Isabel M. Marrucho

University of Lisbon | UL · Instituto Superior Técnico, Chemical Engineering Department

Aqueous biphasic systems (ABS) extraction is a simple, selective, efficient and easy to scale-up technology that, over the years, has attracted a considerable attention from the researcher community as an alternative methodology in downstream processing of a wide variety of biomolecules. This review summarizes and discusses the fundamental features...

The aim of the present research was to develop green and sustainable extraction procedure for β-carotene recovery from pumpkin. A series of hydrophobic natural deep eutectic solvents (NADESs) based on fatty acids were prepared to establish high extraction efficiency of β-carotene and to increase stability of extracted carotenoids from the pumpkin....

The majority of antibiotics display low oral bioavailability due to reduced solubility in water and/or inefficient permeability across biological membranes. Their efficiency is further limited by the frequent presence of polymorphic structures with different pharmaceutical activities. In this communication, we present our latest results on the deve...

This work presents mixed gas separation performance through PIL–IL membranes bearing pyrrolidinium-based PILs with [NTf2]– and [C(CN)3]– anions and different weight percentages of the corresponding ILs using a ternary mixture of H2, CO2 and N2 and different feed pressures ranging from 1 to 4 bar and temperatures from 20 to 80 °C. COSMO-RS was succe...

Since their discovery, deep eutectic solvents (DES) have been explored in multiple applications. However, the complete physicochemical characterization is still nonexistent for many of the proposed and used DES. In particular, vapor pressure, which is a crucial property for the application of DES as solvents, is very rarely available. In this work,...

M13 bacteriophage is a key instrument in phage display applications, as well as a possible antibacterial therapeutic agent due to its highly restrictive bacterial pathogenesis, and other applications. The traditional phage purification process is usually achieved by gradient ultracentrifugation or a combination of precipitation, centrifugation and...

Liquid-liquid phase behavior measurements were performed for binary mixtures of water and ionic liquids (ILs) containing the same 1-ethyl-3-methylimidazolium ([C2mim]+) cation and different imide-based anions, having symmetric (bis(fluorosulfonyl)imide ([FSI]–)) or asymmetric structures (2,2,2-trifluoromethylsulfonyl-N-cyanoamide ([TFSAM]–) and 2,2...

The aim of this work is to develop an optimized enzymatic assisted extraction methodology to extract carotenoids and phenolic compounds from sunflower wastes (petals and florets) using natural hydrophobic green solvents. Several natural green hydrophobic solvents were used as well as natural hydrophobic eutectic solvents composed of d,l-menthol and...

In this contribution, thin poly(ionic liquid) (PIL) coatings with a well-defined pore structure built up from interpolyelectrolyte complexation between a PIL and poly(acrylic acid) (PAA) were successfully used for enhanced solid phase microextraction (SPME). The introduction of porosity with tunable polarity through the highly versatile PIL chemist...

As the development of novel antibiotics has been at a halt for several decades, chemically enhancing existing drugs is a very promising approach to drug development. Herein, we report the preparation of twelve organic salts and ionic liquids (OSILs) from ciprofloxacin and norfloxacin as anions with enhanced antimicrobial activity. Each one of the f...

Owning to its unique properties of breaking down proteins into soluble small peptides, pepsin has been advantageously applied in many different industries, such as food, feed or pharmaceutical. However, industrial production of enzymes is still considered a major bottleneck due to the lack of robust, cost-effective and sustainable purification meth...

The present study explores the preparation of dual nanofibrillar-based bio-sorbent films composed of cellulose nanofibrils (CNFs) and lysozyme nanofibrils (LNFs) for application in the removal of Hg(II) from aqueous solutions. The free-standing films were fabricated via simple vacuum filtration of water suspensions of CNFs and LNFs and disclose goo...

