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应用化学
Chinese Journal of Applied Chemistry    2018, Vol. 35 Issue (4) : 484-490     DOI: 10.11944/j.issn.1000-0518.2018.04.170107
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Preparation and Application of Bisphenol-A TiO2 Gel Molecularly Imprinted Electrochemical Sensor Based on the Sensitivity-Enhancement of Gold Nanoparticles
Lingling LI,Shaoming YANG(),Shaoqing DING,Peiling SHANG,Jie YANG,Qiang CAO,Wenling ZHA
School of Materials Science and Engineering,East China Jiaotong University,Nanchang 330013,China
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Abstract  

A bisphenol-A(BPA) TiO2 gel molecularly imprinted electrochemical sensor was fabricated using gold nanoparticles(AuNPs) as sensitivity-enhanced materials based on surface sol-gel and self-assembly methods. AuNPs were characterized by scanning electron microscopy(SEM) and energy dispersive spectroscopy. BPA, TiO2 gel, and BPA-imprinted TiO2 gel were characterized by Fourier transform infrared(FTIR) spectrometry. Under optimal conditions, the sensor exhibits a good linear response from 1.0×10-8 to 1.0×10-5 mol/L for bisphenol A, with correlation coefficient 0.995 and a low detection limit of 0.6×10-8 mol/L(S/N=3). The prepared sensor was successfully applied in the detection of actual sample with 97.4%~103% recoveries.

Keywords gold nanoparticles      bisphenol A      TiO2      sol-gel method      self-assembly method      molecularly imprinted sensor     
Fund:Supported by the National Natural Science Foundation of China(No.21465012), Natural Science Foundation of Jiangxi Province of China(No.20171BAB203017), Scientific Research Fund of Jiangxi Provincial Education Department(No.GJJ150544), Scientific Research Project of East China Jiaotong University(No.15LX03)
Corresponding Authors: Shaoming YANG     E-mail: yangsm79@163.com
Received: 2017-04-12           Accepted: 2017-06-23
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Lingling LI
Shaoming YANG
Shaoqing DING
Peiling SHANG
Jie YANG
Qiang CAO
Wenling ZHA
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Lingling LI,Shaoming YANG,Shaoqing DING, et al. Preparation and Application of Bisphenol-A TiO2 Gel Molecularly Imprinted Electrochemical Sensor Based on the Sensitivity-Enhancement of Gold Nanoparticles[J]. Chinese Journal of Applied Chemistry, 2018, 35(4): 484-490.
URL:  
http://yyhx.ciac.jl.cn/EN/10.11944/j.issn.1000-0518.2018.04.170107     OR     http://yyhx.ciac.jl.cn/EN/Y2018/V35/I4/484
Fig.1SEM image of AuNPs/GCE(A) and EDS of AuNPs/GCE(B)
Fig.2FTIR spectra of BPA(a), TiO2 gel(b) and BPA-imprinted TiO2 gel(c)
Fig.3Electrochemical impedance specta(EIS) of different sensors in 5 mmol/L K3[Fe(CN)6]/K4[Fe(CN)6](contain 0.1 mol/L KCl) of PBS solution
a.bare GCE; b.AuNPs/GCE; c.MCH/AuNPs/GCE; d.MIP/MCH/AuNPs/GCE after removing the template; e.MIP/MCH /AuNPs/GCE after rebinding BPA; f.MIP/MCH/AuNPs/GCE before removing the template
The top right inset is the equivalent circuit diagram; bottom right inset is the EIS of electrodes e and f
Fig.4DPV of different molecularly imprinted sensors in a 0.1 mol/L NaCl+5.0 mmol/L K3[Fe(CN)6]+PBS(pH=7.4)solution
Electrodes:a.AuNPs/GCE; b.bare GCE; c.MCH/AuNPs/GCE; d.MIP/MCH/AuNPs/GCE after removing the template; e.MIP/MCH/AuNPs/GCE after rebinding BPA; f.MIP/MCH/AuNPs/GCE before removing the template
DPV parameter:ΔE 0.004 V, amplitude 0.05 V, pulse width 0.05 s, pulse period 0.2 s
Fig.5DPV of different modified electrodes in a 0.1 mol/L NaCl+5.0 mmol/L K3[Fe(CN)6]+PBS(pH=7.4) solution
Electrodes:a.MIP/MCH/AuNPs/GCE after removing the template; b.MIP/MCH/GCE after removing the template; c.MIP/MCH/AuNPs/GCE before removing the template; d.NIP/MCH/AuNPs/GCE before removing the template; e.NIP/MCH/AuNPs/GCE after removing the template
DPV parameter:ΔE 0.004 V, amplitude 0.05 V, pulse width 0.05 s, pulse period 0.2 s
Fig.6Influence of different elution solutions on the current response of MIP/MCH/AuNPs/GCE sensor
Fig.7Effect of incubation time on the response of MIP/MCH/AuNPs/GCE sensor
Incubation time:5, 6, 7, 8, 9, 10, 11 and 12 min
Fig.8DPV curves of BPA with different concentrations at MIP/MCH/AuNPs/GCE sensor(A) and linear fitting curve of ΔI-lg c(B)
c(BPA) of curves a~g/(mol·L-1):0, 1.0×10-8, 5.0×10-8, 1.0×10-7, 5.0×10-7, 1.0×10-6, 5.0×10-6, 1.0×10-5&DPV parameter:ΔE 0.004 V, amplitude 0.05 V, pulse width 0.05 s, pulse period 0.2 s
Fig.9Response of MIP/MCH/AuNPs/GCE and NIP/MCH/AuNPs/GCE sensors to different substances
Serum samples c(Added)/(μmol·L-1) c(Found)/(μmol·L-1) Recovery/%
1 0.1 0.098 98
2 1.0 1.03 103
3 10.0 9.74 97.4
Table 1The results of BPA determined by MIP/MCH/AuNPs/GCE sensor
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