Ternary Solvent Research Articles

Eco-compatible solvent-processed high energy level offset ternary strategy for efficient organic photodetecting and photovoltaic applications

Improved VOC and reduced dark current stable OEDs with high energy level offset ternary and non-halogenated solvent processing strategies.

High-purity lignin from selective biomass fractionation with ternary deep eutectic solvents

Green and recyclable ternary deep eutectic solvent was developed to selectively extract lignin of high purity, desirable molecular weight and monomeric yield for applications in reinforcement materials and bio-oil was produced from biomass.

Cu-Based ternary deep eutectic solvents for homo- and cross-coupling reactions of terminal alkynes

The Cu-DES-promoted Glaser-type homo- and cross-coupling of terminal alkynes under exogenous-ligand-free, base-free, and additive-free conditions is described.

Extraction of diazinon, haloxyfop-R-methyl, hexaconazole, diniconazole, and triticonazole in cheese samples using a ferrofluid based liquid phase extraction method prior to gas chromatography.

In the present study, a ternary phase solvent extraction combined with dispersive liquid-liquid microextraction was developed for the extraction of diazinon, haloxyfop-R-methyl, hexaconazole, diniconazole, and triticonazole from cheese samples. The extracted analytes were determined using gas chromatography. In this work, first, the analytes were extracted into an organic phase and then enriched using a dispersive liquid-liquid microextraction. Deep eutectic solvent-based ferrofluid was synthesized and used as an extraction solvent in the dispersive liquid-liquid microextraction step, which makes the method fast and green. After optimization of experimental conditions, under the best extraction conditions, limits of detection and quantification were found in the ranges of 0.18-0.39 and 0.6-1.3 ng g-1, respectively. Enrichment factors and extraction recoveries of the analytes ranged from 138-156 and 69-78%, respectively. In the end, the proposed method was successfully applied to assess the studied pesticides in cheese samples.

Unexpected mechanically robust ionic conductive elastomer constructed from an itaconic acid-involved polymerizable DES.

An ionic conductive elastomer with good comprehensive properties is constructed from a ternary polymerizable deep eutectic solvent (PDES) containing choline chloride, acrylic acid and itaconic acid (IA). The IA component is found to boost the synergetic hydrogen bonds and greatly improve the mechanical strength of elastomer.

A novel ternary deep eutectic solvent pretreatment for the efficient separation and conversion of high-quality gutta-percha, value-added lignin and monosaccharide from Eucommia ulmoides seed shells

A novel ternary deep eutectic solvent (DES), consisted of choline chloride, oxalic acid and ethylene glycol, was developed as a green, low-cost and recyclable pretreatment system for multi-stage utilization of Eucommia ulmoides seed shells. Under optimum conditions, 79.7 % hemicellulose and 65.6 % lignin were quickly removed while 84.0 % cellulose was retained. After DES pretreatment, the yield and purity of gutta-percha achieved 85.1 mg/g and 96.2 %, which increased 1.4 and 1.8 folds higher than that of un-treatment ones. Meanwhile, 69.1 % enzymatic digestibility of cellulose was obtained, that was 2.3 folds higher than that of raw substrates. Moreover, 53.6 % low-condensation lignin with aromatic structures and valuable aryl-ether linkages was well collected. Importantly, the DES that has been recycled five runs can still remove 73.9 % hemicellulose and 58.0 % lignin. Overall, the DES was determined to efficiently promote the separation and conversion of high-quality gutta-percha, value-added lignin and high-yield glucose from Eucommia ulmoides seed shells.

Biomimetic catalytic aerobic oxidative desulfurization of diesel with NHPI-based ternary deep eutectic solvents

It is a challenging issue to achieve efficient aerobic oxidation desulfurization (AODS) under mild conditions. Inspired by respiratory chain system, a metal-free biomimetic system was developed in this paper with a functionalized ternary deep eutectic solvent (DES) containing N-hydroxyphthalimide (NHPI), p-toluene sulfonic acid (p-TsOH), and polyethylene glycol (PEG) for deep oxidative desulfurization. It was found that the NHPI/5PEG4000/p-TsOH system exhibited an outstanding desulfurization activity, and the removal of dibenzothiophene (DBT) reached 100% within 5 h at 80 οC. Significantly, it is the first attempt to use a DES as an extraction agent, reaction medium, catalyst, and electron transfer mediator (ETM) simultaneously. Mechanistic studies revealed that NHPI demonstrated a dual function: namely, producing the PINO radical to initiate the reaction, and acting as an ETM in biomimetic systems to promote the activation of oxygen molecules, thereby finely improving the AODS performance of the acidic DESs. These findings regarding the aforementioned biomimetic oxygen activation mechanism of the NHPI-based ternary DES for AODS provide a novel insight into the construction of biomimetic system in the future.