Clean and sustainable energy production has become a key global issue concerning the world’s energy shortage and environmental problems. Despite the recognized potential of biohydrogen (bioH2) for sustainable development, there are still issues regarding its production and purification, such as the elimination of CO2, N2, and other impurities (H2O...

Simple mixtures of ionic liquids (IL-IL mixtures) can become a promising approach for the substitution of task-specific ILs. Such concept was explored in this article by comparison of thermophysical properties of neat 1-ethyl-3-methylimidazolium 2,2,2-trifluoromethylsulfonyl-N-cyanoamide, [C2mim][TSAM], and equimolar mixtures of two structurally si...

The occurrence of micropollutants in aquatic ecosystems poses a serious public health and environmental problem. For that purpose, the main goal of this work is the removal of an endocrine disruptor micropollutant compound, Bisphenol-A (BPA), from aqueous environments using hydrophobic deep eutectic solvents (DES). In particular, DES composed of DL...

Clean water became one of the major concerns of 21st century. The occurrence of micropollutants in aquatic ecosystems poses serious public health and environmental problems, leading to true challenges in the development of sustainable and cost-effective alternative technologies for wastewater treatment processes. As a result, hydrophobic Deep Eutec...

Due to their unique properties, virus‐like particles (VLPs) have been portrayed as a promising high‐value biopharmaceutical in VLP‐based vaccination and cancer therapy. Nevertheless, due to limited physical and economical capabilities of the current downstream processing of VLPs, their production is still difficult and seen as a major problem that...

During the last years, poly(ionic liquids) (PILs) have been gaining increased attention as materials for analytical chemistry. This success is due to the fact that PILs synthesis is generally based on the polymerization of ionic liquid monomers (ILMs), and thus some of their remarkable properties are shared with their polymeric form. Consequently,...

Non-steroidal anti-inflammatory drugs (NSAIDs) are largely consumed worldwide. As a result, NSAIDs were already found in a variety of environmental aqueous samples, in concentrations ranging from ng/L to µg/L. This is due to the inability of the currently used technologies in sewage treatment plants (STPs) and wastewater treatment plants (WWTPs) to...

BACKGROUND Eutectic solvents are a mixture of two compounds which possess a lower melting temperature than compounds by themselves at low temperatures (below 100ºC), using quaternary ammonium salts, as choline and betaine, and organic acids, polyols and amides as hydrogen bond donors. These solvents can be an alternative as non-aqueous media for en...

The concurrent removal of both nitrogen- and sulfur-containing compounds was studied in this work. Four different Deep Eutectic Solvents (DES) were prepared and ranked according their performance to remove thiophene (Th), dibenzothiophene (DBT), pyridine (Py) and carbazole (Carb), from n-heptane in binary mixtures. The simultaneous extractive desul...

The Cover Feature shows the possibility of using all‐natural components for design of hydrophobic water‐stable deep eutectic solvents (DES), which can replace toxic volatile organic compounds. DESs are essential in modern green and sustainable chemistry and can be used in a host of applications such as solvents, reaction media, catalysts, additives...

Deep eutectic solvents (DESs) consist of a mixture of two or more solid components leading to a drop of the melting point of the mixture when compared to the starting materials. Until recently, only hydrophilic DESs were available, and despite their revolutionary role in the alternative solvents scenario, important issues in chemistry and chemical...

In this work, a facile preparation of SPME fibers with increased surface area is presented. The SPME fibers were prepared by grinding poly(ionic liquids) (PILs) to obtain particles of 1–16 µm and, with the aid of a silicon adhesive, attach these particles to a steel wire support. Three different PILs, poly(1-vinyl-3-benzylimidazolium-co-styrene bro...

Novel functionalized ionic liquid (IL) combining an imidazolium‐based cation with branched alkyl chain bearing silyl group, 1‐methyl‐3‐(2‐methyl‐3‐(trimethylsilyl)propyl)imidazolium ([Si−C1−C3‐mim]+), and bis(trifluoromethylsulfonyl)imide ([NTf2]−) anion was synthesized and its thermophysical properties (density, viscosity, surface tension, surface...

