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Six biphasic systems containing heptane, ethanol, and either hydrogen bond donor compounds (HBD), glycerol, ethylene glycol, levulinic acid, or the corresponding choline chloride-based DES were studied as potential extracting systems for five natural compounds, namely, quercetin, apigenin, coumarin, β-ionone, and α-tocopherol. Phase diagrams for all biphasic systems are reported. It appears that the polarity of the HBD is the most relevant property driving the phase separation and that choline chloride has only a minor influence on the phase diagram. Measurements of the partition coefficients for the five natural compounds mentioned above reveal that the influence of choline chloride on the partition coefficient of a natural compound is only significant when the latter is present in both phases. Finally, binodal curves and partition coefficients were calculated using a conductor-like screening model for real solvents (COSMO-RS). Calculated and experimental results are in good agreement, confirming that COSMO-RS is a useful and promising tool for screening such complex biphasic systems to find the most adequate system for purifying specific natural compounds.
Jean-Baptiste Chagnoleau; Nicolas Papaiconomou; Mona Jamali; Dinis O. Abranches; João A. P. Coutinho; Xavier Fernandez; Thomas Michel. Toward a Critical Evaluation of DES-Based Organic Biphasic Systems: Are Deep Eutectic Solvents so Critical? ACS Sustainable Chemistry & Engineering 2021, 9, 9707 -9716.
AMA StyleJean-Baptiste Chagnoleau, Nicolas Papaiconomou, Mona Jamali, Dinis O. Abranches, João A. P. Coutinho, Xavier Fernandez, Thomas Michel. Toward a Critical Evaluation of DES-Based Organic Biphasic Systems: Are Deep Eutectic Solvents so Critical? ACS Sustainable Chemistry & Engineering. 2021; 9 (29):9707-9716.
Chicago/Turabian StyleJean-Baptiste Chagnoleau; Nicolas Papaiconomou; Mona Jamali; Dinis O. Abranches; João A. P. Coutinho; Xavier Fernandez; Thomas Michel. 2021. "Toward a Critical Evaluation of DES-Based Organic Biphasic Systems: Are Deep Eutectic Solvents so Critical?" ACS Sustainable Chemistry & Engineering 9, no. 29: 9707-9716.
The development of novel green solvents demands the knowledge of their properties, such as polarity, which can be described through solvatochromic parameters. However, while these are available for a wide range of conventional solvents, there is a lack of data for the emergent ones. Considering the need for such data, predictive models to estimate the Kamlet–Taft (K–T) parameters for deep eutectic solvents (DES) are developed here. The models, based on the conductor-like screening model for real solvents (COSMO-RS) descriptors, were initially developed and tested for 175 organic solvents to validate the applicability of the proposed approach. This approach was then extended for DES, which were classified into two categories, acids and nonacids. The developed equations showed a very good performance for all three K–T parameters, and this is the first work to propose models for all K–T parameters for DES. Moreover, a comparison between polarity data of DES and organic compounds showed that DES, rather than replace common solvents, can extend their range of polarities, reinforcing their designer solvent ability.
José Pedro Wojeicchowski; Dinis O. Abranches; Ana M. Ferreira; Marcos R. Mafra; João A.P. Coutinho. Using COSMO-RS to Predict Solvatochromic Parameters for Deep Eutectic Solvents. ACS Sustainable Chemistry & Engineering 2021, 1 .
AMA StyleJosé Pedro Wojeicchowski, Dinis O. Abranches, Ana M. Ferreira, Marcos R. Mafra, João A.P. Coutinho. Using COSMO-RS to Predict Solvatochromic Parameters for Deep Eutectic Solvents. ACS Sustainable Chemistry & Engineering. 2021; ():1.
Chicago/Turabian StyleJosé Pedro Wojeicchowski; Dinis O. Abranches; Ana M. Ferreira; Marcos R. Mafra; João A.P. Coutinho. 2021. "Using COSMO-RS to Predict Solvatochromic Parameters for Deep Eutectic Solvents." ACS Sustainable Chemistry & Engineering , no. : 1.
The differences on the impact of water on the intermolecular interactions present in the deep eutectic solvents betaine/urea and choline/urea are investigated in this work by measuring the solid–liquid phase diagrams of these mixtures with different amounts of added water. These data are analyzed in terms of ternary systems, rather than the usual pseudo-binary approach, and are used to calculate activity coefficients, which provide precious insight into how water affects the interactions of these systems. It is found that the addition of water greatly enhances the intermolecular interactions of betaine/urea near its eutectic composition, hinting at the formation of a 1:1:1 betaine/urea/water aggregate. On the other hand and contrary to what is commonly believed, water has an asymmetric impact on the interactions present in the choline/urea system. The addition of water to choline-rich mixtures leads to weaker interactions, whereas its addition to urea-rich mixtures leads to stronger interactions. This shows that the decrease in the melting temperature of choline/urea mixtures due to the presence of water does not necessarily mean that intermolecular interactions are strengthened. Finally, a minimum in the activity coefficient of urea in the choline/urea system with 2 wt. % of water was found, which coincides with several anomalies in the properties of this system previously reported in the literature.
Dinis O. Abranches; Liliana P. Silva; Mónia A. R. Martins; João A. P. Coutinho. Differences on the impact of water on the deep eutectic solvents betaine/urea and choline/urea. The Journal of Chemical Physics 2021, 155, 034501 .
