Ternary Solvent Research Articles

Nanocomposite of Ag nanoparticles and deep eutectic solvent-derived carbon dots with oxidase mimicking activity as synergistic bactericidal agent.

A new type of nitrogen and chloride co-doped carbon dots (N/Cl-CDs) based on choline chloride-urea-glycine ternary deep eutectic solvents (DESs) was synthesized using a one-step hydrothermal method. The prepared N/Cl-CDs exhibited oxidase-like activity and excellent antibacterial activity against Escherichia coli, Staphylococcus aureus and methicillin-resistant Staphylococcus aureus (MRSA). The addition of silver nanoparticles (Ag NPs) (i.e. N/Cl-CDs + Ag NPs) to the N/Cl-CDs also significantly enhanced the oxidase and antibacterial activities. The nanocomposite (1·8 mg ml-1 ) completely inactivated 105 CFU per ml of MRSA in 90 min. E.coli and S. aureus were labelled with the N/Cl-CDs, enabling multicolour fluorescence imaging at different excitation wavelengths. The nanocomposites have high antibacterial efficiency as a new bactericidal agent, as well as application potential with good biocompatibility and low toxicity.

Synthesis and Characterization of Silver Nanoparticles Using Zinc Chloride-Sugar-Amino Acids Based Novel Ternary Deep Eutectic Solvents

In this study, we had effectively generated four types of ternary deep eutectic solvents using the method of evaporation by mixing zinc chloride(ZC) with hydrogen bond donors such as Glucose(GLU) & Fructose(FRU) and Amino acids such as Glutamine(GLUT) & Glycine (GLY) [i.e.a- ZC-GLU-GLY, b- ZC-FRU-GLY, c- ZC-GLU-GLUT, d- ZC-FRU-GLUT]. After that, physical properties such as pH, conductivity, density, and viscosity were applied to the solvents. The H – bonded interaction between zinc chloride and other components in these TDESs were revealed by the FTIR spectroscopy. The prepared TDESs were used as a solvent medium for the synthesis of silver nanoparticles (Ag NPs) by chemical reduction method using sodium borohydride as reducing agent and sodium hydroxide as stabilizing agent. The synthesized Ag NPs were characterized by FTIR, UV, XRD, EDAX and SEM techniques. Silver has a variety of applications, but one of the most notable usages is an antibacterial disinfectant.

Surfactant-assisted salting-out homogenous liquid–liquid extraction based on deep eutectic solvents using central composite design; application in the extraction of natamycin from fruit juices before its determination by HPLC-UV

In this study, for the first time, surfactant-assisted deep eutectic solvent-based salting-out homogenous liquid-liquid extraction performed in a narrow-bore tube has been introduced as a new sample pretreatment approach and used for the isolation of natamycin from fruit juices. In this method, firstly, tween 80 (as a surfactant) and a water-miscible ternary deep eutectic solvent composed of choline chloride: acetic acid: butanol (as an extractant) were added to the sample solution and a homogenous state was formed. This solution was transferred into a narrow-bore tube and in the following, the homogenous solution was broken by addition of sodium chloride (as a phase separation agent). By this action, the analyte was extracted into the produced tiny droplets of extractant. This phase was quantified by high–performance liquid chromatography-ultraviolet detection. Experimental conditions of the developed extraction procedure were investigated and optimized by means of central composite design with variables including surfactant and extraction solvent volume, pH, and sodium chloride amount. Under optimum conditions, low limits of determination and quantification (0.78 and 2.60 ng mL−1, respectively), acceptable repeatability (relative standard deviations of 4.9 and 7.1% for intra- and inter day precisions at a concentration of 25 ng mL−1), and satisfactory extraction recovery (76%) were obtained using the proposed method. At the end, the suggested method was effectively utilized for the analysis of natamycin in different juice samples.