The development of efficient carbon dioxide capture and separation technologies is at the fore front of the priorities in the climate change policies. Poly(ionic liquid)s (PILs) have been emerging as extremely promising materials for the fabrication of membranes for CO2 separation. This work is a step forward to evaluate the effect of the PIL-based...

Considering the high potential of hydrogen (H2) as a clean energy carrier, the implementation of high performance and cost-effective biohydrogen (bioH2) purification techniques is of vital importance, particularly in fuel cell applications. As membrane technology is a potentially energy-saving solution to obtain high-quality biohydrogen, the most p...

In the last couple of years, deep eutectic solvents (DESs) have been raising a lot of attention mainly due to their versatility and their easy and speedy preparation without the need of further purification. Moreover, the vast array of very different compounds that can be selected for their preparation has led to the full tailoring of their relevan...

Considering the high potential of hydrogen (H2) as a clean energy carrier, the implementation of high performance and cost-effective biohydrogen (bioH2) purification techniques is of vital importance, particularly in fuel cell applications. In this context, membrane technology is a potentially energy-saving solution to obtain high-quality biohydrog...

The introduction of ionic liquids (ILs), either as phase forming components or as adjuvants, in the implementation of aqueous biphasic systems (ABS) enabled to finely tune the properties of the two aqueous phases in equilibrium thus providing the opportunity to increase extraction efficiencies and selectivities of biomolecules. Nevertheless, the ef...

Protein nanofibers are gaining much attention due to their unique mechanical strength, thermal stability and functional properties, thus promoting research on new preparation methodologies. Most fibrillation processes developed so far are time consuming, usually taking from 8h to 15h, which represents a major drawback in their use. The use of alter...

In this work, extractive desulfurization of model fuel containing dibenzothiophene (DBT) and thiophene (Th) as sulfur compounds was carried out using 16 different Deep Eutectic Solvents (DES) based on polyethylene glycol (PEG) and its precursors. The aim of this study is the reduction of the sulfur content of fuels below the en- vironmental regulat...

Supramolecular Hydrogel based on sodium Deep Eutectic Solvent (DES) is here presented for the first time. Phase diagram of DES-based hydrogel was drawn and its rheological properties determined.

Deep eutectic solvents (DESs), a novel generation of ionic solvents, have recently been described as efficient and timesaving fibrillation agents for proteins. In this context, the present work aims at assessing the effect of the hydrogen bond donor (HBD) of cholinium chloride ([Ch]Cl):carboxylic acid based DESs on the dimensions (length and width)...

In this work, poly(ionic liquid)–ionic liquid (PIL–IL) composite membranes were prepared using the solvent casting technique. The studied PILs have pyrrolidinium polycation backbone ([Pyr11]⁺), while the five ILs display either an imidazolium ([C2mim]⁺) or a pyrrolidinium ([Pyr14]⁺) based cation. Both the PIL and IL components comprised cyano-funct...

The design of poly(ionic liquids) (PILs) and their application as solid phase microextraction (SPME) fibers has been attracting enormous attention mainly due to the need for new SPME coating materials with improved analytical sensitivity. In this work, the tunability of PILs is explored by preparing different imidazolium monomers bearing benzyl, na...

Inspired by the use of fatty acids in development of low temperature latent heat storage materials, novel low viscous and hydrophobic deep eutectic solvents (DESs) based exclusively on fatty acids are herein proposed as sustainable solvents. Three DESs were prepared by exclusively combining fatty acids, namely octanoic acid (C8), nonanoic acid (C9)...

M13 is a filamentous, non-lytic bacteriophage that infects Escherichia coli via the F pilus. Currently, phage M13 is widely used in phage display technology and bio-nanotechnology, and is considered a possible antibacterial therapeutic agent, among other applications. Conventional phage purification involves 5-7 operational steps, with high operati...

