Important efforts have been made over the past years to improve the drug acts,which leads to the discovery of novel drug preparations and delivery systems.The optimal design of such processes requires a molecular-leve...Important efforts have been made over the past years to improve the drug acts,which leads to the discovery of novel drug preparations and delivery systems.The optimal design of such processes requires a molecular-level understanding of the interactions between drug molecules and biological membranes.The thermodynamic investigation provides deep and complete knowledge of interactions and the choice of appropriate and suitable production compounds in pharmaceutical fields.Particularly,the analysis of drugs+co-solvents in aqueous media is the central issue in many types of research because they exert their impact by interacting with biological membranes.This work is aimed to measure the density and speed of sound for the thiamine hydrochloride in water+deep eutectic solvents(DESs)mixtures(choline chloride/urea,choline chloride/ethylene glycol and choline chloride/glycerol)at temperature range(293.15-308.15)K.By correlation of the evaluated parameters in some standard relations,the partial molar parameters i.e.apparent molar volumes,Vφ,m,and apparent molar isentropic compression,κ_(s,φ,m),are calculated.In addition,apparent molar isobaric expansion,E^(0)_(φ,m),and Hepler’s constant are computed from the density and speed of sound data.For fitting the experimental Vφ,m andκ_(s,φ,m)the Redlich-Meyer equation was employed that the important quantities;standard partial molar volume,V^(0)_(m),and partial molar isentropic compression,κφ,m0,were obtained.The thermodynamic analysis of the studied system also plays a crucial role in the pharmaceutical industry.展开更多
Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and ...Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.展开更多
Copper nanosheets and sulfur particles were synthesized synchronously by electrolysis,after dissolving Cu_(2)S in ChCl-thiourea(TU)deep eutectic solvent(DES)system.The optimized electrolysis conditions of 0.9 V,80℃,a...Copper nanosheets and sulfur particles were synthesized synchronously by electrolysis,after dissolving Cu_(2)S in ChCl-thiourea(TU)deep eutectic solvent(DES)system.The optimized electrolysis conditions of 0.9 V,80℃,and 2 h resulted in the deposition of pure nano-sized copper sheets with a length of approximately 500 nm and a thickness of approximately 30 nm,and the production of sulfur particles with an average size of approximately 10μm.The morphology of the cathodic products was significantly influenced by the electrolysis voltage.When Cu_(2)S was introduced into ChCl-TU,it dissolved[CuCl_(2)]^(-)without disrupting the structure of the choline ion(Ch^(+)).As the electrolysis time increased,the copper deposition changed from wire to sheet growth,with the growth direction from radial to epitaxial along the substrate and back to radial.展开更多
Recently, deep eutectic solvents (DES) have received great attention in assisting water flooding and surfactant flooding to improve oil recovery because they can reduce the interfacial tension (IFT) between oil and wa...Recently, deep eutectic solvents (DES) have received great attention in assisting water flooding and surfactant flooding to improve oil recovery because they can reduce the interfacial tension (IFT) between oil and water, inhibit surfactant adsorption, and change the wettability of rock. However, the effects of DES on the wettability of rock surface have not been thoroughly investigated in the reported studies. In this study, the effects of various DES samples on the wettability of sandstone samples are investigated using the Amott wettability measurement method. Three DES samples and several DES solutions and DES-surfactant solutions are firstly synthesized. Then, the wettability of the sandstone samples is measured using pure saline water, DES solutions, and DES-surfactant solutions, respectively. The effects of the DES samples on the wettability of the sandstone samples are investigated by comparing the measured wettability parameters, including oil displacement ratio (I_(o)), water displacement ratio (I_(w)), and wettability index (I_(A)). The Berea rock sample used in this study is weakly hydrophilic with I_(o), I_(w), and I_(A) of 0.318, 0.032, and 0.286, respectively. Being processed by the prepared DES samples, the wettability of the Berea sandstone samples is altered to hydrophilic (0.7 > I_(A) > 0.3) by increasing I_(w) but lowering Io. Similarly, DES-surfactant solutions can also modify the wettability of the Berea sandstone samples from weakly hydrophilic to hydrophilic. However, some DES-surfactant solutions can not only increase I_(w) but also increase I_(o), suggesting that the lipophilicity of those sandstone samples will be improved by the DES-surfactant solutions. In addition, micromodel flooding tests confirm the promising performance of a DES-surfactant solution in improving oil recovery and altering wettability. Moreover, the possible mechanisms of DES and DES-surfactant solutions in altering the wettability of the Berea sandstone samples are proposed. DES samples may improve the hydrophilicity by forming hydrogen bonds between rock surface and water molecules. For DES-surfactant solutions, surfactant micelles can capture oil molecules to improve the lipophilicity of those sandstone samples.展开更多
Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are ineffi...Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.展开更多