Role of the Bromide on the Hydrodebenzylation of 2,4,6,8,10,12‐Hexabenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (HBIW)

AbstractThe catalytic hydrogenolysis of 2,4,6,8,10,12‐hexabenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (HBIW) over Pd‐based catalysts in the ternary solvents of acetic anhydride, bromobenzene (PhBr) and N, N’‐dimethylformamide (DMF) was the key step for producing 2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane (HNIW or CL‐20). However, the role of the bromobenzene is still allusive. Herein, Pd/graphite carbon nitride nanosheets (g‐C3N4 NS) was used in the hydrogenolysis of HBIW under the atmospheric pressure, and exhibited a yield of 80 % as well as a faster debenzylation rate than Pd/C. By the virtue of the kinetic study, the effect of the bromide, solvent and proton on the debenzylation rate was investigated and discussed. The bromide worked as a co‐catalyst to promote the desorption of the product of the hydrogenolysis from the surface of the palladium nanoparticle. The observation benefits for elucidating the reaction mechanism and may inspire the design of the novel catalysts for the hydrogenolysis of HBIW.

Rationally Designed Ternary Deep Eutectic Solvent Enabling Higher Performance for Non-Aqueous Redox Flow Batteries

Redox flow batteries hold promise as large-scale energy storage systems for off-grid electrification. The electrolyte is one of the key components of redox batteries. Inspired by the mechanism involved in solvents for extraction, a ternary deep eutectic solvent (DES) is demonstrated, in which glycerol is introduced into the original binary ethaline DES. Redox pairs (active substance) dissolved in the solvent have low charge transfer resistance. The results show that the viscosity of the solvent with the ratio of choline chloride to ethylene glycol to glycerol of 1:2:0.5 decreases from 51.2 mPa·s to 40.3 mPa·s after adding the redox pair, implying that the mass transfer resistance of redox pairs in this solvent is reduced. Subsequent cyclic voltammetry and impedance tests show that the electrochemical performance with the ternary DES as the electrolyte in redox flow batteries is improved. When the ratio of 1:2:0.5 ternary DES is used as the electrolyte, the power density of the battery (9.01 mW·cm−2) is 38.2% higher than that of the binary one (6.52 mW·cm−2). Fourier transform infrared spectroscopy further indicates that the introduction of glycerol breaks the hydrogen bond network of the solvent environment where the redox pair is located, unraveling the hydrogen bond supramolecular complex. Rational solvent design is an effective strategy to enhance the electrochemical performance of redox batteries.

Thermoplastic Starch/Ternary Deep Eutectic Solvent/Lignin Materials: Study of Physicochemical Properties and Fire Behavior

The goal of the work was to prepare thermoplastic starch (TPS), for the first time plasticized with ternary deep eutectic solvents (DESs) based on urea/resorcinol/choline chloride (URCC) in a 2:1:1 molar ratio and enriched with lignin as an environmentally friendly functional alternative for agricultural plastics. Potato starch was effectively modified with DES via twin-screw extrusion in the presence of lignin up to 10 pph (L10) without significant loss of elasticity (tensile strength 7.4 MPa, elongation at break 65%) and good thermocompressing properties (dynamic mechanical thermal analysis (DMTA) results) of highly amorphous materials (X-ray diffractometry (XRD) results) physically modified with DES (Fourier transform infrared (FTIR) results). The URCC mixture acted both as the plasticizer and as dissolving media for lignin, facilitating mutual processing. Moreover, cone calorimetry analysis of TPS materials revealed that they exhibited better fire-retardant properties than polymers commercially used as agricultural plastics (PE, PP, and PLA). Obtained results indicate that TPS/DES and TPS/DES+L materials can be used as, e.g., biodegradable, safe, and functional mulches that do not have to be removed from the cultivating fields.

