JOURNAL OF CHEMICAL THERMODYNAMICS
·
2021
·
IF 3.178
Zhang Youqi,Zhang Qinqin,Xin Hua,Lv Meiheng,Zhang Zhigang
Ionic liquids (ILs) have been extensively used in the separation of alkane + alcohol azeotropes as entrainers by liquid–liquid extraction. n-Butanol is widely added to the fuel because of its high calorific value and low volatility. It is of significance to recovery n-butanol from the azeotropic mixture containing n-butanol. In this work, ionic liquids, formed by combining 17 cations and 12 anions, were screened based on the COSMO-RS model. 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA], 1-butyl-3-methylimidazolium dicyanamide [BMIM][DCA] and 1-hexyl-3-methylimidazolium dicyanamide [HMIM][DCA] were selected as entrainers. The liquid–liquid equilibrium data of the ternary system {n-heptane + n-butanol + [EMIM][DCA], n-heptane + n-butanol + [BMIM][DCA], n-heptane + n-butanol + [HMIM][DCA]} were measured at 298.15 K and 101.3 kPa. The quality of experimental data was tested by Othmer-Tobias, Bachman and Hand equations. The distribution coefficient (β) and selectivity (S) were calculated to evaluate the separation effect of the three ILs. The NRTL model was used to correlate liquid–liquid equilibrium experimental data. Finally, quantum mechanics calculations were performed to study the interactions between ILs and n-butanol through the reduced density gradient (RDG) function and quantum theory of atom in the molecule (QTAIM). The results of quantum chemistry calculation showed that the separation of n-butanol and n-heptane mixture by ionic liquids with [DCA] anions were dominated by hydrogen bonding. The research process is devoted to the development of green entrainers.
研究领域:
化学工程
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量子化学
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Guanfeng Deng,Pingjin Li,Heng Liang,Tao Chen,Lijun Zhou,Hongyu Yang,Xiaoyu Jiang,Chunbang Ding,Shiling Feng
Camellia oleifera leaves were byproduct of the C. oleifera industry which was rich in polysaccharides. Deep eutectic solvent-dual enzyme system (DES-dEAE) was established to achieve the simultaneous hydrolysis reaction of dual enzymes and DES extraction. Currently, there was a lack of research methods that simultaneously deal with the relationship between DES and enzymes and the effect of DES on the polysaccharide extraction rate. In the study, artificial neural network (ANN) and conductor-like screening model for real solvents (COSMO-RS) were used to screen the most suitable DES by predicting the pH and activity coefficient of DESs. Choline chloride and sorbitol constituted the best DES and were used to optimize the process conditions of DES-dEAE by response surface method (RSM). The polysaccharide yield was verified to be 21.46 mg/g with the optimal process conditions: liquid-solid ratio of 33:1, enzyme ratio of 3:1, extraction time of 15 min and water content of 40 %. The C. oleifera polysaccharides obtained by water, DES, and DES-dEAE extractions were observed by scanning electron microscopy and cell wall damage effect of DES-dEAE was confirmed microscopically. The study optimized the complex polysaccharide extraction system using bioinformatics methods, contributing new ideas to the development of simulated extraction.
研究领域:
植物学
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生物化学
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食品科学
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计算生物学
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产品关联
DOI
PubMed
高影响因子
FLUID PHASE EQUILIBRIA
·
2016
·
IF 1.846
Zhen Song,Jingjing Zhang,Qian Zeng,Hongye Cheng,Lifang Chen,Zhiwen Qi
When selecting ionic liquid (IL) as solvent for extraction processes, the cation alkyl chain length is an important structural variation, while research particularly concerning its effect is lacking. In this work, the effect of cation alkyl chain length on the liquid-liquid equilibria of {IL + thiophene + heptane}, an example for extractive desulfurization, was systematically investigated. The COSMO-RS model was employed to calculate the distributional coefficient (β ∞ ) and selectivity (S ∞ ) at infinite dilution for thiophene of the combinations of 17 cations and 63 anions. Two different anion-dependent tendencies of the β ∞ with increasing the cation alkyl chain length were identified and analyzed by COSMO-RS theory. To verify the scarcely-reported decreasing β ∞ with longer cation alkyl chain, acetate ([OAc] − ) was selected as representative and liquid-liquid equilibria {[C n MIM][OAc] + thiophene + heptane} (n = 2, 4, 6, 8) were experimentally determined, which validate the anion-dependency and demonstrate the highest extraction performance of [C 2 MIM][OAc].
