Preparation of Warfarin Molecularly Imprinted Polymer and Analysis on Its Adsorbility
摘 要
采用悬浮聚合法,以华法林(WFR)为模板分子合成了分子印迹聚合物(MIP)。经正交试验优化的MIP合成反应条件给出华法林与功能单体甲基丙烯酸缩水甘油酯(GMA)和交联剂二乙烯苯(DVB)三者的物质的量之比为1:5:60。WFR先与GMA在三氯甲烷(15 mL)介质中超声混合反应5 min生成预聚物。然后加入2%(占单体和交联剂质量加和的百分比)引发剂过氧化苯甲酰三氯甲烷溶液0.17 g和DVB 8.499 mL,并超声混合20 min。将此混合物逐滴加入于10 g·L-1聚乙烯醇溶液100 mL中,滴加完毕后在80℃反应8 h,使生成聚合物。倾去上清液,用沸水反复洗涤所得到的聚合物,直至上层洗液澄清透明,以除去其表面的聚乙烯醇。将呈淡黄色的微球颗粒于60℃干燥,用体积比为4:1的甲醇-乙酸混合液150 mL与干燥的固体置于索氏提取器中回流洗脱以除去WFR。最后用纯甲醇洗涤除去残留乙酸。将所得MIP再次在60℃烘干。按相同方法但不加WFR制得非分子印迹聚合物(NIP)。所得扫描电子显微镜(SEM)图证明所合成的MIP呈球形均匀颗粒,表面无破损,有小孔存在,可保证其有良好的吸附性。吸附性能试验结果表明:随WFR质量浓度的增加,MIP和NIP对其的吸附量都逐渐增大,当WFR为20 mg·L-1时达到吸附平衡;MIP的吸附量均高于NIP的,且符合Langmuir模型,属于单分子层吸附。准二级动力学方程结果说明该吸附为化学相互作用的结果。对WFR及其他2种与WFR部分基团相似的化合物的吸附试验表明,与NIP比较,MIP对WFR的吸附选择性最高。
Abstract
Warfarin (WFR) molecularly imprinted polymer (MIP) was prepared by suspension polymerization using WFR as template. Mole ratio of WFR and other two reactants[i.e. the functional monomer glycidyl methacrylate (GMA) and the cross-linking agent divinylbenzene (DVB)], as optimized by orthogonal test, was found to be WFR:GMA:DVB=1:5:60. In the synthesis, WFR was firstly sonicated with GMA in CHCl3 (15 mL) for 5 min to give a pre-polymer. And then 0.17 g of 2% (propotion of mass sum of the monomers and the cross linker) initiator dibenzoyl peroxide chloro form solution together with DVB 8.499 mL were added to the reaction mixture and sonicated again for 20 min. After which, the mixture was added dropwise to 100 mL of 10 g·L-1 polyvinyl alcohol (PVA) solution, and at the end of the dropwise-addition, the mixture was reacted at 80℃ for 8 h to give the required polymer. The supernatant was separated and discarded. The precipitate was washed repeatedly with boiling water until clear and transparent washings was obtained to remove PVA on its surface, and the solid showed a appearance of slight yellow colored micro-globular particles. The MIP was separated and dried at 60℃. The dried MIP was then washed by refluxing in soxhlet's extractor with 150 mL of a mixed solvent of methanol and acetic acid with a volume ratio of 4:1, to remove WFR and finally washed with methanol to eliminate residual acetic acid. The washed MIP was again dried at 60℃ to give the final product. Non-molecularly imprinted polymer (NIP) was prepared in the same way but without addition of WFR. It was shown by the SEM image that the MIP displayed a state of even micro-globular particles without any damage on their surfaces, but with micro-pores on the surfaces providing the possibility of good adsorbility. As shown by the results of test for its adsorption efficiency, amounts of WFR adsorbed by MIP and NIP were all increased with the increase of mass concentrations of WFR, and adsorption equilibrium was achieved when WFR attained to 20 mg·L-1. Amounts of WFR adsorbed by MIP were higher than those by NIP at all mass concentrations. It was shown by the isotherm, that the adsorption was consistent with the Langmuir mode and belonged to single-molucular layer adsorption, and as shown by the result of the preudo-2nd order kinetic equation, the adsorption was the result of chemical interaction. Test for adsorbility of MIP and NIP towards WFR and 2 other compounds having part of their functional groups similar to that of WFR was made, giving results showing higher selectivity for MIP as compared with NIP.
中图分类号 O631.3 DOI 10.11973/lhjy-hx202003002
所属栏目 试验与研究
基金项目 国家自然科学基金项目(21575034);河南工业大学河南省省属高校基本科研业务费专项资金(2017RCJH10);河南省重点研发与推广专项(202102110057)
收稿日期 2019/7/16
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备注王慧格,硕士研究生,主要从事复杂体系的分离与分析的研究
引用该论文: WANG Huige,SONG Lixin,ZHANG Yunxia,LI Yuanyuan,YOU Liqin,HE Juan. Preparation of Warfarin Molecularly Imprinted Polymer and Analysis on Its Adsorbility[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2020, 56(3): 255~260
王慧格,宋立新,张云霞,李媛媛,游利琴,何娟. 华法林分子印迹聚合物的制备及其吸附性能的分析[J]. 理化检验-化学分册, 2020, 56(3): 255~260
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【4】GOUVEIA F, BICKER J, GONÇALVES J, et al. Liquid chromatographic methods for the determination of direct oral anticoagulant drugs in biological samples:a critical review[J]. Analytica Chimica Acta, 2019,1076:18-31.
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【6】王露,王芹,宋鑫,等.新型磁性分子印迹聚合物快速萃取-高效液相色谱法测定牛血清白蛋白[J].理化检验-化学分册, 2019,55(3):282-286.
【7】RUI C F, HE J, LI Y Y, et al. Selective extraction and enrichment of aflatoxins from food samples by mesoporous silica FDU-12 supported aflatoxins imprinted polymers based on surface molecularly imprinting technique[J]. Talanta, 2019,201:342-349.
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【9】吴姗姗,魏缠玲,赵丽娟,等.新型磁性限进分子印迹复合材料的制备及富集性能[J].高等学校化学学报, 2019,40(6):1150-1157.
【10】李园园,张鑫,陈炜杰,等.溶菌酶分子印迹聚合物膜的制备及其吸附性能[J].色谱, 2019,37(4):392-397.
【11】ZHANG K, ZHOU T C, KETTISEN K, et al. Chromatographic separation of hemoglobin variants using robust molecularly imprinted polymers[J]. Talanta, 2019,199:27-31.
【12】尚成新,刘文献.分散剂对MMA悬浮聚合的影响[J].化学研究与应用, 2018,30(7):1152-1157.
【13】LEE C M, NAM E, CHAE H. Photo-stable cross-linked micron bead with functionalized quantum via suspension polymerization for color conversion[J]. Polymer, 2019,177:19-24.
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