AMA StyleDinis O. Abranches, Liliana P. Silva, Mónia A. R. Martins, João A. P. Coutinho. Differences on the impact of water on the deep eutectic solvents betaine/urea and choline/urea. The Journal of Chemical Physics. 2021; 155 (3):034501.
Chicago/Turabian StyleDinis O. Abranches; Liliana P. Silva; Mónia A. R. Martins; João A. P. Coutinho. 2021. "Differences on the impact of water on the deep eutectic solvents betaine/urea and choline/urea." The Journal of Chemical Physics 155, no. 3: 034501.
Rutin is a known antioxidant compound that displays a broad range of biological activities and health-related benefits but presents a low water solubility that can be overcome by its polymerization. In this work, biocompatible aqueous biphasic systems composed of the ionic liquid cholinium dihydrogen phosphate ([CH][DHph]) and the polymer poly(ethylene glycol) 600 (PEG 600) were investigated as an efficient integrated reaction–separation platform for the laccase-catalyzed oligomerization of rutin. Two different approaches were studied to reuse laccase in several oligorutin production cycles, the main difference between them being the use of monophasic or biphasic regimes during the oligomerization reaction. The use of a biphasic regime in the second approach (heterogeneous reaction medium) allowed the successful reuse of the biocatalyst in three consecutive reaction–separation cycles while achieving noteworthy rutin oligomerization yields (95% in the first cycle, 91% in the second cycle, and 89% in the last cycle). These remarkable results were caused by the combination of the increased solubility of rutin in the PEG-rich phase together with the enhanced catalytic performance of laccase in the [Ch][DHph]-rich phase, alongside with the optimization of the pH of the reaction medium straightly linked to enzyme stability. Finally, a life-cycle assessment was performed to compare this integrated reaction–separation platform to three alternative processes, reinforcing its sustainability.
Abel Muñiz-Mouro; Ana M. Ferreira; João A. P. Coutinho; Mara G. Freire; Ana P. M. Tavares; Patricia Gullón; Sara González-García; Gemma Eibes. Integrated Biocatalytic Platform Based on Aqueous Biphasic Systems for the Sustainable Oligomerization of Rutin. ACS Sustainable Chemistry & Engineering 2021, 9, 9941 -9950.
AMA StyleAbel Muñiz-Mouro, Ana M. Ferreira, João A. P. Coutinho, Mara G. Freire, Ana P. M. Tavares, Patricia Gullón, Sara González-García, Gemma Eibes. Integrated Biocatalytic Platform Based on Aqueous Biphasic Systems for the Sustainable Oligomerization of Rutin. ACS Sustainable Chemistry & Engineering. 2021; 9 (29):9941-9950.
Chicago/Turabian StyleAbel Muñiz-Mouro; Ana M. Ferreira; João A. P. Coutinho; Mara G. Freire; Ana P. M. Tavares; Patricia Gullón; Sara González-García; Gemma Eibes. 2021. "Integrated Biocatalytic Platform Based on Aqueous Biphasic Systems for the Sustainable Oligomerization of Rutin." ACS Sustainable Chemistry & Engineering 9, no. 29: 9941-9950.
Spent coffee grounds (SCGs) are a waste product with no relevant commercial value. However, SCGs are rich in extractable compounds with biological activity. To add value to this coffee byproduct, water and aqueous solutions of cholinium-based ionic liquids (ILs) were studied to extract caffeine from SCGs. In general, all IL aqueous solutions lead to higher extraction efficiencies of caffeine than pure water, with aqueous solutions of cholinium bicarbonate being the most efficient. A factorial planning was applied to optimize operational conditions. Aqueous solutions of cholinium bicarbonate, at a temperature of 80 °C for 30 min of extraction, a biomass–solvent weight ratio of 0.05 and at an IL concentration of 1.5 M, made it possible to extract 3.29 wt% of caffeine (against 1.50 wt% obtained at the best conditions obtained with pure water). Furthermore, to improve the sustainability of the process, the same IL aqueous solution was consecutively applied to extract caffeine from six samples of fresh biomass, where an increase in the extraction yield from 3.29 to 13.10 wt% was achieved. Finally, the cholinium bicarbonate was converted to cholinium chloride by titration with hydrochloric acid envisioning the direct application of the IL-caffeine extract in food, cosmetic and nutraceutical products. The results obtained prove that aqueous solutions of cholinium-based ILs are improved solvents for the extraction of caffeine from SCGs, paving the way for their use in the valorization of other waste rich in high-value compounds.
Ana Ferreira; Hugo Gomes; João Coutinho; Mara Freire. Valorization of Spent Coffee by Caffeine Extraction Using Aqueous Solutions of Cholinium-Based Ionic Liquids. Sustainability 2021, 13, 7509 .
AMA StyleAna Ferreira, Hugo Gomes, João Coutinho, Mara Freire. Valorization of Spent Coffee by Caffeine Extraction Using Aqueous Solutions of Cholinium-Based Ionic Liquids. Sustainability. 2021; 13 (13):7509.
Chicago/Turabian StyleAna Ferreira; Hugo Gomes; João Coutinho; Mara Freire. 2021. "Valorization of Spent Coffee by Caffeine Extraction Using Aqueous Solutions of Cholinium-Based Ionic Liquids." Sustainability 13, no. 13: 7509.
