Article
Chemistry, Multidisciplinary
Ana F. C. S. Rufino, Joana M. Bola, Joao A. . P. Coutinho, Francisca A. . E. Silva, Mara G. Freire, Emanuel Capela
Summary: Aqueous biphasic systems (ABS) have the potential to enhance separation processes by integrating multiple unit operations and operating under continuous mode. This study proposes the use of ionic liquids (ILs) as components of double-stimuli-responsive ABS, showing simultaneous responsiveness to temperature and pH. The findings inspire the development of customizable separation techniques, improving the performance and sustainability of separation processes.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Anusha Basaiahgari, Ramesh L. Gardas
Summary: Ionic liquid (IL)-based aqueous biphasic systems (ABSs) have attracted significant interest for extraction and separation of value-added compounds, serving as alternative solvents for non-biocompatible volatile organic compounds. Significant developments have been made in phase constituting components, temperature, pH, and extraction mechanisms in the field of IL-based ABS.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2021)
Article
Engineering, Chemical
Ana F. C. S. Rufino, Sara C. Ribeiro, Joao A. P. Coutinho, Francisca A. Silva, Mara G. Freire
Summary: This study proposes the use of triblock copolymers to develop double stimuli-responsive aqueous biphasic systems (ABS) with ionic liquids (ILs). The ABS exhibit a Lower Critical Solution Temperature (LCST)-like behavior and only show a simultaneous response to both pH and temperature when using a specific copolymer. Copolymers with an adequate content of polyethylene oxide (PEO) provide a stronger response to the simultaneous action of pH and temperature compared to the homopolymer polypropylene glycol (PPG). The results highlight the importance of adjusting polymer structure/monomer composition in developing ABS with double response to temperature and pH. The enhanced tailoring ability of the proposed systems is demonstrated through the simultaneous separation of two dyes.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Engineering, Chemical
Ana R. F. Carreira, Helena Passos, Nicolas Schaeffer, Lenka Svecova, Nicolas Papaiconomou, Isabelle Billard, Joao A. P. Coutinho
Summary: This study systematically evaluated the factors influencing metal partition in acidic aqueous biphasic systems containing phosphonium-based ILs. The results showed that the IL counter anion, acid concentration, temperature, and other factors had an impact on metal extraction. The extraction efficiency of the metals was influenced by the properties of the metal-complex, temperature and ionic strength changes, and the dissociation degree of the acid.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Paula Berton, Hongzhe Tian, Robin D. Rogers
Summary: This study investigated aqueous biphasic systems (ABS) composed of choline alkanoate ionic liquids mixed with K3PO4 solutions at different pH values. The ability to form ABS varied with different ILs and pH, with decreasing biphasic regions observed as pH increased. Anion exchange between phases in ABS at neutral pH was also observed.
Article
Engineering, Chemical
Sladana Maric, Ana Jocic, Aleksandar Krstic, Milos Momcilovic, Ljubisa Ignjatovic, Aleksandra Dimitrijevic
Summary: This study aimed to investigate and propose a new integrated extraction technology for valorization of active pharmaceutical ingredients (APIs) from unused/expired pharmaceuticals by using eco-friendly components. The results showed that citrate-based ABS induced the strongest salting-out effect for extracting APIs with high recovery efficiencies, while ionic liquid/PL6200-based ABS was used for fractionating acetaminophen and caffeine towards opposite phases. These findings demonstrate the viability and adjustability of PL6200-based ABSs as a sustainable and efficient alternative platform on a larger scale.
SEPARATION AND PURIFICATION TECHNOLOGY
(2021)
Article
Multidisciplinary Sciences
Damien Degoulange, Raj Pandya, Michael Deschamps, Dhyllan A. Skiba, Betar M. Gallant, Sylvain Gigan, Hilton B. de Aguiar, Alexis Grimaud
Summary: High-resolution Raman imaging is used to investigate the interface of salt-salt aqueous biphasic systems (ABSs) at a molecular level, revealing a gradual change of environment instead of a sharp molecular interface. This knowledge is of great importance in understanding aqueous interfaces and has significant implications in various biological and technological settings, including novel battery technologies.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Thermodynamics
Mafalda R. Almeida, Ana F. C. S. Rufino, Diana C. Belchior, Pedro J. Carvalho, Mara G. Freire
Summary: This study aims to characterize aqueous biphasic systems composed of cholinium carboxylate ILs, K3PO4, and water. The experimental results show that ILs can effectively separate high-value compounds, and the alkyl chain length of IL anions exhibits an odd-even effect on the partitioning of alkaloids.
