Self-Associated Engineering in P123 Micelles Rationalizing the Role of Other Pluronics with Varying Hydrophilicity as a Mixed System.

This study explores the atomic-level interactions of different poly(ethylene oxide) (EO)-poly(propylene oxide) (PO)-based block copolymers (BCPs), commercially known as Pluronics, with varying hydrophilicity that influences the solution behavior within Pluronic P123 micelles as a mixed system. The critical insights into the thermoresponsiveness of P123 in the presence of different Pluronics with increasing %EO content (L61, L62, L64, and F68) is hypothesized to modulate the hydrophobic interactions, leading to distinct solution textures such as clear solution (sol), blue point (BP), and cloud point (CP). The solution relative viscosity (η) and rheological analysis will depict the dynamic flow behavior and expose the viscoelastic properties of the blended system.

Examining the potential of type V DESs for the solvent extraction of metal ions.

Growing interest in sustainable and efficient metal ion separation has led to the exploration of non-ionic deep eutectic solvents (DESs), also known as type V DESs, as promising alternatives to conventional organic phases in solvent extraction (SX). This work summarizes recent developments, focusing solely on the use of non-ionic DESs and excluding ionic DESs, for the separation of metal ions from synthetic and real leachates. The review does not aim to exhaustively cover all studies but focuses on the molecular mechanisms of SX, how inherent properties of DESs influence these mechanisms, and how they can be harnessed to improve the separation selectivity.

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.

: 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.

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.

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.

Assessing the hydrotropic effect in the presence of electrolytes: competition between solute salting-out and salt-induced hydrotrope aggregation.

Water solubility enhancement is a long-standing challenge in a multitude of chemistry-related fields. Hydrotropy is a simple and efficient method to improve the solubility of hydrophobic molecules in aqueous media. However, the mechanism behind this phenomenon remains controversial.

Synthesis of Purine-Based Ionic Liquids and Their Applications.

Bio-based ionic liquids (ILs) are being increasingly sought after, as they are more sustainable and eco-friendly. Purines are the most widely distributed, naturally occurring -heterocycles, but their low water-solubility limits their application. In this work, four purines (theobromine, theophylline, xanthine, and uric acid) were combined with the cation tetrabutylammonium to synthesize bio-based ILs.

A HNO -Responsive Aqueous Biphasic System for Metal Separation: Application towards Ce Recovery.

An acidic aqueous biphasic system (AcABS) presenting a desired and reversible phase transition with HNO concentration and temperature was developed herein as an integrated platform for metal separation. The simple, economical, and fully incinerable (C,H,O,N) AcABS composed of tetrabutylammonium nitrate ([N ][NO ])+HNO +H O was characterized and presented an excellent selectivity towards Ce against other rare earth elements and transition metals from both synthetic solutions and nickel metal hydride (NiMH) battery leachates. The acid-driven self-assembly of AcABS bridges the gap between traditional ABS and liquid-liquid extraction whilst retaining their advantageous qualities, including compatibility with highly acidic solutions, water as the primary system component, the avoidance of organic diluents, rapid mass transfer, and the potential integration of the leaching and separation steps.

Using coarse-grained molecular dynamics to understand the effect of ionic liquids on the aggregation of Pluronic copolymer solutions.

This study is aimed to enhance the understanding of the interaction between ionic liquids (ILs) and non-ionic Pluronic triblock copolymers in aqueous two-phase micellar systems (ATPMS) used for the selective separation/purification of hydrophobic biomolecules. The ILs allow a precise control of the cloud point phase separation temperature (CPT), particularly important when the stability of the molecule is highly dependent on temperature. The effect of choline-based ILs, with two different counter-anions, chloride and hexanoate, was evaluated using molecular dynamics simulations (MD) for F-68 and L-35 Pluronic aqueous solutions.

Integrated Leaching and Separation of Metals Using Mixtures of Organic Acids and Ionic Liquids.

In this work, the aqueous phase diagram for the mixture of the hydrophilic tributyltetradecyl phosphonium ([P]Cl) ionic liquid with acetic acid (CHCOOH) is determined, and the temperature dependency of the biphasic region established. Molecular dynamic simulations of the [P]Cl + CHCOOH + HO system indicate that the occurrence of a closed "type 0" biphasic regime is due to a "washing-out" phenomenon upon addition of water, resulting in solvophobic segregation of the [P]Cl. The solubility of various metal oxides in the anhydrous [P]Cl + CHCOOH system was determined, with the system presenting a good selectivity for CoO.