Unveiling the potential of water as a co-solvent in microwave-assisted delignification of sugarcane bagasse using ternary deep eutectic solvents

Deep eutectic solvents (DESs) have become popular owing to their biodegradability and recyclability. In this study, the influence of water as a co-solvent is demonstrated to enhance the properties of choline based ternary DESs. A fast and energy-efficient microwave-assisted pre-treatment process was developed for delignification of sugarcane bagasse (SB). The effectiveness of SB fractionation was revealed by incorporating Lewis acids (MgCl2.6H20, NiCl2.6H20) with the DESs for pre-treatment and Choline chloride: Ethylene glycol: NiCl2.6H20 (CC:EG:NI) at a molar ratio 1:2:0.016 with 20w% water as a co-solvent provided the most promising result, with 84% delignification and 99% enzyme digestibility. Water was also employed as an anti-solvent to facilitate lignin solubility and exhibited up to 26w% lignin yield from DES liquor with maximum DES recovery of 95% (w/w). Water distinctly affects the density, viscosity, and intermolecular hydrogen bonding of the DES and its impact on the process dynamics is worth further exploration.

Ultrahigh Conductive and Stretchable Eutectogel Electrolyte for High-Voltage Flexible Antifreeze Quasi-solid-state Zinc-Ion Hybrid Supercapacitor

The aqueous zinc-ion hybrid supercapacitor (ZHSC) is a prospective energy storage device for next-generation wearable electronics due to its high safety, low cost, and high energy density. However, the preparation of gel electrolytes reported in the literature is complex and time-consuming, which limits their application in practice. Herein, we developed a robust and stretchable eutectogel electrolyte through a one-step gelation process in situ without introducing additional initiators and cross-linkers. The eutectogel electrolyte consists of ternary deep eutectic solvent (DES) based on Zn(ClO4)2, AM(acrylamide), and H2O, among which ClO4– triggers the free-radical polymerization of AM monomer and Zn2+ cross-links the polymer chains. The prepared Zn-PAM-1 gel exhibits a high ionic conductivity of 51.7 mS cm–1. Due to the inhibition of the free water activity in DES, the voltage window of the constructed flexible ZHSC was extended to 0–2.2 V. Moreover, the ZHSC in situ formed manifests a maximum energy density of 117.5 W h kg–1 at a power density of 833.8 W kg–1 and shows admirable cycling stability, retaining 87.6% of its capacitance after 4000 cycles. In addition, the supercapacitor possesses remarkable temperature stability within a range of −20 to 70 °C. Furthermore, the assembled flexible device illustrates favorable bendability from 0° to 180° without scarifying capacitance, displaying great promise as flexible wearable electronic devices. In summary, such a feasible approach provides further insight into the exploration of innovative eutectogel electrolyte systems for assembling quasi-solid-state pliable high energy storing devices.

A Green Approach for Selective Ionometallurgical Separation of Lithium from Spent Li-Ion Batteries by Deep Eutectic Solvent (DES): Process Optimization and Kinetics Modeling

ABSTRACT Failure to recycle valuable metals from lithium-ion batteries (LIBs) could directly lead to various environmental issues, such as ecological toxicity with inevitable impacts on environment and society health. This study presents a green process for selective recovery of Li from spent LIBs based on a ternary deep eutectic solvent. The effects of solid-to-liquid ratio, temperature, and variations of deep eutectic solvent (DES) component concentrations on the selectivity of the leaching process were studied. A ternary DES based on choline chloride, urea and ethylene glycol was found to be more selective than conventional binary DESs and made it possible to extract the Li in the lower temperatures (75–100°C). In such temperatures, DESs present better viscosity and higher stability. In the optimum conditions, 92.83%, 1.61%, 0.72%, and 0.42% recoveries were obtained for Li, Co, Ni, and Mn, respectively. Kinetic modeling indicates that mixed control models were best fitted to all data. Moreover, the results indicated that the activation energy for Li extraction is 21.15 KJ/mol. Pearson correlation assessment relieved that L/S was the most effective factor with a positive impact (r > +0.5) on Li recovery among all variables. Furthermore, temperature impacts the selectivity of the leaching process. The illustrated selectivity coupled with biodegradability and the possibility of re-utilization of the DESs opens a novel way for the greener recovery of values from wastes.