FLUID PHASE EQUILIBRIA
(2022)
Article
Engineering, Chemical
Ana R. F. Carreira, Ana M. Ferreira, Mafalda R. Almeida, Joao A. P. Coutinho, Tania E. Sintra
Summary: The commercialization of chiral drugs is a growing concern in pharmacology due to the potential issues with the pharmacological activities of enantiomers in racemates. This study aimed to develop a platform for the resolution of propranolol using chiral selectors in biphasic systems, with a focus on enantioselective liquid-liquid extraction (ELLE) systems. The most efficient biphasic system identified involved 1,2-dichloroethane-water, dipentyl-L-tartrate, and boric acid as chiral selectors, achieving an enantioselectivity of 2.54.
SEPARATION AND PURIFICATION TECHNOLOGY
(2021)
Article
Food Science & Technology
Liling Wang, Yanbin Wang, Yuchuan Qin, Bentong Liu, Yifeng Zhou
Summary: This study developed a rapid detection method for protein extraction from edible oil using aqueous biphasic systems (ABS) based on hydrophilic ionic liquids (ILs) and salts. Optimal conditions for protein extraction were investigated, and the method was successfully applied to different sources of edible oil.
FOOD AND BIOPROCESS TECHNOLOGY
(2022)
Article
Chemistry, Physical
Shraddha Deshmukh, Aditya Madan Bhatt, Anil Boda, Rohit Singh Chauhan, Sk. Musharaf Ali, Arijit Sengupta
Summary: The efficient separation of tetravalent thorium ion (Th4+) from aqueous phase to ionic liquid phase was explored using two compounds, L1 and L2. The electron density on N in L1 was higher than that in L2 due to the positive inductive effect of the alkyl group. The extraction proceeded via a "cation exchange" mechanism, and each thorium complex was associated with three nitrate ions. The importance of this research is rated as 8 out of 10.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Biochemistry & Molecular Biology
Sandra C. Bernardo, Emanuel V. Capela, Jorge F. B. Pereira, Sonia P. M. Ventura, Mara G. Freire, Joao A. P. Coutinho
Summary: Cholinium-based ionic liquids were studied as electrolytes in ABS composed of PEG and NaPA, showing both enhancement and decrease in the liquid-liquid demixing ability. The distribution of electrolyte ions between phases and polyelectrolyte ion compartmentalization are key factors influencing the formation of PEG-NaPA-based ABS.
Article
Materials Science, Multidisciplinary
Xiangyu Liu, Taiyu Wang, Jiale Fang, Feng Ru Fan
Summary: Low-grade heat energy sources have untapped potential for sustainable power generation, and liquid thermocells offer an innovative solution to convert low-grade heat into electricity. This study proposes an electrochemically active biphasic liquid thermocell (EAB-LTC) using ferrocene and Fe(CN)6(3-) in an ethanol-aqueous biphasic system. The EAB-LTC exhibits significantly enhanced Seebeck coefficient and output power compared to conventional single-phase LTCs.
ADVANCED MATERIALS TECHNOLOGIES
(2023)
Article
Engineering, Chemical
Alexandre M. S. Jorge, Joao A. P. Coutinho, Jorge F. B. Pereira
Summary: This study investigates the hydrodynamics of three cholinium chloride-based aqueous biphasic systems (ABS) through analyzing the relationship between mixing time and phase settling time. The results show that phase settling time is independent of mixing time and is influenced by the nature of the phase-forming compounds. The study also defines the best operating region within the liquid-liquid region of [Ch]Cl/salt-based ABS.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Chuanying Liu, Jianhui Lan, Qibin Yan, Zhipeng Wang, Chao Xu, Weiqun Shi, Chengliang Xiao
Summary: A new temperature-responsive alkaline aqueous biphasic system was developed to remove radioactive (TcO4-)-Tc-99. The micelle formed in the system showed a high affinity toward (TcO4-)-Tc-99 and could extract more than 98.6% of it from the waste supernatant. The loaded (TcO4-)-Tc-99 could be easily stripped using concentrated nitric acid.
