Preparation of a surfacially imprinted polymer based on metal organic framework MIL-101 as support and its adsorption behavior

doi:10.16085/j.issn.1000-6613.2018-0866

Abstract

Abstract: In present work, a surfacially imprinted polymer based on metal organic framework MIL-101 as the support was prepared and its adsorption behavior explored. Firstly, MIL-101 was chemically modified by using ethidene diamine as modifier to obtain ED-MIL-101. Secondly, a surface-imprinting technique was used to prepare MIPs@MIL-101 polymer with geniposide as the template, methacrylic acid as the functional monomer, divinylbenzene as the cross-linker by adopting a surface grafting technique. The molecularly imprinted polymers obtained was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The adsorption dynamics and therodynamics behaivors were tested and the solid phase extraction performance for this polymer evaluated. The adsorption kinetics study showed that when the MIP is used for geniposide, the adsorption equilibrium can reach within 270 minutes. When the temperature was set at 298K, 308K, 318K, 328K, the adsorption capacity for the MIPs toward the template was 55.94mg/g, 46.16mg/g, 38.98mg/g and 31.47mg/g, respectively, with an enthalpy value of ΔH=26.997kJ/mol. This MIP can be used as sorbent for the solid phase extraction of geniposide from crude extract of Eucommia ulmoides, with a total recovery of 95.0%.

Key words: metal organic frameworks MIL-101, polymers, preparation, adsorption, chromatography

摘要： 研究了金属有机骨架材料MIL-101表面印迹聚合物的制备方法及其吸附行为。以MIL-101为载体，先通过化学修饰氨基制备了ED-MIL-101材料，再以京尼平苷为模板，甲基丙烯酸为功能单体，二乙烯基苯为交联剂，表面接枝京尼平苷分子印迹聚合物制备了MIPs@MIL-101印迹聚合物。通过傅里叶红外光谱（FTIR）、X射线衍射光谱（XRD）、扫描电镜（SEM）对聚合物进行结构表征，测试了聚合物的等温吸附及吸附动力学性能，探讨了聚合物的固相萃取性能。红外光谱及XRD衍射分析表明了MIL-101氨基化修饰及表面接枝复合材料的成功制备。吸附动力学研究表明当分子印迹聚合物用于吸附京尼平苷时，可在270min内达到吸附平衡。当温度为298K、308K、318K、328K时，印迹聚合物对模板的吸附量分别为55.94mg/g、46.16mg/g、38.98mg/g、31.47mg/g。吸附热ΔH为26.997kJ/mol。分子印迹固相萃取杜仲提取物中的京尼平苷时，总回收率达95.0%。

关键词: 金属有机骨架MIL-101, 聚合物, 制备, 吸附, 色谱

CLC Number:

TQ31

HUANG Xinhui, SONG Junjie, ZHANG Yue, LI Hui. Preparation of a surfacially imprinted polymer based on metal organic framework MIL-101 as support and its adsorption behavior[J]. Chemical Industry and Engineering Progress, 2018, 37(S1): 154-161.

黄信慧, 宋俊杰, 张月, 李辉. 氨基化MIL-101表面印迹聚合物的制备及其吸附行为[J]. 化工进展, 2018, 37(S1): 154-161.

