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

doi:10.11949/0438-1157.20200346

Abstract

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

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

CLC Number:

R 917

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.

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.

Figures/Tables 9

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

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

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)

Fig.4 Temperature-sensitive adsorption spectra of MTMIPs

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

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

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

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

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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