CHINESE CHEMICAL LETTERS
(2022)
Article
Engineering, Chemical
Emanuel Capela, Jessica Bairos, Augusto Q. Pedro, Marcia C. Neves, M. Raquel Aires-Barros, Ana M. Azevedo, Joao A. P. Coutinho, Ana P. M. Tavares, Mara G. Freire
Summary: This work demonstrates that materials modified with ionic liquids (ILs) can be effectively used for the selective adsorption and purification of antibodies, such as IgG, from complex matrices. The developed strategy showed good purification results in various IgG-containing matrices and preserved the structural integrity and biological activity of IgG. This suggests that ILs have the potential to replace costly chromatographic columns currently used for IgG purification.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Carlos M. N. Mendonc, Nathalia V. Verissimo, Wellison A. . Pereira, Paula M. Cunha, Michele Vitolo, Attilio Converti, Kiki Adi Kurnia, Fernando Segato, Pamela O. S. de Azevedo, Mara G. Freire, Koen Venema, Joao H. P. M. Santos, Ricardo P. S. Oliveira
Summary: Aqueous biphasic systems (ABSs) based on sodium polyacrylate (NaPA), ethylene oxide/propylene oxide (EO/PO) polymers, and (EO)x-(PO)y-(EO)x triblock copolymers were prepared and applied for continuous fructooligosaccharide (FOS) production and separation. The hydrophilicity/hydrophobicity balance of EO/PO had a significant effect on ABS formation. Different carbohydrates and levansucrase showed different partition behavior in these ABSs. By selecting the appropriate ABS composition, high yields of FOS and selective partitioning could be achieved. COSMO-RS suggested that ABS formation was due to competition between NaPA and polymers/copolymers to form hydrogen bonds with water molecules.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Henrique Bastos, Nicolas Schaeffer, Jennifer M. M. Pringle, Joao A. P. Coutinho, Cristina Pozo-Gonzalo
Summary: The study investigates the use of dilute HCl solutions in hydroxylated solvents for dissolving Co, Ni, and Mn oxides in spent lithium-ion batteries. The findings present a simple and greener alternative to current leaching processes, reducing acid consumption and enhancing dissolution efficiency.
Article
Engineering, Chemical
Sergio M. Vilas-Boas, Isabella W. Cordova, Dinis O. Abranches, Joao A. . P. Coutinho, Olga Ferreira, Simao P. Pinho
Summary: In this study, the Abraham and NRTL-SAC semi-predictive models were used to represent the solubility of different solutes in water and organic solvents. The models were calibrated using measured and literature data, and their predictive capabilities were tested on independent solvents. The results showed that NRTL-SAC performed better in the correlation/prediction approach, while COSMO-RS could produce satisfactory predictions even without experimental data.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Engineering, Chemical
Sergio M. Vilas-Boas, Aline Zambom Coelho, Monia A. R. Martins, Joao A. P. Coutinho, Olga Ferreira, Simao P. Pinho
Summary: In this study, the potential use of ionic liquids (ILs) and their mixtures as separation agents in the fractionation of essential oils was investigated. Experimental and modeling approaches showed that chloride-based ILs are effective in fractionating essential oils containing hydrogen-bond donor monoterpenoids.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Ana F. C. S. Rufino, Joana M. Bola, Joao A. . P. Coutinho, Francisca A. . E. Silva, Mara G. Freire, Emanuel Capela
Summary: Aqueous biphasic systems (ABS) have the potential to enhance separation processes by integrating multiple unit operations and operating under continuous mode. This study proposes the use of ionic liquids (ILs) as components of double-stimuli-responsive ABS, showing simultaneous responsiveness to temperature and pH. The findings inspire the development of customizable separation techniques, improving the performance and sustainability of separation processes.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Isis Maximo Dantas Feitosa, Ronnie Emanuel Pereira Pinto, Matheus Mendonca Pereira, Cleide Mara Faria Soares, Alvaro Silva Lima
Summary: This study optimized the extraction of proteins from Brazilwood seeds with proteolytic inhibitory activity using choline-based ionic liquid. The best extraction conditions were 25.42 degrees C, 5.42% (m/v) choline bitartrate, solid-liquid ratio 1:5, 500 rpm and pH 7.0. Under optimized conditions, the protein extract of Brazilwood seeds provided a 60.8% inhibition of trypsin.
