Optimization of Silybin Extraction Using Natural Deep Eutectic Solvents and Mechanism Discussion Based on COSMO-SAC

YAO Jinhao; XIAO Lei; LI Chunlu; LIU Zhihan; GAO Jun; CHEN Yueyuan; CUI Zhifang

doi:10.13386/j.issn1002-0306.2021080054

Volume 43 Issue 8

Apr. 2022

Turn off MathJax

Article Contents

Abstract

References

Science and Technology of Food Industry > 2022 > 43(8): 219-227. > DOI: 10.13386/j.issn1002-0306.2021080054

YAO Jinhao, XIAO Lei, LI Chunlu, et al. Optimization of Silybin Extraction Using Natural Deep Eutectic Solvents and Mechanism Discussion Based on COSMO-SAC[J]. Science and Technology of Food Industry, 2022, 43(8): 219−227. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2021080054.

Citation:

PDF (6132 KB)

Optimization of Silybin Extraction Using Natural Deep Eutectic Solvents and Mechanism Discussion Based on COSMO-SAC

1.
College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China
2.
Guangxi Key Laboratory of Functional Phytochemicals Research and Utilization, Guangxi Institute of Botany, Guangxi Zhuang Autonomous Region and Chinese Academy of Sciences, Guilin 541006, China

More Information

Received Date: August 04, 2021
Available Online: February 16, 2022

Graphical Abstract

Abstract

Abstract

As a bioactive component extracted from the seed of milk thistle, silymarin has many pharmacological functions, such as liver-protective and cholagogic effect. It is categorized as a class of flavonoids, among which silybin is one of the main components. Efficient extraction of silybin with a type of new and green solvent natural deep eutectic solvent (NADES), as well as mechanism discussion were explored in this study. With the degreased milk thistle seed shell powder as raw material and using HPLC for silybin analysis, NADES composed of choline chloride/1,4-butanediol was screened out as optimal solvent for silybin extraction. On the basis of single factor experiments, Box-Behnken Design from response surface methodology was used for process optimization. The generated model predicated that the highest silybin yield of 4.29% would be achieved with solid-liquid ratio of 1:20 g/mL, at 77 °C for 5.6 h. The result from verification experiment was about 4.30%, which fitted well with the prediction. Then, based on conductor-like screening model for segment activity coefficient (COSMO-SAC), structure and energy optimization of silybin and solvent were attempted. The logarithms of infinite dilution activity coefficients in the two solvents, chloride/1,4-butanediol and the traditional organic solvent ethanol, were −6.922 and −6.043, and the intermolecular interaction energies were −51.62 and −25.47 kJ/mol, respectively, which would provide insight into the mechanism explaining performance difference of the solvents during extraction.

FullText(HTML)

References (37)