Candida albicans is one of the most common pathogens causing invasive fungal infections,with a mortality rate of up to 20%-50%.Amphotericin B(AmB),a biopharmaceutics classification system(BCS)IV drug,significantly inh...Candida albicans is one of the most common pathogens causing invasive fungal infections,with a mortality rate of up to 20%-50%.Amphotericin B(AmB),a biopharmaceutics classification system(BCS)IV drug,significantly inhibits Candida albicans.AmB is primarily administered via oral and intravenous infusion,but severe infusion adverse effects,nephrotoxicity,and potential hepatotoxicity limit its clinical application.Deep eutectic solvents(DESs),with excellent solubilization ability and skin permeability,are attractive for transdermal delivery.Herein,we used DESs to deliver AmB for antifungal therapy transdermally.We first prepared and characterized DESs with different stoichiometric ratios of choline(Ch)and geranate(Ge).DESs increased the solubility of AmB by a thousand-fold.In vitro and in vivo,skin permeation studies indicated that DES_(1:2)(Ch and Ge in 1:2 ratio)had the most outstanding penetration and delivered fluorescence dye to the dermis layer.Then,DES_(1:2)-AmB was prepared and in vitro antifungal tests demonstrated that DES_(1:2)-AmB had superior antifungal effects compared to AmB and DES_(1:2).Furthermore,DES_(1:2)-AmB was skin-irritating and biocompatible.In conclusion,DES-AmB provides a new and effective therapeutic solution for fungal infections.展开更多
The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutecti...The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutectic solvents(DESs)are valued as electrolytes for their advantages of low operating temperature and wide electrochemical windows.At present,there is large amount of literature on this emerging field,but there are no specialized reviews of these studies.Here,after a brief introduction of DESs’concept and history,we comprehensively reviewed the lastest progress on the metal/alloy electrodeposition in DESs.Additionally,we discussed the key influence factors of the electrodeposition process and analyzed the corresponding mechanisms.Based on these,we emphasized the importance of the establishment of predictive models for dealing with the challenges in large-scale applications.展开更多
H_(2)S in natural gas and other industrial gas is seriously harmful to human health,environmental protection and the downstream industries.Efficient purification of H_(2)S containing gas is the basic process in the ch...H_(2)S in natural gas and other industrial gas is seriously harmful to human health,environmental protection and the downstream industries.Efficient purification of H_(2)S containing gas is the basic process in the chemical industry.Benefiting from multiple advantages,deep eutectic solvents(DES)can be used as tailor-made green solvents,and have been booming in the fields of harmful gas removal and fuel oil desulfurization.Furthermore,significant scientific research of DES in desulfurization and purification of natural gas has accelerated the process of its practical application.This paper systematically summarizes and analyzes the removal mechanism,impact factors and challenges of DES as emerging green solvent in H_(2)S absorption and conversion.Strategies on H_(2)S removal by DES generally fall into two categories:physical absorption and chemical conversion.Although the chemical conversion of H_(2)S by DES has been less studied compared with the physical absorption,it presents great application potential.At present,the research on H_(2)S removal by DES is still in the initial stage.Therefore,it is necessary to further study the mechanism of H_(2)S removal and construct the relationship between structural properties and desulfurization performance of DES,thereby to solve the issues of sulfur blockage and low quality of sulfur paste which is suffered by conventional liquid redox desulfurization solvent system.Additionally,the methods for efficient solvent regeneration and recycling remain to be explored out to promote the practical application of iron-based DES in the field of gas desulfurization.展开更多
Hydrogels based on Deep Eutectic Solvents(DES)demonstrate remarkable anti-freezing,resilience,and toughness,presenting a promising avenue to the operation of aqueous zincion batteries under extreme conditions.A gel el...Hydrogels based on Deep Eutectic Solvents(DES)demonstrate remarkable anti-freezing,resilience,and toughness,presenting a promising avenue to the operation of aqueous zincion batteries under extreme conditions.A gel electrolyte capable of operating over a wide temperature range is developed based on a DES comprising 1 mol/kg(m)Zn(ClO_(4))_(2)+3.5 m Mg(ClO_(4))_(2).Spectral characterization confirms the synergistic influence of both anions and cations on the freezing point of the DES.With four hydrogen bond(HB)acceptors,Mg^(2+) exhibits strong electrostatic attraction towards the O atoms of H_(2)O,while ClO_(4)^(-)forms numerous HBs with H_(2)O molecules.This dual interaction allows for precise adjustment of the chemical environment around the H and O atoms of H_(2)O,resulting in an exceptionally low freezing point of-116.92℃for the DES.The gel electrolyte derived from this DES demonstrates an impressive ionic conductivity of 0.285 mS/cm at-70℃.Leveraging its excellent low-temperature performance and compatibility with a zinc anode,the flexible Zn-Mn battery constructed with this electrolyte exhibits robust electrochemical performance at low temperatures.Specifically,at-70℃,it achieves a high specific capacity of 76.83 mAh/g,displays excellent rate capability,andmaintains stable cycling performance.Moreover,the Zn-Mn battery operates reliably across a broad temperature range from-70 to 80℃.This study presents innovative insights for advancing Zn-Mn batteries capable of efficient operation across diverse environmental conditions,thereby opening new avenues for their development.展开更多
