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Molecularly imprinted sensor based on Russian Matryoshka structured molecules for enhanced specific identification and double amplification in ultra-trace Tb3+ determination
Biosensors and Bioelectronics ( IF 12.6 ) Pub Date : 2018-03-14 , DOI: 10.1016/j.bios.2018.03.029
Jianping Li , Bin Yang , Hongcheng Pan , Guobao Xu

The selective and sensitive detection of rare earth elements is thought to be difficult because the concentration of those elements in the sample is commonly at a low level and they normally have severe mutual interference which is caused by homologous chemical properties. In this study, a novel molecularly imprinted polymer (MIP) sensor was fabricated for highly sensitive and selective determination of ultra-trace Tb3+. The Tb3+-ethylenediaminetetraacetic acid complex (Tb-EDTA) as the template molecule was incorporated into mono-6-mercapto-β-cyclodextrin (mono-6-SH-β-CD) to form a Russian Matryoshka (RM)-structured molecule (CD/Tb-EDTA). Titanium isopropoxide was utilized in vapor sol–gel polymerization to construct MIP membrane. Moreover, the selectivity of the RM MIP sensor was remarkably enhanced by the “triple-selectivity” recognition of EDTA-to-Tb3+, β-CD-to-(Tb-EDTA), and 3D cavity-to-(CD/Tb-EDTA), while the sensitivity of the MIP sensor was significantly improved by ECL signal enhancement based on double amplification, in other words, the electrochemiluminescence resonance energy transfer (ECL-RET) between the ECL donor of CD/Tb-EDTA and the ECL acceptor of Ru(bpy)32+, and the ECL enhancement by the co-reactant of CD/Tb-EDTA on Ru(bpy)3Cl2. When the imprinted cavities were occupied by Tb-EDTA during rebinding, the host-guest inclusion structured complex was formed and the ECL intensities produced by the Ru(bpy)3Cl2 ECL system increased with increasing concentration of Tb-EDTA. The proposed sensor was used for quantitative analysis of Tb3+ with concentrations ranging from 8.00 × 10–13 mol/L to 4.00 × 10–9 mol/L and successfully applied to detect Tb3+ in seawater samples. The detection limit of the sensor was found to be 3.90 × 10–13 mol/L (DL = 3δb/K), which is lower than previously reported values. Thus, the fabricated sensor is feasible for practical applications.



中文翻译:

基于俄罗斯Matryoshka结构化分子的分子印迹传感器,用于超痕量Tb 3+测定中的增强的特异性鉴定和双重扩增

人们认为很难对稀土元素进行选择性和灵敏的检测,因为样品中这些元素的浓度通常处于较低水平,并且它们通常具有严重的相互干扰,这是由同源化学特性引起的。在这项研究中,一种新型的分子印迹聚合物(MIP)传感器可用于高灵敏度和选择性测定超痕量Tb 3+。Tb 3+-乙二胺四乙酸复合物(Tb-EDTA)作为模板分子被掺入单-6-巯基-β-环糊精(单-6-SH-β-CD)中以形成俄罗斯套娃(RM)结构的分子(CD / Tb-EDTA)。异丙醇钛用于气相溶胶-凝胶聚合反应中,以构建MIP膜。此外,通过“三重选择性”识别EDTA-Tb 3 +,β-CD-(Tb-EDTA)和3D腔-(CD / Tb-EDTA),而基于双倍放大的ECL信号增强显着提高了MIP传感器的灵敏度,换句话说,CD / Tb-EDTA的ECL供体与C / Tb-EDTA之间的电化学发光共振能量转移(ECL-RET) Ru(bpy)3 2+的ECL受体,以及CD / Tb-EDTA的共反应物对Ru(bpy)3 Cl 2的ECL增强作用。当在重新结合过程中Tb-EDTA占据印迹腔时,形成了宿主-客体包裹结构复合物,Ru(bpy)3 Cl 2 ECL系统产生的ECL强度随着Tb-EDTA浓度的增加而增加。所建议的传感器用于定量分析Tb 3+,浓度范围为8.00×10 –13 mol / L至4.00×10 –9 mol / L,并成功地用于检测海水样品中的Tb 3+。传感器的检测极限被发现是3.90×10 -13 mol / L的(DL =3δ b/ K),低于以前报告的值。因此,所制造的传感器对于实际应用是可行的。

更新日期:2018-03-14
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