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天然深共熔溶剂
PROCESS BIOCHEMISTRY · 2019 · IF 2.883

One-pot preparation of quercetin using natural deep eutectic solvents

Yuan-Yuan Zang,Xi Yang,Zhi-Gang Chen,Tao Wu

In this study, we have established a green and efficient preparation method of quercetin. Rutin was first extracted from Sophora japonica using natural deep eutectic solvents (NADESs), then hydrolyzed into quercetin by rutin degrading enzyme (RDE) obtained from germinated tartary buckwheat in situ. Rutin solubility tests showed that most of the 11 NADESs increased the solubility of rutin by 67-3116 times compared to water. Thus, NADESs could be prior candidate to extract rutin. Extraction efficiency of rutin varied with different NADESs, and a maximum of 291.57 mg g −1 was achieved in NADES ChGly, which was prepared by mixing choline chloride and glycerol at a molar ratio of 1:1. After that hydrolysis was performed directly in extraction system by adding RDE with degradation rate of up to 8.36 mg min -1 ·L -1 . Our findings suggest that preparation of quercetin using NADESs was simple and feasible to operate, environmentally friendly, efficient, and inspired the preparation method of bioactive components from a new perspective.

研究领域: 植物化学 · 绿色化学 · 生物工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Natural deep eutectic solvent: A novel and green mordant for the natural dye

Zhe Jiang,Guolin Zheng,Yifan Cui,Wenda Wang,Xianqin Shang,Yimin Wei,Man Zhou,Ping Wang,Yuanyuan Yu,Qiang Wang

Applying natural dye is a green and available approach for the dyeing and simultaneous functionalizing of textiles. However, the commonly used mordant of metal ions to improve the dyeing effect results in massive toxic wastewater production, which decreases the environmentally friendly characteristics. In this work, the mordant and water substitute ability of choline chloride-ethylene glycol natural deep eutectic solvent (NADES), defined as the mixture of two or more primary metabolites at a particular composition becoming liquids via H-bond forces, was investigated during the dyeing process because it has been used as a green extraction and stability agent for the natural dye. To this end, the NADES and metal ion were used in three mordant dyeing wool and cotton processes of Platycodon Grandiflorus root dye, and the color and functionalization effect were compared to verify the method advance. The result indicated that natural deep eutectic solvent had a better effect as a mordant than the metal ion by enhancing the dye solubility, the dye uptake rate of fiber, and the dye polymerization trend via rich H-bonds among fiber, dye, and NADES. The dyed textile had an excellent functional performance, including UV resistance, antibacterial, antioxidation, and burning difficulty, with the preferable fastness. This method also showed good universality for other natural dyes and NADESs. Compared to the existing mordant dyeing technologies, the proposed technology had lower chemical reagent usage, cost, and energy consumption, whose residual solvent had good reusability for at least 10 times and better degradability. Overall, this paper supplied a potential and green approach using NADESs as alternatives to metal ions for the mordant dyeing textile using natural dye.

研究领域: 材料科学 · 纺织工程 · 环境科学
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Molecular Catalysis · 2025 · IF 4.9

Insights into the multiple positive effects of natural deep eutectic solvents for highly efficient synthesis of diacylglycerol through enzymatic esterification

Duan Zhou,Mouming Zhao,Xiaorong Zhong,Xuefeng Chen,Ning Liu,Daoming Li

Diacylglycerol (DAG) has extensive applications in many fields due to its health benefits and amphiphilic property. Herein, enzymatic esterification of oleic acid and glycerol in natural deep eutectic solvents (NADESs) was employed to synthesize DAG. Firstly, Novozym 435 and choline chloride: glycerol (ChCl:Gly) system were selected as the most appropriate immobilized lipase and NADES for DAG synthesis. Subsequently, the reaction conditions of Novozym 435-catalyzed esterification in ChCl:Gly system were optimized, and the content of DAG reached as high as 67.08 wt % ± 0.79 wt % under the optimal conditions (molar ratio of oleic acid to glycerol of 1:4, reaction temperature of 50 °C, enzyme dosage of 4 wt % with respect to the total weight of substrates, reaction time of 7 h). At last, the reasons why ChCl:Gly could induce a higher DAG content were explored from thermodynamics, water activity and reaction interface. The results showed that ChCl:Gly system could absorb the generated water during esterification and increase the reaction interface, thus beneficial to DAG synthesis. Moreover, the activation energy of DAG production (55.36 kJ/mol) was significantly lower than that of monoacylglycerol (MAG) production (62.60 kJ/mol), leading to the priority of DAG production. Briefly, the multiple beneficial effects of NADESs on lipase-catalyzed esterification collectively contributed to an enhancement of DAG content in esterification products.

