::Facultad de Química
A sustainable scaling-up process for the biocatalytic production of new bioactive provitamin-B5 monoacyl esters has been demonstrated. A solvent-free reaction protocol based on the formation of eutectic mixtures between neat substrates render to highly efficient direct esterification of free fatty acids (i.e. from C6 to C18 alkyl chain length) with panthenol catalyzed by lipase. The scale-up from 0.5 to 500 g was evaluated by means of several reaction systems (i.e. ultrasound-assistance, orbital shaking, rotary evaporator, and mechanical stirring coupled to vacuum). For all reactor systems, the yield in panthenyl monoacyl esters was improved by increasing the length of the alkyl chain of the fatty acid (i.e. from 63 % yield for panthenyl butyrate to 83 % yield for panthenyl myristate). The best results (87 % - 95 % product yield, for all cases) were obtained upon a scale-up (50-500 g size) and when a vacuum system was coupled to the biocatalytic reaction unit. Under the optimized conditions a five-fold reduction of the amount of biocatalyst with respect reactors without vacuum was achieved. The recovery and reuse of the immobilized enzyme for 5 operation cycles was also demonstrated. Finally, different metrics have been applied to assess the greenness of the solvent-free biocatalytic synthesis of panthenyl monoesters here reported.
Open Access
Direct biocatalytic processes for CO2 capture as a green tool to produce value-added chemicals
(MDPI (Multidisciplinary Digital Publishing Institute), 2023-07-19) Villa Aroca, Rocío; Nieto Cerón, Susana; Donaire González, Antonio; Lozano Rodríguez, Pedro; Bioquímica y Biología Molecular B e Inmunología; Química Inorgánica; Facultad de Química
Direct biocatalytic processes for CO2 capture and transformation in value-added chemicals may be considered a useful tool for reducing the concentration of this greenhouse gas in the atmosphere. Among the other enzymes, carbonic anhydrase (CA) and formate dehydrogenase (FDH) are two key biocatalysts suitable for this challenge, facilitating the uptake of carbon dioxide from the atmosphere in complementary ways. Carbonic anhydrases accelerate CO2 uptake by promoting its solubility in water in the form of hydrogen carbonate as the first step in converting the gas into a species widely used in carbon capture storage and its utilization processes (CCSU), particularly in carbonation and mineralization methods. On the other hand, formate dehydrogenases represent the biocatalytic machinery evolved by certain organisms to convert CO2 into enriched, reduced, and easily transportable hydrogen species, such as formic acid, via enzymatic cascade systems that obtain energy from chemical species, electrochemical sources, or light. Formic acid is the basis for fixing C1-carbon species to other, more reduced molecules. In this review, the state-of-the-art of both methods of CO2 uptake is assessed, highlighting the biotechnological approaches that have been developed using both enzymes.