References

[1]	FOZOUNI L, PALANG M. Antifungal effects of Silybum marianum extract individually and in combination with fluconazole on clinical Candida isolates in northern Iran[J]. Journal of Kermanshah University of Medical Sciences,2018,22(4):1−5.
[2]	TSIAOUSI A, VASILAKOGLOU I, SPYRIDON D. Comparison of milk thistle (Silybum marianum) and cardoon (Cynara cardunculus) productivity for energy biomass under weedy and weed-free conditions[J]. European Journal of Agronomy,2019,110:125924. doi: 10.1016/j.eja.2019.125924
[3]	WANG Y P. Pharmacopoeia of the People’s Republic of China[J]. China Standardization,2015(4):60−63.
[4]	刘立伟. 水飞蓟宾的提取方法及药理活性研究进展[J]. 河北北方学院学报(自然科学版),2019,35(10):51−56. [LIU L Y. Research advance in extraction methods and pharmacological activities of silymarin[J]. Journal of Hebei North University (Natural Science Edition),2019,35(10):51−56.
[5]	ZI X L, AGARWAL R. Silibinin decreases prostate-specific antigen with cell growth inhibition via G1 arrest, leading to differentiation of prostate carcinoma cells: Implications for prostate cancer intervention[J]. Proceedings of the National Academy of Sciences of the United States of America,1999,96(13):7490−7495. doi: 10.1073/pnas.96.13.7490
[6]	SINGH R P, SHARMA G, DHANALAKSHMI S, et al. Suppression of advanced human prostate tumor growth in athymic mice by silibinin feeding is associated with reduced cell proliferation, increased apoptosis, and inhibition of angiogenesis[J]. Cancer Epidemiology Biomarkers and Prevention,2003,12(9):933−939.
[7]	KELLY E H, ANTHONY R T, DENNIS J B. Flavonoid antioxidants: Chemistry, metabolism and structure-activity relationships[J]. Journal of Nutritional Biochemistry,2002,13(10):572−584. doi: 10.1016/S0955-2863(02)00208-5
[8]	KIM J Y, KIM J Y, JENIS J, et al. Tyrosinase inhibitory study of flavonolignans from the seeds of Silybum marianum (milk thistle)[J]. Bioorganic & Medicinal Chemistry,2019,27(12):2499−2507.
[9]	FERYSIUK K, WJCIAK K M, MATERSKA M. Phytochemical profile of Silybum marianum (L.) Gaertn. and Graminis rhizoma and its influence on the bioactivity and shelf life of industrially produced pâté[J]. International Journal of Food Science & Technology,2020,55(4):1586−1598.
[10]	张丽芳, 林霞, 冯星海, 等. 超声辅助有机溶剂回流提取水飞蓟籽中水飞蓟宾工艺的优化[J]. 中成药,2019,41(1):185−188. [ZHANG L F, LIN X, FENG X H, et al. Optimization of ultrasonic assisted organic solvent reflux extraction of silymarin from silymarin seeds[J]. Chinese Traditional Patent Medicine,2019,41(1):185−188. doi: 10.3969/j.issn.1001-1528.2019.01.036
[11]	杨靖. 高活性水飞蓟油的提取及其微胶囊化研究[D]. 镇江: 江苏大学, 2020: 2−8. YANG J. Study on the extraction of high active Silybum marianum oil and its microencapsulation[D]. Zhenjiang: Jiangsu University, 2020: 2−8.
[12]	ZENG W C, ZAENG Z, GAO H, et al. Chemical composition, antioxidant, and antimicrobial activities of essential oil from pine needle (Cedrus deodara)[J]. Journal of Food Science,2012,77(7):824−829. doi: 10.1111/j.1750-3841.2012.02767.x
[13]	阮洪生, 贾桂燕, 吴志军, 等. 超声辅助双水相体系提取水飞蓟中水飞蓟宾的工艺优选[J]. 黑龙江八一农垦大学学报,2017,29(1):59−63,146. [RUAN H S, JIA G Y, WU Z J, et al. Optimization of ultrasonic-assisted aqueous two-phase system extraction silymarin from Silybum marianum (L.) Gaertn[J]. Journal of Heilongjiang Bayi Agricultural University,2017,29(1):59−63,146. doi: 10.3969/j.issn.1002-2090.2017.01.013
[14]	ABBOTT A P, BOOTHBY D, CAPPER G D L, et al. Deep eutectic solvents formed between choline chloride and carboxylic acids: Versatile alternatives to ionic liquids[J]. Am Chem Soc,2004,126(29):9142−9147. doi: 10.1021/ja048266j
[15]	PAIVA A, CRAVEIRO R, AROSO I, et al. Natural deep eutectic solvents–solvents for the 21st century[J]. ACS Sustainable Chemistry & Engineering,2014,2(5):1063−1071.
[16]	ABBOTT A P, CAPPER G, GRAY S. Design of improved deep eutectic solvents using hole theory[J]. Chemphyschem,2006,7(4):803−806. doi: 10.1002/cphc.200500489
[17]	HADJ-KALI M K, SALLEH Z, ALI E, et al. Separation of aromatic and aliphatic hydrocarbons using deep eutectic solvents: A critical review[J]. Fluid Phase Equilibria,2017,448:152−167. doi: 10.1016/j.fluid.2017.05.011
[18]	HUANG Y, FENG F, JIANG J, et al. Green and efficient extraction of rutin from tartary buckwheat hull by using natural deep eutectic solvents[J]. Food Chemistry,2017,221:1400−1405. doi: 10.1016/j.foodchem.2016.11.013