References

[1] LOCATELLI F, GAMEZ P, LEMAIRE M. Molecular imprinting of polymerised catalytic complexes in asymmetric catalysis[J]. Journal of Molecular Catalysis,1998, 135:89-98.
[2] CHEN Tao, SHAO Mingwang, XU Hongyan, et al. Molecularly imprinted polymer-coated silicon nanowires for proten specific recognition and fast separation[J]. Mater. Chem., 2012, 22:3990-3996.
[3] WU Ningli, LUO Zhimin, GE Yanhui, et al. A novel surface molecularly imprinted polymer as the solid-phase extraction adsorbent for the selective determination of ampicillin sodium in milk and blood samples[J]. Journal of Pharmaceutical Analysis, 2016, 6:157-164.
[4] QIAN Kun, FANG Guozhi, WANG Shuo. A novel core-shell molecularly imprinted polymer base on metal-organic framework as matrix[J]. Chemical Coumnication, 2011, 47:10118-10121.
[5] 张月, 李辉, 王素素, 等. Zn²⁺配位双模板印记聚合物,表征及同时萃取升麻中的阿魏酸和咖啡酸[J]. 化工进展, 2016, 35(4):1132-1139.
[6] 刘曦, 张朝晖, 张华斌, 等. 印迹聚合物改性多壁纳米管固相萃取熊果酸[J]. 分析化学研究报告, 2011, 39(6):839-845.
[7] 颜流水, 井晶, 黄智敏, 等. 槲皮素分子印迹聚合物的制备及固相萃取性能研究[J]. 分析实验室, 2006, 25(5):97-100.
[8] MOSTAFA Khajeh, MASSOUD Kaykhaii, MAJID Mirmoghaddam, et al. Hossein hashemi;separation of zinc from aqueous samples using a molecular imprinting technique[J]. International Journal of Environmental Analytical Chemistry, 2009, 89:981-992.
[9] LI Zhiping, LI Hui, LIU Fen, et al. Preparation, characterization and adsorption behavior of huperzine a imprinted polymers[J]. Chinese J. Appl. Chem., 2013, 30(8):915-921.
[10] OLIVER Brüggemann. Catalytically active polymers obtained by molecular imprinting and their application in chemical reaction engineering[J]. Biomolecular Engineering, 2001, 18:1-7.
[11] WUILLOUD C A, WUILLOUD G, VONDERHEIDE P, et al. Molecularly imprinted solid phase extraction of urinary diethyl thiophosphate and diethyl dithiophosphate and their analysis by gas chromatography-mass spectrometry[J]. Journal of Chromatography B, 2004, 59:755-792.
[12] 袁自遵. 金属有机框架材料MIL-101吸附分离性能研究[D]. 抚州:东华理工大学, 2014.
[13] YANG Kun, SUN Qian, XUE Feng, et al. Adsorption of volatile organic compounds by metal-organic frameworks MIL-101:influence of molecular size and shape[J]. Journal of Hazardous Materials, 2011,195:124-131.
[14] ZHOU Zhenyu, MEI Liang, MA Chen, et al. A novel bimetallic MIL-101(Cr, Mg) with high CO₂ adsorption capacity and CO₂/N₂ selectivity[J]. Chemical Engineering Science, 2016, 147:109-117.
[15] 刘淑芝, 赵福, 临郭齐. 金属有机骨架MIL-101的合成、改性及在催化反应中的应用进展[J]. 化工进展, 2017, 36(3):918-925.
[16] CHEN Hongjun, ZHANG Zhaohui, XIE Duo, et al. Surface-imprinting sensor based on carbon nanotubes/graphene composed for deteminatin of bovine serum albumin[J]. Electroanalysis, 2012, 24:2109-2116.
[17] FERNANDO M, CARLOS P C, REJANE M, et al. Magnetic solid-phase extraction using metal-organic frameworks (MOFs) and their derived carbons[J]. Trends in Analytical Chemistry, 2017, 90:142-152.
[18] 谢生明, 袁黎明. 金属有机框架材料用于色谱固定相[J]. 化学进展, 2013, 25(10):1763-1770.
[19] 张春梅. MIL101系列材料的合成与及性能研究[D]. 哈尔滨:哈尔滨工业大学, 2014.
[20] QIAN Kun, DENG Qiliang, FANG Guozhen, et al. Metal-organic frameworks supported surface-imprinted nanoparticles for the sensitive detection of metolcarb[J]. Biosensors and Bioelectronics, 2016, 79:359-363.
[21] 张春艳, 王培龙, 石雷, 等. 基于金属有机框架材料的分子印迹聚合物电化学传感器检测猪尿中的苯乙酰胺A[J]. 分析化学研究报告, 2016, 12(44):1859-1866.
[22] 戚向阳, 陈维军, 张声华. 反向高效液相色谱法测定杜仲中京尼平苷、京尼平苷酸、绿原酸的含量[J]. 药物分析杂志, 2000, 20(1):22-24.
[23] 李钦, 杜红岩, 杜兰英, 等. HPLC法测定杜仲雄花和杜仲雄花茶中京尼平苷酸、绿原酸和京尼平苷[J]. 中草药, 2009, 40(1):71-74.
[24] QI Chao, CAI Qianqian, ZHAO Pan, et al. The metal-organic framework MIL-101(Cr) as efficient adsorbent in a vortex-assisted dispersive solid-phase extraction of imatinib mesylate in rat plasma coupled with ultra-performance liquid chromatography/mass spectrometry:application to a pharmacokinetic study[J]. Journal of Chromatography A, 2016, 1449:30-38.
[25] LI Hui, XU Miaomiao, WANG Susu, et al. Preparation, characterization and selective recognition for vanillic acid imprinted mesoporous silica polymers[J]. Applied Surface Science, 2015, 328:649-657.
[26] LI Hui, LIU Yingju, ZHANG Zhaohui, et al. Separation and purification of chlorigenic acid by molecularly imprinted polymer monolithic stationary phase[J]. Jouranl of Chromatography A, 2005, 1098(1):66-74
[27] 许苗苗. 几种药物活性小分子印迹聚合物的研制、识别性能及固相萃取研究[D]. 吉首:吉首大学, 2015.