There is a need for handy and fast techniques to purify biomolecules, increasing their stability and value, because the separation units are current bottlenecks in downstream processes. Solid-phase extraction is a technique that enables the purification of a compound by its adsorption from a liquid matrix. The AmberLite™ HPR900 OH resin allows the separation of chlorophylls from complex extracts, however the recovery of the chlorophylls is not easy to achieve. An innovative procedure to elute the chlorophyll from AmberLite™ HPR900 OH, based on the use of aqueous solutions of surface-active ionic liquids is proposed in this work. The operational conditions were optimized, showing that the resin can be reused for at least five cycles without losing its efficiency and the chemical structures of the pigments recovered were identified.
Bárbara M.C. Vaz; Margarida Martins; Leonardo M. De Souza Mesquita; Márcia C. Neves; Andreia P.M. Fernandes; Diana C.G.A. Pinto; João A.P. Coutinho; Sónia P.M. Ventura. Using aqueous solutions of ionic liquids as chlorophyll eluents in solid-phase extraction processes. Chemical Engineering Journal 2021, 428, 131073 .
AMA StyleBárbara M.C. Vaz, Margarida Martins, Leonardo M. De Souza Mesquita, Márcia C. Neves, Andreia P.M. Fernandes, Diana C.G.A. Pinto, João A.P. Coutinho, Sónia P.M. Ventura. Using aqueous solutions of ionic liquids as chlorophyll eluents in solid-phase extraction processes. Chemical Engineering Journal. 2021; 428 ():131073.
Chicago/Turabian StyleBárbara M.C. Vaz; Margarida Martins; Leonardo M. De Souza Mesquita; Márcia C. Neves; Andreia P.M. Fernandes; Diana C.G.A. Pinto; João A.P. Coutinho; Sónia P.M. Ventura. 2021. "Using aqueous solutions of ionic liquids as chlorophyll eluents in solid-phase extraction processes." Chemical Engineering Journal 428, no. : 131073.
Levodopa is an amino acid commonly used in the treatment of Parkinson’s disease found in several plants, such as Mucuna pruriens. The extraction of levodopa from biomass has been achieved using methanol, ethanol:water mixtures in presence of ascorbic acid, chloroform in alkaline media, and acetonitrile. Aiming at finding more sustainable solvents and develop efficient extraction processes, in this work, aqueous solutions of carboxylic acids (acetic, propionic, citric, glycolic, and lactic acid) and (poly)alcohols (ethanol, ethylene glycol and glycerol) were studied for the extraction of levodopa from Mucuna pruriens seeds. An initial screening with aqueous solutions of these compounds (at 50 wt%) was conducted at 50 °C, with an extraction time of 90 min at a solid/liquid (biomass/solvent) ratio of 1:10. Based on these results, citric acid aqueous solutions were identified as the best solvent, and an experimental design was carried out to optimize the temperature (T), solid/liquid ratio (S:L) and concentration of acid (wt.%), with the following optimal extraction conditions found: T = 60 °C, S:L = 1:7 and concentration of acid at 58 wt%. Under these optimal conditions, an extraction efficiency of 9.2 ± 0.1 wt% of levodopa was achieved. The recovery of levodopa from the acidic aqueous solution was achieved using an ion exchange column, allowing the recovery of approximately 84% of levodopa. The solvent was shown to be reusable in three successive extraction cycles, with no significant losses in the extraction efficiency of levodopa. The results here obtained show that citric acid aqueous solutions can lead to the effective extraction of levodopa from seeds of Mucuna pruriens, serving as basis for the development of more effective and environmentally friendly processes to recover natural products with therapeutic properties.
Jordana Benfica; Eduarda S. Morais; Julia S. Miranda; Mara G. Freire; Rita De Cássia Superbi De Sousa; João A.P. Coutinho. Aqueous solutions of organic acids as effective solvents for levodopa extraction from Mucuna pruriens seeds. Separation and Purification Technology 2021, 274, 119084 .
AMA StyleJordana Benfica, Eduarda S. Morais, Julia S. Miranda, Mara G. Freire, Rita De Cássia Superbi De Sousa, João A.P. Coutinho. Aqueous solutions of organic acids as effective solvents for levodopa extraction from Mucuna pruriens seeds. Separation and Purification Technology. 2021; 274 ():119084.
Chicago/Turabian StyleJordana Benfica; Eduarda S. Morais; Julia S. Miranda; Mara G. Freire; Rita De Cássia Superbi De Sousa; João A.P. Coutinho. 2021. "Aqueous solutions of organic acids as effective solvents for levodopa extraction from Mucuna pruriens seeds." Separation and Purification Technology 274, no. : 119084.
Enhancing the structural stability and catalytic activity of Cytochorme c (Cyt C) against harsh process conditions would boost its use in biocatalysis. Herein, a new protein engineering strategy with improved efficacy is demonstrated through judicious task-specific functionalization of Cyt C with quantum dots (QDs) and ionic liquids (ILs). Mn2+ doped ZnS QD and ILs ([Cho][Ac]; [Cho][Dhp]) were concomitantly used to decorate Cyt C, which was characterized using various analytical tools. The peroxidase activity at room temperature of engineered Cyt C (Cyt C-QD-IL) increased markedly (1.2 to 3.5-fold) as compared to that for bare Cyt C, Cyt C with QD, and Cyt C with ILs. Further, Cyt C-QD-IL showed better catalytic activity under various stresses such as high temperature (110 °C), presence of a chemical denaturant (6 M GuHCl), high oxidative stress (30 min H2O2), and presence of proteases. Molecular docking results indicate that QD interacted with the active site of Cyt C and IL interacted with side chain amino acids via electrostatic and H-bonding interactions. Such favorable allosteric interactions might be behind the improved activity of Cyt C-QD-IL. The observed catalytic activity is in harmony with the structural stability of the protein as confirmed by UV–vis, ATR-IR, and CD analysis. Thus, the unveiled strategy represents an innovative dimension of protein packaging foreseeing the development of more robust biocatalysts that can be used at high temperatures.
