Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or a...Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.展开更多
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
Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low pol...Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low polarity(lower than that of methanol,ChCl-based deep eutectic solvents and other reported HDESs),and low density(<0.928 g/mL).A simple one-pot method based on a novel HDES-water two-phase extraction system was constructed for the extraction of weak-polarity bioactive components,anthraquinones,from Rhei Radix et Rhizoma.This HDES-based new extraction method does not consume hazardous organic solvents and can obtain a total anthraquinone yield of 21.52 mg/g,which is close to that obtained by the Chinese pharmacopoeia method(21.22 mg/g)and considerably higher than those by other reported HDESs-based extraction methods(14.20-20.09 mg/g,p<0.01).The high extraction yield can be mainly attributed to the severe destruction of the RRR cell walls by the extraction system and the excellent dissolving ability of novel HDESs for anthraquinones.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)have drawn a growing research interest for applications in a wide range of scientific and industrial arenas.However,a limited effort has been reported in the area of gas separation processe...Deep eutectic solvents(DESs)have drawn a growing research interest for applications in a wide range of scientific and industrial arenas.However,a limited effort has been reported in the area of gas separation processes and particularly the carbon dioxide capture.This study introduces a novel set of DESs that were prepared by complexing ethylenediamine(EDA),monoethanolamine(MEA),tetraethylenepentamine(TEPA),triethylenetetramine(TETA)and diethylenetriamine(DETA)as hydrogen bond donors to monoethanolamide hydrochloride(EAHC)salt as a hydrogen bond acceptor.The absorption capacity of CO2 was evaluated by exploiting a method based on measuring the pressure drop during the absorption process.The solubility of different DESs was studied at a temperature of 313.15 K and initial pressure of 0.8 MPa.The DES systems 1 EAHC:9 DETA,1 EAHC:9 TETA and 1 EAHC:9 TEPA achieved the highest CO2 solubility of 0.6611,0.6572 and 0.7017 mol CO2·(mole DES)-1 respectively.The results showed that CO2 solubility in the DESs increased with increasing the molar ratio of hydrogen bond donor.In addition,the CO2 solubility increased as the number of amine groups in the solvent increases,therefore,increasing the alkyl chain length in the DESs,resulted in increasing the CO2 solubility.FTIR analysis confirms the DES synthesis since no new functional group was identified.The FTIR spectra also revealed the carbamate formation in DES-CO2 mixtures.In addition,the densities and viscosities of the synthesized DESs were also measured.The CO2 initial investigation of reported DESs shows that these can be potential alternative for conventional solvents in CO2 capture processes.展开更多
Parabens are antimicrobial preservatives with extensive applications in cosmetics,toiletries,pharmaceuticals,and food.Considering the legitimate concerns relating to their potential to disrupt multiple endocrine funct...Parabens are antimicrobial preservatives with extensive applications in cosmetics,toiletries,pharmaceuticals,and food.Considering the legitimate concerns relating to their potential to disrupt multiple endocrine functions,it becomes imperative to prioritize the development of innovative bioanalytical techniques for effectively monitoring their presence in biological samples.In this study,an efficient solvent bar microextraction(SBME)was established,utilizing new hydrophobic deep eutectic solvents(DEs)to determine methylparaben and propylparaben in urine and plasma samples.The DEs comprising menthol and tris(2-ethylhexyl)phosphate(M-TEHP)at various molar ratios were synthesized for the first time to enhance the extraction capacity and promote the eco-friendliness of the DE used as an extraction solvent.Fourier-transform infrared(FT-IR)and proton nuclear magnetic resonance(1H NMR)spectroscopies were employed to confirm and investigate the properties of the successful synthesis(M-TEHP)DE at a molar ratio of 1:1.The synthesized DE exhibits low microbial toxicity and can be considered an eco-friendly solvent for extraction.Furthermore,quantum-chemical calculations were utilized to predict synthesized DE's structure and interaction energy with selected parabens.The influential operational factors of DE-SBME on the extraction efficiency(EE%)of both parabens were evaluated using response surface methodology based on central composite design,and a total of 30 extraction tests were conducted to determine the optimal conditions.The optimized DE-SBME,in combination with HPLC-DAD,exhibited low detection limits(0.54–0.91μg L^(−1)),excellent linearity(R^(2)≥0.9993),precise results(RSDs≤7.6%),satisfactory recoveries(92–97%)and negligible matrix effects.Hence,it had remarkable effectiveness and applicability in determining selected parabens in real urine and plasma samples.展开更多