研究领域:
化学工程
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物理化学
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产品关联
DOI
高影响因子
Green Chemical Engineering
·
2023
·
IF 0
Xin Guo,Zhiyuan Wang,Ye Yang,Jiahui Zhang,Yanduo Liu,Zhiyuan Mu,Siqi Jiang,Chunxiao Ren,Dan Lv,Yufeng Hu,Zhichang Liu
A production technique with the high yield and environmentally friendly process need be developed for ε-Caprolactam (CPL) in the chemical industry. This technology is highly desired to design and synthesize high−performance catalysts for liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) to CPL. In this work, 3-methyl-1-(propyl-4-sulfonyl) imidazolium methanesulfonate ([PHSO 3 MIM][MSA]) with highly efficient and excellent yield is synthesized successfully. When the optimum molar ratio of ZnCl 2 over [PHSO 3 MIM][MSA] was 0.02, it exhibits the high selectivity (94%) of CPL at 90 °C for 1 h. Interestingly, Fourier-transform infrared (FT-IR) investigations show that the functional Brønsted−Lewis acidic types of ionic liquids (ILs) are formed by the uniformly distributed ZnCl 2 and [PHSO 3 MIM][MSA]. In addition, the hydrogen bond (H-bond) is formed between CHO and ILs. After ten reaction cycles, no significant structure changes are observed in the recovered [PHSO 3 MIM][MSA]·ZnCl 2 . The solubilities of ILs are predicted by using COSMO-RS model, the results show that [PHSO 3 MIM][MSA] is a promising candidate for the liquid phase Beckmann rearrangement of CHO into CPL. Finally, a theoretical model of the H-bond interactions between ILs and CHO is further confirmed to support the advance of reaction mechanism. A feasible way is provided for the CPL production technique in the liquid phase Beckmann rearrangement reaction.
研究领域:
化学工程
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催化化学
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DOI
SCIENCE OF THE TOTAL ENVIRONMENT
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2022
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IF 10.753
Nan Zhao,Feng Ju,Quanwei Song,Zhiwen Qi,Hao Ling
Soil organic matter (SOM) is considered as a pivotal factor influencing the adsorption of pollutants. However, few prior quantitative investigations of the SOM functional group distribution to the contaminants' fate have been conducted. In this paper, the SOM cluster method based on COSMO-RS theory has been conducted to illustrate the chemical composition variables of SOM that affect the polycyclic aromatic hydrocarbons (PAHs) fate in quantitative terms. In the theoretical simulations, the contributions of carbonyl, carboxyl, aromatic, oxyalkyl and aliphatic groups in SOM to phenanthrene (Phe) and pyrene (Pyr) adsorption are evaluated by calculating the partition coefficients ( LogP ). The results show that the increase in oxyalkyl content leads to a decrease in LogP . Inversely, carbonyl and carboxyl groups of SOMs positively associated with Phe adsorption. The changes in aromatic and alkyl components have a similar magnitude of influence on LogP . Moreover, the effect of non-carbon-based functional groups in SOM on the Phe partitioning has been examined for the first time. The increase of sulfur and nitrogen content in SOM hinder Phe adsorption, while the rise of phosphorus content promotes the adsorption. In soil adsorption experiments, four natural soils, characterized by X-ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform (DRIFT), are selected to verify the influence of SOM functional group distribution. Comparing the experimental SOM-water partition coefficient ( LogK oc ) with the simulation predicted LogP suggests that the COSMO-RS based SOM cluster method can predict PAHs adsorption ability in SOM.