Aiming at investigating the effect of the polymer molecular weight (Mw) on the physical and gas permeation properties of poly(ionic liquid)-ionic liquid (PIL–IL) composites, this work focuses on membranes based on variable Mw pyrrolidinium-PILs having [C(CN)3]– as counter-anion and different amounts (20, 40 and 60 wt%) of free [C2mim][C(CN)3] IL. A...

Deep eutectic solvents (DESs) constitute a new class of ionic solvents that has been developing at a fast pace in recent years. Since these solvents are commonly suggested as green alternatives to organic solvents, it is important to understand their physical properties. In particular, polarity plays an important role in solvation phenomena. In thi...

M13 is a filamentous, non-lytic bacteriophage that infects Escherichia coli via the F pilus. Currently, phage M13 is widely used in phage display technology and bio-nanotechnology, and is considered a possible antibacterial therapeutic agent, among other applications. Conventional phage purification involves 5–7 operational steps, with high operati...

Homogeneous, glossy and transparent nanocomposite films composed of pullulan (PL) and lysozyme nanofibers (LNFs) were developed by simple solvent casting from aqueous suspensions. The incorporation of LNFs into the PL matrix maintained the filmogenic ability of PL and endowed the nanocomposite films with good mechanical properties (Young's modulus...

Seven anions including four imide-based, namely bis[(trifluoromethyl)sulfonyl]imide (TFSI), bis(fluorosulfonyl)imide (FSI), bis[(pentafluoroethyl)sulfonyl]imide (BETI), 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM) and 2,2,2-trifluoro-N-(trifluoromethylsulfonyl) acetamide (TSAC), and two sulfonate anions, trifluoromethanesulfonate (triflate, T...

The CO2 and N2 permeation properties of ionic liquids (ILs) based on the 1-ethyl-3-methylimidazolium cation ([C2mim]+) and different fluorinated anions, namely 2,2,2-trifluoromethylsulfonyl-N-cyanoamide ([TFSAM]–), bis(fluorosulfonyl) imide ([FSI]–), nonafluorobutanesulfonate ([C4F9SO3]–), tris(pentafluoroethyl)trifluorophosphate ([FAP]–), and bis(...

M13 is a filamentous, non-lytic bacteriophage that infects Escherichia coli via the F pilus. Currently, phage M13 is widely used in phage display technology and bio-nanotechnology, and is considered a possible antibacterial therapeutic agent, among other applications. Conventional phage purification involves 5–7 operational steps, with high operati...

Crosslinked pyrrolidinium-based poly(ionic liquids) (Pyrr-PILs) were synthesized through a fast, simple, and solventless photopolymerization scheme, and tested as solid phase microextraction (SPME) sorbents. A series of Pyrr-PILs bearing three different alkyl side chain lengths with two, eight, and fourteen carbons was prepared, characterized, and...

Deep Eutectic Solvents (DESs) have recently emerged as green alternatives to ionic liquids (ILs). Encouraged by the sustainability of this novel class of solvents, the aim of this work is to prepare DESs using three different hydrogen bond acceptors (HBA), such as cholinium chloride, acetylcholinium chloride and benzyldimethyl(2-hydroxyethyl)ammoni...

Fluoroquinolones (FQs) and Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) are two classes of Active Pharmaceutical Ingredients (APIs), widespread used in human healthcare and as veterinary drugs, and that have been found throughout...

Membranes for CO2/N2 separation towards CO2 capture The cover art depicts research work developed at the LAQV-REQUIMTE, Laboratory for Green Chemistry in Nova University of Lisbon led by Luisa A. Neves and Cláudia C. L. Pereira. It shows that confined ionic liquids (ILs) inside metal–organic frameworks (MOFs) form structures that, when incorporated...