Sachin M. Shet; Sarath Kumar Thayallath; Meena Bisht; Matheus M. Pereira; João A. P. Coutinho; Nataraj Sanna Kotrappanavar; Dibyendu Mondal. Engineering Cytochrome C with Quantum Dots and Ionic Liquids: A Win-Win Strategy for Protein Packaging against Multiple Stresses. ACS Sustainable Chemistry & Engineering 2021, 9, 8327 -8335.
AMA StyleSachin M. Shet, Sarath Kumar Thayallath, Meena Bisht, Matheus M. Pereira, João A. P. Coutinho, Nataraj Sanna Kotrappanavar, Dibyendu Mondal. Engineering Cytochrome C with Quantum Dots and Ionic Liquids: A Win-Win Strategy for Protein Packaging against Multiple Stresses. ACS Sustainable Chemistry & Engineering. 2021; 9 (24):8327-8335.
Chicago/Turabian StyleSachin M. Shet; Sarath Kumar Thayallath; Meena Bisht; Matheus M. Pereira; João A. P. Coutinho; Nataraj Sanna Kotrappanavar; Dibyendu Mondal. 2021. "Engineering Cytochrome C with Quantum Dots and Ionic Liquids: A Win-Win Strategy for Protein Packaging against Multiple Stresses." ACS Sustainable Chemistry & Engineering 9, no. 24: 8327-8335.
Criteria for the rational type V DES selection and application are determined through the separation study of Pt(iv) from Pd(ii).
Silvia J. R. Vargas; Germán Pérez-Sánchez; Nicolas Schaeffer; João A. P. Coutinho. Solvent extraction in extended hydrogen bonded fluids – separation of Pt(iv) from Pd(ii) using TOPO-based type V DES. Green Chemistry 2021, 23, 4540 -4550.
AMA StyleSilvia J. R. Vargas, Germán Pérez-Sánchez, Nicolas Schaeffer, João A. P. Coutinho. Solvent extraction in extended hydrogen bonded fluids – separation of Pt(iv) from Pd(ii) using TOPO-based type V DES. Green Chemistry. 2021; 23 (12):4540-4550.
Chicago/Turabian StyleSilvia J. R. Vargas; Germán Pérez-Sánchez; Nicolas Schaeffer; João A. P. Coutinho. 2021. "Solvent extraction in extended hydrogen bonded fluids – separation of Pt(iv) from Pd(ii) using TOPO-based type V DES." Green Chemistry 23, no. 12: 4540-4550.
By using amino acids as anions, ten chiral ionic liquids (CILs) composed of tetrabutylammonium or cholinium as cations were synthesized by neutralization reactions and further characterized by assessing their optical rotation, thermophysical properties (melting and decomposition temperatures, density, viscosity and refractive index) and ecotoxicity against the marine bacterium Aliivibrio fischeri. The CILs are shown to display, in general, high thermal stability (> 439 K) and low to moderate toxicities (86-217 mg∙L−1). It was found that the cation plays an important role in the density and viscosity of the CILs. Additionally, the effect of CILs optical configuration on these properties was evaluated by comparing the tetrabutylammonium D/L-phenylalaninate ([N4444][D/L-Phe]) and cholinium D/L-phenylalaninate ([N1112(OH)][D/L-Phe]) pairs. Finally, the CILs potential to form aqueous biphasic systems with sodium sulfate, citrate buffer and phosphate buffer was assessed and the ternary phase diagrams were determined. These allowed to infer the impact of the CILs’ cation, anion, and salt on the aqueous biphasic system formation. It was shown that the cation has a more pronounced impact on the aqueous biphasic system formation than the anion. Cholinium-based CILs failed to form aqueous biphasic systems with sodium sulfate under the tested conditions, contrary to the more hydrophobic tetrabutylammonium-based CILs. The ability of the tested salt and buffers to induce liquid-liquid demixing shows that citrate buffer and sodium sulfate represent the weakest and the strongest salting-out agents, respectively.
Ana R.F. Carreira; Samuel N. Rocha; Francisca A. e Silva; Tânia E. Sintra; Helena Passos; Sónia P.M. Ventura; João A.P. Coutinho. Amino-acid-based chiral ionic liquids characterization and application in aqueous biphasic systems. Fluid Phase Equilibria 2021, 542-543, 113091 .
AMA StyleAna R.F. Carreira, Samuel N. Rocha, Francisca A. e Silva, Tânia E. Sintra, Helena Passos, Sónia P.M. Ventura, João A.P. Coutinho. Amino-acid-based chiral ionic liquids characterization and application in aqueous biphasic systems. Fluid Phase Equilibria. 2021; 542-543 ():113091.
