江南大学 化学与材料工程学院,江苏 无锡 214122
曹玉华,博士,教授,研究方向:分析化学,E-mail:yuhuacao64@gmail.com
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胡亭屹,张云,赵强等.双亲性无规共聚物自组装磁性分子印迹纳米粒子四环素光子晶体传感器[J].分析测试学报,2023,42(05):628-633.
HU Ting-yi,ZHANG Yun,ZHAO Qiang,et al.Construction of a Photonic Crystal Sensor Based on an Amphiphilic Random Copolymer Self-assembled Magnetic Molecularly Imprinted Nanoparticles and Its Application in Tetracycline Detection[J].Journal of Instrumental Analysis,2023,42(05):628-633.
胡亭屹,张云,赵强等.双亲性无规共聚物自组装磁性分子印迹纳米粒子四环素光子晶体传感器[J].分析测试学报,2023,42(05):628-633. DOI: 10.19969/j.fxcsxb.23010909.
HU Ting-yi,ZHANG Yun,ZHAO Qiang,et al.Construction of a Photonic Crystal Sensor Based on an Amphiphilic Random Copolymer Self-assembled Magnetic Molecularly Imprinted Nanoparticles and Its Application in Tetracycline Detection[J].Journal of Instrumental Analysis,2023,42(05):628-633. DOI: 10.19969/j.fxcsxb.23010909.
以油酸包覆四氧化三铁纳米粒子(OA-Fe,3,O,4,)为磁性内核,双亲性无规共聚物P(St-,co,-VP)为乳化剂,四环素(TC)为模板分子,将光子晶体技术与分子印迹技术相结合,通过细乳液自组装一步法制备了磁性分子印迹纳米颗粒(MMINPs),并基于外界磁场组装构建了可进行裸眼可视化检测的光子晶体传感器。采用透射电镜(TEM)、红外光谱(FT-IR)和热重曲线(TGA)对MMINPs粒子进行了表征。优化了TC-MMINPs的制备条件,考察了TC磁性分子印迹光子晶体传感器(TC-MMIPCs)的灵敏度、响应时间和选择性。结果显示,在TC质量浓度1.0 × 10,-4, ~ 1.0 g/L范围内,质量浓度的对数与反射波长呈线性关系,检出限(,S,/,N ,= 3)为1.0 × 10,-4, g/L。该传感器响应速度较快,在30 s内即可完成响应,印迹因子为3.41。其响应具有特异性,对于与四环素结构相似的氯霉素的选择因子为5.92。该传感器已成功用于某品牌舒缓保湿喷雾中TC的分析。
In this paper,a naked-eye magnetic molecularly imprinted photonic crystal sensor(MMIPCs) based on magnetic molecularly imprinted nanoparticles(MMINPs) for tetracycline(TC) detection was constructed,under the external magnetic field through magnetic assembly of the MMINPs.The MMINPs were prepared by one-step method through miniemulsion self-assembly,with oleic acid modified magnetite nanoparticles as the magnetic cores,the amphiphilic random copolymer P(St-,co,-VP) as both the emulsifier and coating,and TC as the template molecule.PVP molecular chain stretched outward to obtain a steric hindrance between magnetic colloidal nanoparticles(MCNPs) owing to the hydrogen bonding between the PVP and water molecules.A magnetic responsive photonic crystal based on steric hindrance rather than electrostatic interaction as the counterbalance to magnetic attraction was developed.During the self-assembly of the P(St-,co,-VP) aggregating on the surface of MCNPs,the target molecules were added,which were imprinted in the coatings of MCNPs,relying on the hydrogen bond between PVP and the templates without further polymerization reaction.The MMINPs was characterized by transmission electron microscopy(TEM),Fourier transform infrared spectoscopy(FT-IR) and thermal gravimetric analyzer(TGA).In FT-IR spectrum for MMINPs,the stretching vibration peaks of C—O indicated the successful imprinting of TC.TEM showed that the particles were regularly spherical and uniform in size distribution.The average particle diameter of the MMINPs was around 153.6 nm.TGA showed that the content of magnetic substance was high to 67.44%,which was ascribed to ferromagnetic substance (Fe,3,O,4, or Fe,2,O,3,) with high thermal stability.The preparation conditions of TC-MMINPs were optimized and the sensitivity,response time and the selectivity of TC-MMIPCs sensors were also investigated.With the increase of concentration from 1.0 × 10,-4, g/L to 1.0 g/L,the reflection wavelength of TC-MMIPCs redshifts from 500 nm to 578 nm.The logarithm of the concentration of TC exhibits a linear relationship with the reflection wavelength in this range.The detection limit(,S,/,N ,= 3) was 1.0 × 10,-4, g/L and the response equilibrium time of the TC-MMIPCs sensor did not exceed 30 s.Such a rapid response was attributed to the surface imprinting.The imprinting factor of the TC-MMIPCs was 3.41 and the response was specific with the selection factor of 5.92 for chloramphenicol,which is structurally similar to the tetracycline.TC-MMIPCs were successfully applied to determine TC in the actual samples.A brand of soothing moisturizing spray was analyzed,the TC content in the moisturizing spray was obtained based on the linear curve of the TC concentration and the reflection wavelength obtained previously,and no TC was detected in the moisturizing spray.
磁性胶体纳米粒子磁响应性光子晶体分子印迹技术四环素双亲性无规共聚物
magnetic colloidal nanoparticlesmagneto-responsive photonic crystalmolecular imprinting technologytetracyclineamphiphilic random copolymer
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