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Chinese Journal of Applied Chemistry    2016, Vol. 33 Issue (2) : 229-237     DOI: 10.11944/j.issn.1000-0518.2016.02.150184
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Preparation of p-Hydroxybenzoic Acid-Imprinted Polymer Particulates and Application to Solid Phase Extraction
ZHANG Tielia*(),CHAI Guopinga,HE Caixiaab,WANG Leia
aDepartment of Chemistry,Tangshan Nomoral College,Tangshan,Hebei 063000,China
bCollege of Biological Science and Engineering,Hebei University of Science and Technology,Shijiazhuang 050018,China
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p-Hydroxybenzoic acid(p-HBA)-imprinted polymer particulates were prepared using p-HBA as the template, acrylamide(AM) as the functional monomer and ethylene glycol dimethacrylate as the crosslinker in three different amounts of p-HBA and under two different concentrations of pre-polymerization mixtures via precipitation polymerization. Their rebinding performances for p-HBA were characterized by high-performance liquid chromatography. The results reveal that both the amounts of p-HBA and the concentrations of pre-polymerization mixtures exhibit notable influence on the binding performances of p-HBA-imprinted polymers. The p-HBA-imprinted polymer(P2) with high affinity(k'=4.01) and selectivity for p-HBA is obtained when the amount of p-HBA is 1.0 mmol, which is corresponding to the molar ratio of 1:2(p-HBA/AM), in 37.5 mL of acetonitrile solvent. In addition, the imprinted polymer P2 was chosen as the adsorbent to make the molecularly imprinted solid phase extraction(MISPE) column and the MISPE method for the extraction of p-HBA was developed. The MISPE column capacities for p-HBA are 6.91 μg/100 mg and 1.93 μg/100 mg, respectively, which are determined under two different modes of loading samples. The rhizoma gastrodiae samples spiked with three different amounts of p-HBA are extracted and the recoveries of p-HBA range from 76.8% to 86.6%, with the RSD of 3.4%~6.2%(n=3). The results demonstrate that the p-HBA-imprinted polymer particulates prepared using AM as the functional monomer by precipitation polymerization are suitable as the adsorbent of solid phase extraction column for the selective separation and purification of p-HBA in the real sample of rhizoma gastrodiae.

Keywords p-hydroxybenzoic acid      precipitation polymerization      molecular recognition      molecularly imprinted solid phase extraction     
Fund:Supported by the Key Team Project Foundation of Tangshan Normal College(No.2014D07)
Corresponding Authors: ZHANG Tieli     E-mail:
Received: 2015-06-02           Accepted: 2015-10-29
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CHAI Guoping
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ZHANG Tieli,CHAI Guoping,HE Caixia, et al. Preparation of p-Hydroxybenzoic Acid-Imprinted Polymer Particulates and Application to Solid Phase Extraction[J]. Chinese Journal of Applied Chemistry, 2016, 33(2): 229-237.
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Polymer n(p-HBA)/mmol n(AM)/mmol V(ACN)/mL n(EGDMA)/mmol m(AIBN)/mg
BP - 2 37.5 10 44
P1 0.5 2 37.5 10 44
P2 1 2 37.5 10 44
P3 2 2 37.5 10 44
P4 2 4 37.5 20 88
Table 1Components of the prepolymerization mixtures for the preparation of molecularly imprinted polymers
Fig.1The structures of template and its structural analogues
Polymer Parameter p-HBA SA PCA CA VA FA Van
BP k' 0.66 0.64 0.90 0.73 0.21 0.20 0.02
α 1.00 1.03 0.73 0.90 3.14 3.30 33.0
P1 k' 4.14 2.14 4.95 2.26 1.43 0.81 0.19
α 1.00 1.93 0.84 1.83 2.90 5.11 21.8
IF 6.27 3.34 5.50 3.10 6.81 4.05 9.50
P2 k' 4.01 0.48 4.26 1.78 1.27 0.68 0.14
α 1.00 8.35 0.94 2.25 3.16 5.90 28.6
IF 6.08 0.75 4.73 2.44 6.05 3.40 7.00
P3 k' 1.56 0.50 1.87 0.78 0.61 0.36 0.09
α 1.00 3.12 0.83 2.00 2.56 4.33 17.3
IF 2.36 0.78 2.08 1.07 2.90 1.80 4.50
P4 k' 3.04 2.62 5.60 1.52 0.89 0.31 0.07
α 1.00 1.16 0.54 2.00 3.42 9.81 43.4
Table 2The retention of p-HBA and its structural analogues on molecular imprinted polymers P1, P2, P3 , P4 and non-molecular imprinted polymer BP
Fig.2The separation chromatograms of different p-HBA mixtures on non-molecular imprinted polymer BP column(A,C) and molecular imprinted polymer P2 column(B,D)(detection wavelength:251 nm)
Fig.3Infrared spectra of molecular imprinted polymer P2(a) and non-molecular imprinted polymer BP(b)
Fig.4Chromatograms of rhizoma gastrodiae extract(A), spiked extract with 10 μmol/L p-HBA(B) and its eluents after MISPE(C) and NISPE(D)
Sample No. Original/(μg·g-1) Spiked/(μg·g-1) Found/(μg·g-1) Recovery/% RSD/%
1 6.99 11.1 16.6 86.6 3.4
2 6.99 16.6 20.8 83.2 6.2
3 6.99 27.6 28.2 76.8 4.9
Table 3Recoveries of p-HBA in rhizoma gastrodiae spiked at different levels(n=3)
Fig.5Schematic diagram of the molecular imprinting and recognition processes
[1] Cheong W J, Ali F, Choi J H,et al.Recent Applications of Molecular Imprinted Polymers for Enantio-Selective Recognition[J]. Talanta,2013,106(15):45-59.