Efficient recognition and selective capture of NH_(3)is not only beneficial for increasing the productivity of the synthetic NH_(3)industry but also for reducing air pollution.For this purpose,a group of deep eutectic...Efficient recognition and selective capture of NH_(3)is not only beneficial for increasing the productivity of the synthetic NH_(3)industry but also for reducing air pollution.For this purpose,a group of deep eutectic solvents(DESs)consisting of glycolic acid(GA)and phenol(PhOH)with low viscosities and multiple active sites was rationally designed in this work.Experimental results show that the GA^(+)PhOH DESs display extremely fast NH_(3)absorption rates(within 51 s for equilibrium)and high NH_(3)solubility.At 313.2 K,the NH_(3)absorption capacities of GA^(+)PhOH(1:1)reach 6.75 mol/kg(at 10.7 kPa)and 14.72 mol/kg(at 201.0 kPa).The NH_(3)solubility of GA^(+)PhOH DESs at low pressures were minimally changed after more than 100 days of air exposure.In addition,the NH_(3)solubility of GA^(+)PhOH DESs remain highly stable in 10 consecutive absorption-desorption cycles.More importantly,NH_(3)can be selectively captured by GA^(+)PhOH DESs from NH_(3)/CO_(2)/N_(2)and NH_(3)/N_(2)/H_(2)mixtures.1H-NMR,Fourier transform infrared and theoretical calculations were performed to reveal the intrinsic mechanism for the efficient recognition of NH_(3)by GA^(+)PhOH DESs.展开更多
Biomass is renewable, abundant, cheap, biocompatible, and biodegradable materials and has been used to produce chemicals, materials,energy, and fuels. However, most of the biomass, especially most of the biomass polym...Biomass is renewable, abundant, cheap, biocompatible, and biodegradable materials and has been used to produce chemicals, materials,energy, and fuels. However, most of the biomass, especially most of the biomass polymers are not soluble in common solvents, which hinders their pretreatment and conversion. Deep eutectic solvents(DESs) are environmental-friendly, cheap, and highly tunable, with high solubility,which renders them potential applications in biomass pretreatment and conversion. They could be used as solvents or catalysts and so on. This paper intends to review the application of DESs for the pretreatment of biomass and conversion of biomass to value-added products. We focus on the following topics related to biomass and DESs:(1) DESs for the pretreatment of biomass;(2) DESs for the dissolution and separation of biomass or extraction of chemicals from biomass;(3) DESs for biomass conversion;(4) Drawbacks, and recyclability of DESs for pretreatment and conversion of biomass.展开更多
Here we firstly report a series of new deep eutectic solvents(DESs) induced by small amounts of crown ether complex and mainly formed by polyethylene glycol. These DESs not only presented the ultra-deep extraction of ...Here we firstly report a series of new deep eutectic solvents(DESs) induced by small amounts of crown ether complex and mainly formed by polyethylene glycol. These DESs not only presented the ultra-deep extraction of non-basic N-compounds from fuel oils, but also opened up the possibility of other new applications in chemistry and materials science.展开更多
Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot m...Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.展开更多
Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to...Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to its potential to reduce the consumption of energy and threat to the environment.However,the simultaneous realization of green,efficient and closed-loop recycling is still challenging.Herein,we report a closed-loop and highly efficient approach to recycle lithium cobalt oxide from spent LIBs based on a choline chloride:oxalic acid(ChCl:OA)type deep eutectic solvent(DES).An ultrafast leaching process is observed at 180°C for 10 s with no observable residues.The energy barrier during leaching is calculated to be 113.9 kJ/mol.Noteworthy,the solubility of cobalt ions can be reversibly tuned by simply adding/evaporating deionized water,thus avoiding the addition of precipitant and enabling the easy recovery of the leaching solvent for realizing a closed-loop recycling process.The simultaneous realization of high efficiency,green and closed-loop process is expected to push the DES into practical application for recycling the electrodes of LIBs.展开更多
Deep eutectic solvents(DESs) are a kind of potential lixiviant for selective metal processing due to their versatile complexation properties. In this study, we investigated the recovery of zinc from zinc oxide dust us...Deep eutectic solvents(DESs) are a kind of potential lixiviant for selective metal processing due to their versatile complexation properties. In this study, we investigated the recovery of zinc from zinc oxide dust using choline chloride-ureaethylene glycol(ChCl-urea-EG) DESs. The zinc extraction efficiency can be up to 85.2% when the slurry concentration is 50 g/L, leaching temperature is 80 °C and stirring speed is 600 r/min. The leaching process is controlled by the diffusion and the corresponding activation energy is 32.1 k J/mol. The resultant solution was directly used for the electrodeposition of zinc. The pure zinc deposit is obtained with a current efficiency of 82.6%. Furthermore, the ChCl-urea-EG DESs can be recycled. This approach is shown to be promising for the recycling of zinc from the zinc-containing dust.展开更多
This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified...This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.展开更多
Dissolution in choline-chloride based deep eutectic solvents(DES) of rare earth elements(REE) from high-purity single carbonate salts of Y, La, Ce, Nd and Sm and from their multicomponent mixtures and also bastn€asite...Dissolution in choline-chloride based deep eutectic solvents(DES) of rare earth elements(REE) from high-purity single carbonate salts of Y, La, Ce, Nd and Sm and from their multicomponent mixtures and also bastn€asite mineral was assessed with a prospect to gain an understanding on the leaching behavior of bastn€asite ores as REE source from DES suspensions. Urea, malonic acid and citric acid were used in different proportions with choline chloride in order to form deep eutectic solvents with desired viscosity and functionality. The results obtained prove promising for use insolvato-metallurgical processes in terms of selective dissolution of the higher-atomic-number(Z) rare earth elements at the expense of the lower-ZREEs and the gangue-originating metal impurities, thus initiating separation among the different REE members from the early hydrometallurgical steps.展开更多
