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用于高盐胁迫下番茄叶片脱落酸检测的传感器研制及试验

Development and Test of a BiOI/g-C3N4 Type-II Heterojunction Photoelectrochemical Aptasensor for Detecting Abscisic Acid in Tomato Leaves under High-Salinity Stress

  • 摘要: 脱落酸(Abscisic acid, ABA)是平衡植物内源激素和有关生长活性物质代谢的关键因子。针对盐胁迫下番茄叶片缺乏高灵敏、准确且能实现ABA原位检测的传感器,本研究构建了一种基于碘氧化铋/g-氮化碳(BiOI/g-C3N4) II型异质结的光电化学(Photoelectrochemical,PEC)适配体传感器。首先,利用g-C3N4作为高效载体和光敏化剂,大幅增强了BiOI的光电响应。得益于II型异质结能带结构对电荷分离的促进作用,复合材料的光电流强度较纯 BiOI 提升了约13倍。在此基础上,进一步耦合适配体(Aptamer,Apt)的靶向识别功能构建了一种“信号增强”型识别界面,实现了1 pmol/L~300 nmol/L范围内ABA的定量检测,检出限为0.33 pmol/L。该传感器对100倍浓度共存干扰物仍保持较好的选择性,储存14 d后光电流保持率为91.8%,在15~35 ℃范围内响应稳定。将其用于盐胁迫下番茄叶片ABA的原位监测,结果显示ABA表观浓度随胁迫时间先升高后降低,24 h达到0.896 nmol/L,72 h降至0.417 nmol/L。研究结果表明,该传感器可用于植物叶片ABA的快速、原位检测,并为作物逆境诊断和精准农业传感提供技术参考。

     

    Abstract: Abscisic acid (ABA) is a key endogenous hormone involved in the regulation of seed dormancy, stomatal movement, root architecture and plant responses to abiotic stresses. Rapid and reliable monitoring of ABA in living leaves is therefore important for evaluating crop stress status and supporting precision agricultural management. However, conventional methods such as high-performance liquid chromatography, liquid chromatography–mass spectrometry and enzyme-linked immunosorbent assay generally require co the type-II band alignment and the resulting suppression of electron-hole recombination. On this basis, an ABA-specific aptamer was immobilized on the BiOI/g-C3N4/ITO electrode to construct a signal-enhanced PEC sensing interface. The binding between ABA and the aptamer induced conformational rearrangement of the recognition layer, reduced the interfacial charge-transfer resistance and further promoted electron transport, leading to an increased cathodic photocurrent. Under optimized conditions, the fabricated aptasensor showed a good linear relationship between photocurrent intensity and the logarithm of mplex sample pretreatment, expensive instruments and laboratory-based operation, which limits their use for on-site and dynamic analysis. In this study, a photoelectrochemical (PEC) aptasensor based on a bismuth oxyiodide/graphitic carbon nitride (BiOI/g-C3N4) type-II heterojunction was developed for in situ detection of ABA in tomato leaves under salt stress. BiOI was selected as the main visible-light-responsive semiconductor, while g-C3N4 was introduced as both a carrier and a photosensitizer to improve the separation and transfer of photogenerated charge carriers. The BiOI/g-C3N4 composite was prepared by a simple physical mixing and stirring-assisted method and was systematically characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and ultraviolet-visible diffuse reflectance spectroscopy. The results confirmed that g-C3N4 nanosheets were tightly coupled with flower-like BiOI microspheres, forming an effective heterojunction interface with enhanced visible-light absorption and improved interfacial charge transport. Compared with pure BiOI, the BiOI/g-C3N4-modified electrode exhibited an approximately 13-fold higher photocurrent response, which was attributed toABA concentration in the range of 1 pmol/L to 300 nmol/L, with a correlation coefficient of 0.974 and a detection limit of 0.33 pmol/L. The sensor also exhibited high selectivity against common coexisting substances, including inorganic ions, amino acids, sugars and other plant hormones, even when the interferents were present at 100-fold higher concentrations. In addition, stable responses were maintained within the temperature range of 15~35℃, and 91.8% of the initial signal was retained after 14 days of storage at 4℃. Recovery tests in tomato leaf extracts gave recoveries of 93%~106% with relative standard deviations of 1.1%~2.1%, indicating acceptable accuracy and precision in complex plant matrices. Finally, the paper-based PEC sensing system was applied to the in situ monitoring of ABA in tomato leaves during salt stress. The ABA level increased rapidly at the early stage of stress, reached 0.896 nmol/L at 24 h and then decreased to 0.417 nmol/L at 72 h. This trend was consistent with the physiological role of ABA in early osmotic stress adaptation and subsequent metabolic adjustment. These results demonstrate that the proposed BiOI/g-C3N4 PEC aptasensor provides a sensitive, selective and practical approach for dynamic ABA monitoring in plant leaves and offers a useful sensing strategy for crop stress diagnosis and precision agriculture.

     

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