[2] Díaz-Díaz G,Antuña-Jiménez D, Blanco-López M C, et al. New Materials for Analytical Biomimetic Assays Based on Affinity and Catalytic Receptors Prepared by Molecular Imprinting[J]. TrAC-Trend Anal Chem,2012,33:68-80.
[3] Khajeh M,Sanchooli E. Imprinted Polymer Particles for Preconcentration of Copper from Water and Biological Samples[J]. Environ Chem Lett,2011,9(2):177-183.
[4] HU Yanyun,XU Huiqun,YAO Jian,et al.Selective Detection of 20 Triazoles Residues in Food Using Molecularly Imprinted Solid Phase Extraction Coupled with Liquid Chromatography Tandem Mass Spectrometry[J]. Chinese J Anal Chem,2014,42(2):227-232(in Chinese). 胡艳云,徐慧群,姚剑,等. 分子印迹固相萃取-液相色谱-质谱法测定果蔬中20种三唑类农药残留[J]. 分析化学,2014,42(2):227-232.
[5] Zhang H H,Xu F F,Duan Y Q,et al. Selective Adsorption and Pre-concentration of Morin by Molecularly Imprinted Polymers with Chitosan Beads as Functional Matrix[J]. Adv Mater Res,2013,781-784:756-759.
[6] XUE Min,WANG An,WANG Yu,et al.Application of Molecularly Imprinted Solid Phase Extraction for Determination of Estrogens in River Water, Milk and Urine Samples[J]. Chinese J Anal Chem,2011,39(6):793-798(in Chinese). 薛敏,王安,王瑜,等. 分子印迹固相萃取技术检测江水、尿液及牛奶中雌激素残留[J]. 分析化学,2011,39(6):793-798.
[7] JIANG Xuhong,TU Weiping. Research Progress in Preparation of Molecularly Imprinted Polymer Microspheres[J]. Mater Rev,2007,21(12):52-55 (in Chinese). 蒋旭红,涂伟萍. 分子印迹聚合物微球制备方法研究进展[J]. 材料导报,2007,21(12):52-55.
[8] LEI Xiulan,YI Xiang,YUAN Yang,et al.Preparation of Rodamine 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.
[9] XU Miaomiao,WANG Susu,LI Hui,et al.Preparation of Puerarin-Imprinted Polymer Microsphere by Precipitation Polymerization Technique for Solid Phase Extraction of Flavonoid from Pueraria Root Powder[J]. Food Sci,2015,36(10):11-15.(in Chinese). 许苗苗,王素素,李辉,等. 沉淀聚合法制备葛根素印迹微球及其固相萃取葛根粉[J], 食品科学,2015,36(10):11-15.
[10] DU Ziwei,LIU Xueyong,ZHAO Xiaodong. Preparation and Properties of TNT Imprinted Polymer Microspheres[J]. Acta Polym Sin,2010,1(3):360-365 (in Chinese). 杜自卫,刘学涌,赵小东. TNT分子印迹聚合物微球的合成与性能研究[J]. 高分子学报,2010,1(3):360-365.