Chicago/Turabian StyleAna R.F. Carreira; Samuel N. Rocha; Francisca A. e Silva; Tânia E. Sintra; Helena Passos; Sónia P.M. Ventura; João A.P. Coutinho. 2021. "Amino-acid-based chiral ionic liquids characterization and application in aqueous biphasic systems." Fluid Phase Equilibria 542-543, no. : 113091.
Inverse gas chromatography was used to obtain the activity coefficients at infinite dilution (γ13∞) of several organic solutes and water in the thermotropic ionic liquid crystal phases of both [C12mim][BF4] and [C14mim][BF4] and their isotropic phases. In the smectic to isotropic transition, a change in the linear representation of the natural logarithm of γ13∞ with the reciprocal temperature was observed for [C14mim][BF4], and was more evident for alkanes, alkylbenzenes, esters, and alcohols, that can be related to structural modifications of the stationary phase. Results are interpreted in terms of the enthalpic and entropic contributions of solute-IL interactions. Selectivities and capacities of important separation problems, such as octane/benzene and cyclohexane/benzene, were calculated and compared with literature values for separating agents such as N-methyl-2-pyrrolidinone, sulfolane, and ionic liquids presenting the [BF4]− anion combined with several imidazolium-based cations. It is shown that to achieve maximum separation efficiency, imidazolium cations with short alkyl chain lengths such as [C2mim][BF4] should be used, whereas high capacities require larger alkyl chain lengths.
Mónia A. R. Martins; Sérgio M. Vilas-Boas; Isabella Weber Cordova; Pedro J. Carvalho; Urszula Domańska; Olga Ferreira; João A. P. Coutinho; Simão P. Pinho. Infinite Dilution Activity Coefficients in the Smectic and Isotropic Phases of Tetrafluoroborate-Based Ionic Liquids. Journal of Chemical & Engineering Data 2021, 66, 2587 -2596.
AMA StyleMónia A. R. Martins, Sérgio M. Vilas-Boas, Isabella Weber Cordova, Pedro J. Carvalho, Urszula Domańska, Olga Ferreira, João A. P. Coutinho, Simão P. Pinho. Infinite Dilution Activity Coefficients in the Smectic and Isotropic Phases of Tetrafluoroborate-Based Ionic Liquids. Journal of Chemical & Engineering Data. 2021; 66 (6):2587-2596.
Chicago/Turabian StyleMónia A. R. Martins; Sérgio M. Vilas-Boas; Isabella Weber Cordova; Pedro J. Carvalho; Urszula Domańska; Olga Ferreira; João A. P. Coutinho; Simão P. Pinho. 2021. "Infinite Dilution Activity Coefficients in the Smectic and Isotropic Phases of Tetrafluoroborate-Based Ionic Liquids." Journal of Chemical & Engineering Data 66, no. 6: 2587-2596.
Mixtures of carbohydrates are often reported in the literature as deep eutectic solvents yet, in most cases, their solid-liquid phase diagrams are poorly characterized and no evidence is available to validate this classification. In this work, the phase diagrams of the binary systems composed of the sugar alcohols mannitol or maltitol and meso-erythritol, xylitol, or sorbitol, were experimentally determined. The results obtained reveal that these systems have a thermodynamic ideal behavior, questioning their classification as deep eutectic solvents and showing that intermolecular hydrogen bonding between the components of a mixture is not a sufficient condition to prepare deep eutectic solvents. The phase diagrams of the systems composed of mannitol or maltitol and cholinium chloride were also measured in this work. In sharp contrast to the mixtures composed solely by sugar alcohols, and unlike numerous other choline-based eutectic systems reported in the literature, these systems revealed significant deviations to thermodynamic ideality, leading to significant melting temperature depressions. The Cl-OH interaction between cholinium chloride and the sugar alcohols is identified as the main reason for these deviations to ideality, paving the way for the rational choice of hydrogen bond acceptors to prepare deep eutectic solvents.
Liliana P. Silva; Mónia A. R. Martins; Dinis O. Abranches; Simão P. Pinho; João A. P. Coutinho. Solid-liquid phase behavior of eutectic solvents containing sugar alcohols. Journal of Molecular Liquids 2021, 337, 116392 .
AMA StyleLiliana P. Silva, Mónia A. R. Martins, Dinis O. Abranches, Simão P. Pinho, João A. P. Coutinho. Solid-liquid phase behavior of eutectic solvents containing sugar alcohols. Journal of Molecular Liquids. 2021; 337 ():116392.
Chicago/Turabian StyleLiliana P. Silva; Mónia A. R. Martins; Dinis O. Abranches; Simão P. Pinho; João A. P. Coutinho. 2021. "Solid-liquid phase behavior of eutectic solvents containing sugar alcohols." Journal of Molecular Liquids 337, no. : 116392.