The electrodeposition of aluminium on glassy carbon and aluminium substrates from AlCl3-urea deep eutectic solvent(DES) system at near room temperatures was investigated,without additional purification of the chemical...The electrodeposition of aluminium on glassy carbon and aluminium substrates from AlCl3-urea deep eutectic solvent(DES) system at near room temperatures was investigated,without additional purification of the chemicals used to prepare the electrolyte and without rigorous control of moisture and oxygen present in the working space.The effects of changing temperature,working potential,controlled deposition current density and deposition time on the morphology of deposited aluminium without stirring of the electrolyte were recorded.Using potentiostatic and galvanostatic techniques,aluminium was electrodeposited from the deep eutectic solvent(n(AlCl3):n(urea)=1.6:1) onto glassy carbon and aluminium substrates at temperatures ranging from 25 to 50℃.Using SEM,EDS and XRD techniques,substrates were studied and confirmed the presence of aluminium deposits following both potentiostatic and galvanostatic regimes.The shape and size of Al grains deposited depended on the time of deposition and varied in size from nanometers to micrometers and in shape from regular crystal forms to needle-like and flake-like structures.展开更多
Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,whic...Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,which means that the precursors of DESs with different structures and properties can be screened to customize DESs for specific functions.Researchers have found that during the sample preparation process involving DESs,the specific properties of some“smart”DESs can be switched by directing external driving forces,leading to a reversible phase transition of the target solution.These"smart"DESs are called switchable deep eutectic solvents(SDESs).The advent of SDES simplifies the sample pretreatment steps,reduces the use of organic solvents,and makes solvents easy to recycle,which matches the concept of green and sustainable chemistry.Compared with the number of previous experimental studies,the reviews and summaries on SDESs are rare.Therefore,this review made a summary of the concept and research progress of SDESs based on some related works in the past decade,including composition and type,characterization,switching mechanism,etc.It is expected to provide a certain reference and guidance for the subsequent in-depth research of SDESs in the analytical sample pretreatment.展开更多
The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results...The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results indicate that chemical-based ILs/DESs are superior to physical-based ILs/DESs for CO_(2)capture,especially those ILs have functionalized cation and anion,and superbase DESs;some of the superbase DESs have higher CO_(2)solubilities than those of ILs;the best physical-and chemical-based ILs,as well as physical-and chemicalbased DESs are[BMIM][BF4](4.20 mol kg^(-1)),[DETAH][Im](11.91 mol kg^(-1)),[L-Arg]-Gly 1:6(4.92 mol kg^(-1))and TBD-EG 1:4(12.90 mol kg^(-1)),respectively.Besides the original COSMO-RS mainly providing qualitative predictions,six corrected COSMO-RS models have been proposed to improve the prediction performance based on the experimental data,but only one model is with universal parameters.The newly determined experimental results were further used to verify the perditions of original and corrected COSMO-RS models.The comparison indicates that the original COSMO-RS qualitatively predicts CO_(2)solubility for some but not all ILs/DESs,while the quantitative prediction is incapable at all.The original COSMO-RS is capable to predict CO_(2)Henry’s constant qualitatively for both physical-based ILs and DESs,and quantitative prediction is only available for DESs.For the corrected COSMO-RS models,only the model with universal parameters provides quantitative predictions for CO_(2)solubility in physical-based DESs,while other corrected models always show large deviations(>83%)compared with the experimental CO_(2)Henry’s constants.展开更多
基金financial support from the graduate council of the University of Tabriz,Tabriz,Iran.
文摘Important efforts have been made over the past years to improve the drug acts,which leads to the discovery of novel drug preparations and delivery systems.The optimal design of such processes requires a molecular-level understanding of the interactions between drug molecules and biological membranes.The thermodynamic investigation provides deep and complete knowledge of interactions and the choice of appropriate and suitable production compounds in pharmaceutical fields.Particularly,the analysis of drugs+co-solvents in aqueous media is the central issue in many types of research because they exert their impact by interacting with biological membranes.This work is aimed to measure the density and speed of sound for the thiamine hydrochloride in water+deep eutectic solvents(DESs)mixtures(choline chloride/urea,choline chloride/ethylene glycol and choline chloride/glycerol)at temperature range(293.15-308.15)K.By correlation of the evaluated parameters in some standard relations,the partial molar parameters i.e.apparent molar volumes,Vφ,m,and apparent molar isentropic compression,κ_(s,φ,m),are calculated.In addition,apparent molar isobaric expansion,E^(0)_(φ,m),and Hepler’s constant are computed from the density and speed of sound data.For fitting the experimental Vφ,m andκ_(s,φ,m)the Redlich-Meyer equation was employed that the important quantities;standard partial molar volume,V^(0)_(m),and partial molar isentropic compression,κφ,m0,were obtained.The thermodynamic analysis of the studied system also plays a crucial role in the pharmaceutical industry.
