Bimetallic MOF synergy molecularly imprinted ratiometric electrochemical sensor based on MXene decorated with polythionine for ultra-sensitive sensing of catechol

作者：Lu, Zhiwei^*; Wei, Kai; Ma, Hao; Duan, Rongtao; Sun, Mengmeng; Zou, Ping; Yin, Jiajian; Wang, Xianxiang; Wang, Yanying; Wu, Chun; Su, Gehong; Wu, Mingjun; Zhou, Xinguang; Ye, Jianshan^*; Rao, Hanbing^*

来源：Analytica Chimica Acta, 2023, 1251: 340983.

DOI：10.1016/j.aca.2023.340983

• Ratiometric strategy
• Electrochemical sensor
• Molecularly imprinted polymer
• MXene
• Catechol

Dual-signal ratiometric molecularly imprinted polymer (MIP) electrochemical sensors with bimetallic active sites and high-efficiency catalytic activity were fabricated for the sensing of catechol (CC) with high selectivity and sensitivity. The amino-functionalization bimetallic organic framework materials (Fe@Ti-MOF-NH2), coupled with two-dimensional layered titanium carbide (MXene) co-modified glassy carbon electrode provides an expanded surface while amplifying the output signal through the electropolymerization immobilization of pol-ythionine (pTHi) and MIP. The oxidation of CC and pTHi were presented as the response signal and the internal reference signal. The oxidation peak current at +0.42 V rose with increased concentration of CC, while the peak currents of pTHi at-0.20 V remained constant. Compared to the common single-signal sensing system, this one (MIP/pTHi/MXene/Fe@Ti-MOF-NH2/GCE), a novel ratiometric MIP electrochemical sensor exhibited two segments wide dynamic range of 1.0-300 mu M (R2 = 0.9924) and 300-4000 mu M (R2 = 0.9912), as well as an ultralow detection limit of 0.54 mu M (S/N = 3). Due to the specific recognition function of MIPs and the ad-vantages of built-in correction of pTHi, the prepared surface imprinting sensor presented an excellent perfor-mance in selectivity and reproducibility. Besides, this sensor possessed superior anti-interference ability with ions and biomolecules, excellent reproducibility, repeatability, and acceptable stability. Furthermore, the pro-posed sensing system exhibits high specific recognition in the determination of environmental matrices and biological fluids in real samples with satisfactory results. Therefore, this signal-enhanced ratiometric MIP elec-trochemical sensing strategy can accurately and selectively analyze and detect other substances.