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一种对作物Mg2+活体检测的全固态微针型传感器制备及应用

Development and application of an all-solid-state Mg2+ microneedle sensor for crop in-situ detection

  • 摘要: 镁元素对作物的生长发育至关重要,通过监测作物体内镁离子的浓度变化,即可监测作物的生长状态。为实现作物茎杆Mg2+快速准确原位活体检测,研制了一款微针型全固态离子选择性电极(all-solid-state ion-selective electrodes, ASS-ISEs)。该传感器以不锈钢微针为导电基底材料,在其尖端构建石墨烯-聚(3,4-乙烯二氧噻吩) / 聚 (苯乙烯磺酸盐) (PEDOT) 固态转接层,并在固态转接层表面涂附离子选择性敏感膜(ion selective membrane, ISM)。首先,对传感器进行电位校准;然后,通过扫描电子显微镜 (scanning electron microscopy, SEM) 测试、水层测试、电化学阻抗谱(electrochemical impedance spectroscopy, EIS)测试等传感器性能表征方法,对针-石墨烯-PEDOT-ISM型和针-ISM型两种传感器进行对比测试;最后,将传感器应用于小麦苗茎秆Mg2+原位活体检测,并设置对照试验。结果表明,传感器响应时间为7.0 s,检测限低至1.0×10−7 mol/L、能斯特斜率为27.04 mV/dec,寿命可达30 d以上;两种传感器的水层测试及EIS测试结果表明,石墨烯-PEDOT固态转接层结构,可以显著增加离子选择性薄膜和不锈钢基底之间的低频电容,有效抑制水层的形成,降低传感器表面的电荷转移电阻,减少信号漂移,提高响应电位的稳定性。小麦苗茎杆Mg2+原位活体检测结果及纯琼脂和去离子水对照试验结果表明,该传感器可以有效检测其茎杆中Mg2+浓度变化,变化范围为10−3.42~10−3.03 mol/L,检测结果可靠。综上所述,该传感器检测限低、电位响应稳定,可用于作物茎秆Mg2+浓度变化原位活体检测,应用前景广泛。

     

    Abstract: A microneedle all-solid-state selective electrode (ASS-ISE) was developed to rapidly in-situ detect Mg2+ in the crop stems. The electrode consists 3 parts from the inner to the outer layer, consisting of stainless-steel microneedle, solid contact and ion ion-selective membrane (ISM). This sensor was prepared as follows. Firstly, a stainless-steel microneedle was used as the conductive substrates. The graphene conductive layer was coated on the tip of the microneedle after drying for 12 h. And then, a solid-state contact of Poly (3,4-ethylenedioxythiophene) / Poly (styrene sulfonate, PEDOT/PSS) was electroplated onto the graphene surface; After the second drying for 12 h, an ion selective membrane (ISM) was coated on the tip of the microneedle; The sensor was fabricated after the third drying time of 12 h and activation. A series of the accurate measurements were carried out on the sensor. Initially, the sensor was calibrated using a standard concentration of MgCl2 solution. The performance of the graphene-PEDOT solid-state contact was tested using scanning electron microscopy (SEM), water layer test, and electrochemical impedance spectroscopy (EIS). A comparison test was then made on two types of sensors, the needle-graphene-PEDOT-ISM and the needle-ISM sensors. Finally, the sensor was applied to detect the Mg2+ in wheat seedling stalks. Both pure agar and deionized water were used to verify the reliability of the detection. The potentiometric calibration demonstrated that the sensor exhibited a rapid response with a response time of 7.0 s, and a detection limit as low as 1.0 × 10-7 mol/L. The better detection was achieved with a Nernst slope of 27.04 mV/dec and a lifetime of at least 30 days. The SEM test demonstrated that the graphene-PEDOT solid-state contact was substantially improved in the low-frequency capacitance between the ion-selective membrane and the stainless-steel substrate. The water layer test demonstrated that the graphene-PEDOT solid-state contact was effectively inhibited the formation of the water layer for the high stability of the ion-electron transfer of the sensor, thus reducing the signal drift. The EIS fitting test showed that there were the similar equivalent circuit diagrams of the two types of sensors. In addition, the graphene-PEDOT solid-state contact structure was effectively reduced the charge transfer resistance on the sensor surface. The stability of the response potential was improved during the process. The sensor was performed best to detect the concentration of Mg2+ in the stems of the wheat seedlings in the range of about 1.0 ×10-3.42-10-3.03 mol/L. In summary, a wide range of the promising prospects was also gained in the low detection limit, the stable potential response, in-situ detection of Mg2+ concentration in the crop stalks.

     

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