基金financially supported by the Original Exploration Project of the National Natural Science Foundation of China(No.52150079)the National Natural Science Foundation of China(Nos.U22A20130,U2004215,and 51974280)+1 种基金the Natural Science Foundation of Henan Province of China(No.232300421196)the Project of Zhongyuan Critical Metals Laboratory of China(Nos.GJJSGFYQ202304,GJJSGFJQ202306,GJJSGFYQ202323,GJJSGFYQ202308,and GJJSGFYQ202307)。
文摘Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.
基金the financial support from the National Natural Science Foundation of China(Nos.51904005,52304362)the Key Research Foundation of University in Anhui Province,China(No.2023AH051113)+1 种基金the Key Laboratory of Ionic Rare Earth Resources and Environment,Ministry of Natural Resources,China(No.2022IRERE203)the Distinguished Young Research Project of Anhui Higher Education Institution,China(No.2023AH020017)。
文摘Copper nanosheets and sulfur particles were synthesized synchronously by electrolysis,after dissolving Cu_(2)S in ChCl-thiourea(TU)deep eutectic solvent(DES)system.The optimized electrolysis conditions of 0.9 V,80℃,and 2 h resulted in the deposition of pure nano-sized copper sheets with a length of approximately 500 nm and a thickness of approximately 30 nm,and the production of sulfur particles with an average size of approximately 10μm.The morphology of the cathodic products was significantly influenced by the electrolysis voltage.When Cu_(2)S was introduced into ChCl-TU,it dissolved[CuCl_(2)]^(-)without disrupting the structure of the choline ion(Ch^(+)).As the electrolysis time increased,the copper deposition changed from wire to sheet growth,with the growth direction from radial to epitaxial along the substrate and back to radial.
基金supported by the Scientific Research and Technology Development Projects of PetroChina(2023ZZ22-02)the Local Efficient Reform and Development Funds for Personnel Training Projectsthe China Scholarship Council(CSC)via a Ph.D.Scholarship(No.202008510128).
文摘Recently, deep eutectic solvents (DES) have received great attention in assisting water flooding and surfactant flooding to improve oil recovery because they can reduce the interfacial tension (IFT) between oil and water, inhibit surfactant adsorption, and change the wettability of rock. However, the effects of DES on the wettability of rock surface have not been thoroughly investigated in the reported studies. In this study, the effects of various DES samples on the wettability of sandstone samples are investigated using the Amott wettability measurement method. Three DES samples and several DES solutions and DES-surfactant solutions are firstly synthesized. Then, the wettability of the sandstone samples is measured using pure saline water, DES solutions, and DES-surfactant solutions, respectively. The effects of the DES samples on the wettability of the sandstone samples are investigated by comparing the measured wettability parameters, including oil displacement ratio (I_(o)), water displacement ratio (I_(w)), and wettability index (I_(A)). The Berea rock sample used in this study is weakly hydrophilic with I_(o), I_(w), and I_(A) of 0.318, 0.032, and 0.286, respectively. Being processed by the prepared DES samples, the wettability of the Berea sandstone samples is altered to hydrophilic (0.7 > I_(A) > 0.3) by increasing I_(w) but lowering Io. Similarly, DES-surfactant solutions can also modify the wettability of the Berea sandstone samples from weakly hydrophilic to hydrophilic. However, some DES-surfactant solutions can not only increase I_(w) but also increase I_(o), suggesting that the lipophilicity of those sandstone samples will be improved by the DES-surfactant solutions. In addition, micromodel flooding tests confirm the promising performance of a DES-surfactant solution in improving oil recovery and altering wettability. Moreover, the possible mechanisms of DES and DES-surfactant solutions in altering the wettability of the Berea sandstone samples are proposed. DES samples may improve the hydrophilicity by forming hydrogen bonds between rock surface and water molecules. For DES-surfactant solutions, surfactant micelles can capture oil molecules to improve the lipophilicity of those sandstone samples.
基金supported by the National Key Research and Development Program of China(2022YFB3504702)support from Horizon-EIC,Pathfinder challenges(101070976)+3 种基金support from the National Natural Science Foundation of China(22278402,22478389)the Key Research and Development Program of Henan Province(231111241800)State Key Laboratory of Mesoscience and Engineering(MESO-23-A08)the Frontier Basic Research Projects of Institute of Process Engineering,CAS(QYJC-2023-03).
文摘Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.
基金supported by the National Natural Science Foundation of China(Nos.81872823,82073782,and 82241002)the Key R&D Plan of Ganjiang New District of Jiangxi(No.2023010).
