CIESC Journal ›› 2020, Vol. 71 ›› Issue (10): 4711-4719.doi: 10.11949/0438-1157.20200346

• Separation engineering • Previous Articles     Next Articles

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. 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:2020-07-07
  • Contact: Qihui ZHANG E-mail:201818021132@cqu.edu.cn;qhzhang@cqu.edu.cn

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

CLC Number: 

  • R 917

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LangmuirFreundlich
R2KL/(ml/mg)R2αm
MTNIPs0.9940.0100.9510.3640.537
MTMIPs0.9660.0050.8050.1850.798

Table 2

The fitting parameters of adsorption kinetics model"

材料Pseudo-first-orderPseudo-second-order
K1/min-1R2K2/(g/(mg·min))R2
MTNIPs0.0530.8600.0500.955
MTMIPs0.0610.9180.0070.988

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"

SamplesRegression analysisPrecision
Standard curvesCorrelation coefficientLinear range/(μg/ml)LOD/(μg/ml)LOQ/(μg/ml)Intra-day RSD/%Inter-day RSD/%
daidzeiny=521.8x-66.350.9925—1000.0150.0450.611.52
formononetiny=520.5x-202.70.9935—1000.0170.0630.891.28
genisteiny=481.2x-34.310.9925—1000.0270.1250.621.54

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."