Development of salt-induced homogenous liquid-liquid extraction based on ternary deep eutectic solvent coupled with dispersive liquid-liquid microextraction for the determination of heavy metals in honey

In this work, a homogenous liquid–liquid extraction method was combined with dispersive liquid–liquid microextraction and utilized for the extraction of Co, Zn, Ni, Cu, Pb, and Tl from honey samples before their determination by inductively coupled plasma-atomic emission spectrometry. For this purpose, firstly, diluted honey solution was transferred into a glass test tube and mixed with a few milliliters of a mixture of n-butanol and choline chloride: menthol: p-aminophenol deep eutectic solvent. A homogenous solution was obtained. After that an appropriate amount of sodium chloride was added into the solution and sonicated for 6 min. During this step, the homogenous solution was broken and the mixture of n-butanol and the deep eutectic solvent mixture was collected on top of the solution. The supernatant phase was removed and quickly injected into deionized water. After centrifugation, the collected phase at the bottom of the tube was injected into the determination system. Under the optimum situations, low limits of detection (0.24–0.74 ng g–1) and quantification (0.79–2.46 ng g–1), high extraction recoveries (80–92%), and good repeatability (relative standard deviations equal to or less than 3.6% and 3.9% for intra– and inter-day precisions, respectively) were acquired. Finally, the offered method was employed for determination of the studied heavy metals in various honey samples marketed in Tabriz city, Iran.

Thermodynamic models for determination of solid–liquid equilibrium of para-tert-butylbenzoic acid in binary and ternary solvent system

Accurate solubility data is essential to make critical decisions from the earliest stage of drug discovery, through the entire process development, formulation, and up to process design. The present research work aims to evaluate the solid–liquid equilibrium data of para-tert-butylbenzoic acid (PTBBA) in binary systems such as acetonitrile + water, isopropyl alcohol + water, and isopropyl alcohol + acetonitrile at 288.15 to 328.15 K and a ternary solvent mixture of isopropyl alcohol + acetonitrile + water system in the temperature range of 298.15 to 323.15 K with varying mass fraction of the binary mixture (isopropyl alcohol + acetonitrile) for a constant mass fraction of water (0.1 and 0.3) using gravimetric and titrimetric methods. It is observed that the solubility of PTBBA increases with an increase in temperature for all the selected solvent systems. Moreover, the solubility of PTBBA in the binary and ternary system is affected by an increase in the mass fraction of water at a given temperature, which acts as an antisolvent. The measured data is correlated with various thermodynamic models such as Van’t Hoff equation, Modified Apelblat equation, Buchowski equation, and Wilson models. It is observed that there is a good agreement between measured and calculated values with an average relative deviation of 0.95 for isopropyl alcohol + acetonitrile system in the case of the modified Apelblat equation.

A new green alternative solvent for extracting echinacoside and acteoside from Cistanche deserticola based on ternary natural deep eutectic solvent

Echinacoside and acteoside, the representative constituents of Cistanche deserticola Y. C. Ma (C. deserticola), are known for its many important biological activities. In this study, a novel ternary natural deep eutectic solvent (NADES) (citric acid, fructose and glucose in a 1:2:1 molar ratio, 30 % water content) was obtained through the adjustment and optimization of single-factor experiments. And through the Box-Behnken design optimization, the optimal extraction conditions were obtained, at the moment, the yields of echinacoside and acteoside were 6.16 and 2.13 mg/g, respectively. In addition, through computer molecular simulation, it was found that there are strong hydrogen bonds and interactions between the molecules of NADES, and the hydrogen bonds, van der Waals forces and π-π interactions played an important role in the extraction of echinacoside and acteoside from C. deserticola by NADES. Finally, compared with the traditional method, NADES ultrasound-assisted extraction of echinacoside and acteoside has a shorter time (15 min), the maximum extraction yield is 1.54–2.86 times and 1.26–2.52 times than that of traditional extraction methods for echinacoside and acteoside, respectively. This study demonstrates that NADES can provides a new direction for developing new sustainable alternatives, improving green extraction process and efficiency for extracting natural active substances.

