磁性温敏分子印迹材料用于药用植物中富集单一成分——芒柄花黄素的分离与富集

doi:10.11949/0438-1157.20200346

化工学报 ›› 2020, Vol. 71 ›› Issue (10): 4711-4719.DOI: 10.11949/0438-1157.20200346

磁性温敏分子印迹材料用于药用植物中富集单一成分——芒柄花黄素的分离与富集

何家垣¹(),蒋壮飞¹,马蓉蓉¹,杨莉莉¹,李清瑶¹,谭玲²,陈志涛¹,张起辉¹()

^1.重庆大学化学化工学院，重庆 400044
^2.重庆大学药学院，重庆 400044

收稿日期:2020-04-01 修回日期:2020-05-22 出版日期:2020-10-05 发布日期:2020-10-05
通讯作者: 张起辉
作者简介:何家垣（1995-），男，硕士研究生，201818021132@cqu.edu.cn
基金资助:
国家自然科学基金项目(819734512);医工联合项目(2019CDYGYB027);2019技术预见与制度创新项目(cstc2019jsyj-yzysbAX00204);重庆市科委项目(cstc2018jcyjAX06615);重庆市教育委员会科学技术研究项目(KJZD-K2018001036);重庆市研究生创新基金项目(CYS180337);中央高校基本科研业务费(2019CDXYHG00131)

Magnetic temperature-sensitive molecularly imprinted materials for separation and enrichment of single component of formononetin in medicinal plants

Jiayuan HE¹(),Zhuangfei JIANG¹,Rongrong MA¹,Lili YANG¹,Qingyao LI¹,Ling TAN²,Zhitao CHEN¹,Qihui ZHANG¹()

^1.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
^2.School of Pharmacy, Chongqing University, Chongqing 400044, China

Received:2020-04-01 Revised:2020-05-22 Online:2020-10-05 Published:2020-10-05
Contact: Qihui ZHANG

摘要/Abstract

摘要：

以四氧化三铁（Fe₃O₄）纳米粒子为支撑材料，模板选用芒柄花黄素，温敏功能单体和辅助功能单体分别选用N-异丙基丙烯酰胺（NIPAM）和甲基丙烯酸（MAA），制备出磁性和温度双响应型分子印迹材料（MTMIPs），并结合高效液相色谱法（HPLC）将其用于红车轴草中芒柄花黄素的定向萃取研究。利用扫描电镜（SEM）、透射电镜（TEM）、红外光谱（FT-IR）、热重分析（TGA）、磁性分析（VSM）等手段对MTMIPs进行表征，随后对其温敏及吸附性能进行考察。结果表明，MTMIPs为核壳型结构，热稳定性好，具有良好的吸附性能（16.43 mg/g）和温敏特性，对芒柄花黄素的吸附动力学符合准二级动力学模型，吸附过程符合Langmuir单分子层吸附。HPLC检测结果显示MTMIPs可用于从复杂样品中分离富集芒柄花黄素。

关键词: 磁性温敏材料, 分子印迹材料, 聚合物, 吸附剂, 纳米材料

Abstract:

The magnetic and temperature double response molecularly imprinted polymers for formononetin-specific adsorption (MTMIPs) were successfully prepared by using Fe₃O₄ as supporting matrix, formononetin as template, N-isopropyl acrylamide as the thermo-sensitive type functional monomer and methacrylic acid as auxiliary functional monomer. SEM, TEM, FT-IR, TGA and magnetic analysis were used to characterize the structure of MTMIPs, and then their adsorption properties and reproducibility were investigated. The results showed that MTMIPs was a core-shell structure with good thermal stability, good adsorption performance (16.43 mg/g) and fast adsorption performance. The adsorption kinetics of formononetin was consistent with the quasi-second-order kinetics model, and the adsorption process was consistent with the Langmuir monolayer adsorption with good reproducibility. HPLC test results show that MTMIPs can be used to separate and enrich formononetin from complex samples.

Key words: magnetic temperature-sensitive materials, molecular imprinted materials, polymers, adsorbents, nanomaterials

中图分类号:

R 917

何家垣, 蒋壮飞, 马蓉蓉, 杨莉莉, 李清瑶, 谭玲, 陈志涛, 张起辉. 磁性温敏分子印迹材料用于药用植物中富集单一成分——芒柄花黄素的分离与富集[J]. 化工学报, 2020, 71(10): 4711-4719.