The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.I...The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.In this work,serials of deep eutectic solvents(DES)with intermolecular-hydrogen-bonding interaction were constructed as catalysts and medium for actuating reversible complexation-mediated polymerization(RCMP)for the first time,yielding methacrylate polymers with high monomer conversion and narrow dispersion molecular weight in both water and oil systems.The mechanism and elementary reaction of RCMP were explored deeply,revealing that the complexation of initiator with DES to generate radicals was a ratecontrolling step and intermolecular-hydrogen-bond was primary factor to influence polymerization rate.Moreover,the insights of density functional theory calculations revealed that negative electrostatic potential ensured nucleophilic capacity.This investigation demonstrated the considerable potential of DES for RCMP,which is anticipated for other polymerization applications as a novel medium mode.展开更多
Recent advances in novel electroactive devices have placed new requirements on material development.High-performance dielectric elastomers with good mechanical stretchability and high dielectric constant are under hig...Recent advances in novel electroactive devices have placed new requirements on material development.High-performance dielectric elastomers with good mechanical stretchability and high dielectric constant are under high demand.However,the current strategy for fabricating these materials suffers from high cost or low thermal stability,which greatly hinders large-scale industrial production.Herein,we have successfully developed a novel strategy for improving the dielectric constant of polymeric elastomers via deep eutectic solvent inclusion by taking advantage of the low cost,convenient and environmentally benign synthesis process and high ionic conductivity from deep eutectic solvents.The as-prepared composite elastomers showed good stretchability and a greatly enhanced dielectric constant with a negligible increase in dielectric dissipation.Moreover,we have proven the universality of our strategy by using different types of deep eutectic solvents.It is believed that low-cost,easy-synthesis and environmentally friendly deep eutectic solvents including composite elastomers are highly suitable for large-scale industrial production and can greatly broaden the application fields of dielectric elastomers.展开更多
基金supported by the Key Area Research&Development Program of Guangdong Province(2020B0101070001)the National Natural Science Foundation of China(21978053,51508547)。
文摘Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.
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the National Natural Science Foundation of China (Grant Nos.: 81673394 and 82073811)the Fundamental Research Funds for the Central Universities (Grant No.: 2042020kf1010)the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University (Grant No.: LF20170838)
文摘Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low polarity(lower than that of methanol,ChCl-based deep eutectic solvents and other reported HDESs),and low density(<0.928 g/mL).A simple one-pot method based on a novel HDES-water two-phase extraction system was constructed for the extraction of weak-polarity bioactive components,anthraquinones,from Rhei Radix et Rhizoma.This HDES-based new extraction method does not consume hazardous organic solvents and can obtain a total anthraquinone yield of 21.52 mg/g,which is close to that obtained by the Chinese pharmacopoeia method(21.22 mg/g)and considerably higher than those by other reported HDESs-based extraction methods(14.20-20.09 mg/g,p<0.01).The high extraction yield can be mainly attributed to the severe destruction of the RRR cell walls by the extraction system and the excellent dissolving ability of novel HDESs for anthraquinones.
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Sultan Qaboos University for providing financial。
文摘Deep eutectic solvents(DESs)have drawn a growing research interest for applications in a wide range of scientific and industrial arenas.However,a limited effort has been reported in the area of gas separation processes and particularly the carbon dioxide capture.This study introduces a novel set of DESs that were prepared by complexing ethylenediamine(EDA),monoethanolamine(MEA),tetraethylenepentamine(TEPA),triethylenetetramine(TETA)and diethylenetriamine(DETA)as hydrogen bond donors to monoethanolamide hydrochloride(EAHC)salt as a hydrogen bond acceptor.The absorption capacity of CO2 was evaluated by exploiting a method based on measuring the pressure drop during the absorption process.The solubility of different DESs was studied at a temperature of 313.15 K and initial pressure of 0.8 MPa.The DES systems 1 EAHC:9 DETA,1 EAHC:9 TETA and 1 EAHC:9 TEPA achieved the highest CO2 solubility of 0.6611,0.6572 and 0.7017 mol CO2·(mole DES)-1 respectively.The results showed that CO2 solubility in the DESs increased with increasing the molar ratio of hydrogen bond donor.In addition,the CO2 solubility increased as the number of amine groups in the solvent increases,therefore,increasing the alkyl chain length in the DESs,resulted in increasing the CO2 solubility.FTIR analysis confirms the DES synthesis since no new functional group was identified.The FTIR spectra also revealed the carbamate formation in DES-CO2 mixtures.In addition,the densities and viscosities of the synthesized DESs were also measured.The CO2 initial investigation of reported DESs shows that these can be potential alternative for conventional solvents in CO2 capture processes.
