Novel Deep Eutectic Solvent Based on Levulinic Acid and 1,4-Butanediol as an Extraction Media for Bioactive Alkaloid Rutaecarpine

Deep eutectic solvents (DESs) are increasingly receiving interest as a new type of green and sustainable alternative to hazardous organic solvents. In this work, a novel DES based on levulinic acid (La) and 1,4-butanediol (Buta) as an extraction media was developed for extracting the bioactive alkaloid rutaecarpine from the unripe fruits of Tetradium ruticarpum. 24 different DESs consisting of choline chloride, betaine, sugar alcohols, organic acids, amides, and sugars were prepared and tailored to test their extraction efficiency. After initial screening, a hydrophilic DES composed of La and Buta with 1:0.5 molar ratio containing 25% water was tailored for the highest extraction efficiency, followed by the optimizations of molar ratio and water content. The interaction between the molecules of La-Buta DES was investigated by nuclear magnetic resonance spectroscopy in order to confirm its deep eutectic supermolecular structure feature. The extraction conditions were optimized by single-factor experiments, including extraction temperature, extraction time, and solid-liquid ratio. The developed La-Buta DES extraction procedure was successfully applied for the analysis of rutaecarpine in Chinese patent medicines containing the unripe fruits of T. ruticarpum. The excellent property of La-Buta DES indicated its potential as a promising green solvent instead of conventional organic solvent for the extraction of rutaecarpine from the unripe fruits of T. ruticarpum, and that it can used as a sustainable and safe extraction media for other applications.

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Optimizing Ultrasound-Assisted Deep Eutectic Solvent Extraction of Bioactive Compounds from Chinese Wild Rice

Molecules ◽

10.3390/molecules24152718 ◽

2019 ◽

Vol 24 (15) ◽

pp. 2718 ◽

Cited By ~ 8

Author(s):

Jia Zeng ◽

Yuqing Dou ◽

Ning Yan ◽

Na Li ◽

Huaibao Zhang ◽

...

Keyword(s):

Bioactive Compounds ◽

Wild Rice ◽

Choline Chloride ◽

Extraction Procedure ◽

Radical Scavenging ◽

Deep Eutectic Solvent ◽

Total Phenolic ◽

Extraction Temperature ◽

Green Solvents ◽

Ultrasound Assisted

In this study, deep eutectic solvents (DESs) were used for the ultrasound-assisted extraction (UAE) of valuable bioactive compounds from Chinese wild rice (Zizania spp.). To this end, 7 different choline chloride (CC)-based DESs were tested as green extraction solvents. Choline chloride/1,4-butanediol (DES-2) exhibited the best extraction efficiency in terms of parameters such as the total flavonoid content (TFC), total phenolic content (TPC), and free radical scavenging capacity (DPPH● and ABTS●+). Subsequently, the UAE procedure using 76.6% DES-2 was also optimized: An extraction temperature of 51.2 °C and a solid–liquid ratio of 37.0 mg/mL were considered optimal by a Box–Behnken experiment. The optimized extraction procedure proved efficient for the extraction of 9 phenolic and 3 flavonoid compounds from Chinese wild rice as determined by quantification based on ultra-performance liquid chromatography–triple quadrupole tandem mass spectrometry (UPLC-QqQ-MS). This work, thus, demonstrates the possibility of customizing green solvents that offer greater extraction capacity than that of organic solvents.

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Continuous Integrated Process of Biodiesel Production and Purification—The End of the Conventional Two-Stage Batch Process?

Energies ◽

10.3390/en14020403 ◽

2021 ◽

Vol 14 (2) ◽

pp. 403

Author(s):

Matea Bačić ◽

Anabela Ljubić ◽

Martin Gojun ◽

Anita Šalić ◽

Ana Jurinjak Tušek ◽

...

Keyword(s):