1 王晓燕. 红车轴草异黄酮提取、分离纯化及其抗氧化活性的研究[D]. 西安: 西北大学, 2013.
Wang X Y. The effect on extraction, isolation and purification and antioxidant activity of the isoflavones in Trifolium pratense L[D]. Xi'an: Northwest University, 2013.
2 Mu H, Bai Y H, Wang S T, et al. Research on antioxidant effects and estrogenic effect of formononetin from Trifolium pratense (red clover)[J]. Phytomedicine International Journal of Phytotherapy & Phytopharmacology, 2009, 16(4): 314-319.
3 Brad K, Zhang Y, Gao J. Extraction and purification of formonometin from Trifolium pratense L: physicochemical properties of its complex with lecithin[J]. Tropical Journal of Pharmaceutical Research, 2017, 16(8): 1757-1764.
4 Snauwaert C, Vos M D, Looze D D. Formononetin induces cell cycle arrest of human breast cancer cells via IGF1/PI3K/Akt pathways in vitro and in vivo[J]. Hormone and Metabolic Research, 2011, 43(10): 681-686.
5 Park J, Kim S H, Cho D, et al. Formononetin, a phyto-oestrogen, and its metabolites up-regulate interleukin-4 production in activated T cells via increased AP-1 DNA binding activity[J]. Insect Science, 2005, 116(1): 71-81.
6 Gao D, Wang D D, Fu Q F, et al. Preparation and evaluation of magnetic molecularly imprinted polymers for the specific enrichment of phloridzin[J]. Talanta, 2018, 178: 299-307.
7 Pedrazza G P R, Morais C B, Dettenborn G R, et al. Anti-inflammatory activity and chemical analysis of extracts from Trifolium riograndense[J]. Brazilian Journal of Pharmacognosy, 2017, 27(3): 334-338.
8 Ganzera M. Supercritical fluid chromatography for the separation of isoflavones[J]. Journal of Pharmaceutical and Biomedical Analysis, 2015, 107: 364-369.
9 Renda G, Yalcin F N, Nemutlu E, et al. Comparative assessment of dermal wound healing potentials of various Trifolium L. extracts and determination of their isoflavone contents as potential active ingredients[J]. Journal of Ethnopharmacology, 2013, 148(2): 423-432.
10 Zgorka G. Pressurized liquid extraction versus other extraction techniques in micropreparative isolation of pharmacologically active isoflavones from Trifolium L. species[J]. Talanta, 2009, 79(1): 46-53.
11 Zhang Y, Liu C, Pan Y, et al. Ultrasound-assisted dynamic extraction coupled with parallel countercurrent chromatography for simultaneous extraction, purification, and isolation of phytochemicals: application to isoflavones from red clover[J]. Analytical and Bioanalytical Chemistry, 2015, 407(16): 4597-4606.
12 Visnevschi-Necrasov T, Cunha S C, Nunes Eugénia, et al. Optimization of matrix solid-phase dispersion extraction method for the analysis of isoflavones in Trifolium pratense[J]. Journal of Chromatography A, 2009, 1216(18): 3720-3724.
13 Chrzanowska A M, Poliwoda A, Wieczorek P P. Surface molecularly imprinted silica for selective solid-phase extraction of biochanin A, daidzein and genistein from urine samples[J]. Journal of Chromatography A, 2015, 1392(Complete): 1-9.
14 Feng F, Zheng J, Qin P, et al. A novel quartz crystal microbalance sensor array based on molecular imprinted polymers for simultaneous detection of clenbuterol and its metabolites[J]. Talanta, 2017, 167(Complete): 94-102.
15 Li W, Zhang Q, Wang Y, et al. Controllably prepared aptamer-molecularly imprinted polymer hybrid for high-specificity and high-affinity recognition of target proteins[J]. Analytical Chemistry, 2019, 91(7): 4831-4837.
16 Liu Y L, Liu R, Qin Y, et al. Flexible electrochemical urea sensor based on surface molecularly imprinted nanotubes for detection of human sweat[J]. Analytical Chemistry, 2018, 90(21): 13081-13087.
17 Xie J, Xiong J, Ding L S, et al. A efficient method to identify cardioprotective components of Astragali Radix using a combination of molecularly imprinted polymers-based knockout extract and activity evaluation[J]. Journal of Chromatography A, 2018, 1576: 10-18.
18 Zhang Y, Liu D H, Peng J, et al. Magnetic hyperbranched molecularly imprinted polymers for selective enrichment and determination of zearalenone in wheat proceeded by HPLC-DAD analysis[J]. Talanta, 2019, 209: 120555.
19 Zhou Y, Liu H C, Li J M, et al. Restricted access magnetic imprinted microspheres for directly selective extraction of tetracycline veterinary drugs from complex samples[J]. Journal of Chromatography A, 2019, 1613: 460684.
20 Li H J, Wang Y, Li Y, et al. High-sensitive molecularly imprinted sensor with multilayer nanocomposite for 2, 6-dichlorophenol detection based on surface-enhanced Raman scattering[J]. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2019, 228: 117784.
21 Kazemifard N, Ensafi A A, Rezaei B. Green synthesized carbon dots embedded in silica molecularly imprinted polymers, characterization and application as a rapid and selective fluorimetric sensor for determination of thiabendazole in juices[J]. Food Chemistry, 2020, 310: 125812.
22 Liu Y, Chen P, Zheng S, et al. Novel fluorescent sensor using molecularly imprinted silica microsphere coated CdSe@CdS quantum dots and its application in the detection of 2, 4, 6‐trichlorophenol from environmental water samples[J]. Luminescence, 2019, 34(7): 680-688.
23 Piletsky S, Canfarotta F, Poma A, et al. Molecularly imprinted polymers for cell recognition[J]. Trends of Biotechnology, 2020, 38(4): 368-387.
24 Wang X L, Yao H F, Li X Y, et al. pH/temperature-sensitive hydrogel-based molecularly imprinted polymers (hydroMIPs) for drug delivery by frontal polymerization[J]. RSC Advances, 2016, 6(96): 94038-94047.
25 Tuwahatu C A, Yeung C C, Lam Y W, et al. The molecularly imprinted polymer essentials: curation of anticancer, ophthalmic, and projected gene therapy drug delivery systems[J]. Journal of Controlled Release: Official Journal of the Controlled Release Society, 2018, 287: 24-34.
26 Abdollahi E, Khalafi-Nezhad A, Mohammadi A, et al. Synthesis of new molecularly imprinted polymer via reversible addition fragmentation transfer polymerization as a drug delivery system[J]. Polymer, 2018, 143: 245-257.
27 Xu S, Lu H, Zheng X, et al. Stimuli-responsive molecularly imprinted polymers: versatile functional materials[J]. Journal of Materials Chemistry C, 2013, 1(29): 4406-4422.
28 Wu X, Wang X, Lu W, et al. Water-compatible temperature and magnetic dual-responsive molecularly imprinted polymers for recognition and extraction of bisphenol A[J]. Journal of Chromatography A, 2016, 1435: 30-38.
29 Wang J, Pan J, Yin Y, et al. Thermo-responsive and magnetic molecularly imprinted Fe3O4@carbon nanospheres for selective adsorption and controlled release of 2, 4, 5-trichlorophenol[J]. Journal of Industrial & Engineering Chemistry, 2015, 25: 321-328.
30 Zhu L, Cao Y, Ni X, et al. Facile and versatile strategy to prepare magnetic molecularly imprinted particles based on the coassembly of magnetic nanoparticles and amphiphilic random copolymers[J]. Journal of Separation Science, 2018, 41(2): 578-581.
31 Wu Y, Yan M, Lu J, et al. Facile bio-functionalized design of thermally responsive molecularly imprinted composite membrane for temperature-dependent recognition and separation applications[J]. Chemical Engineering Journal, 2017, 309: 98-107.
32 Hashemi-Moghaddam H, Maddah S. Coating of optical fiber with a smart thermosensitive polymer for the separation of phthalate esters by solid-phase microextraction[J]. Journal of Separation Science, 2018, 41(4): 886-892.
33 Liu X, Zhou T, Du Z, et al. Recognition ability of temperature responsive molecularly imprinted polymer hydrogels[J]. Soft Matter, 2011, 7(5): 1986-1993.
34 Zhang Y, Kuang M, Zhang L, et al. An accessible protocol for solid-phase extraction of N-linked glycopeptides through reductive amination by amine-functionalized magnetic nanoparticles[J]. Analytical Chemistry, 2013, 85(11): 5535-5541.
35 Shi S, Fan D, Xiang H, et al. Effective synthesis of magnetic porous molecularly imprinted polymers for efficient and selective extraction of cinnamic acid from apple juices[J]. Food Chemistry, 2017, 237: 198-204.
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[5] ZHANG Fang;LI Guangming;ZHANG Zhigang;HU Huikang;Sheng Yi.

Characteristics of electrochemical oxidation of phenol with Mn-Sn-Sb/γ-Al2O3 particle-electrodes

[J]. , 2006, 57(10): 2515 -2521 .
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