文摘Candida albicans is one of the most common pathogens causing invasive fungal infections,with a mortality rate of up to 20%-50%.Amphotericin B(AmB),a biopharmaceutics classification system(BCS)IV drug,significantly inhibits Candida albicans.AmB is primarily administered via oral and intravenous infusion,but severe infusion adverse effects,nephrotoxicity,and potential hepatotoxicity limit its clinical application.Deep eutectic solvents(DESs),with excellent solubilization ability and skin permeability,are attractive for transdermal delivery.Herein,we used DESs to deliver AmB for antifungal therapy transdermally.We first prepared and characterized DESs with different stoichiometric ratios of choline(Ch)and geranate(Ge).DESs increased the solubility of AmB by a thousand-fold.In vitro and in vivo,skin permeation studies indicated that DES_(1:2)(Ch and Ge in 1:2 ratio)had the most outstanding penetration and delivered fluorescence dye to the dermis layer.Then,DES_(1:2)-AmB was prepared and in vitro antifungal tests demonstrated that DES_(1:2)-AmB had superior antifungal effects compared to AmB and DES_(1:2).Furthermore,DES_(1:2)-AmB was skin-irritating and biocompatible.In conclusion,DES-AmB provides a new and effective therapeutic solution for fungal infections.
基金financially supported from the National Natural Science Foundation of China(Nos.52274291,52204305)Beijing Institute of Technology Research Fund Program for Young Scholars,China(No.1740011182102).
文摘The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutectic solvents(DESs)are valued as electrolytes for their advantages of low operating temperature and wide electrochemical windows.At present,there is large amount of literature on this emerging field,but there are no specialized reviews of these studies.Here,after a brief introduction of DESs’concept and history,we comprehensively reviewed the lastest progress on the metal/alloy electrodeposition in DESs.Additionally,we discussed the key influence factors of the electrodeposition process and analyzed the corresponding mechanisms.Based on these,we emphasized the importance of the establishment of predictive models for dealing with the challenges in large-scale applications.
基金supported by Research Project of Petro-China Southwest Oil&Gas Field Company,China(No.2024D106-03-02).
文摘H_(2)S in natural gas and other industrial gas is seriously harmful to human health,environmental protection and the downstream industries.Efficient purification of H_(2)S containing gas is the basic process in the chemical industry.Benefiting from multiple advantages,deep eutectic solvents(DES)can be used as tailor-made green solvents,and have been booming in the fields of harmful gas removal and fuel oil desulfurization.Furthermore,significant scientific research of DES in desulfurization and purification of natural gas has accelerated the process of its practical application.This paper systematically summarizes and analyzes the removal mechanism,impact factors and challenges of DES as emerging green solvent in H_(2)S absorption and conversion.Strategies on H_(2)S removal by DES generally fall into two categories:physical absorption and chemical conversion.Although the chemical conversion of H_(2)S by DES has been less studied compared with the physical absorption,it presents great application potential.At present,the research on H_(2)S removal by DES is still in the initial stage.Therefore,it is necessary to further study the mechanism of H_(2)S removal and construct the relationship between structural properties and desulfurization performance of DES,thereby to solve the issues of sulfur blockage and low quality of sulfur paste which is suffered by conventional liquid redox desulfurization solvent system.Additionally,the methods for efficient solvent regeneration and recycling remain to be explored out to promote the practical application of iron-based DES in the field of gas desulfurization.
基金supported by the National Natural Science Foundation of China(Nos.52072136,51972257,51872104,and 52172229)Hubei Key Laboratory of Biomass Fibers&Eco-Dyeing&Finishing(Wuhan Textile University)(Nos.STRZ202225,and STRZ202406).
文摘Hydrogels based on Deep Eutectic Solvents(DES)demonstrate remarkable anti-freezing,resilience,and toughness,presenting a promising avenue to the operation of aqueous zincion batteries under extreme conditions.A gel electrolyte capable of operating over a wide temperature range is developed based on a DES comprising 1 mol/kg(m)Zn(ClO_(4))_(2)+3.5 m Mg(ClO_(4))_(2).Spectral characterization confirms the synergistic influence of both anions and cations on the freezing point of the DES.With four hydrogen bond(HB)acceptors,Mg^(2+) exhibits strong electrostatic attraction towards the O atoms of H_(2)O,while ClO_(4)^(-)forms numerous HBs with H_(2)O molecules.This dual interaction allows for precise adjustment of the chemical environment around the H and O atoms of H_(2)O,resulting in an exceptionally low freezing point of-116.92℃for the DES.The gel electrolyte derived from this DES demonstrates an impressive ionic conductivity of 0.285 mS/cm at-70℃.Leveraging its excellent low-temperature performance and compatibility with a zinc anode,the flexible Zn-Mn battery constructed with this electrolyte exhibits robust electrochemical performance at low temperatures.Specifically,at-70℃,it achieves a high specific capacity of 76.83 mAh/g,displays excellent rate capability,andmaintains stable cycling performance.Moreover,the Zn-Mn battery operates reliably across a broad temperature range from-70 to 80℃.This study presents innovative insights for advancing Zn-Mn batteries capable of efficient operation across diverse environmental conditions,thereby opening new avenues for their development.
