漆酚酯键合SiO2色谱柱分离纯化天麻素及其热力学研究

doi:10.3969/j.issn.0253-2417.2022.05.005

林产化学与工业 ›› 2022, Vol. 42 ›› Issue (5): 30-36.doi: 10.3969/j.issn.0253-2417.2022.05.005

漆酚酯键合SiO₂色谱柱分离纯化天麻素及其热力学研究

曾磊¹, 易冯梅¹, 曹宇², 史伯安¹^,², 雷福厚¹^,*()

1. 广西民族大学化学化工学院；广西林产化学与工程重点实验室；林产化学与工程国家民委重点实验室; 广西林产化学与工程协同创新中心，广西南宁 530006
2. 湖北民族大学化学与环境工程学院，湖北恩施 445000

收稿日期:2021-06-23 出版日期:2022-10-28 发布日期:2022-11-02
通讯作者: 雷福厚 E-mail:leifuhou@163.com
作者简介:雷福厚，教授，博士生导师，主要从事天然药物分离研究；E-mail: leifuhou@163.com
曾磊(1996—)，男，湖北武汉人，硕士生，研究方向为生漆的改性与应用
基金资助:
国家自然科学基金资助项目(31460172);广西科技基地和人才专项(AD18126005);广西林产化学与工程重点实验室开放项目(GXFC2004)

Separation and Purification of Gastrodin by Urushiol Methacrylate Bonded SiO₂ Column and Its Thermodynamic Study

Lei ZENG¹, Fengmei YI¹, Yu CAO², Bo'an SHI¹^,², Fuhou LEI¹^,*()

1. College of Chemistry and Chemical Engineering, Guangxi Minzu University; Guangxi Key Laboratory of Chemistry and Engineering of Forest Products; Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission; Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Nanning 530006, China
2. School of Chemical and Environmental Engineering, Hubei Minzu Unirensity, Enshi 445000, China

Received:2021-06-23 Online:2022-10-28 Published:2022-11-02
Contact: Fuhou LEI E-mail:leifuhou@163.com

摘要/Abstract

摘要：

利用天麻素(GAS)的结构类似物苯基-β-D-吡喃葡萄糖苷(PGL)和4-甲氧基苯基-β-D-吡喃葡萄糖苷(MGL)作为竞争分子，考察漆酚酯键合SiO₂色谱柱对天麻素的分离性能，并对其分离过程进行热力学分析。研究发现：漆酚酯键合SiO₂色谱柱分离天麻素的最佳色谱条件为以乙腈-0.05%磷酸水溶液(体积比3∶97)为流动相，流速0.4 mL/min，柱温25 ℃，检测波长220 nm，进样量20 mL。在该色谱条件下，漆酚酯键合SiO₂色谱柱对PGL-GAS的分离度达到7.8，对MGL-GAS的分离度达到14.0。热力学研究发现：分离过程中PGL-GAS和MGL-GAS的ΔH、ΔΔH和ΔΔG均小于0，ΔΔS均大于0，表明漆酚酯键合SiO₂色谱柱对天麻素及其结构类似物的分离过程是一个自发的放热过程，分离既受熵驱动又受焓驱动；随着柱温的升高，分析物的保留因子与分离度均有所下降。天麻粗提物经漆酚酯键合SiO₂色谱柱纯化后，杂质明显降低，天麻素的纯度由粗提物中的17.06% 提升至93.45%，纯化过程中漆酚酯键合SiO₂色谱柱表现出良好的分离性能和稳定性。

关键词: 漆酚酯键合SiO₂色谱柱, 天麻素, 分离, 纯化, 热力学

Abstract:

Using phenyl-β-D-glucopyranoside(PGL) and 4-methoxyphenyl-β-D-glucopyranoside(MGL) as the competitive molecules owing to its structural analogues of gastrodin(GAS), the separation performance of GAS by usurushiol methacrylate bonded SiO₂ column was investigated, and its thermodynamics behavior was also analyzed. The result showed that the optimum separation conditions of urushiol methacrylate bonded SiO₂ chromatographic column were as follows: 0.05% phosphoric acid water solution(3∶97, volume ratio), flow rate 0.4 mL/min, column temperature 25 ℃, detection wavelength 220 nm and injection volume 20 L. Under this chromatographic condition, the resolution of urushiol methacrylate bonded SiO₂ chromatographic column to PGL-GAS and MGL-GAS was 7.8 and 14.0, respectively. The thermodynamic studies revealed that the ΔH, ΔΔH and ΔΔG values of both PGL-GAS and MGL-GAS were negative, and the ΔΔS values were greater than zero, during the process of separation. It indicated that the separation of GAS and its structural analogues on urushiol methacrylate bonded SiO₂ column was a thermodynamic spontaneous process, which was driven both by the entropy and enthalpy. The retention and resolution of analytes decrease with the increasing column temperature. After the crude extract was purified by usurushiol methacrylate bonded SiO₂ column, the impurities were significatly reduced, and the purity of gastrodin increased from 17.06% to 93.45%. The urushiol methacrylate bonded SiO₂ column exhibited good separation performance and stability during the separation process.