研究领域: 生物化学 · 食品科学
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LANGMUIR · 2024 · IF 3.7

pH-Responsive Natural Deep Eutectic Solvent: An Environmental Alternative for the Sustainable Extraction of Petroleum Hydrocarbons from Oil Sands

Shaoyang Liu,Jie Qi,Yuzhe Li,Ruiyao Wang,Li Wang,Hongsheng Lu,Zheng Zhang

The reversible shift in polarity or hydrophilicity/hydrophobicity of switchable solvents greatly simplifies the recovery capacity in extraction applications. However, the environmental and economical advantages of switchable solvents are not significant. In this work, we designed three pH-responsive natural deep eutectic solvents (NADESs) by combining the pH-switchable solvent fatty acids with the nonswitchable solvent ethyl lactate (EL), followed by the exploration of the solubilization and separation performance of these NADESs for petroleum hydrocarbons. EL can be miscible in fatty acids and water; however, when in contact with both at the same time, EL binds to fatty acids through stronger intermolecular hydrogen bonds, whereas when fatty acids are deprotonated to fatty acid salts, EL can bind to water. The deprotonation/protonation of fatty acids could reversibly change the NADES hydrophilicity, and the recovery of NADES HA/EL could exceed 95% after three cycles. Furthermore, after extractive separation of simulated oils of differing complexity, NADES HA/EL was selected as the best extractant. Compared with the extraction of oil sands with a single solvent, NADES provides better wetting of the sand surface, better stripping efficiency of the heavy components that adhere to the surface of oil sands, and better dispersion of the stripped petroleum hydrocarbons. Petroleum hydrocarbons can be separated by NaOH-induced hydrophilic changes in NADES, which can be regenerated upon the addition of HCl. The recovered NADES showed good reusability in the cleaning of oil sands. The oil removal rates were 96.9%, 94.4%, and 91.9% after three cycles of cleaning with NADES at 25 °C. This method is expected to expand the application of nonswitchable solvents in sustainable extraction.

研究领域: 环境科学 · 化学工程 · 能源技术
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JOURNAL OF MOLECULAR LIQUIDS · 2025 · IF 5.2

A novel efficient method for the simultaneous recycle of amygdalin and oil from bitter apricot kernels: Ultrasonication based on natural deep eutectic solvent

Jiawei Bao,Lu Li,Lanzhen Ban,Xia Pi,Chunmei Li

Bitter apricot kernel (BAK) is a good source of amygdalin and oil. However, the current production process faces challenges including the inability to simultaneously extract amygdalin and oil, and the risk of toxicity due to amygdalin contamination in the oil. A novel, green and efficient ultrasonication-assisted extraction (UAE) method based on a natural deep eutectic solvent (NADES) composed of choline chloride-lactic acid (CC-LA) was established for simultaneous extraction of amygdalin and oil from BAK for the first time. Under optimizing conditions of a liquid-to-solid ratio of 18 mL/g, ultrasonic power of 420 W, temperature of 42 °C, and extraction time of 32 min, the highest yields of amygdalin and oil were achieved at 10.22 ± 0.04 % and 45.64 ± 0.24 %, respectively. The yield of amygdalin in UAE based on CC-LA was twice and nineteen times that of methanol (90 %, v/v) and water, respectively. Meanwhile, the yield of oil obtained by this new method was comparable to that by organic solvent extraction methods. The fatty acid composition of oil obtained by this method was consistent with that by conventional extraction methods. Scanning electron microscopy (SEM) analysis indicated that CC-LA and UAE had a synergistic effect on the destruction of BAK’s microstructure, which facilitated the recovery of amygdalin and oil. Molecular dynamics simulation results showed that amygdalin in CC-LA reached a higher solvent-accessible surface area (SASA) and formed more hydrogen bonds with longer lifetimes and greater stability. Furthermore, this new method demonstrated potential for industrial scalability.