[19]	ZDANOWICZ M, WILPISZEWSKA K, SPYCHAJ T. Deep eutectic solvents for polysaccharides processing. A review[J]. Carbohydrate Polymers,2018,200:361−380. doi: 10.1016/j.carbpol.2018.07.078
[20]	LI D, DOU L L, GUO L, et al. Comprehensive evaluation of deep eutectic solvents in extraction of bioactive natural products[J]. ACS Sustainable Chemistry and Engineering,2016,4(4):2405−2411. doi: 10.1021/acssuschemeng.6b00091
[21]	CHOI Y H, VAN SPRONSEN J, DAI Y, et al. Are natural deep eutectic solvents the missing link in understanding cellular metabolism and physiology?[J]. Plant Physiology,2011,156(4):1701−1705. doi: 10.1104/pp.111.178426
[22]	ESPINO M, FERNÁNDEZ M D L Á, GOMEZ F J V, et al. Natural designer solvents for greening analytical chemistry[J]. TrAC-Trends in Analytical Chemistry,2016,76:126−136. doi: 10.1016/j.trac.2015.11.006
[23]	KLAMT A, SCHÜÜRMANN G. COSMO: A new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient[J]. Journal of the Chemical Society Perkin Transactions,1993,2(5):799−805.
[24]	ZUROB E, CABEZAS R, VILLARROEL E, et al. Design of natural deep eutectic solvents for the ultrasound-assisted extraction of hydroxytyrosol from olive leaves supported by COSMO-RS[J]. Separation and Purification Technology,2020,248:117054. doi: 10.1016/j.seppur.2020.117054
[25]	FANALIA C, POSTAA S D, DUGOA L, et al. Choline-chloride and betaine-based deep eutectic solvents for green extraction of nutraceutical compounds from spent coffee ground[J]. Journal of Pharmaceutical and Biomedical Analysis,2020,189:113421. doi: 10.1016/j.jpba.2020.113421
[26]	CUI Z F, DJOCKI A V, YAO J H, et al. COSMO-SAC-supported evaluation of natural deep eutectic solvents for the extraction of tea polyphenols and process optimization[J]. Journal of Molecular Liquids,2021,328:115406. doi: 10.1016/j.molliq.2021.115406
[27]	孙晶. 水飞蓟果托总黄酮的分离纯化及其生物活性研究[D]. 沈阳: 沈阳农业大学, 2017: 28−39. SUN J. Separation and purification of total flavonoids from milk thistle fruit receptalcle and their bioactivity evaluation[D]. Shenyang: Shenyang Agricultural University, 2017: 28−39.
[28]	中华人民共和国卫生部药典委员会. 中华人民共和国药典(一部)[M]. 北京: 化学工业出版社, 2010: 82. Chinese Pharmacopoeia Commission. Chinese pharmacopoeia[M]. Beijing: Chemical Industry Press, 2010: 82.
[29]	ZHANG L Z, XU D M, GAO J, et al. Extraction and mechanism for the separation of neutral N-compounds from coal tar by ionic liquids[J]. Fuel,2017,194:27−35. doi: 10.1016/j.fuel.2016.12.095
[30]	丁珊, 魏立纲, 王艳涛, 等. 有机溶质在双烷烃咪唑醋酸盐离子液体中无限稀释活度系数的测定[J]. 大连工业大学学报,2016,35(1):29−32. [DING S, WEI L G, WANG Y T, et al. Determination of infinite dilution activity coefficient of organic solutes in bisalkane imidazole acetate ionic liquids[J]. Journal of Dalian University of Technology,2016,35(1):29−32.
[31]	BOYS S F, BERNARDI F. The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors[J]. Molecular Physics,2002,100(1):65−73. doi: 10.1080/00268970110088901
[32]	张连正. 煤热解油杂环含氮组分萃取用离子液体分子设计与分离实验研究[D]. 青岛: 山东科技大学, 2017: 23-32. ZHANG L Z. Study on the design of ionic liquids and its extraction experiment for the nitrogen heterocyclic components of coal pyrolysis oil[D]. Qingdao: Shandong University of Science and Technology, 2017: 23-32.
[33]	王涛, 翟晨, 李梦瑶, 等. 基于氨基功能化离子液体萃取番茄中超氧化物歧化酶的研究[J/OL]. 北京: 食品科学, (2020-12-08)[2021-07-28]. http://kns.cnki.net/kcms/detail/11.2206.TS.20201207.1504.088.html. WANG T, ZHAI C, LI M Y, et al. Extraction of SOD from tomato based on amino functionalized ionic liquid[J/OL]. Beijing: Food Science, (2020-12-08)[2021-07-28]. http://kns.cnki.net/kcms/detail/11.2206.TS.20201207.1504.088.html.
[34]	汪绪龙, 朱红薇, 贾阳月, 等. 水飞蓟种壳中水飞蓟素提取及生物活性的研究[J]. 广州化工,2017,45(23):97−99. [WANG X L, ZHU H W, JIA Y Y, et al. Study on extraction and bioactivity of silymarin from seed shell[J]. Guangzhou Chemical Industry,2017,45(23):97−99. doi: 10.3969/j.issn.1001-9677.2017.23.035
[35]	BARANSE O, MARIA G M. Alkanediol-based deep eutectic solvents for isolation of terpenoids from citrus essential oil: Experimental evaluation and COSMO-RS studies[J]. Separation and Purification Technology,2019,227:115707. doi: 10.1016/j.seppur.2019.115707
[36]	DELLEY B. From molecules to solids with the DMol³ approach[J]. The Journal of Chemical Physics,2000,113(18):7756−7764. doi: 10.1063/1.1316015
[37]	KLAMT A. COSMO-RS: From quantum chemistry to fluid phase thermodynamics and drug design[M]. Amsterdam: Elsevier Science, 2005.

