Separation of metals using formation of DES-DES biphasic systems.

A biphasic system composed of two deep eutectic solvents (DES) sharing a common hydrogen-bond donor exhibits a tuneable phase behavior and efficient metal partitioning, yielding an improved separation selectivity of trivalent from divalent metal ions compared to the equivalent aqueous system.

Widening the Stimuli-Responsiveness of Aqueous Biphasic Systems by Changing the Ionic Liquid Cation Basicity.

Herein we demonstrate the formation of new stimuli-responsive aqueous biphasic systems (ABS), able to respond simultaneously to temperature and pH, or just to one stimulus, therefore allowing the design of more sustainable separation processes. This dual behavior is achieved with ABS formed by mono- or dicationic protic ionic liquids as phase-forming components, being defined by the ionic liquid cation chemical structure or its basicity. While ABS comprising monocationic ionic liquids only respond to the effect of temperature, systems comprising dicationic ionic liquids are simultaneously affected by both temperature and pH variations.

Investigation of laccase activity in cholinium-based ionic liquids using experimental and molecular dynamics techniques.

Laccases hold great potential for biotechnological applications, particularly in environmental pollutant remediation. Laccase activity is governed by the solvent environment, and ionic liquids (ILs) emerge as a versatile solvent for activation or stabilization of enzymes. Herein, effects of cholinium-based ILs formulated with carboxylic acids, inorganic acid, and amino acids as anionic species, on the catalytic activity of laccase from Trametes versicolor were investigated by experimental and computational approaches.

Designing type V deep eutectic solvents with antimalarial pharmaceutical ingredients.

This work studies the formation of deep eutectic solvents formed by one active pharmaceutical ingredient (quinine, pyrimethamine, or 2-phenylimidazopyridine) and a second component potentially acting as an excipient (betaine, choline chloride, tetramethylammonium chloride, thymol, menthol, gallic acid, vanillin, acetovanillone, 4-hydroxybenzaldehyde, syringaldehyde, propyl gallate, propylparaben, or butylated hydroxyanisole), aiming to address challenges regarding drug solubility, bioavailability, and permeability. A preliminary screening was carried out using the thermodynamic model COSMO-RS, narrowing down the search to three promising excipients (thymol, propyl gallate, and butylated hydroxyanisole). Nine solid-liquid equilibrium (SLE) phase diagrams were experimentally measured combining the three model drugs with the screened excipients, and using a combination of a visual melting method and differential scanning calorimetry.

: introducing 12 green extraction principles and a novel metric for assessing sustainability in biomass valorization.

We propose an innovative approach to address the pressing need for efficient and transparent evaluation techniques to assess extraction processes' sustainability. In response to society's growing demand for natural products and the consequent surge in biomass exploration, a critical imperative arises to ensure that these processes are genuinely environmentally friendly. Extracting natural compounds has traditionally been regarded as a benign activity rooted in ancient practices.

Unveiling Dissolution Kinetics of CuO Nanofertilizer Using Bio-Based Ionic Liquids Envisaging Controlled Use Efficiency for Sustainable Agriculture.

The need for sustainable agriculture amid a growing population and challenging climatic conditions is hindered by the environmental repercussions of widespread fertilizer use, resulting in the accumulation of metal ions and the loss of micronutrients. The present study provides an approach to improve the efficiency of nanofertilizers by controlling the release of copper (Cu) ions from copper oxide (CuO) nanofertilizers through bioionic liquids based on plant growth regulators (PGR-ILs). A 7-day study was conducted to understand the kinetics of Cu ion release in aqueous solution of five different PGR-ILs, with choline ascorbate ([Cho][Asc]) or choline salicylate ([Cho][Sal]) leading to 200- to 700-fold higher dissolution of Cu ions in comparison to choline indole-3-acetate ([Cho][IAA]), choline indole-3-butyrate ([Cho][IBA]), and choline gibberellate ([Cho][GA]).

Role of Deep Eutectic Solvent Precursors as Hydrotropes: Unveiling Synergism/Antagonism for Enhanced Kraft Lignin Dissolution.

Lignin holds significant potential as a feedstock for generating valuable aromatic compounds, fuels, and functional materials. However, achieving this potential requires the development of effective dissolution methods. Previous works have demonstrated the remarkable capability of hydrotropes to enhance the aqueous solubility of lignin, an amphiphilic macromolecule.

Role of Unimers to Polymersomes Transition in Pluronic Blends for Controlled and Designated Drug Conveyance.

This study investigates the nanoscale self-assembly from mixtures of two symmetrical poly(ethylene oxide)-poly(propylene oxide)-pol(ethylene oxide) (PEO-PPO-PEO) block copolymers (BCPs) with different lengths of PEO blocks and similar PPO blocks. The blended BCPs (commercially known as Pluronic F88 and L81, with 80 and 10% PEO, respectively) exhibited rich phase behavior in an aqueous solution. The relative viscosity (η) indicated significant variations in the flow behavior, ranging from fluidic to viscous, thereby suggesting a possible micellar growth or morphological transition.