Efficient extraction of chitin from crustacean waste via a novel ternary natural deep eutectic solvents

Extraction of chitin from crustacean waste with acidic natural deep eutectic solvents (NADESs) is usually accompanied by degradation of chitin, which lowers the yield and molecular weight of product. Herein, this study proposed a eco-friendly and feasible route for effectively improving the yield and molecular weight of chitin by introducing N-acetyl-D-glucosamine into ternary NADESs. A high molecular weight chitin with molecular weight of 3.92 × 105 Da, purity of 90.2% and yield of 85.6% was obtained from crab shell. Compared with conventional acid/alkali and binary NADESs method, the maximum yield of chitin extracted by ChCl-G-FA2 was increased by 1.57 times and 1.39 times respectively. Molecular weight of chitin was 3.16 times that of acid/alkali method. Recycling performance evaluation revealed that the purity of chitin could still reach 80.4% after five cycles of NADESs. This study provided a eco-friendly utilization strategy for crustacean waste based on multifunctional NADESs.

Study of system properties in reversed-phase liquid chromatography for binary and ternary solvent mobile phase compositions using the solvation parameter model

System maps for the individual system constant of the solvation parameter model and five binary solvent containing 20–70% (v/v) acetonitrile, acetone, methanol, 2-propanol, and tetrahydrofuran on a single octadecylsiloxane-bonded silica column (Luna C18) are used to provide insight into the variation of system properties with mobile phase composition and solvent type. Selectivity differences are dominated by variation in solute size and hydrogen-bond basicity with solvent-dependent variation in dipole-type and hydrogen-bond acid interactions. Interactions involving lone pair electrons are important only in the case of the alcohols and to a lesser extent tetrahydrofuran. Selectivity differences are also dependent on solvent strength. To expand the selectivity space four ternary solvent systems (acetonitrile-methanol-water, acetonitrile-2-propanol-water, methanol-tetrahydrofuran-water, and tetrahydrofuran-2-propanol-water) 1:1:2% (v/v) containing 50% (v/v) total organic solvent are compared with the binary solvent systems at the same organic solvent composition. There is no simple model that links the system properties of the ternary solvents to the binary solvent systems, but it is demonstrated that the ternary solvent systems expand the selectivity space available for reversed-phase separations. The solvation properties of the bulk organic solvents provide insufficient information to predict selectivity in RPLC because of the dominant contribution of water and effects related to the selective solvation of the stationary phase and possible changes in the solvent-dependent microstructure of the mobile phase.

A deep eutectic-based, self-emulsifying subcutaneous depot system for apomorphine therapy in Parkinson’s disease

Apomorphine, a dopamine agonist, is a highly effective therapeutic to prevent intermittent off episodes in advanced Parkinson's disease. However, its short systemic half-life necessitates three injections per day. Such a frequent dosing regimen imposes a significant compliance challenge, especially given the nature of the disease. Here, we report a deep eutectic-based formulation that slows the release of apomorphine after subcutaneous injection and extends its pharmacokinetics to convert the current three-injections-a-day therapy into an every-other-day therapy. The formulation comprises a homogeneous mixture of a deep eutectic solvent choline-geranate, a cosolvent n-methyl-pyrrolidone, a stabilizer polyethylene glycol, and water, which spontaneously emulsifies into a microemulsion upon injection in the subcutaneous space, thereby entrapping apomorphine and significantly slowing its release. Ex vivo studies with gels and rat skin demonstrate this self-emulsification process as the mechanism of action for sustained release. In vivo pharmacokinetics studies in rats and pigs further confirmed the extended release and improvement over the clinical comparator Apokyn. In vivo pharmacokinetics, supported by a pharmacokinetic simulation, demonstrate that the deep eutectic formulation reported here allows the maintenance of the therapeutic drug concentration in plasma in humans with a dosing regimen of approximately three injections per week compared to the current clinical practice of three injections per day.