Supplements (0)

Cited By

Cited by

Periodical cited type(7)

1.	肖志刚，高岩，毕崇慧，周廉瞬，元沅，段玉敏，王鹏. 海藻酸钠添加量对米糠蛋白理化性质和结构特性的影响. 现代食品科技. 2025(04): 63-70 .
2.	孙保剑，王笛，崔相勇，王立华，刘军. 素肉排组织蛋白生产工艺. 食品工业. 2024(06): 65-69 .
3.	寇锟，杜艳，姚飞，贾立奥，孟丹阳，陈复生. 高水分大豆组织蛋白的品质特性及营养功能研究进展. 粮食与油脂. 2024(08): 1-6 .
4.	刘远琨，高婷婷，张丽，高泽岳，陈晨，乌玉洁，付宸睿. 挤压型植物基人造肉的来源及加工工艺研究进展. 粮食加工. 2024(04): 80-82+99 .
5.	张智霞，马鑫淼，许慧，车丽娜，李玉，王稳航，王楠. 人造肉技术的研究现状及展望. 食品工业科技. 2024(17): 416-425 . 本站查看
6.	尹思睿，冯娇，杨晓宇，李良. 植物蛋白复配对植物肉品质的影响. 轻工学报. 2024(05): 18-28 .
7.	陶相锦，黄立强，王冬玲，马文平，马世岷. 植物蛋白肉生产的关键因素分析. 食品安全导刊. 2023(30): 160-162 .