悬浮聚合法制备罗丹明B磁性分子印迹微球及其性能

doi:10.3724/SP.J.1095.2013.20594

摘要/Abstract

摘要： 以罗丹明B（RhB）为模板分子，采用悬浮聚合法制备了罗丹明B磁性印迹微球（M-MIPs），对其进行了结构表征，并与本体聚合的印迹材料进行了对比。结果表明，2种聚合物中的Fe3O4均呈现良好的晶形。悬浮法制得的M-MIPs呈球形，粒径在50 μm左右，其饱和磁化强度(5.406 emu/g)比本体法制得的M-MIP（1.772 emu/g）更大，有利于快速磁性分离。悬浮法所得M-MIPs的吸附量是本体法所得M-MIPs吸附量的近1.8倍，且在吸附速率、选择性、重复使用性能等方面，均明显优于后者。 2种材料均符合Langmuir吸附模型；悬浮法所得M-MIPs对RhB的吸附过程更符合二级动力学方程，而本体法所得M-MIPs较符合一级动力学方程。悬浮法制得的M-MIPs更适合于RhB的识别、富集与分析应用。

关键词: 磁性分子印迹聚合物, 磁性分离, 悬浮聚合, 本体聚合, 罗丹明B

Abstract: We used a suspension polymerization method to prepare magnetic molecularly imprinted polymers by using Rhodamine B as the template molecule. The obtained materials were characterized, and their properties were compared with those obtained from bulk polymerization. The results reveal that, Fe3O4 magnetic nanoparticles of the two kinds of polymers show good crystal morhpologies. The shape of M-MIPs prepared by suspension polymerization are regular with the microspheres size about 50 μm. Saturation magnetization of the M-MIPs(suspension polymerization) is 5.406 emu/g, which is larger than that obtained from bulk polymerization(1.772 emu/g). In addition, the former is in favour of the fast magnetic separation than the latter. Compared with bulk polymerization, the adsorption of M-MIPs(suspension polymerization) is 1.8 times higher. In terms of adsorption′s capacity, selectivity and reusability, the results of M-MIPs(suspension polymerization) are superior to those of bulk polymerization. Two kinds of adsorbents follow the Langmuir adsorption model. The processes of suspension polymerization and bulk polymerization can be fitted to the second-order and first-order kinetics adsorption, respectively. Through comparative studies, the M-MIPs of suspension polymerization possess high selective adsorption properties to Rhodamine B molecules, which can be used in enrichment and analysis application.

Key words: magnetic molecularly imprinted polymers, magnetic separation, suspension polymerization, bulk polymerization, Rhodamine B

中图分类号:

O656

吴云霞, 黄静, 尹争志, 曾延波, 张祖磊, 李蕾. 悬浮聚合法制备罗丹明B磁性分子印迹微球及其性能[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20594.

WU Yunxia1,2, HUANG Jing1,2, YIN Zhengzhi2, ZENG Yanbo2, ZHANG Zulei2, LI Lei2*. Properties of Rhodamine B′ Magnetic Molecularly Imprinted Polymers Prepared from the Suspension Polymerization Method[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20594.

参考文献

[1] ZHANG Zhaohui，ZHANG Huabin，LUO Lijuan,et al. Preparation and Application of the Multi-walled Carbon Nanotubes Surface Benzoyl Peroxide Imprinted Composite Solid-Phase Extraction Materials[J]. Acta Chim Sin,2009,67(24):2883-2889(in Chinese).

张朝晖,张华斌,罗丽娟,等. 多壁碳纳米管表面过氧化苯甲酰印迹复合材料的制备及固相萃取应用[J]. 化学学报,2009,67(24):2883-2889.

[2] Lee M H,Thomas J L,Ho M H,et al. Synthesis of Magnetic Molecularly Imprinted Poly(ethylene-co-vinyl alcohol) Nanoparticles and Their Uses in the Extraction and Sensing of Target Molecules in Urine[J]. Mater Interfaces,2010,2(6):1729-1736.

[3] Lu F G,Li H J,SUN M,et al. Flow Injection Chemiluminescence Sensor Based on Core-shell Magnetic Molecularly Imprinted Nanoparticles for Determination of Sulfadiazine[J]. Anal Chim Acta,2012,718:84-91.