CAS / MDL: 67-48-1
研究领域: 食品科学 · 植物化学 · 药学
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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Natural deep eutectic solvents efficient catalytic conversion of cellulose to total reducing sugars (TRS)

Hongwei Ren,Ruiquan Gong,Meiyu Li,Yize Liu,Hongyu Zhu,Can Wang,Erhong Duan

Lignocellulosic biomass contains about 45% cellulose . The total reducing sugars (TRS) obtained from lignocellulosic materials is beneficial to the sustainable development. Natural deep eutectic solvents (NADESs) provide an attractive alternative for the “green” conversion of cellulose. In this work, series of amino acids based NADESs with FeCl 3 . 6H 2 O as ligands catalyst were synthesized and characterized by in situ IR, FT-IR, 1 H NMR and TG-DTA. NADESs showed great thermal stability. The efficient hydrolysis performance of cellulose in NADESs was investigated under mild conditions. The influencing factors such as the type of NADESs, reaction temperature, reaction time, and FeCl 3 . 6H 2 O addition on the TRS yield were studied. The optimized process conditions for hydrolyzing cellulose in L-Proline/ Ethylene glycol/FeCl 3 . 6H 2 O were molar ratio 1: 2: 1, reaction time 120 min and temperature 120 °C. The yield of total reducing sugar was 66.7%. The conversion mechanism was also investigated.

研究领域: 生物化学 · 可再生资源与环境科学
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JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY · 2019 ·Vol. 96 ·期 6 ·671-679 · IF 1.72

An Efficient Strategy for the Production of Epoxidized Oils: Natural Deep Eutectic Solvent-Based Enzymatic Epoxidation

Tianyu Zhang,Yunjian Ma,Chin Ping Tan,Frank Hollmann,Jianrong Wang,Bo Yang,Yonghua Wang

Poor H 2 O 2 -resistance by enzymes is a key bottleneck in the epoxidation process of oil by enzymatic methods. In this study, the stability of three lipases, from Aspergillus oryzae lipase (AOL), Aspergillus fumigatus lipase B (AflB), and marine Janibacter (MAJ1), in the presence of H 2 O 2 was evaluated in different types of natural deep eutectic solvents (NADES). This stability was strengthened significantly in the NADES compared to the buffer. Specifically, AOL retained 84.7% of its initial activity in the presence of choline chloride/sorbitol (1:1 M ratio) and 3 mol L −1 H 2 O 2 after 24 h incubation at 40°C. In addition, the two-phase epoxidation process was optimized with AOL in ChCl/sorbitol to reach up to 96.8% conversion under the optimized conditions (molar ratio of octanoic acid/H 2 O 2 /C=C-bonds = 0.3:1.5:1, enzyme loading of 15 U g −1 of soybean oil, ChCl/sorbitol content of 70.0% of the weight of hydrophilic phase, and reaction temperature of 50°C). Moreover, the lipase dispersed in NADES retained approximately 66% of its initial activity after being used for seven batch cycles. Overall, NADES-based enzymatic epoxidation is a feasible and promising strategy for the synthesis of epoxidized oils.

研究领域: 生物化学 · 绿色化学
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JOURNAL OF CHROMATOGRAPHIC SCIENCE · 2024 · IF 1.5

Optimization of Extraction of Four Components from Radix Scrophulariae with Natural Deep Eutectic Solvents and Evaluation of Extract’s Antioxidant Activity