Herein a straightforward approach for the enhancement of water solubility of common antibiotic and NSAID Active Pharmaceutical Ingredients (APIs) is presented. The APIs are converted into Ionic Liquids (API-ILs) and molten salts by combination with the organic superbases TMG, DBU and DBN. The prepared superionic liquids were characterized by 1H and...

M13 is a filamentous, non-lytic bacteriophage that infects Escherichia coli via the F pilus. Currently, phage M13 is widely used in phage display technology and bio-nanotechnology, and is considered a possible antibacterial therapeutic agent, among other applications. Conventional phage purification involves 5–7 operational steps, with high operati...

Immobilization of ionic liquids (ILs) into 3D metal-organic frameworks (MOFs) is reported. The incorporation of these composites in a polyimide-based matrix (Matrimid®5218) to yield [[email protected]/* */]@Matrimid®5218 is an efficient strategy to improve the permeability and selectivity toward CO2/N2 mixtures, presenting also a remarkable improve...

Wastewater treatment plants do not properly address the removal of emerging micropollutants, such as pesticides, and thus these compounds contaminate water sources of public drinking water systems. In this context, this work focuses on the development of hydrophobic deep eutectic solvents (DESs), as cheap extractants for the removal of four neonico...

Aqueous biphasic systems based on ionic liquids (ILs) have been researched as promising extraction and purification routes for a huge diversity of compounds. The inherent tunability offered by ILs combined with the large variety of salts available underlines the reliable phase equilibrium data. In this vein, this work presents novel aqueous biphasi...

This work explores ionic liquid-based membranes with siloxane functionalized cations using two different approaches: supported ionic liquid membranes (SILMs) and poly(ionic liquid)–ionic liquid (PIL–IL) composite membranes. The CO2, CH4 and N2 permeation properties of the prepared membranes were measured at T = 293 K with a trans-membrane pressure...

In the current era of human life, we have been facing an increased consumption of Non-Steroidal Anti-Inflammatory Drugs (NSAIDs). Nevertheless, NSAIDs are not entirely metabolized by humans, and are thus excreted into domestical effluents, whereas expired medications are recurrently straightly disposed into wastewaters. Several studies already demo...

To advance the ionic liquid (IL) platform to tailor fluorinated surfactant properties, the aim of this work is to evaluate the surfactant properties of cholinium-based salts bearing perfluoroalkanoate anions. Novel surfactant ILs containing the cholinium cation [Ch](+) combined with different perfluoroalkanoate anions, namely perfluoropentanoate [P...

The efficient and sustainable separation of azeotropic mixtures remains a challenge in chemical engineering. In this work, the performance of benign solvents, namely Deep Eutectic Solvents (DES) in the separation of aromatic-aliphatic hydrocarbons azeotropic mixtures via liquid-liquid extraction (LLE) is evaluated. The DES studied in this work were...

Density and dynamic viscosity data of binary mixtures of ionic liquids (ILs) were determined in this work, at temperatures from 283.15 to 363.15 K and at 0.1 MPa. The mixtures of two ILs comprise a common cation and different anions, combining 1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide with eight other ionic liquids, namely, 1-b...

Amyloid fibrils have recently gained a lot of attention due to their morphology, functionality and mechanical strength, allowing for their application in nanofiber-based materials, biosensors, bioactive membranes and tissue engineering scaffolds. The in vitro production of amyloid fibrils is still a slow process, thus hampering the massive producti...

In this work, the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate, [C2MIM][Ac], was combined with the inorganic salts (ISs) ammonium acetate, [NH4][Ac], ammonium chloride, [NH4]Cl, and ammonium thiocyanate, [NH4][SCN], and used as an extraction solvent for the separation of the azeotropic mixture of n-heptane + ethanol. The liquid-liquid equi...

This work explores the widening of properties of cholinium-based ionic liquids (ILs) through their combination with perfluoroalkanoate anions so that higher number of aqueous biphasic systems (ABSs) containing nontoxic cholinium-based ILs is available. For that purpose, six cholinium perfluoroalkanoate ILs were synthesized and their cytotoxicity wa...