Extraction Efficiency ◽

Deep Eutectic Solvent ◽

International Standards ◽

Biodiesel Production ◽

Molar Ratio ◽

Process Conditions ◽

Integrated Process ◽

Free Glycerol ◽

Mass Ratio ◽

Glycerol Content

In this research, optimization of the integrated biodiesel production process composed of transesterification of edible sunflower oil, catalyzed by commercial lipase, with simultaneous extraction of glycerol from the reaction mixture was performed. Deep eutectic solvents (DESs) were used in this integrated process as the reaction and extraction media. For two systems, choline chloride:glycerol (ChCl:Gly) and choline chloride:ethylene glycol (ChCl:EG), respectively, the optimal water content, mass ratio of the phase containing the mixture of reactants (oil and methanol) with an enzyme and a DES phase (mass ratio of phases), and the molar ratio of deep eutectic solvent constituents were determined using response surface methodology (RSM). Experiments performed with ChCl:Gly resulted in a higher biodiesel yield and higher glycerol extraction efficiency, namely, a mass ratio of phases of 1:1, a mass fraction of water of 6.6%, and a molar ratio of the ChCl:Gly of 1:3.5 were determined to be the optimal process conditions. When the reaction was performed in a batch reactor under the optimal conditions, the process resulted in a 43.54 ± 0.2% yield and 99.54 ± 0.19% glycerol extraction efficiency (t = 2 h). Unfortunately, the free glycerol content was higher than the one defined by international standards (wG > 0.02%); therefore, the process was performed in a microsystem to enhance the mass transfer. Gaining the same yield and free glycerol content below the standards (wG = 0.0019 ± 0.003%), the microsystem proved to be a good direction for future process optimization.

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Application of Deep Eutectic Solvent (DES) as a Reaction Media for the Esterification of Acrylic Acid with n-Butanol

International Journal of Chemical Reactor Engineering ◽

10.1515/ijcre-2014-0164 ◽

2015 ◽

Vol 13 (3) ◽

pp. 389-393 ◽

Cited By ~ 3

Author(s):

Emine Sert

Keyword(s):

Catalytic Activity ◽

Acrylic Acid ◽

Batch Reactor ◽

Choline Chloride ◽

Deep Eutectic Solvent ◽

Molar Ratio ◽

Catalyst Loading ◽

Toluene Sulfonic Acid ◽

Effects Of Temperature ◽

Reaction Media

Abstract Within the framework of green chemistry, catalysts should be met different criteria such as biodegradability, recyclability, flammability, non-toxicity and low price. Acidic deep eutectic solvent (DES) have been synthesized for this purpose, by mixing para-toluene sulfonic acid and choline chloride. The catalytic activity of DES was studied in the esterification of acrylic acid with n-butanol. The usage of DES as catalyst is simple, safe and cheap. The effects of temperature, catalyst loading, n-butanol/acrylic acid molar ratio on the conversion of acrylic acid were performed. The batch reactor experiments were carried out at temperatures of 338, 348, 358 and 368 K, molar ratio of butanol to acrylic acid of 1, 2,3 and catalyst loading of 10, 15, 20 and 90 g/L. 90.2% of acrylic acid conversion was achieved at a temperature of 358 K and catalyst loading of 20 g/L. Reusability of DES was investigated. Reusability and catalytic activity makes DES efficient as catalyst.

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Deep Eutectic Solvent-Based Microwave-Assisted Extraction of Baicalin from Scutellaria baicalensis Georgi

Journal of Chemistry ◽

10.1155/2018/9579872 ◽

2018 ◽

Vol 2018 ◽

pp. 1-10 ◽

Cited By ~ 6

Author(s):

Hui Wang ◽

Xiaodi Ma ◽

Qibin Cheng ◽

Xiaoli Xi ◽

Liwei Zhang

Keyword(s):

Maximum Yield ◽

Deep Eutectic Solvent ◽

Extraction Yield ◽

Scutellaria Baicalensis ◽

Molar Ratio ◽

Extraction Temperature ◽

Microwave Assisted Extraction ◽

Scutellaria Baicalensis Georgi ◽

Microwave Assisted ◽

Assisted Extraction

Deep eutectic solvents (DESs) have attracted significant attention as green media for the extraction and separation of natural compounds from Chinese medicine. In this study, a hydrophobic DESs-based microwave-assisted extraction (MAE) was successfully used to efficiently extract baicalin from Scutellaria baicalensis Georgi. Firstly, DecA: N4444-Cl (DES-1 , molar ratio 1 : 2) was screened and selected as the most appropriate DES by comparing the extraction yield in different hydrophobic DESs. Based on the extraction yield of baicalin, response surface methodology (RSM) was employed to model and optimize the parameters (extraction temperature, liquid-solid ratio, and extraction time). Furthermore, the maximum yield of 106.96 mg·g−1 was achieved under optimum conditions in DES-containing aqueous solutions (33 vol% water content), which reached a similar level that was conducted using the pharmacopoeia procedure (104.94 mg·g−1). These results indicated that the proposed method is an excellent alternative for the extraction of baicalin.

