Preparation of Magnetic Molecularly Imprinted Polymer Used for Separation and Enrichment of Diethylstilbestrol and Its Application to Analysis of Environmental Water Samples
摘 要
制备了以己烯雌酚为模板分子的磁性分子印迹聚合物(MMIP),萃取富集环境水样中的己烯雌酚并用高效液相色谱法(HPLC)测定其含量。其操作过程:取MMIP 20 mg,加入5 mL甲醇并制成悬浮液,用蠕动泵取悬浮液推至带有磁铁的玻璃管中,MMIP由于磁铁的吸力使其吸附在玻璃管内壁,在玻璃管两端用玻璃棉塞住,并接入试验系统。将样品(酸度在pH 7.5)用1.0 mL·min-1的流量推至上述含有MMIP的磁性固相萃取柱中,在流动过程中,目标分子(己烯雌酚)被吸附在MMIP表面。用水洗去磁性材料表面的杂质,然后用甲醇-乙酸(9+1)混合溶液2 mL洗脱目标分子,洗脱液供HPLC测定。经试验证明:MMIP对己烯雌酚选择性较好,性质结构相似的物质不干扰其测定,重复使用次数小于25次时,MMIP对己烯雌酚的吸附能力无明显变化,说明其在实际分析中可重复使用;MMIP对己烯雌酚的饱和吸附容量为93.6 mg·g-1。在上述测定条件下,己烯雌酚的质量浓度在0.20~50 μg·L-1内与其对应峰面积之间呈线性关系,其检出限(3S/N)为0.06 μg·L-1。加标回收试验的结果表明,其平均回收率在87.2%~104%之间,测定值的相对标准偏差(n=6)在1.9%~4.6%之间。
Abstract
A magnetic molecularly imprinted polymer with diethylstilbestrol (DESB) as model molecule (MMIP) was prepared and used for separation and pre-enrichment of DESB from environmental water samples and its determination by HPLC. The procedure was given as follows:20 mg of the MMIP is dispersed in 5 mL of methanol to give a suspension which is carried over by wriggling pump into a glass tube with magnets installed on its outer surface. The MMIP particles due to its magnetic property will be pulled and adsorbed on the inner surface of the glass tube, during passing through the tube and then two ends of the tube are plugged with glass wool. Water sample having its acidity adjusted to 7.5, is introduced into the analytical system by passing through the glass tube at a flow-rate of 1.0 mL·min-1, during which DESB in the sample will be adsorbed on the surface of MMIP adsorbed on the inner surface of the glass tube. Water is used to wash the surface of the MMIP to remove impurities, and then 2 mL of CH3OH-CH3COOH (9+1) mixture are used to elute DESB from MMIP. The eluate is used for HPLC determination. It was shown that MMIP had high selectivity for DESB, compounds with similar molecular structure and chemical property did not interfere with the determination of DESB, and that MMIP could be used repeatedly for at least 25 times, showing no significant difference in its adsorption capacity. Value of saturated adsorption of DESB was found to be 93.6 mg·g-1. Linearity range of DESB found under the conditions described was between 0.20 to 50 μg·L-1. Detection limit (3S/N) was found 0.06 μg·L-1. Test for recovery was performed by standard addition method, giving average recoveries in the range of 87.2%-104%. Values of RSDs (n=6) were found in the range of 1.9%-4.6%.
中图分类号 O657.7 DOI 10.11973/lhjy-hx201910011
所属栏目 工作简报
基金项目 江苏省卫生计生委预防医学科研项目(Y2015035);江苏省卫生计生委预防医学科研项目(Y2018048);江苏省“333工程”科研项目(BRA2016234);淮安市科技局科技支撑(社会发展)项目(HAS2015030)
收稿日期 2019/3/7
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联系人作者王媛(785565133@qq.com)
备注王露,主管技师,硕士主要从事卫生检验
引用该论文: WANG Lu,WANG Qin,SONG Xin,HANG Xueyu,FENG Xiaoqing,WANG Yuan. Preparation of Magnetic Molecularly Imprinted Polymer Used for Separation and Enrichment of Diethylstilbestrol and Its Application to Analysis of Environmental Water Samples[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2019, 55(10): 1180~1185
王露,王芹,宋鑫,杭学宇,冯晓青,王媛. 用于分离富集己烯雌酚的磁性分子印迹聚合物的制备及其在环境水样检测中的应用[J]. 理化检验-化学分册, 2019, 55(10): 1180~1185
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参考文献
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【2】JAN S T, DEVANESAN P D, STACK D E, et al. Metabolic activation and formation of DNA adducts of hexestrol, a synthetic nonsteroidal carcinogenic estrogen[J]. Chemical Research in Toxicology, 1998,11(5):412-419.
【3】YIN Y, LIN C X, MA L. Msx2 promotes vaginal epithelial differentiation and wolffian duct regression and dampens the vaginal response to diethylstilbestrol[J]. Molecular Endocrinology, 2006,20(7):1535-1546.
【4】HUANG D L, WANG R Z, LIU Y G, et al. Application of molecularly imprinted polymers in wastewater treatment:A review[J]. Environmental Science and Pollution Research, 2015,22(2):963-977.
【5】SIRIPAIROJ W, KAEWCHADA A, JAREE A. Synthesis of molecularly imprinted polymers for the separation of gamma-oryzanol by using methacrylic acid as functional monomer[J]. Journal of the Taiwan Institute of Chemical Engineers, 2014,45(2):338-346.
【6】LIU H J, YANG F, ZHENG Y M, et al. Improvement of metal adsorption onto chitosan/Sargassum sp. composite sorbent by an innovative ion-imprint technology[J]. Water Research, 2011,45(1):145-154.
【7】ZHU J, HE J, DU X Y, et al. A facile and flexible process of β-cyclodextrin grafted on Fe3O4 magnetic nanoparticles and host-guest inclusion studies[J]. Applied Surface Science, 2011,257(21):9056-9062.
【8】ZHOU X Y, WEI J F, LIU K, et al. Adsorption of bisphenol A based on synergy between hydrogen bonding and hydrophobic interaction[J]. Langmuir, 2014,30(46):13861-13868.
【9】BINELLO A, CRAVOTTO G, NANO G M, et al. Synthesis of chitosan-cyclodextrin adducts and evaluation of their bitter-masking properties[J]. Flavour and Fragrance Journal, 2004,19(5):394-400.
【10】REN Y M, WEI X Z, ZHANG M L. Adsorption character for removal Cu(Ⅱ) by magnetic Cu(Ⅱ) ion imprinted composite adsorbent[J]. Journal of Hazardous Materials, 2008,158(1):14-22.
【11】WANG S, WANG R Y, WU X L, et al. Magnetic molecularly imprinted nanoparticles based on dendritic-grafting modification for determination of estrogens in plasma samples[J]. Journal of Chromatography B, 2012,905:105-112.
【12】危晶,何奕轩,王邃.石墨烯/Fe3O4磁性纳米材料分散固相萃取环境水样中的己烯雌酚[J].分析测试学报, 2012,31(10):1223-1228.
【13】金莹,赵晓磊,李龙飞.分子印迹固相萃取与高效液相色谱在线联用检测饮用水中己烯雌酚痕量残留[J].分析测试学报, 2012,31(z1):71-75.
【14】ZHAO C D, JI Y S, SHAO Y L, et al. Novel molecularly imprinted polymer prepared by nanoattapulgite as matrix for selective solid-phase extraction of diethylstilbestrol[J]. Journal of Chromatography A, 2009,1216(44):7546-7552.
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