新型磁性限进分子印迹复合材料的制备及富集性能

doi:10.7503/cjcu20180772

摘要/Abstract

摘要：

采用浸渍热解法制备磁性凹凸棒土(MATP), 以磺胺二甲氧嘧啶(SDM)为模板分子, 4-乙烯基吡啶(4-VP)为功能单体, 采用反相原子转移自由基聚合(RATRP)法在MATP表面包覆印迹聚合物薄膜, 得到磁性分子印迹聚合物(MATP-MIPs), 最后在MATP-MIPs表面接枝亲水性单体甲基丙烯酸羟乙酯(HEMA), 得到新型磁性限进分子印迹复合材料(MATP-RAM-MIPs). 采用傅里叶变换红外光谱(FTIR)仪、扫描电子显微镜(SEM)、热重分析(TGA)仪、振动样品磁强计(VSM)和X射线衍射(XRD)仪对材料进行了表征. 通过静态水接触角和考马斯亮蓝G-250方法证明材料外表面具有良好的亲水性和排阻蛋白的特性; 采用静态和选择性吸附实验证实MATP-RAM-MIPs对SDM具有良好的吸附选择性和较高的吸附容量. 将该材料直接用于牛血清中磺胺类药物的富集分离, 加标回收率为86.2%~100.6%, 相对标准偏差为2.1%~4.2%, 可见该材料在复杂样品前处理中具有良好的实际应用价值.

关键词: 磁性凹凸棒土, 反相原子转移自由基聚合, 限进分子印迹聚合物, 吸附性能

Abstract:

The magnetic attapulgite(MATP) was preparrd by pyrolysis method. Then, using sulfadimethoxine(SDM) as template molecule, 4-vinylpyridine(4-VP) as functional monomer, the imprinted layer was coated on the surface of modified MATP via reverse atom transfer radical polymerization(RATRP), getting magnetic molecularly imprinted polymers(MATP-MIPs). Finally, novel magnetic restricted access media-molecularly imprinted composites(MATP-RAM-MIPs) was obtained by grafting hydrophilic monomer hydroxyethyl methacrylate(HEMA) onto the surface of MATP-MIPs. The polymer was characterized by means of Fourier transform infrared(FTIR) spectrum, scanning electron microscope(SEM), thermogravimetric analysis(TGA), vibrating sample magnetometer(VSM) and X-ray diffraction(XRD). The hydrophilicity of MATP-RAM-MIPs and the ability of exclusion of proteins were studied by the water contact angle and Coomassie brilliant blue G-250 method. The adsorption characters of MATP-RAM-MIPs on SDM were studied by adsorption isothermal and selectivity in detail, and MATP-RAM-MIPs were used as solid phase extraction packing to separate and enrichment of SAs from bovine samples. The spiked recoveries were 86.2%—100.6%, and the relative standard deviations(RSD) were 2.1%—4.2%, indicating that this material has application value in the pretreatment of complex samples.

Key words: Magnetic attapulgite, Reverse atom transfer radical polymerization, Restricted access mediamolecularly imprinted polymer, Adsorption property

中图分类号:

O657

TrendMD:

吴姗姗, 魏缠玲, 赵丽娟, 田央, 王霞, 龚波林. 新型磁性限进分子印迹复合材料的制备及富集性能. 高等学校化学学报, 2019, 40(6): 1150.

WU Shanshan,WEI Chanling,ZHAO Lijuan,TIAN Yang,WANG Xia,GONG Bolin. Preparation and Enrichment Properties of Novel Magnetic Restricted Access Media-molecularly Imprinted Composites^†. Chem. J. Chinese Universities, 2019, 40(6): 1150.

图/表 10

Fig.1 Synthetic procedure of MATP-RAM-MIPs

Fig.2 FTIR spectra of ATP(a), MATP(b), KHMATP(c),MATP-MIPs(d) and MATP-RAM-MIPs(e)

Fig.3 SEM images of ATP(A), KHATP(B), MATP-MIPs(C) and MATP-RAM-MIPs(D)

Fig.4 Water contact angle profiles of MATP-RAM-MIPs(A) and MATP-MIPs(B)

Fig.5 MATP-RAM-MIPs(a), MATP-MIPs(b), MATP-RAM-NIPs(c) and MATP-NIPs(d) absorption of bovine serum albumin by coomassic brilliant blue G-250 method(A) and UV-Vis absorption spectra(B) of SDM(a), BSA(b) and MATP-RAM-MIPs-SPE(c)

Fig.6 Adsorption isotherm curves of MATP-RAM-MIPs(a) and MATP-RAM-NIPs(b)

Table 1 Comparison of adsorption capacities of various adsorbents

Solid support	Preparation method	Analyte	Adsorption capacity/(mg·g^-1)	Ref.
Polymer particles	Ultraviolet initiation for bulk polymerization	Sulfadiazine	6.73	[22]
Magnetic polymer microspheres	Ultraviolet initiation for bulk polymerization	Sulfadiazine	2.24	[23]
Molecularly imprinted column	Ultraviolet initiation for bulk polymerization	Sulfadiazine	0.87	[24]
Graphene oxide	Precipitation polymerization	Sulfadimethoxine	8.69	[25]
Magnetic nanoparticles	Surface grafting polymerization	Sulfadimethoxine	0.16	[26]
Polymeric substance	Silica gel as sacrificial materials	Sulfadimethoxine	0.31	[27]
Magnetic attapulgite	Reverse atom transfer radical polymerization	Sulfadimethoxine	8.79	This work

Fig.7 Selective absorption of MATP-RAM-MIPs and MATP-RAM-NIPs on SDM, SMR and SIZ

Fig.8 Chromatograms of bovine samples by HPLC a. Elution solutions of MATP-RAM-MIPs; b. elution solutions of MATP-RAM-NIPs; c. elution solutions of MATP-MIPs; d. elution solutions of MATP-MIPs; e. blank bovine sample. Spiked level: 50 μg/mL.

Table 2 Spiked recoveries and relative standard deviations(RSDs) of the SDM, SMR and SIZ in bovine samples(n=5)

Added substance	Added concentration/(μg·mL^-1)	Recovery(%)	RSD(%)
Sulfadimethoxine	25	93.7	3.7
	50	100.6	2.1
	100	99.3	3.0
Sulfamerazine	25	91.5	4.2
	50	87.3	2.5
	100	95.0	3.9
Sulfisoxazole	25	86.2	3.4
	50	92.8	2.6
	100	89.1	3.3

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