There is a strong industrial interest in the development of greener and more sustainable processes based on the use of renewable resources, and a biorefinery based on marine resources, such as macroalgae, stands as a major opportunity toward that end. In this work, Saccharina latissima (Linnaeus), a brown macroalga, was used as a source of pigments to develop an integrated platform that is able to promote the extraction and separation of chlorophyll and fucoxanthin in one single step. The process was studied, and its operational conditions were optimized with yields of extraction of chlorophyll and fucoxanthin of 4.93 ± 0.22 mgchl·gdry biomass–1 and 1956 ± 84 μgfuco·gdry biomass–1, respectively. These results were achieved with extraction systems composed of 84% of an aqueous solution of a tensioactive phosphonium-based ionic liquid (IL) at 350 mM + 16% of sunflower oil, during 40 min, using a solid–liquid ratio of 0.017 gdry biomass·mLsolvent–1. After the separation of both aqueous IL-rich and oil-rich phases, the IL content in both phases was investigated, the oil phase being free of IL. Envisioning the industrial potential of the process developed in this work, the recovery of the IL from the aqueous IL-rich phase of the initial system was attempted by a back-extraction using organic solvents immiscible in water, being shown that 82% of the IL can be recovered and reused in new cycles of extraction. The environmental and economic impacts of the final process proposed for the extraction and fractionation of chlorophyll and fucoxanthin were evaluated. Different scenarios were considered, but summing up the main results, the solvents’ recycling allowed better results, proving the economic and environmental viability of the overall process.
Margarida Martins; Leonardo M. De Souza Mesquita; Bárbara M.C. Vaz; Ana C.R.V. Dias; Mario A. Torres-Acosta; Benoit Quéguineur; João A.P. Coutinho; Sónia P.M. Ventura. Extraction and Fractionation of Pigments from Saccharina latissima (Linnaeus, 2006) Using an Ionic Liquid + Oil + Water System. ACS Sustainable Chemistry & Engineering 2021, 9, 6599 -6612.
AMA StyleMargarida Martins, Leonardo M. De Souza Mesquita, Bárbara M.C. Vaz, Ana C.R.V. Dias, Mario A. Torres-Acosta, Benoit Quéguineur, João A.P. Coutinho, Sónia P.M. Ventura. Extraction and Fractionation of Pigments from Saccharina latissima (Linnaeus, 2006) Using an Ionic Liquid + Oil + Water System. ACS Sustainable Chemistry & Engineering. 2021; 9 (19):6599-6612.
Chicago/Turabian StyleMargarida Martins; Leonardo M. De Souza Mesquita; Bárbara M.C. Vaz; Ana C.R.V. Dias; Mario A. Torres-Acosta; Benoit Quéguineur; João A.P. Coutinho; Sónia P.M. Ventura. 2021. "Extraction and Fractionation of Pigments from Saccharina latissima (Linnaeus, 2006) Using an Ionic Liquid + Oil + Water System." ACS Sustainable Chemistry & Engineering 9, no. 19: 6599-6612.
Zwitterionic compounds are less ecotoxic than their analogous ionic liquids.
Fátima Jesus; Helena Passos; Ana M. Ferreira; Kosuke Kuroda; Joana Luísa Pereira; Fernando J. M. Gonçalves; João A. P. Coutinho; Sónia P. M. Ventura. Zwitterionic compounds are less ecotoxic than their analogous ionic liquids. Green Chemistry 2021, 23, 3683 -3692.
AMA StyleFátima Jesus, Helena Passos, Ana M. Ferreira, Kosuke Kuroda, Joana Luísa Pereira, Fernando J. M. Gonçalves, João A. P. Coutinho, Sónia P. M. Ventura. Zwitterionic compounds are less ecotoxic than their analogous ionic liquids. Green Chemistry. 2021; 23 (10):3683-3692.
Chicago/Turabian StyleFátima Jesus; Helena Passos; Ana M. Ferreira; Kosuke Kuroda; Joana Luísa Pereira; Fernando J. M. Gonçalves; João A. P. Coutinho; Sónia P. M. Ventura. 2021. "Zwitterionic compounds are less ecotoxic than their analogous ionic liquids." Green Chemistry 23, no. 10: 3683-3692.
Hydrotropy is a well-established strategy to enhance the aqueous solubility of hydrophobic drugs, facilitating their formulation for oral and dermal delivery. However, most hydrotropes studied so far possess toxicity issues and are inefficient, with large amounts being needed to achieve significant solubility increases. Inspired by recent developments in the understanding of the mechanism of hydrotropy that reveal ionic liquids as powerful hydrotropes, in the present work the use of cholinium vanillate, cholinium gallate, and cholinium salicylate to enhance the aqueous solubility of two model drugs, ibuprofen and naproxen, is investigated. It is shown that cholinium vanillate and cholinium gallate are able to increase the solubility of ibuprofen up to 500-fold, while all three ionic liquids revealed solubility enhancements up to 600-fold in the case of naproxen. Remarkably, cholinium salicylate increases the solubility of ibuprofen up to 6000-fold. The results obtained reveal the exceptional hydrotropic ability of cholinium-based ionic liquids to increase the solubility of hydrophobic drugs, even at diluted concentrations (below 1 mol·kg−1), when compared with conventional hydrotropes. These results are especially relevant in the field of drug formulation due to the bio-based nature of these ionic liquids and their low toxicity profiles. Finally, the solubility mechanism in these novel hydrotropes is shown to depend on synergism between both amphiphilic ions.
Tânia E. Sintra; Dinis O. Abranches; Jordana Benfica; Bruna P. Soares; Sónia P.M. Ventura; João A.P. Coutinho. Cholinium-based ionic liquids as bioinspired hydrotropes to tackle solubility challenges in drug formulation. European Journal of Pharmaceutics and Biopharmaceutics 2021, 164, 86 -92.