[4] Griffete N,Li H,Lamouri A,et al. Magnetic Nanocrystals Coated by Molecularly Imprinted Polymers for the Recognition of Bisphenol A[J]. J Mater Chem,2012,22:1807-1811.

[5] He C Y,Long Y Y,Pan J L,et al. Application of Molecularly Imprinted Polymers to Solid Phase Extraction of Analytes from Real Samples[J]. J Biochem Biophys Methods,2007,70:133-150.

[6] Hu Y L,Li Y W,Liu R J,et al. Magnetic Molecularly Imprinted Polymer Beads Prepared by Microwave Heating for Selective Enrichment of β-Agonists in Pork and Pig Liver Samples[J]. Talanta,2011,84(2):462-470.

[7] Chen F F，Xie X Y，Shi Y P. Magnetic Molecularly Imprinted Polymer for the Detection of Rhaponticin in Chinese Patent Medicines[J]. J Chromatogr A,2012,(1252):8-14.

[8] Wang X H，Fang Q X，Chen L,et al. Preparation of a Magnetic Molecularly Imprinted Polymer with Pseudo Template for Rapid Simultaneous Determination of Cyromazine and Melamine in Bio-Matrix Samples[J]. Anal Bioanal Chem,2012,(404):1555-1564.

[9] Luo X B,Zhan Y C,Huang Y N,et al. Removal of Water-soluble Acid Dyes from Water Environment Using a Novel Magnetic Molecularly Imprinted Polymer[J]. J Hazard Mater,2011,187:274-282.

[10] Xu L C，Pan J M，Li X X,et al. Preparation of Thermal-Responsive Magnetic Molecularly Imprinted Polymers for Selective Removal of Antibiotics from Aqueous Solution[J]. J Hazard Mater,2012,(233/234):48-56.

[11] Baggiani C,Anfossi L,Baravalle P,et al. Determination of Banned Sudan Dyes in Food Samples by Molecularly Imprinted Solid Phase Extraction-High Performance Liquid Chromatography[J]. J Sep Sci,2009,32:3292-3300.

[12] HU Xia,XIAO Guang,PAN Wei,et al. Simultaneous Determination of 7 Rhodamine Dyes in Hot Chili Products by High Performance Liquid Chromatography-tandem Mass Spectrometry[J]. Chinese J Chromatogr,2010,28(6):590-595(in Chinese).

胡侠，肖光，潘炜，等. 高效液相色谱串联质谱法同时测定辣椒粉及辣椒油中的7种罗丹明染料[J]. 色谱,2010,28(6):590-595.

[13] WANG Sui,WANG Yongzhen,GONG Guoquan,et al. Studies on the Molecular Recognition and Binding Characteristics in Rhodamine B Molecularly Imprinted Polymer[J]. J Lanzhou Univ,2003,39(2):57-60(in Chinese).

王邃,王永珍,龚国权,等. 罗丹明B分子印迹聚合物的分子识别与结合特性的研究[J]. 兰州大学学报,2003,39(2):57-60.

[14] LEI Xiulan,YI Xiang,YUAN Yang,et al. Preparation of Rhodamine B Molecularly Imprinted Polymer Microspheres and Its Application in Solid Phase Extraction[J].Chinese J Appl Chem,2011,28(5):531-536(in Chinese).

雷秀兰,易翔,袁洋,等. 罗丹明B分子印迹聚合物微球的合成及其在固相萃取中的应用[J]. 应用化学,2011,28(5):531-536.

[15] Abareshi M,Goharshadi E K,Zebarjad S M,et al. Fabrication, Characterization and Measurement of Thermal Conductivity of Fe3O4 Nanofluids[J]. J Magn Magn Mater,2010,322(24):3895-3901.

[16] JIANG Bo,GUAN Yueping,WANG Jing,et al. Synthesis and Characterization of PEG-modified Polymer Mangetic Micropheres[J]. Chinese J Process Eng,2001,1(4):382-386(in Chinese).

姜波,官月平,王靖,等. 聚乙二醇修饰的高分子磁性微球的合成及表征[J]. 过程工程学报,2001,1(4):382-386.