肿瘤标志物PHPAA分子印迹聚合物的合成与性能研究

Study on Synthesis of Tumor Marker PHPAA Molecular Imprinted Polymers and Its Performance

目的:合成对羟基苯乙酸(PHPAA)分子印迹聚合物(MIPs),为肿瘤患者尿液中PHPAA的分离富集提供参考。方法:以PHPAA为模板分子,以偶氮二异丁腈为引发剂,分别以4-乙烯基吡啶(4-V)、丙烯酰胺(AM)、1-乙烯基咪唑(1-V)、邻苯二胺为功能单体,以二甲基丙烯酸乙二醇酯(EGDMA)、三羟甲基丙烷三甲基丙烯酸酯(TRIM)为交联剂,采用沉淀聚合法合成MIPs。采用扫描电镜、红外光谱、静态吸附试验、分子识别性能试验对其微球结构和性能进行表征。结果:MIPs1(4-V、EGDMA)微球粘连严重,MIPs2(AM、EGDMA)微球呈聚集状;MIPs3(1-V、TRIM)、MIPs4(邻苯二胺、TRIM)微球较为分散,且球形度好。MIPs的红外光谱中未见PHPAA的特征吸收峰。各MIPs的吸附量均高于不含模板分子的空白印迹聚合物,且随着模板分子浓度的升高,其吸附量也随之增加。MIPs3的吸附量显著高于其他MIPs,其对PHPAA的静态分配系数(0.14)高于其他结构类似物[对羟基苯丙酸(PHPA)(0.06)、酪氨酸(TA)(0.01)],对PHPAA与PHPA、PHPAA与TA的选择性分离因子分别为2.3、11.5。结论:以1-V为功能单体、TRIM为交联剂合成的MIPs对PHPAA分子具有特异性吸附和选择性识别能力,可将其作为固相萃取剂,用以分离富集肿瘤患者尿液中低含量的PHPAA。

OBJECTIVE:To synthesize 4-hydroxyphenylacetic acid(PHPAA)molecular imprinted polymers(MIPs),and to provide reference for separation and enrichment of PHPAA in urine of cancer patients.METHODS:With PHPAA as template molecule and azobisisobutyronitrile as evocating agent,MIPs was synthesized by precipitation polymerization using 4-vinyl pyridine(4-V),acrylamide(AM),1-vinyl imidazole(1-V)and o-diaminobenzene as functional monomers,ethylene glycol dimethacrylate(EGDMA)and trimethylolpropane trimethacrylate(TRIM)as crosslinking agent.Using scanning electron microscope,infrared spectrum,static adsorption test and molecular recognition performance test used adopted to characterize the structure and performance of MIPs.RESULTS:MIPs1(4-V,EGDMA)microspheres adhered seriously,and MIPs2(AM,EGDMA)microspheres are aggregated.MIPs3(1-V,TRIM),MIPs4(o-diaminobenzene,TRIM)microspheresare were dispersed and had good sphericity.Characteristic absorption peak of PHPAA was not found in infrared spectrum of MIPs.The adsorption capacity of each MIPs was higher than that of blank imprinted polymer without the template molecule,and increased as the increase of template molecular concentration.The adsorption capacity of MIPs3 was significantly higher than that of other MIPs,and its static distribution coefficient(0.14)of PHPAA was higher than that of other structural analogues[PHPA(0.06),TA(0.01)],selective separation factors of PHPAA to PHPA,PHPAA to TA were 2.3,11.5,respectively.CONCLUSIONS:MIPs synthesized with 1-V as functional monomer and TRIM as crosslinking agent has the ability of specific adsorption and selective recognition.It can used as solid phase extractant to separate and enrich low content of PHPAA in the urine of tumor patients.