Jiayuan HE, Zhuangfei JIANG, Rongrong MA, Lili YANG, Qingyao LI, Ling TAN, Zhitao CHEN, Qihui ZHANG. Magnetic temperature-sensitive molecularly imprinted materials for separation and enrichment of single component of formononetin in medicinal plants[J]. CIESC Journal, 2020, 71(10): 4711-4719.

图/表 9

图1 磁性温敏MTMIPs的合成过程

Fig.1 Schematic diagram of the synthesis process of magnetic temperature-sensitive MTMIPs

图2 Fe3O4@SiO2和MTMIPs 电镜表征图：Fe3O4@SiO2扫描电镜图（a）；MTMIPs 扫描电镜图（b）；MTMIPs 透射电镜图（c）

Fig.2 SEM images of Fe3O4@SiO2NPs (a), MTMIPs (b), and TEM of MTMIPs (c)

图3 MTMIPs与Fe3O4@SiO2的FT-IR图（a）；MTMIPs 的TGA分析曲线（b）；MTMIPs与Fe3O4的磁性分析（VSM）曲线（1 Oe=79.5775 A/m）（c）；Fe3O4、MTMIPs与Fe3O4@SiO2的XRD谱图（d）

Fig.3 FT-IR spectra of MTMIPs and Fe3O4@SiO2 (a); TGA analysis curves of MTMIPs (b); Magnetization curves of MTMIPs and Fe3O4 nanoparticles (c); XRD pattern of Fe3O4, Fe3O4@SiO2 and MTMIPs nanoparticles(d)

图4 MTMIPs的温敏吸附图

Fig.4 Temperature-sensitive adsorption spectra of MTMIPs

表1 等温吸附模型拟合参数

Table 1 The fitting parameters of isothermal adsorption model

材料	Langmuir		Freundlich
材料	R²	K_L/(ml/mg)	R²	α	m
MTNIPs	0.994	0.010	0.951	0.364	0.537
MTMIPs	0.966	0.005	0.805	0.185	0.798

表2 吸附动力学模型拟合参数

Table 2 The fitting parameters of adsorption kinetics model

材料	Pseudo-first-order		Pseudo-second-order
材料	K₁/min^-1	R²	K₂/(g/(mg·min))	R²
MTNIPs	0.053	0.860	0.050	0.955
MTMIPs	0.061	0.918	0.007	0.988

图5 MTMIPs选择性考察的HPLC图（a）;MTMIPs和MTNIPs对芒柄花黄素、染料木素和大豆苷元选择性考察（b）

Fig.5 HPLC diagrams of MTMIPs selectivity study (a); Selection adsorption of formononetin, genistein and daidzein by MTMIPs and MTNIPs (b)

表3 选择性研究中的方法学考察数据

Table 3 Data of methodological examination in selective research

Samples	Regression analysis					Precision
Samples	Standard curves	Correlation coefficient	Linear range/（μg/ml)	LOD/(μg/ml)	LOQ/(μg/ml)	Intra-day RSD/%	Inter-day RSD/%
daidzein	y=521.8x-66.35	0.992	5—100	0.015	0.045	0.61	1.52
formononetin	y=520.5x-202.7	0.993	5—100	0.017	0.063	0.89	1.28
genistein	y=481.2x-34.31	0.992	5—100	0.027	0.125	0.62	1.54

图6 MTMIPs实际应用HPLC图：（1）芒柄花黄素母液HPLC图;（2）洗脱液的HPLC图;（3）粗提物经萃取后的HPLC图;（4）粗提物的HPLC图

Fig.6 HPLC diagrams of the MTMIPs practical application: (1) HPLC diagram of the formononetin mother solution; (2) The HPLC diagram of MTMIPs eluents; (3) HPLC diagram of crude extracts after MTMIPs absorbed; (4) HPLC diagram of crude extracts from Trifolium pratense L.

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磁性温敏分子印迹材料用于药用植物中富集单一成分——芒柄花黄素的分离与富集

Magnetic temperature-sensitive molecularly imprinted materials for separation and enrichment of single component of formononetin in medicinal plants

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