During the past decade, significant advances in ionic liquid-based materials for the development of CO2 separation membranes have been accomplished. This review presents a perspective on different strategies that use ionic liquid-based materials as a unique tuneable platform to design task-specific advanced materials for CO2 separation membranes. B...

Aiming at developing improved liquid phases for facilitated CO2 separation from post-combustion processes through supported ionic liquid membranes (SILMs), this work explores the use of binary equimolar IL mixtures containing a common imidazolium cation combined with tricyanomethane and five amino acid-based anions, glycinate, l-alaninate, taurinat...

Separation of alkanols and alkanes is a complex process in the production of oxygenated additives and fuels due their close boiling points and azeotrope formation. In this work, liquid-liquid extraction of ethanol from n-heptane + ethanol mixtures using high ionicity ionic liquids (HIILs) as extraction solvents is studied. Three different HIILs, wi...

In the past few years, the improvement of advanced analytical tools confirmed the presence of trace amounts of metabolized and unchanged active pharmaceutical ingredients (APIs) in wastewater treatment plants (WWTPs) as well as in freshwater surfaces. It is known that the continuous contact with APIs, even at very low concentrations (ng/L – μg/L),...

White biotechnology is the use of enzymes and microorganisms in industrial production through applied biocatalysis. This allows for milder reaction conditions (pH and temperature) and the use of more environmentally-compatible catalysts and solvents. This, in turn, leads to processes which are shorter, generate less waste, making them both environm...

During the past decade, ionic-liquid-based aqueous biphasic systems (IL-based ABS) have been the focus of a significant amount of research, and excellent and comprehensive reviews are nowadays available. Rather than focusing on the phase equilibria and the phase separation mechanisms of ABS, this chapter provides an assessment of the current status...

In this work, mixtures of five ionic liquids (ILs) based on a common cation, 1-ethyl-3-methylimidazolium ([C2mim]+), and amino acid anions, namely glycinate ([Gly]a), l-alaninate ([l-Ala]a), taurinate ([Tau]a), l-serinate ([l-Ser]a), and l-prolinate ([l-Pro]a) with 1-ethyl-3-methylimidazolium tricyanomethane, [C2mim][C(CN)3], were prepared. The the...

In an attempt to improve the mechanical and thermal properties of poly(ionic liquid)s (PILs), a new synthetic method for the modification of polyimides is here reported for the first time. The proposed methodology consists in the transformation of polyimides into their ionic form via subsequent N-alkylation and quaternization of benzimidazole or qu...

Aqueous biphasic systems (ABSs) provide a sustainable and efficient alternative to conventional liquid-liquid extraction techniques with volatile organic solvents, and can be used for the extraction, recovery, and purification of diverse solutes. In this work, and for the first time, ABSs composed of poly(ionic liquid)s (PILs) and inorganic salts w...

Inspired by one of the major problems in the pharmaceutical industry, we advantageously used the formation of eutectic mixtures to synthesize new solvents. The aim of this work is to identify low viscosity, cheap, biodegradable and hydrophobic eutectic solvents from natural resources. Consequently, novel eutectic mixtures based on L-menthol and nat...

This work represents an essential step towards the understanding of the dynamics and thermodynamic characteristics of a novel family of ionic liquids, namely fluorinated ionic liquids based on the combination of 1-alkyl-3-methylimidazolium cations with perfluoroalkylsulfonates or perfluoroalkylcarboxylates anions. The so far scarce information abou...

Significant antiproliferative effects against various tumor cell lines were observed with novel ampicillin salts as ionic liquids. The combination of anionic ampicillin with appropriate ammonium, imidazolium, phosphonium, and pyridinium cations yielded active pharmaceutical ingredient ionic liquids (API-ILs) that show potent antiproliferative activ...