Miniaturized ternary deep eutectic solvent-based matrix solid-phase dispersion: A green sample preparation method for the determination of chlorophenols in river sediment.

New ternary deep eutectic solvents were prepared and applied as efficient green dispersing solvents in miniaturized matrix solid-phase dispersion to extract chlorophenols from river sediments for the first time. High-performance liquid chromatography coupled with a photodiode array detector was used to analyze the target analytes. The significant factors affecting the extraction were optimized as follows: dispersant (100mg), sample (100mg), ternary eutectic solvents (150μl), grinding for 1min, 450μl of acetonitrile as the elution solvent, and vortex mixing for 20s. Under the optimal conditions, the method exhibited excellent linearity (correlation coefficient>0.9980), low limits of detection between 1.039-2.478μg/g, and extraction recoveries between 93.9% and 99.2%. Furthermore, the method demonstrated excellent precision in the intra- and inter-day analysis with a relative standard deviation below 6%. When compared to conventional extraction techniques, the miniaturized matrix solid-phase dispersion considerably reduced samples and solvent usag, offering important environmental benefits. The green profile of the method was assessed using the complementary green analytical procedure index tool confirming its eco-friendship. The technique was finally employed to evaluate sediment samples from three distinct locations along the Zuibaiji River, indicating its applicability for monitoring environmental samples.

Efficient continuous dehydration of fructose to 5-hydroxymethylfurfural in ternary solvent system

Biomass-derived 5-hydroxymethylfurfural (HMF) has been identified as a versatile precursor for clean fuels and degradable polymers. Here, we developed an efficient flow-through system to continuously produce HMF in high selectivity from fructose dehydration. Effects of solvent, the relative ratio of aqueous to organic phase, the proportion of different cosolvents in the organic phase as well as the reaction variables on reactivity of fructose dehydration to HMF were comprehensively investigated to obtain the optimal results. The conduction of a H2O/dioxane/methyl isobutyl ketone (MIBK) ternary solvent system in combination with Amberlyst 70 as catalyst contributed to 93 % selectivity and 84 % yield of HMF in residence time as short as 1.6 min. The strengthened hydrogen bonding interactions by the addition of dioxane accounted for an increase in the interactions of fructose with water and cosolvent molecules, accelerating the dehydration rate. Meanwhile, the in-situ extraction of HMF from active aqueous phase to organic phase by MIBK protected it from unfavorable side reactions. The reaction system exhibited good stability without significant change on the catalytic performance over 10 h reaction. Additionally, fructose was selectively dehydrated from fructose-glucose mixtures, holding great promises for the integration with the industrial operations producing mixture of sugars (such as fructose corn syrup).

Hydrogen bonding boosted oxidative desulfurization by ZnCl2/boric acid/polyethylene glycol-based ternary deep eutectic solvents

Deep eutectic solvents, as the novel and green solvents, are widely applied in various fields because of its unique and excellent quality, such as simple synthesis, non-toxic, biodegradable, wide range of liquids and strong solvation ability. In this work, a series of ternary deep eutectic solvents were synthesized using ZnCl2, boric acid (BA) and polyethylene glycol (PEG) with appropriate molar ratios by hydrogen bonds. Compared with binary DESs, ZnCl2/2BA/2PEG showed a better desulfurization performance, and 98.7 % sulfur removal was achieved. The hydrogen bonding interaction is considered as the key factor to the formation of DES and to promote the desulfurization reaction. In addition, BA and ZnCl2 play a synergistic and positive role in the desulfurization system. The DES was immiscible with fuel and could be reused for six cycles without a significant reduction in activity. The possible mechanism of the positive effect of hydrogen bonding interaction and O2•− free radicals was proposed. This work offers more possibility for designing new types of DESs for deep desulfurization of fuel oils and other applications in relation to extraction or catalysis.