Key words: urushiol methacrylate bonded SiO₂ column, gastrodin, separation, purification, thermodynamic

中图分类号:

TQ35

曾磊, 易冯梅, 曹宇, 史伯安, 雷福厚. 漆酚酯键合SiO₂色谱柱分离纯化天麻素及其热力学研究[J]. 林产化学与工业, 2022, 42(5): 30-36.

Lei ZENG, Fengmei YI, Yu CAO, Bo'an SHI, Fuhou LEI. Separation and Purification of Gastrodin by Urushiol Methacrylate Bonded SiO₂ Column and Its Thermodynamic Study[J]. Chemistry and Industry of Forest Products, 2022, 42(5): 30-36.

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参考文献 19

1	国家药典委员会. 中华人民共和国药典[M]. 2020年版北京: 中国医药科技出版社, 2020: 59.
	Chinese Pharmacopoeia Commission . Pharmacopoeia of the People's Republic of China[M]. 2020 ed 北京: China Medical Science Press, 2020: 59.
2	SHAO Q H , ZHANG X L , CHEN Y , et al. Anti-neuroinflammatory effects of 20C from Gastrodia elata via regulating autophagy in LPS-activated BV-2 cells through MAPKs and TLR4/Akt/mTOR signaling pathways[J]. Molecular Immunology, 2018, 99, 115- 123.
3	曹韦, 陈小鹏, 刘娜, 等. 天麻素对过氧化氢损伤大鼠原代皮层神经元保护作用研究[J]. 亚太传统医药, 2016, 12 (24): 17- 20.
	CAO W , CHEN X P , LIU N , et al. Protective effect of gastrodine on H₂O₂ injured rat primary cortical neurons[J]. Asia-Pacific Traditional Medicine, 2016, 12 (24): 17- 20.
4	DING Y F , BAO X M , LAO L F , et al. p-Hydroxybenzyl alcohol prevents memory deficits by increasing neurotrophic factors and decreasing inflammatory factors in a mice model of Alzheimer's disease[J]. Journal of Alzheimer's Disease, 2019, 67 (3): 1007- 1019.
5	SHI A H, XIANG J M, HE F Y, et al. The phenolic components of gastrodia elata improve prognosis in rats after cerebral ischemia/reperfusion by enhancing the endogenous antioxidant mechanisms[J/OL]. Oxidative Medicine and Cellular Longevity, 2018(2): 7642158[2021-05-15]. https://doi.org/10.1155/2018/7642158.
6	张玲, 杨萍, 姜永良, 等. 天麻素通过蛋白激酶B/p38丝裂原活化蛋白激酶信号通路抑制H9c2心肌细胞凋亡[J]. 解剖学报, 2019, 50 (1): 40- 48.
	ZHANG L , YANG P , JIANG Y L , et al. Gastrodin inhibits apoptosis of H9c2 cardiomyocytes through protein kinase B/p38mitogen actived protein kinase signaling pathway[J]. Acta Anatomica Sinica, 2019, 50 (1): 40- 48.
7	ZHANG Y , WANG C , YU B , et al. Gastrodin protects against ethanol-induced liver injury and apoptosis in HepG2 cells and animal models of alcoholic liver disease[J]. Biological and Pharmaceutical Bulletin, 2018, 41 (5): 670- 679.
8	ZHANG T H , HUANG C M , GAO X , et al. Gastrodin inhibits high glucose-induced human retinal endothelial cell apoptosis by regulating the SIRT1/TLR4/NF-κBp65 signaling pathway[J]. Molecular Medicine Reports, 2018, 17 (6): 7774- 7780.
9	CHEN J , GU Y T , XIE J J , et al. Gastrodin reduces IL-1β-induced apoptosis, inflammation, and matrix catabolism in osteoarthritis chondrocytes and attenuates rat cartilage degeneration in vivo[J]. Biomed Pharmacother, 2018, 97, 642- 651.