SUSTAINABLE CHEMISTRY AND PHARMACY
(2023)
Article
Chemistry, Analytical
Filipa C. Flora, Sofia B. Relvas, Francisca A. e Silva, Mara G. Freire, Virginia Chu, Joao Pedro Conde
Summary: Prostate cancer (PCa) is a major global health concern, and improved diagnostic strategies are urgently needed. This study shows that prostate-specific antigen (PSA) can be detected through an immunoassay performed in a microbead-based microfluidic device after being extracted and purified from a serum sample using an aqueous biphasic system (ABS). Ionic liquids (ILs) and polymers were used in combination with buffered salts to optimize the extraction process. The results demonstrate the potential of this method for future point-of-care measurements.
Article
Energy & Fuels
Matthieu Habrioux, Djamel Nasri, Joao A. P. Coutinho, Jean-Luc Daridon
Summary: This study presents experimental data on the sound velocities and densities of two biodiesel fuels, namely sunflower methyl ester and a blend of Palm, Rapeseed, and Soybean methyl esters. The measurements were conducted at pressures ranging from atmospheric to 200 MPa and temperatures from 293.15 to 393.15 K. The data obtained were compared with existing models to predict the density and sound velocity of biodiesels under high pressure based on their fatty acid ester composition.
Article
Engineering, Chemical
Sandra S. Silva, Dinis O. Abranches, Ana S. Pinto, Bruna P. Soares, Helena Passos, Ana M. Ferreira, Joao A. P. Coutinho
Summary: Improving the aqueous solubility of poorly soluble hydrophobic compounds is important in various industries. This study investigated the use of biobased solvents, such as γ-valerolactone (GVL) and ethyl lactate, to enhance the solubility of two model compounds (syringic acid and ferulic acid) in water. The results showed that GVL and other biobased solvents were effective in increasing the solubility of these compounds.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Engineering, Chemical
Thomas Brouwer, Emanuel A. Crespo, Antoon ten Kate, Joao A. P. Coutinho, Sascha R. A. Kersten, Gerrald Bargeman, Boelo Schuur
Summary: This study systematically assessed the feasibility of determining vapor-liquid equilibrium (VLE) data based on excess molar enthalpy (h(E)) results. Twelve cubic Equation of State (cEoS) models combined with eight mixing rules and the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) were evaluated. The results showed that the developed h(E)-cEoS-VLE methodology can accurately predict VLE data for systems with unavailable binary interaction parameters, and the h(E)-PC-SAFT-VLE model can accurately predict VLE data for highly nonideal and associating systems.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Mariam Kholany, Nicolas Schaeffer, Ines P. E. Macario, Telma Veloso, Tania Caetano, Joana L. Pereira, Ana C. R. V. Dias, Joao A. P. Coutinho, Soinia P. M. Ventura
Summary: Haloarchaea, a class of marine microbial resources, can be a promising source of valuable compounds such as bacterioruberin. Natural and biocompatible hydrophobic eutectic solvents (HES) based on menthol and carboxylic acids were investigated for the extraction of bacterioruberin. The menthol and levulinic acid mixture showed the best results and proteins could be recovered by adding water to the extract, forming a protein-rich interfacial precipitate. The process intensification was achieved by reusing the eutectic phase over multiple extraction cycles, resulting in a bacterioruberin-rich extract.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Ines S. Cardoso, Filipe H. B. Sosa, Armando J. D. Silvestre, Anthony Robert, Mara G. Freire, Aminou Mohamadou
Summary: The use of biobased and bioactive compounds has led to the development of sustainable extraction and purification processes using ionic liquids. In this study, six novel analogues of glycine-betaine ILs (AGB-ILs) were investigated for their potential use in IL-based ABS. The synthesized ILs showed relatively low ecotoxicity and good thermal stability. The extraction efficiency of furfural using AGB-ILs-based ABS was found to be up to 98%, suggesting the potential of these novel ABS for separation of bioactive compounds.
SUSTAINABLE CHEMISTRY AND PHARMACY
(2023)
Article
Chemistry, Physical
Jean -Baptiste Chagnoleau, Nicolas Papaiconomou, Xavier Fernandez, Joao A. P. Coutinho
Summary: This study evaluates the potential of the conductor-like screening model for designing biphasic systems for natural compound separation. The model accurately predicts binodal curves and phases composition and shows excellent agreement with experimental data for partition coefficients of natural compounds. The model is able to capture the influence of changes in system composition on partition coefficients.
JOURNAL OF MOLECULAR LIQUIDS
(2024)