研究领域:
环境科学
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化学
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产品关联
DOI
PubMed
高影响因子
MICROCHEMICAL JOURNAL
·
2025
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IF 5.1
Hua Du,Yaodeng Wang,Yi Wu,Wenhui Wu,Bixing Gao,Jiaqi Yang,Jing Leng,Min Yang
Traditional extraction methods of essential oil suffer from limitations such as low extraction efficiency or the use of toxic solvents, which fail to meet the principles of green chemistry. To address these issues, this study established a high-efficiency, eco-friendly method for extracting essential oils from Fructus Aurantii by integrating natural deep eutectic solvents (NADES) with the COSMO-RS tool. We initially screened 18 types of NADESs through theoretical analysis (COSMO-RS) and experimental validation, ultimately identifying the optimal extraction solvent (Gly-Laa, molar ratio 1:3). Subsequently, the extraction process was optimized using a Box-Behnken design (BBD) approach. The results revealed that the optimal conditions were 10 % water content, a 5:1 (g/g) liquid/solid ratio, and 7 h extraction time, respectively—achieved a maximum yield of 2.82 %. This represents a 4.7-fold increase compared to steam distillation (0.6 %) and a 1.76-fold enhancement over petroleum ether extraction (1.6 %). Furthermore, the extraction mechanism was investigated through MD simulations and RDG analysis. The results indicated that NADES enhanced its interactions with limonene via hydrogen bonding (average bond length: 0.14–0.22 nm) and van der Waals forces. Finally, the biological activities of the extracted essential oil were analyzed and compared. The results revealed that the NADES-extracted essential oil exhibited superior antioxidant capacity (DPPH and ABTS scavenging rates >80 %), significant antibacterial efficacy against pathogens such as Staphylococcus aureus (inhibition zone diameter >10 mm), and demonstrated notable anti-tumor activity. In summary, the combination of NADES and COSMO-RS model is a sustainable and efficient essential oil extraction strategy.
研究领域:
绿色化学
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提取技术
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计算化学
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植物化学
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药理学
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分子生物学
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产品关联
DOI
高影响因子
MOLECULES
·
2022
·Vol. 27
·期 4
·1220
·
IF 4.927
Yanmin Qin,Xiaopeng Chen,Linlin Wang,Xiaojie Wei,Weijian Nong,Xuejuan Wei,Jiezhen Liang
The solubility of dehydroabietic acid in (−)-α-pinene, p-cymene, (−)-β-caryophyllene, (−)-α-pinene + p-cymene, (−)-β-caryophyllene + p-cymene and (−)-α-pinene + (−)-β-caryophyllene were determined using the laser monitoring method at atmospheric pressure. The solubility of dehydroabietic acid was positively correlated with temperature from 295.15 to 339.46 K. (−)-α-pinene, p-cymene, and (−)-β-caryophyllene were found to be suitable for the solubilization of dehydroabietic acid. In addition, the non-random two liquid (NRTL), universal quasi-chemical (UNIQUAC), modified Apelblat, modified Wilson, modified Wilson–van’t Hoff, and λh models were applied to correlate the determined solubility data. The modified Apelblat model gave the minor deviation for dehydroabietic acid in monosolvents, while the λh equation showed the best result in the binary solvents. A comparative analysis of compatibility between solutes and solvents was carried out using Hansen solubility parameters. The thermodynamic functions of ΔsolH0, ΔsolS0, ΔsolG0were calculated according to the van’t Hoff equation, indicating that the dissolution was an entropy-driven heat absorption process. The Conductor-like Screening Model for Real Solvents (COSMO-RS) combined with an experimental value was applied to predict the reasonable solubility data of dehydroabietic acid in the selected solvents systems. The interaction energy of the dehydroabietic acid with the solvent was analyzed by COSMO-RS.Keywords:COSMO-RS;solubility;dehydroabietic acid
研究领域:
化学工程
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物理化学
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产品关联
DOI
PubMed
高影响因子
AICHE JOURNAL
·
2019
·Vol. 65
·期 8
·e16625
·
IF 3.463
Zhen Song,Xutao Hu,Yageng Zhou,Teng Zhou,Zhiwen Qi,Kai Sundmacher