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The Anodic Behaviour of Bulk Copper in Ethaline and 1-Butyl-3-Methylimidazolium Chloride

Applied Sciences ◽

10.3390/app9204401 ◽

2019 ◽

Vol 9 (20) ◽

pp. 4401 ◽

Cited By ~ 4

Author(s):

Karim ◽

Aziz ◽

Brza ◽

Abdullah ◽

Kadir

Keyword(s):

Electrochemical Impedance ◽

Choline Chloride ◽

Metallic Copper ◽

Electrochemical Techniques ◽

Deep Eutectic Solvent ◽

Molar Ratio ◽

Interfacial Region ◽

Dissolution Mechanism ◽

Spectroscopic Techniques ◽

Electrochemical Dissolution

The anodic dissolution of bulk metallic copper was conducted in ionic liquids (ILs)—a deep eutectic solvent (DES) ((CH3)3NC2H4OH) comprised of a 1:2 molar ratio mixture of choline chloride Cl (ChCl), and ethylene glycol (EG)—and imidazolium-based ILs, such as C4mimCl, using electrochemical techniques, such as cyclic voltammetry, anodic linear sweep voltammetry, and chronopotentiometry.To investigate the electrochemical dissolution mechanism, electrochemical impedance spectroscopy (EIS) was used. In addition to spectroscopic techniques, for instance, UV-visible spectroscopy, microscopic techniques, such as atomic force microscopy (AFM), were used. The significant industrial importance of metallic copper has motivated several research groups to deal with such an invaluable metal. It was confirmed that the speciation of dissolved copper from the bulk phase at the interface region is [CuCl3]− and [CuCl4]2− in such chloride-rich media, and the EG determine the structure of the interfacial region in the electrochemical dissolution process. A super-saturated solution was produced at the electrode/solution interface and CuCl2 was deposited on the metal surface.

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Deep Eutectic Solvents Based Ultrasonic Extraction of Polysaccharides from Edible Brown Seaweed Sargassum horneri

Journal of Marine Science and Engineering ◽

10.3390/jmse8060440 ◽

2020 ◽

Vol 8 (6) ◽

pp. 440

Author(s):

Jinggui Nie ◽

Danting Chen ◽

Yanbin Lu

Keyword(s):

Choline Chloride ◽

Brown Seaweed ◽

Deep Eutectic Solvents ◽

Significant Inhibition ◽

Hot Water ◽

Ultrasonic Extraction ◽

Sargassum Horneri ◽

Molar Ratio ◽

Extraction Temperature

In this work, a method for ultrasonic extraction of polysaccharides from Sargassum horneri using deep eutectic solvents was proposed. The studied deep eutectic solvents were composed of choline chloride, 1,2-propanediol and water. Based on the single-factor experiment results, four experimental factors were systematically evaluated, giving the optimal extraction conditions as follows: molar ratio of choline chloride to 1,2-propanediol of 1:2, water content of 30% (v/v), solid-liquid ratio of 1:30 (g/mL), and the extraction temperature of 70 °C. Fourier transform infrared spectroscopy and X-ray diffraction were utilized to investigate changes in the chemical characteristic of extracted polysaccharides. The results indicated that deep eutectic solvents had stronger protein and calcium carbonate removal ability than that of a conventional hot water extraction method. Moreover, in vitro antioxidant activity tests exhibited that the obtained polysaccharides had significant inhibition effects on DPPH and ABTS radicals. The proposed deep eutectic solvents assisted ultrasonic extraction protocol was considered to be a green, fast and effective protocol for extracting polysaccharides from Sargassum horneri.

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Study on the Effect of Deep Eutectic Solvent Liquid Phase Microextraction on Quality Standard, Antitussive, and Expectorant of Sangbaipi Decoction

Journal of Analytical Methods in Chemistry ◽

10.1155/2021/9999406 ◽

2021 ◽

Vol 2021 ◽

pp. 1-11

Author(s):

Lijing Li ◽

Yuejie Wang ◽

Fangxin Liu ◽

Yang Xu ◽

Huiwei Bao

Keyword(s):

Liquid Phase ◽

Extraction Method ◽

Choline Chloride ◽

Deep Eutectic Solvent ◽

Quality Standard ◽

Molar Ratio ◽

Phenol Red ◽

Liquid Ratio ◽

Liquid Phase Microextraction ◽

Low Efficiency

The SD was extracted with a new green eutectic solvent, and the extraction method of TCM decoction was developed. In the quantitative analysis by HPLC, choline chloride phenol was selected as the eutectic solvent, THF was used as the extractant, and investigation of DES type, DES molar ratio, DES-to-THF ratio, vortex time, and material-to-liquid ratio was carried out. The experimental results showed that the optimal extraction method was as follows: the molar ratio of DES was 1 : 3, and the material-liquid ratio was 5 : 1200 (mL/μL). The volume ratio of DES to THF was 1200 : 800 (μL), the vortex time was 3 min, and the extraction was repeated two times. The eutectic solvent liquid phase microextraction method was adopted to optimize the extraction method of SD and reduce the complicated processing, long time, and low efficiency of traditional methods. At the same time, in the mouse ammonia water inducing cough and phenol red excretion and expectorant experiments, SD high- and medium-dose groups have a significant inhibitory effect on the frequency of antitussive in mice and both can increase the excretion of phenol red to varying degrees, indicating that SD has good cough-relieving and expectorant effect. The present study suggests a scientific basis and basis for the clinical research and quality standard formulation of SD.