文摘Parabens are antimicrobial preservatives with extensive applications in cosmetics,toiletries,pharmaceuticals,and food.Considering the legitimate concerns relating to their potential to disrupt multiple endocrine functions,it becomes imperative to prioritize the development of innovative bioanalytical techniques for effectively monitoring their presence in biological samples.In this study,an efficient solvent bar microextraction(SBME)was established,utilizing new hydrophobic deep eutectic solvents(DEs)to determine methylparaben and propylparaben in urine and plasma samples.The DEs comprising menthol and tris(2-ethylhexyl)phosphate(M-TEHP)at various molar ratios were synthesized for the first time to enhance the extraction capacity and promote the eco-friendliness of the DE used as an extraction solvent.Fourier-transform infrared(FT-IR)and proton nuclear magnetic resonance(1H NMR)spectroscopies were employed to confirm and investigate the properties of the successful synthesis(M-TEHP)DE at a molar ratio of 1:1.The synthesized DE exhibits low microbial toxicity and can be considered an eco-friendly solvent for extraction.Furthermore,quantum-chemical calculations were utilized to predict synthesized DE's structure and interaction energy with selected parabens.The influential operational factors of DE-SBME on the extraction efficiency(EE%)of both parabens were evaluated using response surface methodology based on central composite design,and a total of 30 extraction tests were conducted to determine the optimal conditions.The optimized DE-SBME,in combination with HPLC-DAD,exhibited low detection limits(0.54–0.91μg L^(−1)),excellent linearity(R^(2)≥0.9993),precise results(RSDs≤7.6%),satisfactory recoveries(92–97%)and negligible matrix effects.Hence,it had remarkable effectiveness and applicability in determining selected parabens in real urine and plasma samples.
基金financially supported by the State Key Program of National Natural Science Foundation of China(U21A20313)the Key Program of Qingyuan Innovation Laboratory(00221003)+2 种基金the“111”Program of Fuzhou Universitythe Natural Science Foundation of Fujian Province(2019J05040)the China Postdoctoral Science Foundation(2022M20739)。
文摘The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.In this work,serials of deep eutectic solvents(DES)with intermolecular-hydrogen-bonding interaction were constructed as catalysts and medium for actuating reversible complexation-mediated polymerization(RCMP)for the first time,yielding methacrylate polymers with high monomer conversion and narrow dispersion molecular weight in both water and oil systems.The mechanism and elementary reaction of RCMP were explored deeply,revealing that the complexation of initiator with DES to generate radicals was a ratecontrolling step and intermolecular-hydrogen-bond was primary factor to influence polymerization rate.Moreover,the insights of density functional theory calculations revealed that negative electrostatic potential ensured nucleophilic capacity.This investigation demonstrated the considerable potential of DES for RCMP,which is anticipated for other polymerization applications as a novel medium mode.
基金the National Natural Science Foundation of China(Grant No.22078276)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(Grant No.2017ZT07C291)+2 种基金Shenzhen Science and Technology Program(Grant No.KQTD20170810141424366)Shenzhen Key Laboratory of Advanced Materials Product Engineering(Grant No.ZDSYS20190911164401990)Qi Zhang thanks the Presidential Fund(Grant No.PF01000949)for supporting his research at CUHK-Shenzhen.
文摘Recent advances in novel electroactive devices have placed new requirements on material development.High-performance dielectric elastomers with good mechanical stretchability and high dielectric constant are under high demand.However,the current strategy for fabricating these materials suffers from high cost or low thermal stability,which greatly hinders large-scale industrial production.Herein,we have successfully developed a novel strategy for improving the dielectric constant of polymeric elastomers via deep eutectic solvent inclusion by taking advantage of the low cost,convenient and environmentally benign synthesis process and high ionic conductivity from deep eutectic solvents.The as-prepared composite elastomers showed good stretchability and a greatly enhanced dielectric constant with a negligible increase in dielectric dissipation.Moreover,we have proven the universality of our strategy by using different types of deep eutectic solvents.It is believed that low-cost,easy-synthesis and environmentally friendly deep eutectic solvents including composite elastomers are highly suitable for large-scale industrial production and can greatly broaden the application fields of dielectric elastomers.