Salt-free reactive dyeing of cotton fibers in a ternary solvent system with different reactive dye chemistries

Salt-free reactive dyeing of cotton fibers in a ternary solvent system with different reactive dye chemistries

One-pot synthesis of 5-Hydroxymethylfurfural from glucose and corn stover in an aqueous choline chloride/ acetone ternary solvent

Aqueous choline chloride/acetone was developed as a green ternary solvent for catalytic conversion of glucose and raw corn stover into 5-HMF. The results illustrated that acidic ChCl solution played a vital role in promoting the tandem isomerization/dehydration reaction of glucose to 5-HMF, while acetone was identified as an efficient extracting solvent to simultaneously remove 5-HMF from the aqueous phase. The composition of the ternary solvent system was found to have a significant impact on the 5-HMF yield, reaction selectivity, and preventing the further degradation of 5-HMF. A competitive 5-HMF yield of 73.3 mol% was achieved from glucose catalyzed by an ultra-low H2SO4 loading of 2 mmol at 190 °C for 10 min in the ternary ChCl-H2O-acetone solvent with a mass ratio of 1:2:3. This novel solvent system exhibited good stability, high efficiency, and excellent recyclability, employing in catalytic conversion of both glucose and lignocellulose to produce 5-HMF.

Multimode ultrasound and ternary deep eutectic solvent sequential pretreatments enhanced the enzymatic saccharification of corncob biomass

Corncob (CB) is a valuable agricultural waste in high abundance. It is mainly composed of cellulose, hemicellulose and lignin that link in a complex interlocking matrix. The key to its utilization depends on separating cellulose from lignin and hemicellulose using an environment-friendly and effective pretreatment method to improve glucose yield. The study aimed to investigate the effect of sequential pretreatment of CB with ultrasound (US) in conjunction with ternary deep eutectic solvent (TDES). The US, type and molar ratio of TDES, temperature, and time were optimized. The results showed that under the optimum conditions, US (40 +60 kHz, 60 min) + TDES (ChCl-Gly-LA, 1:1:2, 120 ℃, 3 h), the removal of lignin and hemicellulose were 87.54 % and 67.00 %, respectively, and the recovery of cellulose was 82.18 %. After 72 h of enzymatic hydrolysis , the yield of glucose and xylose were 76.94 % and 41.26 %, respectively. Comparatively, pretreated CB yielded 61.58 % glucose and 26.90 % xylose higher than the untreated. Scanning electron microscopy revealed that the surface of the CB became cracked and rugged. X-ray diffraction showed that the CrI increased significantly from 36 % to 59 %. Fourier transform mid-infrared spectroscopy indicated significant changes in the characteristic functional groups of lignin and hemicellulose. Increases in Tonset, Tendset, Tp, Vmax and decreases in Char at 600 °C all corresponded to increases in thermal stability. These results further confirmed that TDES combined with ultrasonic pretreatment effectively removed lignin and hemicellulose. In conclusion, this approach could greenly and efficiently pretreat CB as a new method for biomass pretreatment. • Double hydrogen bond acceptor (donor) ternary pretreatment DES was studied. • The lignin removal efficiency of ternary DES was higher than binary DES. • TDES containing lactic acid reduced significantly the lignin content. • TDES combined with ultrasonic pretreatment increased lignin removal rate. • TDES combined with ultrasonic pretreatment enhanced sugar yields.

Improved glucose yield and concentration of sugarcane bagasse by the pretreatment with ternary deep eutectic solvents and recovery of the pretreated liquid

In this study, a novel ternary deep eutectic solvents (DES) consisting of choline chloride/PEG/hydroxyethyl sulfonic acid (HSA) was developed to effectively improve glucose yield and concentration of sugarcane bagasse, and the conditions of the pretreatment were optimized by response surface method (RSM). Under the optimal conditions, the maximum glucose concentration (GC) could reach 12.39 g/L (HSA concentration 1.34 %, PEG400, 2.3 h, 150 °C), and the maximum glucose yield (GY) was 0.2497 g/g (HSA concentration 1.41 %, PEG400, 2.1 h, 150 °C). Hemicellulose was completely removed, and the maximum lignin removal rate was 86.89 %. After pretreatment, 95 % of the pretreated liquid can be recycled. Finally, the structural and morphological changes of bagasse before and after pretreatment were investigated by scanning electron microscopy (SEM), Fourier Transform infrared analyzer (FT-IR) and X-ray diffraction (XRD).