A water-compatible magnetic dual-template molecularly imprinted polymer fabricated from a ternary biobased deep eutectic solvent for the selective enrichment of organophosphorus in fruits and vegetables

A water-compatible magnetic dual template molecularly imprinted polymer using a ternary deep eutectic solvent as a functional monomer was synthesized via a green synthesis method based on one-pot reversible addition/fragmentation chain transfer precipitation polymerization. The resulting material, DES-MDMIP, shows excellent adsorption capacity (218.62 mg g−1) in rapid adsorption time (30 s) and outstanding selectivity factors of 4.45 for organophosphorus pesticides. The sorbent was applied in magnetic solid-phase extraction prior to HPLC analysis. The developed methodology provides linearity between 0.05 and 2000.00 μg L−1. Low detection limits of 0.015–0.030 μg L−1 and enrichment factors of up to 691 were achieved. The applicability of the method facilitates the efficient determination of fruit and vegetable samples with satisfactory recoveries in the range of 80–117%. The newly designed water-compatible DES-MDMIP sorbent, along with a simple and rapid extraction process, demonstrated a powerful analytical approach for the practical analysis of pesticide residues.

Managing Phase Orientation and Crystallinity of Printed Dion–Jacobson 2D Perovskite Layers via Controlling Crystallization Kinetics

AbstractTwo‐dimensional perovskites have attracted substantial attention for solar cell applications because of their higher stability as compared to their 3D analogs. To achieve efficient charge transport in thin‐film devices, obtaining high crystalline perovskite crystals perpendicularly aligned to the substrate is of great importance. This article reports the scalable printing of high‐quality Dion–Jacobson (DJ) perovskite thin films via tailoring crystallization kinetics. Introducing a small amount of 1‐methyl‐2‐pyrrolidinone to the conventional N,N‐dimethylformamide:dimethyl sulfoxide‐based precursor, the strong coordination with ammonium spacers enables a notably retarded crystallization, which results in perovskite films with distinctly enhanced crystallinity, highly vertical orientation, and graded phase distribution. Accordingly, efficient charge generation and ultrafast interphase charge transfer are realized. The champion DJ perovskite device delivers a high current density of 17.10 mA cm–2, an impressive open‐circuit voltage of 1.21 V, leading to a stabilized efficiency of 16.19%. In addition, the devices processed from the ternary solvent exhibit remarkably improved stability under stimuli with light, heat, and humidity, benefiting from their superb phase stability. This work demonstrates an important advancement in scalable deposition of DJ perovskite thin films for efficient and stable photovoltaic devices.

Modelling of lithium extraction with TBP/P507–FeCl3 system from salt-lake brine

• A thermodynamic model was developed for Li extraction by TBP/P507/FeCl 3 system. • The model parameters were optimized by fitting the calculated to experimental data. • Extraction mechanism was clarified by modelling species distribution in organic. Recovery of lithium from Mg-rich salt-lake brines by solvent extraction has been widely studied for high Li + /Mg 2+ selectivity and Li + extraction efficiency. In a previous study, a ternary synergistic solvent extraction system consisting of tributyl phosphate (TBP), 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507, denoted as HL) and FeCl 3 was developed, in which high Li + selectivity and efficient Li + stripping simply with water were realized. In this study, to further elucidate the extraction mechanism of the TBP/P507/FeCl 3 system and minimize the efforts on the process optimization for Li extraction from Mg-rich salt-lake brines with different component concentrations from different sources, a thermodynamic empirical model based on mass balances and equilibrium equations has been developed. The model parameters were optimized by fitting the calculated data to experimental results. By calculating the distribution of species in the organic phase with the model, it was found that Li + primarily existed in the form of [Li(TBP) 2 ][FeCl 4 ], followed by [Li(TBP)][FeCl 4 ]. When Li + was stripped with water, Fe 3+ mainly existed in the form of FeCl 2 L·HL·2TBP in the organic phase at low O/A ratios but converted to [H(TBP) 2 ][FeCl 4 ] at high O/A ratios. This thermodynamic model provides a guide for the design of practical process flow.