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Structural elucidation of lignins from corncob acid hydrolysis residue by enzymatic mild acidolysis and deep eutectic solvent pretreatment

BioResources ◽

10.15376/biores.15.2.4362-4372 ◽

2020 ◽

Vol 15 (2) ◽

pp. 4362-4372

Author(s):

Na Li ◽

Chao Cao ◽

Lupeng Shao ◽

Chao Wang ◽

Yu Liu ◽

...

Keyword(s):

Acid Hydrolysis ◽

31P Nmr ◽

Structural Characteristics ◽

Choline Chloride ◽

Deep Eutectic Solvent ◽

Gel Permeation Chromatography ◽

Structural Features ◽

Molar Ratio ◽

Efficient Extraction ◽

Hydrolysis Residue

Achieving mild and efficient extraction of high purity lignin from corncob acid hydrolysis residue is essential for efficient lignin application. In this study, enzymatic/mild acidolysis lignin (EMAL) and deep eutectic solvent (DES)-lignin were extracted from corncob acid hydrolysis residue. The structural features of the two lignin fractions were investigated by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), and 31P-nuclear magnetic resonance (31P-NMR). The highest DES-lignin yield of 58.8 wt% was achieved at 120 °C with a choline chloride-to-lactic acid (ChCl-to-Lac) molar ratio of 1:10 and a reaction time of 12 h. The FTIR analysis indicated a higher amount of guaiacyl units in EMAL than DES-lignin. Furthermore, condensation and fragmentation occurred simultaneously under DES pretreatment, but the fragmentation reaction was dominant. The structural characteristics investigated will allow for more effective lignin usage.

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Deacidification of Crude Rice Bran Oil (CRBO) to Remove FFA and Preserve γ-Oryzanol Using Deep Eutectic Solvents (DES)

Materials Science Forum ◽

10.4028/www.scientific.net/msf.964.109 ◽

2019 ◽

Vol 964 ◽

pp. 109-114 ◽

Cited By ~ 2

Author(s):

Siti Zullaikah ◽

Nizar Dwi Wibowo ◽

I Made Gede Eris Dwi Wahyudi ◽

M. Rachimoellah

Keyword(s):

Hydrogen Bond ◽

Rice Bran ◽

Rice Bran Oil ◽

Choline Chloride ◽

Deep Eutectic Solvents ◽

Molar Ratio ◽

Extraction Temperature ◽

Hydrogen Bond Donor ◽

Hydrogen Bond Acceptor ◽

C 50

High content of free fatty acids (FFA) in crude rice bran oil (CRBO) needs to be separated through deacidification. Generally, deacidification process that is widely used are chemical and physical processes which causes the loss of bioactive compounds (γ-oryzanol) and un-environmentally friendly. The liquid-liquid extraction (LLE) using deep eutectic solvents (DES) to remove FFA and preserve g-oryzanol would be implemented in this study. DES with different hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) with certain molar ratio such as Choline Chloride (ChCl)-Ethylene glycol 1:2 (DES I), ChCl-Glycerol 1:1 (DES II), ChCl-Urea 1:2 (DES III), ChCl-Oxalic acid 1:2 (DES IV), and Betaine Monohydrate-Glycerol 1:8 (NADES) were used as solvent to extract FFA from dewaxed/degummed RBO (DDRBO) for certain extraction time (30, 60, 120, 180, and 240 min) and extraction temperature (30°C, 40°C, 50°C, 60°C, and 70°C) under stirring (200 rpm). Deacidification using DES I for 240 min. and temperature of 50 °C was the optimum solvent to remove FFA (19.03 ± 2.33 %) and preserve g-oryzanol (recovery of g-oryzanol was 51.30 ± 1.77 %). The results also revealed that the longer time of extraction would be increased removal of FFA and decreased recovery of g-oryzanol. The higher temperature of extraction would be increased removal of FFA. In this work, temperature of 50 °C was the best extraction temperature of FFA since DES has highest solubility at this temperature.

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