Although double salt ionic liquids (DSILs) offer significant advantages over classical two-ion ionic liquids as separation solvents, relevant studies are still scarce and a systematic DSIL selection method is thus highly desirable. In this contribution, a rational method for designing DSILs as extraction solvents is proposed and exemplified by the thiophene/ n -octane separation. The effects of additional degrees of freedom for DSIL design (i.e., double cations and/or anions and the ion ratio) on the thermodynamic properties are first analyzed by COSMO-RS. Then, a multilevel DSIL design method combining the prediction of infinite dilution thermodynamic properties, the estimation of physical properties, the evaluation of phase equilibrium behavior, and the experimental validation is proposed. By applying this method, [C 2 MIm][OAc] x [NO 3 ] 1- x ( x = [0, 1]) and [C 2 MIm][OAc] x [SCN] 1- x ( x = [0.70, 1]) are identified as promising DSIL solvents for the thiophene/ n -octane separation. Correspondingly, the liquid–liquid equilibria of {DSILs + thiophene + n -octane} with the designed DSILs are experimentally studied.
研究领域:
化学工程
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分离科学
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产品关联
DOI
高影响因子
FLUID PHASE EQUILIBRIA
·
2021
·
IF 2.775
Maolin Li,Yumin Liu,Mengya Li,Zeren Shang,Mingdi Liu,Dandan Han
The solubility of kaempferol monohydrate (KFM) in five mono-solvents (ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol) and three binary solvents (ethanol + water, 1-propanol + water, 2-propanol + water) was measured by gravimetric method from 283.15 K to 323.15 K at the pressure of 0.1 MPa. It is concluded that solubility of KFM is a function of temperature and solvent composition. Statistical method was used to analyze the impact of physicochemical parameters of solvents on solubility of KFM, indicating that comprehensive factors, such as the hydrogen bonding donor capacity and cohesive energy density would influence on solubility of KFM. In addition, the COSMO-RS model was used to explore the effects of solvent-solute interactions on solubility of KFM. Further, the solubility data was correlated by the modified Apelblat equation, λh equation, and van't Hoff equation, in which the modified Apelblat equation showed the best correlation result. In the final, the apparent thermodynamic properties ( Δ sol H 0 , Δ sol G 0 , Δ sol S 0 ) of KFM were derived through the van't Hoff equation, demonstrating the dissolution process of KFM in the selected solvents was endothermic. We hope the solubility of KFM determined in this work provides data can support for its further purification.
研究领域:
化学工程
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药学
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DOI
高影响因子
RSC Advances
·
2020
·Vol. 11
·期 2
·700-710
·
IF 3.119
Shurong Gao,Jiaxin Jin,Masroor Abro,Ruozhen Song,Miao He,Xiaochun Chen
Extractive denitrification (EDN) of shale oil using ionic liquids (ILs) as the extracting agent has good industrial prospects. In such processes, ILs with higher selectivity to N-compounds and lower solubility in shale oil are desired to improve the EDN efficiency, and reduce the loss of ILs and the contamination of shale oil. In the present study, we employed COSMO-RS to calculate the selectivity of 70 ILs to the typical N-compounds (pyridine, quinoline and indole). The influence of the IL structural characteristics, composition of shale oil and properties of N-compounds are investigated from a micro-level view with the σ-surface and σ-profile. The selectivity strongly depends on anionic species and it is greatly influenced by hydrogen bonding (HB) and π–π interaction between N-compounds and ILs. ILs composed of [H2PO4]− and [MeSO3]− with larger HB donor energy show higher selectivity to the basic N-compounds, while ILs composed of [Ac]− with larger π-electron cloud density show higher selectivity to the non-basic N-compounds. Anions with stronger polarity have lower solubility in shale oil. Moreover, experimental determinations of EDN indicated that [C4py][H2PO4]/[C4mim][H2PO4] and [C2mim][Ac]/[C2py][Ac] have good EDN performance for quinoline/pyridine with efficiency of 100% and for indole with efficiency of 91%, respectively. This work presents a theoretical basis to design and select ILs having higher selectivity for N-compounds and lower solubility in shale oil for use in denitrification.