A Universal Ternary-Solvent-Ink Strategy toward Efficient Inkjet-Printed Perovskite Quantum Dot Light-Emitting Diodes.

Toward next-generation electroluminescent quantum dot (QD) displays, inkjet printing technique has been convinced as one of the most promising low-cost and large-scale manufacturing of patterned quantum dot light-emitting diodes (QLEDs). The development of high-quality and stable QD inks is a key step to push this technology toward practical applications. Herein, a universal ternary-solvent-ink strategy is proposed for the cesium lead halides (CsPbX3 ) perovskite QDs and their corresponding inkjet-printed QLEDs. With this tailor-made ternary halogen-free solvent (naphthene, n-tridecane, and n-nonane) recipe, a highly dispersive and stable CsPbX3 QD ink is obtained, which exhibits much better printability and film-forming ability than that of the binary solvent (naphthene and n-tridecane) system, leading to a much better qualitied perovskite QD thin film. Consequently, a record peak external quantum efficiency (EQE) of 8.54% and maximum luminance of 43883.39cdm-2 is achieved in inkjet-printed green perovskite QLEDs, which is much higher than that of the binary-solvent-system-based devices (EQE = 2.26%). Moreover, the ternary-solvent-system exhibits a universal applicability in the inkjet-printed red and blue perovskite QLEDs as well as cadmium (Cd)-based QLEDs. This work demonstrates a new strategy for tailor-making a general ternary-solvent-QD-ink system for efficient inkjet-printed QLEDs as well as the other solution-processed electronic devices in the future.

Morphology optimization and charge characteristics in PM6-based solar cells via ternary solvent processing

Morphology optimization and charge characteristics in PM6-based solar cells via ternary solvent processing

Tailored ternary hydrophobic deep eutectic solvents for synergistic separation of yttrium from heavy rare earth elements

Clean, efficient and economical separation of yttrium (Y) from heavy rare earth elements (HREEs) has always attracted attention.

Understanding the bulk and interfacial structures of ternary and binary deep eutectic solvents with a constant potential method: a molecular dynamics study

In the last decade, deep eutectic solvents (DESs) have emerged as promising electrolytes in supercapacitors and rechargeable batteries due to their unique properties, wide electrochemical windows, low viscosity, and high ionic conductivity. The molecular structural behavior of these solvents, which plays an important role in their efficiency is not deeply understood. Therefore, in this work, by considering two types of DES electrolytes, we investigate their bulk and interfacial structures at the molecular level using molecular dynamics studies. In this regard, two different DESs-a binary DES including choline chloride and urea in a 1 : 2 molar ratio, and a ternary DES containing choline chloride, urea, and ethylene glycol with a molar ratio of 1 : 1 : 2-are considered. For the bulk phase, the partial site-site and center of mass radial distribution functions (RDFs), the mean square displacement (MSD), and the self-diffusion coefficient of the ternary system are explored. We demonstrate that in deep eutectic solvents, in addition to hydrogen-bonding and long-range and short-range correlations, a variety of neutral species play crucial roles in the properties of the bulk phase. Furthermore, considering two graphene sheets as electrodes on both sides of the DES samples, the profiles of the number density, charge density, orientational order parameter, and electrostatic potentials at different potential conditions near the electrodes are investigated. The results reveal the presence of multilayers of the neutral species in the vicinity of electrodes in addition to the ionic components of both DES systems. Finally, the computed differential capacitances (Cd) for DESs disclose that the positive electrode capacitance is higher than that of the negative electrode, and in the ternary system, the total capacitance is greater than in the binary system. Our findings give a better perspective of a new generation of electrolytes at the molecular level for electric double-layer capacitors.

Molecular Dynamics Simulation on the Crystal Morphology of Β-Hmx Affected by Binary and Ternary Solvent Systems

Molecular Dynamics Simulation on the Crystal Morphology of Β-Hmx Affected by Binary and Ternary Solvent Systems