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Theoretical analysis of hydrogen solubility in direct coal liquefaction solvents 被引量:1
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作者 Xiaobin Zhang Aoqi Wang +1 位作者 Xingbao Wang Wenying Li 《International Journal of Coal Science & Technology》 EI CAS CSCD 2024年第2期187-197,共11页
The cyclic hydrogenation technology in a direct coal liquefaction process relies on the dissolved hydrogen of the solvent or oil participating in the hydrogenation reaction.Thus,a theoretical basis for process optimiz... The cyclic hydrogenation technology in a direct coal liquefaction process relies on the dissolved hydrogen of the solvent or oil participating in the hydrogenation reaction.Thus,a theoretical basis for process optimization and reactor design can be established by analyzing the solubility of hydrogen in liquefaction solvents.Experimental studies of hydrogen solubility in liquefaction solvents are challenging due to harsh reaction conditions and complex solvent compositions.In this study,the composition and content of liquefied solvents were analyzed.As model compounds,hexadecane,toluene,naphthalene,tetrahydronaphthalene,and phenanthrene were chosen to represent the liquefied solvents in chain alkanes and monocyclic,bicyclic,and tricyclic aromatic hydrocarbons.The solubility of hydrogen X(mol/mol)in pure solvent components and mixed solvents(alkanes and aromatics mixed in proportion to the chain alkanes+bicyclic aromatic hydrocarbons,bicyclic saturated aromatic hydrocarbons+bicyclic aromatic hydrocarbons,and bicyclic aromatic hydrocarbons+compounds containing het-eroatoms composed of mixed components)are determined using Aspen simulation at temperature and pressure conditions of 373–523 K and 2–10 MPa.The results demonstrated that at high temperatures and pressures,the solubility of hydrogen in the solvent increases with the increase in temperature and pressure,with the pressure having a greater impact.Further-more,the results revealed that hydrogen is more soluble in straight-chain alkanes than in other solvents,and the solubility of eicosanoids reaches a maximum of 0.296.The hydrogen solubility in aromatic ring compounds decreased gradually with an increase in the aromatic ring number.The influence of chain alkanes on the solubility of hydrogen predominates in a mixture of solvents with different mixing ratios of chain alkanes and aromatic hydrocarbons.The solubility of hydrogen in mixed aromatic solvents is less than that in the corresponding single solvents.Hydrogen is less soluble in solvent compounds containing heteroatoms than in compounds without heteroatoms. 展开更多
关键词 Direct coal liquefaction Liquefaction solvents Process simulation Hydrogen solubility
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Alcohol solvent effect on the self-assembly behaviors of lignin oligomers
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作者 Ya Ma Zhicheng Jiang +4 位作者 Yafei Luo Xingjie Guo Xudong Liu Yiping Luo Bi Shi 《Green Energy & Environment》 SCIE EI CAS CSCD 2024年第4期597-603,共7页
The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with th... The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly. 展开更多
关键词 Lignin oligomers Alcohol solvent SELF-ASSEMBLY LNPs solvent effects
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Low-melting mixture solvents:extension of deep eutectic solvents and ionic liquids for broadening green solvents and green chemistry
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作者 Yu Chen Zhiwu Yu 《Green Chemical Engineering》 EI CSCD 2024年第4期409-417,共9页
Green solvents such as water and ionic liquids(ILs)are pillars of the great mansion of green chemistry and green processing.Initially proposed as a new family of ILs,deep eutectic solvents(DESs)have received fast deve... Green solvents such as water and ionic liquids(ILs)are pillars of the great mansion of green chemistry and green processing.Initially proposed as a new family of ILs,deep eutectic solvents(DESs)have received fast development in the past two decades.In this contribution,DESs are reviewed critically and the concept is extended to lowmelting mixture solvents(Lo MMSs),which cover all kinds of materials including ionic compounds,molecular compounds,and metals.Six classes of Lo MMSs are proposed as the new classification system and examples are given.Finally,several thermodynamic issues concerning Lo MMSs are discussed.Two new concepts,robustness of Lo MMSs and high-entropy Lo MMSs,are proposed. 展开更多
关键词 Green solvents Deep eutectic solvents Low transition temperature mixture solvents Phase diagram EGaIn
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Solvent transport dynamics and its effect on evolution of mechanical properties of nitrocellulose(NC)-based propellants under hot-air drying process
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作者 Enfa Fu Mingjun Yi +1 位作者 Qianling Liu Zhenggang Xiao 《Defence Technology(防务技术)》 SCIE EI CAS CSCD 2024年第2期262-270,共9页
Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics... Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants. 展开更多
关键词 Nitrocellulose-based propellants solvent transport dynamics Mechanical properties Drying kinetics Effective solvent diffusion coefficient
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Simultaneous purification of minor components in natural products using twin-column recycling chromatography with a step solvent gradient
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作者 Guangxia Jin Yuxue Wu Feng Wei 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第5期212-219,共8页