[11] Chen F F,Wang G Y,Shi Y P. Molecularly Imprinted Polymer Microspheres for Solid-Phase Extraction of Protocatechuic Acid in Rhizoma Homalomenae[J]. J Sep Sci,2011,34(19):2602-2610.
[12] Chem S J. Status Quo and Development Trends of PHBA in China[J]. Fine Spec Chem,2003,11(12):6-7(in Chinese). Chem S J. 我国对羟基苯甲酸的现状和发展趋势[J]. 精细与专用化学品,2003,11(12):6-7.
[13] WANG Tiejie,LI Lu,JIANG Kun,et al. Simultaneous Determination of the Contents of Protocatechuic acid, p-Hydroxybenzoic Acid and Protocatechuic Aldehydein in the Aerial Root of Ficus Microcarpa by RP-HPLC[J]. J Shenyang Pharm Univ,2014, 31(9):706-710/725 (in Chinese). 王铁杰,李璐,江坤,等. RP-HPLC法同时测定榕树须中原儿茶酸、对羟基苯甲酸和原儿茶醛的含量[J]. 沈阳药科大学学报,2014,31(9):706-710,725.
[14] YAN Baoqing,ZHANG Huifen,FENG Nanan,et al.RP-HPLC Simultaneous Determination of p-Hydroxybenzoic Acid and 4,4-Dihydroxybenzyl Sulfone in the Rhizome of Gastrodia Elata BI[J]. Chinese J Pharm Anal,2010,30(9):1729-1731(in Chinese). 闫宝庆,张晖芬,逢楠楠,等. RP-HPLC同时测定天麻中对羟基苯甲酸和4,4-二羟基二苄砜的含量[J]. 药物分析杂志,2010,30(9):1729-1731.
[15] Zhang T L,Liu F,Chen W,et al.Influence of Intramolecular Hydrogen Bond of Templates on Molecular Recognition of Molecularly Imprinted Polymers[J]. Anal Chim Acta,2001,450(1/2):53-61.
[16] SUN Baowei,WU Liqing,LI Yuanzong. Experimental and Theoretical Study on p-Hydroxybenzoic Acid Imprinted Polymers with Different Functional Monomers[J]. Acta Chim Sin,2004,62(6):598-602(in Chinese). 孙宝维,武利庆,李元宗. 由不同功能单体合成的对羟基苯甲酸分子印迹聚合物识别特性的实验和理论研究[J]. 化学学报,2004,62(6):598-602.
[17] WANG Cheli,ZHAO Xingli,FANG Lei,et al.Study on p-Hydroxybenzoic Acid Imprinted Polymers with Different Functional Monomers and Their Molecular Recognition Characteristics[J]. J Chem Ind Eng,2011,62(7):1938-1942(in Chinese). 王车礼,赵兴丽,方磊,等. 对羟基苯甲酸分子印迹聚合物合成功能单体选择与分子识别性能[J]. 化工学报,2011,62(7):1938-1942.
[18] Shi S Y,Guo J F,You Q P,et al.Selective and Simultaneous Extraction and Determination of Hydroxybenzoic Acids in Aqueous Solution by Magnetic Molecularly Imprinted Polymers[J]. Chem Eng J,2014,243:485-493.
[19] ZHANG Tieli,LIU Feng,LI Kean. Influence of the Number and Relative Position of Interacting Groups in the Template Molecule on Molecular Imprinting Effect[J]. Chem J Chinese Univ,2010,31(6):1126-1130(in Chinese). 张铁莉,刘锋,李克安. 模板分子中作用基团的数目及位置对印迹聚合物印迹效应的影响[J]. 高等学校化学学报,2010,31(6):1126-1130.
[20] Phutthawong N,Pattarawarapan K. Synthesis of Highly Selective Spherical Caffeine Imprinted Polymers via Ultrasound-Assisted Precipitation Polymerization[J]. J Appl Polym Sci,2013,128(6):3893-3899.
[21] Zhao C Y,Dai J D,Zhou Z P,et al.One-Pot Method for Obtaining Hydrophilic Tetracycline-Imprinted Particles via Precipitation Polymerization in Ethanol[J]. J Appl Polym Sci,2014,131(7):40071-40081.
[22] González-Mariño I,Quintana J B,Rodríguez I,et al.Comparison of Molecularly Imprinted, Mixed-Mode and Hydrophilic Balance Sorbents Performance in the Solid-Phase Extraction of Amphetamine Drugs from Wastewater Samples for Liquid Chromatography-Tandem Mass Spectrometry Determination[J]. J Chromatogr A,2009,1216(48):8435-8441.
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