Huang Ping,Zhou Yanxia,Ruan Fei,Sun Jianyu,Shen Jinglin,Chen Hongmei

In this research, eight natural deep eutectic solvents (NaDESs) consisting of food-grade ingredients were screened for the extraction of four bioactive compounds (acteoside, cinnamic acid, angoroside C and harpagoside) from radix scrophulariae (RS). Among these NaDESs, Proline-Glycerol NaDES with higher comprehensive score was selected. The Criteria Importance Through Intercriteria Correlation (CRITIC) was applied to calculate the information entropy and the weight of indexes, and figured out a comprehensive score. The weights of acteoside, cinnamic acid, angoroside C and harpagoside were 0.369, 0.172, 0.241 and 0.218, respectively. Response surface methodology (RSM) mathematical model was used to optimize the extraction parameters. The optimal extraction parameters were as follows: extraction time with 42.21 min, NaDES concentration with 52.89%, solid-to-liquid ratio with 1 : 37.05 g/mL and the predicted value of comprehensive score was 0.885. Under the optimal condition, the comprehensive score was 0.903 ± 0.005. Finally, the antioxidant activity experiment revealed that the 1,1-Diphenyl-2-picrylhydrazyl · radical scavenging activity and hydroxyl radical scavenging activity of the extract at 2.0 mg/mL and 1.5 mg/mL were approximately equal to those of ascorbic acid, respectively. The results showed that the extraction condition optimized by RSM combined with CRITIC was reasonable and dependable, and the extract of radix scrophulariae exhibited good antioxidant activity.

研究领域: 药用植物学 · 分析化学 · 生物化学
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LWT-FOOD SCIENCE AND TECHNOLOGY · 2021 · IF 4.952

An alternative strategy for enhancing stability and antimicrobial activity of catechins by natural deep eutectic solvents

Pengfei Zhou,Daobang Tang,Jinhao Zou,Xuping Wang

The low stability and loss of antimicrobial activity of catechins limited their application in food preservation. In this study, four kinds of catechins including (−)-epicatechin (EC), (−)-epigallocatechin (EGC), (−)-epicatechin-3-gallate (ECG), and (−)-epigallocatechin-3-gallate (EGCG) were selected as model compounds. Natural deep eutectic solvents (NADES) are a new generation of green solvents that have attracted much attention due to their unique characteristics. The effects of NADES on the stability and antimicrobial activity of catechins were investigated in the present study. Eight typical NADES, especially choline chloride/glycerol (ChG), were found to significantly enhance the thermal and storage stability of catechins. This finding accounted for by hydrogen bonding network formation between ChG and catechins, confirmed by FT-IR and 2D NMR analysis. Additionally, ChG decreased the minimum inhibitory concentration of catechins on Gram-positive and Gram-negative bacteria, which may be associated with its stabilizing property. The stability of catechins combined with NADES revealed their potential of applications in the food industry.

研究领域: 食品科学 · 生物化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Partitioning behavior of rutin in novel liquid–liquid biphasic systems formed by choline chloride/ maltose natural deep eutectic solvents and n-propanol

Feng Liu,Li Chen,Kangling Yin,Taotao Fan,Zongcheng Yan

The development of promising environmentally friendly extraction tools has been one of the hottest topics in green chemistry. Among these, natural deep eutectic solvents (NADESs) as green extraction media have received widespread recognition. In this paper, with the aim of exploring the potential applications of NADESs in the extraction field, water-soluble n -propanol was used to form liquid–liquid biphasic systems with choline chloride/ maltose NADESs. The phase behavior of those systems was designed by adjusting the molar proportion of the hydrogen bond acceptors (HBA): hydrogen bond donors (HBD) and temperature. This allows for the systems tailored to the specific requirements of the target molecule, as shown by their application in the extraction of rutin. Investigation of the distribution behavior of rutin suggested that the partition coefficient and the extraction efficiency of rutin in the bottom phase increase significantly with decreasing temperature and increasing HBA : HBD molar ratio. And with the temperature of 288.15 K, the highest TLL of NADES (ChCl: Mal = 1:2) + NPA + water system achieved higher E% of 94.27 %. The interaction force between NADES and rutin was studied using the Hansen solubility parameter, it turned out that Δ δ i , j Δδi,j of the 2:1 and 1:2 M ratio of NADES was only 8.91, 5.12, which meaning that there may be strong interactions between NADES and rutin. In addition, the hydrogen bond ( Δ δ H ΔδH ) of the NADES (HBA: HBD = 1:2) was 25.47, which is greater than other interaction force, revealing that the hydrogen bond is the maximum force between rutin and the NADES (HBA: HBD = 1:2). The energy ( Δ G T ΔGT ), enthalpy ( Δ H T ΔHT ) and entropy ( Δ S T ΔST ) calculated from the partition data of rutin was consistent with the free energy ( Δ G C ) (ΔGC) , enthalpy ( Δ H C ) (ΔHC) and entropy ( Δ S C ) (ΔSC) changes of system, which confirmed that the driving force of the phase separation of the system drives the transfer of rutin to the lower phase. In addition, we used eco-friendly water to regenerate NADES. The recovery efficiency of rutin was explored while NADES was reused in three cycles. This result showed there was no change observed in the extraction capability for rutin in those system. Finally, a larger aggregate of size 1315 nm was observed by dynamic light scattering, which furthermore demonstrated that the hydrogen bonding interaction between NADES (HBA: HBD = 1:2) and rutin is the main driving force tool for enhancing rutin partitioning. This method presents a newly system constructed by NADES and NPA for the green extraction, revealing the feasibility of the system for rutin extraction and facilitating industrial applications.