研究领域:
化学工程
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材料科学
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产品关联
DOI
PubMed
高影响因子
Crystals
·
2022
·Vol. 12
·期 12
·1722
·
IF 2.67
Yujiang Xie,Genpei Shi,Jie Sun,Si Li,Wei Gao,Yimin Hu,Chang Zu,Weiwei Tang,Junbo Gong
Developing multicomponent crystal forms, especially cocrystals and salts, is becoming a promising pathway to improve the solubility and bioavailability of drugs. Herein, new multicomponent crystals of SHR0302, a new generation of Janus Kinase (JAK) inhibitor that suffers from poor solubility, were developed based on a cooperative approach of computational and experimental coformer screenings. Virtual screening methods, including the conductor-like screening model for realistic solvents (COSMO-RS) and molecular complementary (MC) analysis, were employed to predict the binding affinity between SHR0302 and selected coformers. The developed screening method was capable of reducing the screening database to 30 coformers from a total of 42 proposed coformers. The proof-of-concept experimental screening study was performed to demonstrate the efficiency of computational screening, wherein three new multicomponent crystalline forms were found and fully characterized by powder X-ray diffraction, thermal analysis, and IR and1H-NMR spectroscopy. Further, the measurements of the solubility property of these new multicomponent crystal forms reveal an apparent promotion compared with the drug alone. Finally, the receiver operator characteristic (ROC) curve was used to assess the prediction performance of the COSMO-RS model. It was found that the established screening model can effectively shorten the experimental screening time and efforts.Keywords:multicomponent crystals;cocrystals;COSMO-RS;cocrystal prediction;solubility enhancement
研究领域:
药物化学
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计算化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2016
·Vol. 18
·期 23
·6246-6254
·
IF 8.506
Yan-Rong Liu,Kaj Thomsen,Yi Nie,Suo-Jiang Zhang,Anne S. Meyer
In this work, 357 ionic liquids (ILs) formed from 17 cations and 21 anions were selected for evaluation of their ability to dissolve cellulose by COSMO-RS. In order to evaluate the predictive model and method, experimental measurements of the solubility of microcrystalline cellulose (MCC) in 7 of these ILs were also conducted. Predicted results from logarithmic activity coefficients were generally in good agreement with the experimental results. Three different models were used for describing cellulose, and the mid-monomer part of the cellotriose model was found to be closer to the experimental results than a neat glucose model and the model of the mid-dimer part of cellotetraose. Excess enthalpy calculations indicated that hydrogen-bond (H-bond) interactions between cellulose (i.e. the three cellulose models) and the 7 studied ILs are key factors for the solubility of cellulose, and the anions play a crucial role in the cellulose dissolution process. Importantly, the cations of methylimidazolium+, pyridinium+, ethylmorpholinium+ and methylpyrrolidinium+ structured with functional groups including ethyl, allyl, 2-hydroxylethyl, 2-methoxyethyl and acryloyloxypropyl, combined with anions Ac−, Dec−, HCOO−, Cl−, BEN−, DMPO4−, DEP−, DBP− and Br− were predicted to be the best for dissolving cellulose.
研究领域:
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）