基金supported by the National Natural Science Foundation of China(22008033)the Major Program of Qingyuan Innovation Laboratory.
文摘Efficient recognition and selective capture of NH_(3)is not only beneficial for increasing the productivity of the synthetic NH_(3)industry but also for reducing air pollution.For this purpose,a group of deep eutectic solvents(DESs)consisting of glycolic acid(GA)and phenol(PhOH)with low viscosities and multiple active sites was rationally designed in this work.Experimental results show that the GA^(+)PhOH DESs display extremely fast NH_(3)absorption rates(within 51 s for equilibrium)and high NH_(3)solubility.At 313.2 K,the NH_(3)absorption capacities of GA^(+)PhOH(1:1)reach 6.75 mol/kg(at 10.7 kPa)and 14.72 mol/kg(at 201.0 kPa).The NH_(3)solubility of GA^(+)PhOH DESs at low pressures were minimally changed after more than 100 days of air exposure.In addition,the NH_(3)solubility of GA^(+)PhOH DESs remain highly stable in 10 consecutive absorption-desorption cycles.More importantly,NH_(3)can be selectively captured by GA^(+)PhOH DESs from NH_(3)/CO_(2)/N_(2)and NH_(3)/N_(2)/H_(2)mixtures.1H-NMR,Fourier transform infrared and theoretical calculations were performed to reveal the intrinsic mechanism for the efficient recognition of NH_(3)by GA^(+)PhOH DESs.
基金supported by the National Natural Science Foundation of China(21773307)
文摘Biomass is renewable, abundant, cheap, biocompatible, and biodegradable materials and has been used to produce chemicals, materials,energy, and fuels. However, most of the biomass, especially most of the biomass polymers are not soluble in common solvents, which hinders their pretreatment and conversion. Deep eutectic solvents(DESs) are environmental-friendly, cheap, and highly tunable, with high solubility,which renders them potential applications in biomass pretreatment and conversion. They could be used as solvents or catalysts and so on. This paper intends to review the application of DESs for the pretreatment of biomass and conversion of biomass to value-added products. We focus on the following topics related to biomass and DESs:(1) DESs for the pretreatment of biomass;(2) DESs for the dissolution and separation of biomass or extraction of chemicals from biomass;(3) DESs for biomass conversion;(4) Drawbacks, and recyclability of DESs for pretreatment and conversion of biomass.
基金supported by the National Natrual Sciece Foundation of China (Nos. 21650110454, 21675164, 2 822407)the CAS-President International Fellowship Initiative (No. 2017PC0014)the Funds for Distinguished Young Scientists of Gansu (No. 1506RJDA281)
文摘Here we firstly report a series of new deep eutectic solvents(DESs) induced by small amounts of crown ether complex and mainly formed by polyethylene glycol. These DESs not only presented the ultra-deep extraction of non-basic N-compounds from fuel oils, but also opened up the possibility of other new applications in chemistry and materials science.
基金financially supported by the National Natural Science Foundation of China (Nos. 21506080 and 21766007)Natural Science Foundation of Jiangsu Province (No. BK20150485)+1 种基金Advanced Talents of Jiangsu University (No. 15JDG053)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.
基金supported by the Talented Program of Guizhou University(702759203301)the Natural Science Foundation of Guizhou Science and Technology Department(QKHJC-ZK[2021]-YB257)。
文摘Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to its potential to reduce the consumption of energy and threat to the environment.However,the simultaneous realization of green,efficient and closed-loop recycling is still challenging.Herein,we report a closed-loop and highly efficient approach to recycle lithium cobalt oxide from spent LIBs based on a choline chloride:oxalic acid(ChCl:OA)type deep eutectic solvent(DES).An ultrafast leaching process is observed at 180°C for 10 s with no observable residues.The energy barrier during leaching is calculated to be 113.9 kJ/mol.Noteworthy,the solubility of cobalt ions can be reversibly tuned by simply adding/evaporating deionized water,thus avoiding the addition of precipitant and enabling the easy recovery of the leaching solvent for realizing a closed-loop recycling process.The simultaneous realization of high efficiency,green and closed-loop process is expected to push the DES into practical application for recycling the electrodes of LIBs.
基金Project(51764027) supported by the National Natural Science Foundation of ChinaProject(2014CB643404) supported by the National Basic Research Program of China
文摘Deep eutectic solvents(DESs) are a kind of potential lixiviant for selective metal processing due to their versatile complexation properties. In this study, we investigated the recovery of zinc from zinc oxide dust using choline chloride-ureaethylene glycol(ChCl-urea-EG) DESs. The zinc extraction efficiency can be up to 85.2% when the slurry concentration is 50 g/L, leaching temperature is 80 °C and stirring speed is 600 r/min. The leaching process is controlled by the diffusion and the corresponding activation energy is 32.1 k J/mol. The resultant solution was directly used for the electrodeposition of zinc. The pure zinc deposit is obtained with a current efficiency of 82.6%. Furthermore, the ChCl-urea-EG DESs can be recycled. This approach is shown to be promising for the recycling of zinc from the zinc-containing dust.