研究领域: 化学工程 · 环境科学 · 植物化学
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INDUSTRIAL CROPS AND PRODUCTS · 2021 · IF 5.645

Simultaneous transformation and extraction of resveratrol from Polygonum cuspidatum using acidic natural deep eutectic solvent

Jian-Dong Wang,Li-Na Fu,Li-Tao Wang,Zi-Hui Cai,Yan-Qiu Wang,Qing Yang,Yu-Jie Fu

Resveratrol, as a natural antioxidant, has been studied widely for its antioxidant, anti-inflammatory, anti-apoptotic, and anticancer properties. In this study, a strategy was developed to transform and extract resveratrol from Polygonum cuspidatum on the basis of NADES (natural deep eutectic solvent). In the series of adjustments and optimizations by single-factor experimental, the optimum NADES system (choline chloride to oxalic acid was 1:1) and other experimental conditions were determined, including water content of NADES, solid-liquid ratio, extraction time, extraction temperature and ultrasonic power. At the same time, RSM combined with BBD further optimized the experimental process, the results obtained by RSM optimization showed that the resveratrol yield of 12.31 mg/g was achieved when solid-liquid ratio was 1:50, temperature was 75℃ and time was 80 min. Meantime, the conversion efficiency of polydatin was 96.11 % and the content of resveratrol increased 6-fold higher than that of untreated sample. The kinetic of extraction and thermodynamic analysis were performed at different extraction temperatures to examine the temperature on the impact of the resveratrol extraction from P. cuspidatum . Ethyl acetate was used for back extraction in order to achieve the recycling of solvent and the recovery of resveratrol from NADES. The results showed that ethyl acetate had a good extraction effect and NADES still had a high capacity to convert and extract resveratrol after three cycles. In addition, the extracts exhibited superior antioxidant activity with higher content of recovered resveratrol. This established process can therefore be used to extract and recover resveratrol from plants as an environmental, pollution-free alternative approach.

研究领域: 植物化学 · 药用植物学 · 分析化学
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ChemCatChem · 2019 ·Vol. 12 ·期 4 ·989-994 · IF 4.495

Natural Deep Eutectic Solvents as Performance Additives for Peroxygenase Catalysis

Yunjian Ma,Yongru Li,Shahid Ali,Peilin Li,Wuyuan Zhang,Marine C. R. Rauch,Sébastien J.-P. Willot,Doris Ribitsch,Young Hae Choi,Miguel Alcalde,Frank Hollmann,Yonghua Wang

Graphical Natural Deep Eutectic Solvents : Envisioned bienzymatic cascade for the selective oxyfunctionalisation of ethyl benzene or cis-ß-methylstyrene comprising the evolved peroxygenase from Agrocybe aegerita (r Aae UPO) and choline oxidase from Arthrobacter nicotianae ( An ChOx) to provide r Aae UPO with H 2 O 2 . Natural deep eutectic solvents (NADES) are proposed as alternative solvents for peroxygenase-catalysed oxyfunctionalization reactions. Choline chloride-based NADES are of particular interest as they can serve as solvent, enzyme-stabiliser and sacrificial electron donor for the in situ H 2 O 2 generation. This report provides the first proof-of-concept and basic characterisation of this new reaction system. Highly promising turnover numbers for the biocatalysts of up to 200,000 have been achieved.

研究领域: 生物化学 · 酶工程 · 绿色化学
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