刘畅,王园,袁修华,等. 电场调控激光诱导石墨烯基重金属电化学检测装置的研制[J]. 农业工程学报,2024,40(4):221-229. DOI: 10.11975/j.issn.1002-6819.202310023
    引用本文: 刘畅,王园,袁修华,等. 电场调控激光诱导石墨烯基重金属电化学检测装置的研制[J]. 农业工程学报,2024,40(4):221-229. DOI: 10.11975/j.issn.1002-6819.202310023
    LIU Chang, WANG Yuan, YUAN Xiuhua, et al. Fabrication of electric field-regulated electrochemical sensing device with laser-induced graphene for heavy metal detection[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2024, 40(4): 221-229. DOI: 10.11975/j.issn.1002-6819.202310023
    Citation: LIU Chang, WANG Yuan, YUAN Xiuhua, et al. Fabrication of electric field-regulated electrochemical sensing device with laser-induced graphene for heavy metal detection[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2024, 40(4): 221-229. DOI: 10.11975/j.issn.1002-6819.202310023

    电场调控激光诱导石墨烯基重金属电化学检测装置的研制

    Fabrication of electric field-regulated electrochemical sensing device with laser-induced graphene for heavy metal detection

    • 摘要: 为了快速、精准分析农田重金属,该文设计了一款基于施加电场与激光诱导石墨烯(laser-induced graphene,LIG)电极阵列的功能核酸比率电化学检测装置,用于农田中典型重金属离子Hg2+、Pb2+的分析。该装置主要包括电场施加模块与LIG电极阵列传感器两个部分,前者以AT89S52单片机作为主控芯片、DAC0832作为电压输出端口,设计单片机控制电压输出的电场施加装置,实现了可编程电压的稳定输出;后者则通过结合CO2激光直写和环氧树脂转印技术,提出了LIG电极阵列的快速制备方法,并进一步构建了LIG基功能核酸比率电化学传感器。在检测过程中,通过调控施加电场的性质,该装置实现了Hg2+、Pb2+在传感器表面的快速特异性富集以及响应信号的稳定获取,其对Hg2+、Pb2+检测限分别低至8.5×10−12 mol/L(4.25×10−11 mg/L)和4.6×10−13 mol/L(2.22×10−12 mg/L)(S/N=3),实现了农田灌溉用水中Hg2+、Pb2+的现场精准检测。该装置利用施加电场与LIG阵列传感器,实现了重金属离子的快速、精准、现场分析需求,对于农田环境重金属污染的监测及治理具有重要意义。

       

      Abstract: Heavy metal pollution is one of the most serious risks to sustainable agriculture in China. Among them, mercury (Hg) and lead (Pb) are two of the most hazardous heavy metals. Typically, Hg2+ and Pb2+ are believed to threaten the growth of crops and the quality of agricultural products, when entering the farmland via atmospheric sedimentation and irrigation. As a result, it is urgent to develop efficient devices for the accurate, rapid and on-site detection of Hg2+ and Pb2+ in farmland. In this work, a functional nucleic acid (FNA)-based ratiometric and electrochemical device was developed to couple the microcontroller unit (MCU) voltage application and laser-induced graphene (LIG) electrode array. A series of experiments were carried out to verify the feasibility of this device for the Hg2+ and Pb2+ detection in farmland. The electric field was designed to improve the analytical performance. Briefly, the 3.0V electric field was applied to push the Hg2+ and Pb2+ approaching FNA, while retaining the orientation of FNA at the surface of the LIG electrode; The 2.5 V electric field was also used to collect the signals, where the FNA orientation was remained to provide a constant current as a reference signal. The single-chip microcomputer (AT89S52) was selected as the main control chip on the applied voltage, while the DAC0832 was the output port of voltage. The electric field generator was developed to control the output voltage using a single-chip microcomputer. The programmable output of voltage was realized to verify the stability of voltage signal output by oscilloscope. The electric field was utilized to enhance the preconcentration of heavy metals. The output voltage and time were directly displayed on the LCM display. LIG electrode array was applied to fabricate the FNA-based biosensor. The CO2 laser direct writing was utilized to prepare the LIG electrode. One step free of any treatment was realized to prepare the working, reference, and counter electrodes. The large surface area and high conductivity of graphene allowed for the high performance of the as-prepared sensor. The epoxy resin transfer was also developed to efficiently fabricate the LIG electrode array. The LIG-based reference electrode showed higher stability and reliability, compared with the commercial Ag/AgCl ones. The ferrocene (Fc)-labeled FNA for Hg2+, and methylene blue (MB)-labeled FNA for Pb2+ were bound to the anthraquinone-2-carboxylic acid (AQ)-labeled complementary DNA (cDNA), in order to assemble the sensing interface at the LIG electrode array. Double-stranded DNA (dsDNA) was obtained to assemble on the LIG electrode array. Then, the MCU voltage module and LIG electrode array were combined to assemble the detection device. And the currents of MB (IMB), Fc (IFc), and AQ (IAQ) were recorded by the electrochemical workstation. The ratios of IAQ/IFc and IAQ/IMB increased at the higher concentration of Hg2+ and Pb2+, thus representing the response signal for the detection of Hg2+ and Pb2+, respectively. Consequently, the higher limits of detection were achieved in 8.5×10−12 mol/L (4.25×10−11 mg/L) and 4.6×10−13 mol/L (2.22×10−12 mg/L) (S/N=3) for Hg2+ and Pb2+, respectively. The linear ranges of this device were 1.0×10−11-1.0×10−8 mol/L (5×10−11-5×10−8 mg/L), 1.0×10−12-1.0×10−9 mol/L (4.8×10−12-4.8×10−9 mg/L) for the detection of Hg2+ and Pb2+, respectively. Moreover, the high selectivity was realized in the field of accurate detection of Hg2+ and Pb2+. This device was successfully used to analyze the water for agricultural irrigation. At last, the reliability of the detection was also validated by the gold standard of inductively coupled plasma mass spectrometry (ICP-MS). The findings can offer scientific information to monitor and remediate heavy metal pollution.

       

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