AMA StyleTânia E. Sintra, Dinis O. Abranches, Jordana Benfica, Bruna P. Soares, Sónia P.M. Ventura, João A.P. Coutinho. Cholinium-based ionic liquids as bioinspired hydrotropes to tackle solubility challenges in drug formulation. European Journal of Pharmaceutics and Biopharmaceutics. 2021; 164 ():86-92.
Chicago/Turabian StyleTânia E. Sintra; Dinis O. Abranches; Jordana Benfica; Bruna P. Soares; Sónia P.M. Ventura; João A.P. Coutinho. 2021. "Cholinium-based ionic liquids as bioinspired hydrotropes to tackle solubility challenges in drug formulation." European Journal of Pharmaceutics and Biopharmaceutics 164, no. : 86-92.
Coarse-grained computer simulation models are valuable tools for guiding experiments in industry and diverse research areas.
Emanuel A. Crespo; Lourdes F. Vega; Germán Pérez-Sánchez; João A. P. Coutinho. Unveiling the phase behavior of CiEj non-ionic surfactants in water through coarse-grained molecular dynamics simulations. Soft Matter 2021, 17, 5183 -5196.
AMA StyleEmanuel A. Crespo, Lourdes F. Vega, Germán Pérez-Sánchez, João A. P. Coutinho. Unveiling the phase behavior of CiEj non-ionic surfactants in water through coarse-grained molecular dynamics simulations. Soft Matter. 2021; 17 (20):5183-5196.
Chicago/Turabian StyleEmanuel A. Crespo; Lourdes F. Vega; Germán Pérez-Sánchez; João A. P. Coutinho. 2021. "Unveiling the phase behavior of CiEj non-ionic surfactants in water through coarse-grained molecular dynamics simulations." Soft Matter 17, no. 20: 5183-5196.
New experimental density data in a wide range of temperatures (283–363) K and pressures (0.1–95) MPa is here reported for five protic ILs based on the N,N-diethylethanolammonium ([DEEA]) cation, combined with the following anions: acetate ([Ace]), propanoate ([Prop]), butanoate ([But]), pentanoate ([Pent]) and hexanoate ([Hex]) in a 1:1 acid:base proportion. The molar volumes of the different ILs and derivative properties such as the isothermal compressibility and isobaric thermal expansivity were determined from the experimental density data. Moreover, considering the importance of having a robust and transferable thermodynamic model of these ILs that can be used in further studies including CO2 capture, the new experimental data was used to develop a coarse-grain molecular model of the studied ILs, in the framework of the soft-SAFT EoS, employing a 2/2 association scheme to account for the hydrogen bonding character of the ILs. The proposed model was found to provide an excellent description of the experimental pρT data with average relative deviations lower than 0.11% for all the ILs, while still providing reasonable predictions of the second-order derivative properties. Furthermore, the optimized molecular parameters were found to be correlated with the ILs molecular weight, highlighting the physical meaning and consistency of the parameters obtained.
Emanuel A. Crespo; Liliana P. Silva; Cristina I.P. Correia; Mónia A.R. Martins; Ramesh L. Gardas; Lourdes F. Vega; Pedro J. Carvalho; João A.P. Coutinho. Development of a robust soft-SAFT model for protic ionic liquids using new high-pressure density data. Fluid Phase Equilibria 2021, 539, 113036 .
AMA StyleEmanuel A. Crespo, Liliana P. Silva, Cristina I.P. Correia, Mónia A.R. Martins, Ramesh L. Gardas, Lourdes F. Vega, Pedro J. Carvalho, João A.P. Coutinho. Development of a robust soft-SAFT model for protic ionic liquids using new high-pressure density data. Fluid Phase Equilibria. 2021; 539 ():113036.
Chicago/Turabian StyleEmanuel A. Crespo; Liliana P. Silva; Cristina I.P. Correia; Mónia A.R. Martins; Ramesh L. Gardas; Lourdes F. Vega; Pedro J. Carvalho; João A.P. Coutinho. 2021. "Development of a robust soft-SAFT model for protic ionic liquids using new high-pressure density data." Fluid Phase Equilibria 539, no. : 113036.
Novel liquid supports for enzyme immobilization and reuse based on aqueous biphasic systems (ABS) constituted by cholinium‐based ionic liquids (ILs) and polymers for the degradation of dyes are here proposed. The biocatalytic reaction for dye decolorization using laccase occurs in the biphasic medium, with the enzyme being “supported” in the IL‐rich phase and the dye and degradation products being enriched in the polymer‐rich phase. An initial screening of the laccase activity in aqueous solutions of ABS constituents, namely cholinium dihydrogen citrate ([Ch][DHC]), cholinium dihydrogen phosphate ([Ch][DHP]), cholinium acetate ([Ch][Acet]), polypropylene glycol 400 (PPG 400), polyethylene glycol 400 (PEG 400) and K2HPO4 was carried out. Compared to the buffered control, a relative laccase activity of up to 170%, 257% and 530% was observed with PEG 400, [Ch][DHP] and [Ch][DHC], respectively. These ABS constituents were then investigated for the in situ enzymatic biodegradation of the Remazol Brilliant Blue R (RBBR) dye. At the optimized conditions, the ABS constituted PPG 400 at 46 wt% and [Ch][DHC] at 16 wt% leads to the complete degradation of the RBBR dye, further maintaining the enzyme activity. This ABS also allows an easy immobilization, recovery and reuse of the biocatalyst for six consecutive reaction cycles, achieving a degradation yield of the dye of 96% in the last cycle. In summary, if properly designed, high enzymatic activities and reaction yields are obtained with ABS as liquid supports, while simultaneously overcoming the safety and environmental concerns of conventional organic solvents used in liquid‐liquid heterogeneous reactions, thus representing more sustainable biocatalytic processes.