基金The financial support from National Natural Science Foundation of China(21776074,21576081,and 2181101120)is greatly acknowledged
文摘This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.
基金Project supported by the Natural Sciences and Engineering Research Council of Canada through its Cooperative Research&Development Grants Program
文摘Dissolution in choline-chloride based deep eutectic solvents(DES) of rare earth elements(REE) from high-purity single carbonate salts of Y, La, Ce, Nd and Sm and from their multicomponent mixtures and also bastn€asite mineral was assessed with a prospect to gain an understanding on the leaching behavior of bastn€asite ores as REE source from DES suspensions. Urea, malonic acid and citric acid were used in different proportions with choline chloride in order to form deep eutectic solvents with desired viscosity and functionality. The results obtained prove promising for use insolvato-metallurgical processes in terms of selective dissolution of the higher-atomic-number(Z) rare earth elements at the expense of the lower-ZREEs and the gangue-originating metal impurities, thus initiating separation among the different REE members from the early hydrometallurgical steps.
基金supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia (Grant No. 172060)
文摘The electrodeposition of aluminium on glassy carbon and aluminium substrates from AlCl3-urea deep eutectic solvent(DES) system at near room temperatures was investigated,without additional purification of the chemicals used to prepare the electrolyte and without rigorous control of moisture and oxygen present in the working space.The effects of changing temperature,working potential,controlled deposition current density and deposition time on the morphology of deposited aluminium without stirring of the electrolyte were recorded.Using potentiostatic and galvanostatic techniques,aluminium was electrodeposited from the deep eutectic solvent(n(AlCl3):n(urea)=1.6:1) onto glassy carbon and aluminium substrates at temperatures ranging from 25 to 50℃.Using SEM,EDS and XRD techniques,substrates were studied and confirmed the presence of aluminium deposits following both potentiostatic and galvanostatic regimes.The shape and size of Al grains deposited depended on the time of deposition and varied in size from nanometers to micrometers and in shape from regular crystal forms to needle-like and flake-like structures.
基金financially supported by the National Natural Science Foundation of China(No.22174129)the Natural Science Foundation of Zhejiang Province(No.LZY21E030001)。
文摘Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,which means that the precursors of DESs with different structures and properties can be screened to customize DESs for specific functions.Researchers have found that during the sample preparation process involving DESs,the specific properties of some“smart”DESs can be switched by directing external driving forces,leading to a reversible phase transition of the target solution.These"smart"DESs are called switchable deep eutectic solvents(SDESs).The advent of SDES simplifies the sample pretreatment steps,reduces the use of organic solvents,and makes solvents easy to recycle,which matches the concept of green and sustainable chemistry.Compared with the number of previous experimental studies,the reviews and summaries on SDESs are rare.Therefore,this review made a summary of the concept and research progress of SDESs based on some related works in the past decade,including composition and type,characterization,switching mechanism,etc.It is expected to provide a certain reference and guidance for the subsequent in-depth research of SDESs in the analytical sample pretreatment.
基金financially supported by Carl Tryggers Stiftelse foundation(No.18:175)the financial support from the Swedish Energy Agency(P47500-1)+5 种基金K.C.Wang Education Foundation(No.GJTD-201804)the financial support from the National Natural Science Foundation of China(No.21890764)the financial supports from the National Natural Science Foundation of China(No.21838010)the financial support from the National Natural Science Foundation of China(No.21776276)the National Natural Science Foundation of China(21701024)the Foundation for Distinguished Young Talents in Higher Education of Fujian Province(GY-Z17067)
文摘The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results indicate that chemical-based ILs/DESs are superior to physical-based ILs/DESs for CO_(2)capture,especially those ILs have functionalized cation and anion,and superbase DESs;some of the superbase DESs have higher CO_(2)solubilities than those of ILs;the best physical-and chemical-based ILs,as well as physical-and chemicalbased DESs are[BMIM][BF4](4.20 mol kg^(-1)),[DETAH][Im](11.91 mol kg^(-1)),[L-Arg]-Gly 1:6(4.92 mol kg^(-1))and TBD-EG 1:4(12.90 mol kg^(-1)),respectively.Besides the original COSMO-RS mainly providing qualitative predictions,six corrected COSMO-RS models have been proposed to improve the prediction performance based on the experimental data,but only one model is with universal parameters.The newly determined experimental results were further used to verify the perditions of original and corrected COSMO-RS models.The comparison indicates that the original COSMO-RS qualitatively predicts CO_(2)solubility for some but not all ILs/DESs,while the quantitative prediction is incapable at all.The original COSMO-RS is capable to predict CO_(2)Henry’s constant qualitatively for both physical-based ILs and DESs,and quantitative prediction is only available for DESs.For the corrected COSMO-RS models,only the model with universal parameters provides quantitative predictions for CO_(2)solubility in physical-based DESs,while other corrected models always show large deviations(>83%)compared with the experimental CO_(2)Henry’s constants.