10	HE P, HU Y W, HUANG C Z, et al. N-butanol extract of Gastrodia elata suppresses inflammatory responses in lipopolysaccharide-stimulated macrophages and complete freund's adjuvant-(CFA-) induced arthritis rats via inhibition of MAPK signaling pathway[J/OL]. Evidence-based Complementary and Alternative Medicine, 2020: 1658618[2021-05-15]. https://doi.org/10.11555/2020/1658618.
11	谢世虎. 天麻的鉴定和药理作用研究[J]. 中国卫生产业, 2016, 13 (21): 167- 169.
	XIE S H . Identification and pharmacological action of Gastrodia elata[J]. China Health Industry, 2016, 13 (21): 167- 169.
12	陈琛, 李新生, 周建军, 等. 天麻素提取纯化及检测技术研究进展[J]. 陕西理工学院学报(自然科学版), 2013, 29 (3): 69- 74.
	CHEN C , LI X S , ZHOU J J , et al. Research progress on extraction, purification and determination technology for gastrodin[J]. Journal of Shaanxi University of Technology(Natural Science Edition), 2013, 29 (3): 69- 74.
13	LIANG Z Y , ZHANG J Y , HUANG Y C , et al. Identification of flavonoids in Dendrobium huoshanense and comparison with those in allied species of Dendrobium by TLC, HPLC and HPLC coupled with electrospray ionization multistage tandem MS analyses[J]. Journal of Separation Science, 2019, 42 (5): 1088- 1104.
14	QIU H D , LIANG X , SUN M , et al. Development of silica-based stationary phases for high performance liquid chromatography[J]. Analytical & Bioanalytical Chemistry, 2011, 399, 3307- 3322.
15	于世林. 高效液相色谱方法及应用[M]. 3版北京: 化学工业出版社, 2018.
	YU S L . High Performance Liquid Chromatography and Its Application[M]. 3rd ed Beijing: Chemical Industry Press, 2018.
16	曾磊, 曹宇, 雷福厚, 等. 漆酚酯键合硅胶液相色谱固定相的制备与应用[J]. 色谱, 2020, 38 (11): 1257- 1262.
	ZENG L , CAO Y , LEI F H , et al. Preparation and application of urushiol methacrylate-bonded silica liquid chromatographic stationary phase[J]. Chinese Journal of Chromatography, 2020, 38 (11): 1257- 1262.
17	QIU H X , ARMSTRONG D W , BERTHOD A . Thermodynamic studies of a zwitterionic stationary phase in hydrophilic interaction liquid chromatography[J]. Journal of Chromatography A, 2013, 1272, 81- 89.
18	BOGUSLAW B , RENATA G , MICHEL M . Thermodynamic description of retention mechanism in liquid chromatography[J]. Accreditation & Quality Assurance, 2011, 16 (5): 237- 244.
19	COLE L A , DORSEY J G , DILL K A . Temperature dependence of retention in reversed-phase liquid chromatography.1:Stationary-phase considerations[J]. Analytical Chemistry, 1992, 64 (13): 1317- 1323.

分析物 analyte	van't Hoff方程 van't Hoff equations	R²	ΔH/ (kJ·mol^-1)	ΔS/ (J·mol^-1·K^-1)	ΔG/ (kJ·mol^-1)	ΔΔH/ (kJ·mol^-1)	ΔΔS/ (J·mol^-1·K^-1)	ΔΔG/ (kJ·mol^-1)
GAS	lnk=246.67/T-3.95	0.96	-2.07	-16.46	2.84
PGL	lnk=452.94/T-2.44	0.98	-3.77	-3.91	-2.60
PGL-GAS	lnα=232.85/T+1.42	0.94				-1.94	11.81	-5.46
MGL	lnk=782.36/T-2.91	0.97	-6.50	-7.82	-4.17
MGL-GAS	lnα=574.09/T+0.92	0.99				-4.77	7.65	-7.05

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漆酚酯键合SiO₂色谱柱分离纯化天麻素及其热力学研究

Separation and Purification of Gastrodin by Urushiol Methacrylate Bonded SiO₂ Column and Its Thermodynamic Study

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