The isolation of minor components from complex natural product matrices presents a significant challenge in the field of purification science due to their low concentrations and the presence of structurally similar co... The isolation of minor components from complex natural product matrices presents a significant challenge in the field of purification science due to their low concentrations and the presence of structurally similar compounds.This study introduces an optimized twin-column recycling chromatography method for the efficient and simultaneous purification of these elusive constituents.By introducing water at a small flowing rate between the twin columns,a step solvent gradient is created,by which the leading edge of concentration band would migrate at a slower rate than the trailing edge as it flowing from the upstream to downstream column.Hence,the band broadening is counterbalanced,resulting in an enrichment effect for those minor components in separation process.Herein,two target substances,which showed similar peak position in high performance liquid chromatography(HPLC)and did not exceed 1.8%in crude paclitaxel were selected as target compounds for separation.By using the twin-column recycling chromatography with a step solvent gradient,a successful purification was achieved in getting the two with the purity almost 100%.We suggest this method is suitable for the separation of most components in natural produces,which shows higher precision and recovery rate compared with the common lab-operated separation ways for natural products(thin-layer chromatography and prep-HPLC). 展开更多
关键词 solvent gradient Twin-column recycling chromatography PURIFICATION Minor component Natural products
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Elucidating solvent effects on the stability of phenoxyl radicals in monohydric alcohols via electron paramagnetic resonance
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作者 Xinyu Wang Wenjing Sun +1 位作者 Yongtao Wang Haoran Li 《Green Chemical Engineering》 EI CSCD 2024年第4期483-488,共6页
Research on solvent effects is an important and long-standing topic,but there still is some room,especially for the special solvent effect of fluoroalcohols.In this work,we investigated the stability of phenoxyl radic... Research on solvent effects is an important and long-standing topic,but there still is some room,especially for the special solvent effect of fluoroalcohols.In this work,we investigated the stability of phenoxyl radical in monohydric alcohol solvents through in-situ electron paramagnetic resonance detections.The decay behavior of phenoxyl radical showed a reasonable relationship with the mesoscopic structure of alcohols,characterized by smalland wide-angle X-ray scattering.Moreover,the distinct solvent effects of fluoroalcohols were emphasized,and the significant influence of van der Waals distance in the solvents was suggested.Overall,the stability of phenoxyl radical in alcohols was quantified and correlated with the solvent structures.We believe that the established method for stability study on radicals will encourage solvent effect studies on various organic reactions,and the proposed solvent effects in fluoroalcohols may inspire the development of green solvents in both industrial conversions and organic synthesis. 展开更多
关键词 solvent effect FLUOROALCOHOL Phenoxyl radical STABILITY Electron paramagnetic resonance
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Study on the green extraction of corncob xylan by deep eutectic solvent
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作者 Bingyu Jiao Le Wang +3 位作者 Haitao Gui Zifu Ni Rong Du Yuansen Hu 《Grain & Oil Science and Technology》 CAS 2024年第1期50-59,共10页
Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other ... Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other problems.As one of the most abundant polymers in nature,xylan is widely used in food,medicine,materials and other fields.Corn cob is rich in xylan,which is an ideal raw material for extracting xylan.However,the intractable lignin is covalently linked to xylan,which increases the difficulty of xylan extraction.It has been reported that the deep eutectic solvent(DES)could preferentially dissolve lignin in biomass,thereby dissolving the xylan.Then,the xylan in the extract was separated by ethanol precipitation method.The xylan precipitate was obtained after centrifugation,while the supernatant was retained.The components of the supernatant after ethanol precipitation were separated by the rotary evaporator.The ethanol,water and DES were collected for the subsequent extraction of corn cob xylan.In this study,a novel way was provided for the green production of corn cob xylan.The DES was used to extract xylan from corn cob which was used as the raw material.The effects of solid-liquid ratio,reaction time,reaction temperature and water content of DES on the extraction rate of corn cob xylan were investigated by the single factor test.Furthermore,the orthogonal test was designed to optimize the xylan extraction process.The structure of corn cob xylan was analyzed and verified.The results showed that the optimum extraction conditions of corn cob xylan were as follows:the ratio of corn cob to DES was 1:15(g:mL),the extraction time was 3 h,the extraction temperature was 60℃,and the water content of DES was 70%.Under these conditions,the extraction rate of xylan was 16.46%.The extracted corn cob xylan was distinctive triple helix of polysaccharide,which was similar to the structure of commercially available xylan.Xylan was effectively and workably extracted from corn cob by the DES method.This study provided a new approach for high value conversion of corn cob and the clean production of xylan. 展开更多