Preparation, characterization of light-colored lignin from corn stover by new ternary deep eutectic solvent extraction

The industrial lignin has shown great potential to replace some of petrochemical. But the deep color of lignin limits their application in high-value field. The extraction of light-colored lignin from lignocellulose still remains challenging. Here, we reported a strategy for rapid extraction of lignin from corn stover by using a new ternary deep eutectic solvent (TDES) composed of choline chloride (ChCl), formic acid (FA) and maleic acid (MA). The color feature and structural characterization of obtained lignin was comprehensively elucidated. The results revealed that the lignin streams had light color (brightness ISO 23.44 %) with a high yield (76.3 %), purity (93.5 %), low molecular weight (Mw 1544–2040 g/mol), and low polydispersity (PDI ≤ 1.76). The introduction of MA could reduce the destruction of lignin substructure during the treatment process and avoid the deepening of lignin color. Quantitative analysis of conjugated carbonyl and quinone carbonyl and semi-quantitative analysis of lignin by 2D NMR showed that temperature had a great influence on its structure.

Poly(methylene blue)-ternary deep eutectic solvent/Au nanoparticle modified electrodes as novel electrochemical sensors: Optimization, characterization and application

A new electrochemical sensor based on a nanocomposite formed by the electroactive redox polymer poly(methylene blue) (PMB) formed in a ternary deep eutectic solvent (DES) mixture, and gold nanoparticles (AuNP) was developed. The polymerisation of MB was carried out by potential cycling in ternary DES formed by choline chloride, ethylene glycol and fructose, containing 84% of the choline chloride: ethylene glycol mixture, in the presence of an acid dopant. The composition of the AuNP-chitosan dispersion was optimized by studying the effect of different concentrations of the nanoparticles and the polymer in the dispersion on the PMB film growth. The nanocomposite films obtained under different conditions were characterized by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy. The nanocomposite with the best characteristics was also obtained in aqueous media for comparison. The nanocomposite-based sensor formed by AuNP and PMB in DES was used for determining ascorbic acid (AA) and 5-aminosalicylic acid (5-ASA) by fixed potential amperometry at +0.20 V in 0.10 mol L−1 KCl and at +0.40 V in Britton-Robinson buffer at pH 7, respectively. Limits of detection of 0.40 μmol L−1 and 0.064 μmol L−1 were obtained for AA and 5-ASA, respectively, with the PMBDES/AuNP/GCE. The sensor was successfully applied to determine both analytes in pharmaceutical samples.

Electrochemical Sensing of Nitrofurazone and Semicarbazide on an Au-Ag Film Fabricating from a Deep Eutectic Solvent

A facile electrochemical sensor is reported for the highly selective and sensitive detection of nitrofurazone (NFZ) and its metabolites, semicarbazide (SC), by using an Au-Ag modified electrode. The Au-Ag film was produced on a Cu foil by electrodeposition in a choline chloride-urea-glycerol ternary deep eutectic solvent containing gold (III) ions and silver (I) ions. Cyclic voltammetry (CV) indicates that the co-deposition of Au-Ag would be feasible. The morphology, crystallinity, and composition of Au-Ag deposits were characterized via scanning electron microscopy (SEM), powder X-ray diffractometer, and X-ray photoelectron spectroscopy (XPS). Under the optimal condition, the Au-Ag modified electrode shows a wider linear concentration range of 1.99–643.49 μM with a low detection limit of 0.2 μM for NFZ. The corresponding linear range of SC is 7.94 to 482 μM, and the detection limit is 1.01 μM. It also demonstrated good anti-interference ability against various common interfering substances. Finally, the modified electrode was successfully applied in the real samples, and the average recoveries for NFZ and SC were 100.59% and 101.01%, respectively. The present electrochemical strategy is promising to broaden the practical electrochemical application in the environment.