Ana M. Ferreira; Ana I. Valente; Leonor S. Castro; João A. P. Coutinho; Mara G. Freire; Ana P. M. Tavares. Sustainable liquid supports for laccase immobilization and reuse: Degradation of dyes in aqueous biphasic systems. Biotechnology and Bioengineering 2021, 118, 2514 -2523.
AMA StyleAna M. Ferreira, Ana I. Valente, Leonor S. Castro, João A. P. Coutinho, Mara G. Freire, Ana P. M. Tavares. Sustainable liquid supports for laccase immobilization and reuse: Degradation of dyes in aqueous biphasic systems. Biotechnology and Bioengineering. 2021; 118 (7):2514-2523.
Chicago/Turabian StyleAna M. Ferreira; Ana I. Valente; Leonor S. Castro; João A. P. Coutinho; Mara G. Freire; Ana P. M. Tavares. 2021. "Sustainable liquid supports for laccase immobilization and reuse: Degradation of dyes in aqueous biphasic systems." Biotechnology and Bioengineering 118, no. 7: 2514-2523.
Ionic liquids (ILs) are salts with low melting points that can be used as solvents for mild extraction and selective fractionation of biomolecules (e.g., proteins, carbohydrates, lipids, and pigments), enabling the valorisation of microalgal biomass in a multiproduct biorefinery concept, while maintaining the biomolecules' structural integrity and activity. Aqueous biphasic systems and emulsions stabilised by core-shell particles have been used to fractionate disrupted microalgal biomass into hydrophobic (lipids and pigments) and hydrophilic (proteins and carbohydrates) components. From nondisrupted biomass, the hydrophobic components can be directly extracted using ILs from intact cells, while the most fragile hydrophilic components can be obtained upon further mechanical cell disruption. These multiproduct biorefinery concepts will be discussed in an outlook on future separations using IL-based systems.
Michel H.M. Eppink; Sónia P.M. Ventura; João A.P. Coutinho; Rene H. Wijffels. Multiproduct Microalgae Biorefineries Mediated by Ionic Liquids. Trends in Biotechnology 2021, 1 .
AMA StyleMichel H.M. Eppink, Sónia P.M. Ventura, João A.P. Coutinho, Rene H. Wijffels. Multiproduct Microalgae Biorefineries Mediated by Ionic Liquids. Trends in Biotechnology. 2021; ():1.
Chicago/Turabian StyleMichel H.M. Eppink; Sónia P.M. Ventura; João A.P. Coutinho; Rene H. Wijffels. 2021. "Multiproduct Microalgae Biorefineries Mediated by Ionic Liquids." Trends in Biotechnology , no. : 1.
The observed imbalance between the unsustainable consumption of available natural metal resources and finite deposits makes the recovery and recycling of metals from metal-containing wastes an imperative. Here, ionic-liquid-based aqueous biphasic systems (IL-based ABSs) are proposed as an efficient alternative for selective metal recovery from real copper acid mine drainage (AMD) effluents. ABSs composed of different ILs and Na2SO4 were evaluated for Zn, Al, Cu, Co, and Ni extraction from both model solutions and AMD samples. It is shown that IL composed of thiocyanate anion ([SCN]−) presented a remarkable ability to extract metals from AMD through the formation of stable metal complexes. The addition of NaSCN to ABSs composed of tetrabutylammonium chloride ([N4444]Cl) allowed to mimic the use of [SCN]-based IL with additional advantages: tunable metal selectivity by the concentration of [SCN]− added to the ABS and a reduction in system cost and environmental impact. Furthermore, at the [SCN]− concentration range studied here, the formation of a hydrophobic salt composed of IL cations and metal complex anions is observed, which allows the selective extraction and recovery of transition metals in a single step. The IL-rich phase recyclability in three extraction cycles is demonstrated, showing the possibility to recover two times more Zn than with a single extraction cycle while using the same amount of IL and thiocyanate. Salt-rich phases were also recycled in a new IL-based ABS for the subsequent Cu extraction and recovery. These results allow the development of a sustainable process for the selective sequential recovery of transition metals from AMD.
Helena Passos; Brayan Cruz; Nicolas Schaeffer; Carla Patinha; Eduardo Ferreira da Silva; João A. P. Coutinho. Selective Sequential Recovery of Zinc and Copper from Acid Mine Drainage. ACS Sustainable Chemistry & Engineering 2021, 9, 3647 -3657.
AMA StyleHelena Passos, Brayan Cruz, Nicolas Schaeffer, Carla Patinha, Eduardo Ferreira da Silva, João A. P. Coutinho. Selective Sequential Recovery of Zinc and Copper from Acid Mine Drainage. ACS Sustainable Chemistry & Engineering. 2021; 9 (10):3647-3657.
Chicago/Turabian StyleHelena Passos; Brayan Cruz; Nicolas Schaeffer; Carla Patinha; Eduardo Ferreira da Silva; João A. P. Coutinho. 2021. "Selective Sequential Recovery of Zinc and Copper from Acid Mine Drainage." ACS Sustainable Chemistry & Engineering 9, no. 10: 3647-3657.