关键词 CORNCOB Deep eutectic solvent XYLAN Process optimization EXTRACTION
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Insight into the experiment and extraction mechanism for separating carbazole from anthracene oil with quaternary ammonium-based deep eutectic solvents
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作者 Xudong Zhang Yanhua Liu +4 位作者 Jun Shen Yugao Wang Gang Liu Yanxia Niu Qingtao Sheng 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第1期188-199,共12页
Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in che... Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar. 展开更多
关键词 CARBAZOLE Model anthracene oil Deep eutectic solvents COSMO-RS Extraction mechanism
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Reviewing electrochemical stability of ionic liquids-/deep eutectic solvents-based electrolytes in lithium-ion,lithium-metal and post-lithium-ion batteries for green and safe energy
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作者 Yu Chen Shuzi Liu +4 位作者 Zixin Bi Zheng Li Fengyi Zhou Ruifen Shi Tiancheng Mu 《Green Energy & Environment》 SCIE EI CAS CSCD 2024年第6期966-991,共26页
Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electroly... Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy. 展开更多
关键词 Green solvents Decomposition Sustainable chemistry Lithium-oxygen batteries Lithium-sulphur batteries Sodium-ion batteries
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Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study
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作者 Zijiang Dou Weiqiang Tang +1 位作者 Peng Xie Shuangliang Zhao 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第2期180-188,共9页
Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However... Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions. 展开更多
关键词 solvent effect Ionic liquids Diels-Alder reaction Reaction density functional theory
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Efficient and reversible separation of NH_(3) by deep eutectic solvents with multiple active sites and low viscosities
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作者 Jiayin Zhang Lu Zheng +4 位作者 Siqi Fang Hongwei Zhang Zhenping Cai Kuan Huang Lilong Jiang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第3期97-105,共9页
The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)... The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations. 展开更多
关键词 SEPARATION Absorption Ionic liquid Deep eutectic solvent Multiple active site Low viscosity
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Experimental investigation on coal pore-fracture variation and fractal characteristics synergistically affected by solvents for improving clean gas extraction
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作者 Feilin Han Sheng Xue +3 位作者 Chunshan Zheng Zhongwei Chen Guofu Li Bingyou Jiang 《International Journal of Mining Science and Technology》 SCIE EI CAS CSCD 2024年第3期413-425,共13页
Chemical solvents instead of pure water being as hydraulic fracturing fluid could effectively increase permeability and improve clean methane extraction efficiency.However,pore-fracture variation features of lean coal... Chemical solvents instead of pure water being as hydraulic fracturing fluid could effectively increase permeability and improve clean methane extraction efficiency.However,pore-fracture variation features of lean coal synergistically affected by solvents have not been fully understood.Ultrasonic testing,nuclear magnetic resonance analysis,liquid phase mass spectrometry was adopted to comprehensively analyze pore-fracture change characteristics of lean coal treated by combined solvent(NMP and CS_(2)).Meanwhile,quantitative characterization of above changing properties was conducted using geometric fractal theory.Relationship model between permeability,fractal dimension and porosity were established.Results indicate that the end face fractures of coal are well developed after CS2and combined solvent treatments,of which,end face box-counting fractal dimensions range from 1.1227 to 1.4767.Maximum decreases in ultrasonic longitudinal wave velocity of coal affected by NMP,CS_(2)and combined solvent are 2.700%,20.521%,22.454%,respectively.Solvent treatments could lead to increasing amount of both mesopores and macropores.Decrease ratio of fractal dimension Dsis 0.259%–2.159%,while permeability increases ratio of NMR ranges from 0.1904 to 6.4486.Meanwhile,combined solvent could dissolve coal polar and non-polar small molecules and expand flow space.Results could provide reference for solvent selection and parameter optimization of permeability-enhancement technology. 展开更多
关键词 Clean gas extraction Chemical solvent Experimental investigation Fractal characteristics Pore fracture
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Rational surface charge engineering of haloalkane dehalogenase for boosting the enzymatic performance in organic solvent solutions
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作者 Yin Wu Yan Sun 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第1期276-285,共10页
Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy... Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy to improve the catalytic performance of haloalkane dehalogenase DhaA in OSs based on the energetic analysis of substrate binding to the DhaA surface.Several variants with enhanced OS resistance were obtained by replacing negative charged residues on the surface with positive charged residue(Arg).Particularly,a four-substitution variant E16R/E93R/E121R/E257R exhibited the best catalytic performance(five-fold improvement in OS resistance and seven-fold half-life increase in 40%(vol)dimethylsulfoxide).As a result,the overall catalytic performance of the variant could be at least 26 times higher than the wild-type DhaA.Fluorescence spectroscopy and molecular dynamics simulation studies revealed that the residue substitution mainly enhanced OS resistance from four aspects:(a)improved the overall structural stability,(b)increased the hydrophobicity of the local microenvironment around the catalytic triad,(c)enriched the hydrophobic substrate around the enzyme molecule,and(d)lowered the contact frequency between OS molecules and the catalytic triad.Our findings validate that computationaided surface charge engineering is an effective and ingenious rational strategy for tailoring enzyme performance in OSs. 展开更多
关键词 Surface charge engineering Organic solvent resistance Molecular dynamics simulation Haloalkane dehalogenase
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Oxidative Desulfurization of Fuel Oil with H_(3)PO_(4)-based Deep Eutectic Solvents
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作者 Li Xiuping Zhang Jiayin +1 位作者 Hou Liangpei Zhao Rongxiang 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第2期178-186,共9页
A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were ch... A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results. 展开更多
关键词 deep eutectic solvents phosphoric acid zinc chloride oxidative desulfurization
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Sodium Nitrate/Formamide Deep Eutectic Solvent as Flame-Retardant and Anticorrosive Electrolyte Enabling 2.6 V Safe Supercapacitors with Long Cyclic Stability
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作者 Huachao Yang Yiheng Qi +6 位作者 Zifan Wang Qinghu Pan Chuanzhi Zhang Jianhua Yan Kefa Cen Zheng Bo Kostya(Ken)Ostrikov 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2024年第3期374-383,共10页
Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are ... Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors. 展开更多
关键词 cyclic stability deep eutectic solvents electrical conductivity electrochemical stability window SUPERCAPACITORS
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Machine-Learning-Assisted Design of Deep Eutectic Solvents Based on Uncovered Hydrogen Bond Patterns
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作者 Usman L.Abbas Yuxuan Zhang +4 位作者 Joseph Tapia Selim Md Jin Chen Jian Shi Qing Shao 《Engineering》 SCIE EI CAS CSCD 2024年第8期74-83,共10页
Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a... Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs. 展开更多
关键词 Machine learning Deep eutectic solvents Molecular dynamics simulations Hydrogen bond Molecular design
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Lithium-ion and solvent co-intercalation enhancing the energy density of fluorinated graphene cathode
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作者 Hao Wang Jie Jiang +5 位作者 Pengyu Chen Zhenrui Wu Xiaobin Niu Chuying Ouyang Jian Liu Liping Wang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第2期208-215,I0006,共9页
Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it ... Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode. 展开更多
关键词 Fluorinated carbon Conversion reaction High-energy-density primary battery Li^(+)-solvation structure solvent co-intercalation
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Effect of solvent on the initiation mechanism of living anionic polymerization of styrene:A computational study
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作者 Shen Li Yin-Ning Zhou +1 位作者 Zhong-Xin Liu Zheng-Hong Luo 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第5期135-142,共8页
For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of sol... For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics. 展开更多
关键词 Living anionic polymerization solvent effect Reaction kinetics Computational chemistry Mathematical modeling Kinetic modeling
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Research Progress of Deep Eutectic Solvents in Extraction of Plant Flavonoids
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作者 Zhen LIN Shengmei XU +2 位作者 Shaomei CHEN Cui WANG Jian CHEN 《Agricultural Biotechnology》 2024年第3期34-40,44,共8页
As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application pote... As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application potential in the field of plant flavonoid extraction.In this paper,the definition,classification and preparation methods of DESs were introduced.The effects of DES composition,molar ratio of DES components,water content of DES systems,liquid-material ratio,extraction temperature,extraction time and extraction auxiliary techniques on the extraction yield of plant flavonoids were expounded.The recycling methods of DESs were summarized.Existing problems of DESs in the field of plant flavonoids extraction were pointed out,and further research direction and trend were analyzed and prospected. 展开更多
关键词 Deep eutectic solvent Plant flavonoid EXTRACTION Assistive technique REGENERATION
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Stoichiometry and Stability Constant Values for Copper (II) Chelates with Ethylene Diamine in Deep Eutectic Solvents (DES) (Ethaline) Solutions
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作者 Khalid El Ttaib Abdolhadi Benhmid Rifat Hasan Omar 《Open Journal of Applied Sciences》 2024年第9期2592-2609,共18页
In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements ha... In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values. 展开更多
关键词 CU(II) Ethylene Diamine (en) Deep Eutectic solvents Job’s Method Ionic Liquids and Stability Constant
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