Human Platelet Lysate-Derived Nanofibrils as Building Blocks to Produce Free-Standing Membranes for Cell Self-Aggregation.

Amyloid-like fibrils are garnering keen interest in biotechnology as supramolecular nanofunctional units to be used as biomimetic platforms to control cell behavior. Recent insights into fibril functionality have highlighted their importance in tissue structure, mechanical properties, and improved cell adhesion, emphasizing the need for scalable and high-kinetics fibril synthesis. In this study, we present the instantaneous and bulk formation of amyloid-like nanofibrils from human platelet lysate (PL) using the ionic liquid cholinium tosylate as a fibrillating agent.

Enhanced Antimalarial Activity of Extracts of L. Achieved with Aqueous Solutions of Salicylate Salts and Ionic Liquids.

Artemisinin, a drug used to treat malaria, can be chemically synthesized or extracted from L. However, the extraction method for artemisinin from biomass needs to be more sustainable while maintaining or enhancing its bioactivity. This work investigates the use of aqueous solutions of salts and ionic liquids with hydrotropic properties as alternative solvents for artemisinin extraction from L.

Unravelling the molecular interactions behind the formation of PEG/PPG aqueous two-phase systems.

The understanding of molecular interactions that control phase separation in polymer/polymer aqueous two-phase systems (ATPS) has been a subject of debate up to this day. In light of this, we set out to investigate the molecular interactions occurring in ternary mixtures composed of polyethylene glycol (PEG600), polypropylene glycol (PPG400) and water. The ternary phase diagram was plotted at two temperatures (298 K and 323 K), revealing a transition from a type 0 to a type I diagram.

Repurposing Kraft black Liquor as Reductant for Enhanced Lithium-Ion Battery Leaching.

The economic advantages of HSO make it the acid of choice for the hydrometallurgical treatment of waste lithium-ion batteries (LIBs). However, to facilitate the full dissolution of the higher valency metal oxides present in the cathode black mass, a suitable reducing agent is required. Herein, the application of industrial black liquor (BL) obtained from the Kraft pulping for papermaking is investigated as a renewable reducing agent for the enhanced leaching of transition metals from LIB powder with HSO.

Improved accuracy in pentraxin-3 quantification assisted by aqueous biphasic systems as serum pretreatment strategies.

Although pentraxin-3 holds promise as a diagnosis/prognosis biomarker of microbial infections and lung cancer, its analysis in human serum can be constrained by matrix effects caused by high abundance proteins - human serum albumin and immunoglobulin G. Aqueous biphasic systems composed of polymers and citrate buffer are here proposed as a serum pretreatment step to improve the accuracy of pentraxin-3 analysis. Binodal curves were determined to identify the compositions required to form two phases and to correlate the polymers' properties and performance in serum pretreatment and biomarker extraction.

Exploring the impact of sodium salts on hydrotropic solubilization.

Some ionic liquids (ILs) were shown to display a strong ability to enhance the solubility of phenolic compounds through hydrotropy. However, evidence shows that salt ions in hydrotropic aqueous solutions may change the behavior of molecules by promoting possible interactions between the components of the system, thus causing changes in solubility. Herein, we study the impact of sodium salt anions on the hydrotropic dissolution of syringic acid using 1-butyl-3-methylimidazolium chloride ([Cmim]Cl) as a hydrotrope, with a focus on dicyanamide Na[N(CN)] and thiocyanate Na[SCN] salts.

Enhanced Dissolution of Metal Oxides in Hydroxylated Solvents - Towards Application in Lithium-Ion Battery Leaching.

The recovery of critical metals from spent lithium-ion batteries (LIBs) is rapidly growing. Current methods are energy-intensive and hazardous, while alternative solvent-based strategies require more studies on their 'green' character, metal dissolution mechanism and industrial applicability. Herein, we bridged this gap by studying the effect of dilute HCl solutions in hydroxylated solvents to dissolve Co, Ni and Mn oxides.

The path towards type V deep eutectic solvents: inductive effects and steric hindrance in the system -butanol + perfluoro -butanol.

The solid-liquid phase behaviour of two tertiary alcohols, perfluoro--butanol and -butanol, was studied here using experimental (ITC, DSC and density measurements) and theoretical (MD simulations) approaches. The phase diagram of the binary mixture reveals highly negative deviations from ideality at low concentrations, as well as the formation of co-crystals and is characterized by two eutectic points, a congruent melting point and a peritectic reaction corresponding to TBH : TBF stoichiometries of 2 : 1 and 1 : 1 respectively. Excess molar enthalpies and volumes were calculated, showing negative and positive deviations from ideality, respectively.