Using coarse-grained molecular dynamics to rationalize biomolecule solubilization mechanisms in ionic liquid-based colloidal systems.

Solubilizing agents are widely used to extract poorly soluble compounds from biological matrices. Aqueous solutions of surfactants and hydrotropes are commonly used as solubilizers, however, the underlying mechanism that determines their action is still roughly understood. Among these, ionic liquids (IL) are often used not only for solubilization of a target compound but in liquid-liquid extraction processes.

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems.

The tunable properties of surface-active ionic liquids (SAILs) and Pluronics are dramatically magnified by combining them in aqueous solutions. The thermo-controlled character of both, essential in the extraction of valuable compounds, can be fine-tuned by properly selecting the Pluronic and SAIL nature. However, further understanding of the nanoscale interactions directing the aggregation in these complex mixtures is needed to effectively design and control these systems.

Improved coarse-grain model to unravel the phase behavior of 1-alkyl-3-methylimidazolium-based ionic liquids through molecular dynamics simulations.

Hypothesis: Imidazolium-based ionic liquids (ILs) in water exhibit a surfactant-like behavior that is only partially characterized by experimental techniques with molecular dynamic (MD) simulations emerging as a complimentary tool to study their phase behavior. However, while atomistic models suffer of time and size scale limitations, higher-level models (e.g.

The Role of Charge Transfer in the Formation of Type I Deep Eutectic Solvent-Analogous Ionic Liquid Mixtures.

It was recently shown that tetramethylammonium chloride presented negative deviations to ideality when mixed with tetraethylammonium chloride or tetrapropylammonium chloride, leading to a strong decrease of the melting points of these salt mixtures, in a behavior akin to that observed in the formation of deep eutectic solvents. To better rationalize this unexpected melting point depression between two structurally similar compounds devoid of dominant hydrogen bonding capability, new solid-liquid equilibria data for tetramethylammonium-based systems were measured and analyzed in this work. Molecular dynamics was used to show that the strong negative deviations from ideality presented by these systems arise from a synergetic share of the chloride ions.

Phenolic hydrogen bond donors in the formation of non-ionic deep eutectic solvents: the quest for type V DES.

Mixtures of non-ionic compounds have been reported as DES but most are just ideal mixtures. In the thymol-menthol system, an abnormal strong interaction was identified stemming from the acidity difference of the phenolic and aliphatic hydroxyl groups. This type of interaction is found to be the key to prepare non-ionic DES, that may be classified as type V.

Temperature-responsive extraction of violacein using a tuneable anionic surfactant-based system.

A tuneable thermoresponsive system based on combinations of sodium dodecyl sulfate surfactant with tetrabutylammonium chloride salt is presented as an integrated process for the solid-liquid extraction of violacein from bio-engineered Yarrowia lipolytica yeast and its purification by cloud-point separation from contaminant proteins.

Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems.

The temperature responsive solubility of ionic liquids with 'bulky' polar regions, such as tributyltetradecyl phosphonium chloride ([P44414]Cl), in acidic aqueous solutions is elucidated through a combined experimental and computational approach. The temperature effect in the acidic aqueous biphasic system HCl/[P44414]Cl/H2O was characterised in the range 273 K to 373 K and was found to significantly deviate from the corresponding aqueous biphasic system with NaCl. A new transferable coarse grained MARTINI model for [P44414]Cl was developed, validated and applied to provide a molecular understanding of the experimental results.

Sustainable hydrophobic terpene-based eutectic solvents for the extraction and separation of metals.

Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and fatty acids, were used for the extraction and separation of Cu(ii) from other transition metals in mildly acidic solutions. Multiple parameters were evaluated for metal extraction and the hydrophobic eutectic solvent was successfully recovered and reused.

Understanding the fundamentals of acid-induced ionic liquid-based aqueous biphasic system.

Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated exceptional performance in bioseparation processes. However, IL-based ABS are of limited interest for metal extraction as most metals are not stable in their neutral or alkaline pH conditions. In the quest for better extraction systems for metals, the development of IL-based ABS with highly acidic solutions (AcABS), induced by the mixture of a hydrophilic IL ([P44414]Cl), a mineral acid (HCl, HNO3 or H2SO4) and water, opens new possibilities.