Modeling the Solubility of Monoterpenoids with Hybrid and Predictive Thermodynamic Tools.

The Abraham and NRTL-SAC semipredictive models were employed to represent the solubility of (-)-borneol, (1R)-(+)-camphor, l-(-)-menthol, and thymol in water and organic solvents, using data measured in this work and collected from the literature. A reduced set of solubility data was used to estimate the model parameters of the solutes, and global average relative deviations (ARDs) of 27% for the Abraham model and 15% for the NRTL-SAC model were obtained. The predictive capability of these models was tested by estimating the solubilities in solvents not included in the correlation step.

Everything You Wanted to Know about Deep Eutectic Solvents but Were Afraid to Be Told.

Are deep eutectic solvents (DESs) a promising alternative to conventional solvents? Perhaps, but their development is hindered by a plethora of misconceptions. These are carefully analyzed here, beginning with the very meaning of DESs, which has strayed far beyond its original scope of eutectic mixtures of Lewis or Brønsted acids and bases. Instead, a definition that is grounded on thermodynamic principles and distinguishes between eutectic and deep eutectic is encouraged, and the types of precursors that can be used to prepare DESs are reviewed.

Juçara Fruit ( Martius) Valorization Combining Emergent Extraction Technologies and Aqueous Solutions of Alkanediols.

Anthocyanins from juçara fruits were extracted by pressurized liquid extraction (PLE) or ultrasound-assisted extraction (UAE), using aqueous solutions of 1,2-alkanediols and glycerol ethers as biobased solvents. The PLE (100 bar, 13 min, 1 mL/min flow rate) in the optimal extraction conditions originated 23.1 mg·g.

Rationalizing the Design of Pluronics-Surfactant Mixed Micelles through Molecular Simulations and Experiments.

Aqueous systems comprising polymers and surfactants are technologically important complex fluids with tunable features dependent on the chemical nature of each constituent, overall composition in mixed systems, and solution conditions. The phase behavior and self-assembly of amphiphilic polymers can be changed drastically in the presence of conventional ionic surfactants and need to be clearly understood. Here, the self-aggregation dynamics of a triblock copolymer (Pluronics L81, EOPOEO) in the presence of three cationic surfactants (with a 12C long alkyl chain but with different structural features), viz.

The role of biomass elemental composition and ion-exchange in metal sorption by algae.

The use of macroalgae, microalgae and cyanobacteria for metal sorption has been widely reported. Still, there are no studies allowing a direct comparison of the performance of these biomasses, especially while evaluating metal competition. The simultaneous sorption of Co, Cu, Ni and Zn present in a multi-elemental solution by six macroalgae, two microalgae and three cyanobacteria was evaluated.

Selective Separation of Vanillic Acid from Other Lignin-Derived Monomers Using Centrifugal Partition Chromatography: The Effect of pH.

In this work, centrifugal partition chromatography (CPC) assisted by a polyethylene glycol (PEG)/sodium polyacrylate (NaPA) aqueous biphasic system (ABS) was applied in the separation of five lignin-derived monomers (vanillin, vanillic acid, syringaldehyde, acetovanillone, and -hydroxybenzaldehyde). The influence of the system pH (unbuffered, pH 5, and pH 12) and added electrolytes (inorganic salts or ionic liquids (ILs)) on the compound partition was initially evaluated. The obtained data revealed that ILs induced more adequate partition coefficients ( < 5) than inorganic salts ( > 5) to enable separation performance in CPC, while alkaline conditions (pH 12) demonstrated a positive impact on the partition of vanillic acid.

Imidazolium Chloride Ionic Liquid Mixtures as Separating Agents: Fuel Processing and Azeotrope Breaking.

Relevant chemical separations for the petrochemical and chemical industries include the removal of aromatic hydrocarbons from aliphatics, the desulfurization and denitrification of fuels, and the separation of azeotropic mixtures containing alkanols. In an attempt to contribute to the development of novel technologies, the potentialities of imidazolium chloride ionic liquid (IL) mixtures as separation agents were investigated. Selectivities, capacities, and solvent performance indices were calculated through the activity coefficients at infinite dilution of organic solutes and water in the imidazolium chloride IL: [Cmim]Cl, [Cmim]Cl, and the equimolar mixture of [Cmim]Cl and [Cmim]Cl.

Solubilities of Amino Acids in Aqueous Solutions of Chloride or Nitrate Salts of Divalent (Mg or Ca) Cations.

The solubilities of glycine, l-leucine, l-phenylalanine, and l-aspartic acid were measured in aqueous MgCl, Mg(NO), CaCl, and Ca(NO) solutions with concentrations ranging from 0 to 2 mol/kg at 298.2 K. The isothermal analytical method was used combined with the refractive index measurements for composition analysis guaranteeing good accuracy.