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Smart Agriculture ›› 2022, Vol. 4 ›› Issue (3): 143-151.doi: 10.12133/j.smartag.SA202205006

• 专刊--智慧果园关键技术与装备 • 上一篇    

基于卟啉和半导体单壁碳纳米管的场效应气体传感器检测草莓恶疫霉

王辉1(), 陈睿鹏1, 余志雪1, 贺越1,2, 张帆1,2, 熊本海1()   

  1. 1.中国农业科学院北京畜牧兽医研究所 动物营养国家重点实验室, 北京 100193
    2.中国农业大学 动物科技学院, 北京 100193
  • 收稿日期:2022-05-18 出版日期:2022-09-30 发布日期:2022-11-23
  • 基金资助:
    国家自然科学基金(2202738);2021年新一代人工智能(2030)任务书项目(2021ZD0113801);中国农业科学院基本业务费专项(2021-YWF-ZYSQ-05)
  • 作者简介:王 辉(1988-),男,博士,助理研究员,研究方向为农业信息感知、疾病诊断。E-mail:wanghui_lunwen@163.com
  • 通讯作者: 熊本海 E-mail:wanghui_lunwen@163.com;xiongbenhai@caas.cn

Porphyrin and Semiconducting Single Wall Carbon Nanotubes based Semiconductor Field Effect Gas Sensor for Determination of Phytophthora Strawberries

WANG Hui1(), CHEN Ruipeng1, YU Zhixue1, HE Yue1,2, ZHANG Fan1,2, XIONG Benhai1()   

  1. 1.State Key Laboratory of Animal Nutrition, Institute of Animal Science, Chinese Academy of Agricultural Sciences, Beijing 100193
    2.College of Animal Science and Technology, China Agricultural University, Beijing 100193, China
  • Received:2022-05-18 Online:2022-09-30 Published:2022-11-23
  • corresponding author: XIONG Benhai E-mail:wanghui_lunwen@163.com;xiongbenhai@caas.cn

摘要:

草莓恶疫霉会引起草莓革腐病和冠腐病,影响草莓的经济效益,但感染恶疫霉早期植株没有明显的症状,无法被及时准确地诊断,因此迫切需要低成本诊断方法实现早期预防。草莓植株感染恶疫霉会释放一种独特的有机挥发性气体4-乙基苯酚,可作为该疾病快速诊断的标志性气体。本研究使用半导体单壁碳纳米管(Single-Wall Carbon Nanotube,SWNT)和场效应传感器(Field Effect Transistor,FET)制备半导体场效应气体传感器(SWNT/FET),进而修饰对4-乙基苯酚灵敏度高、选择性好的金属卟啉MnOEP获得MnOEP-SWNT/FET。通过拉曼光谱、紫外光谱、伏安分析法研究MnOEP-SWNT/FET,分析理化性能及优化检测条件,提高MnOEP-SWNT/FET对4-乙基苯酚的气体敏感性能。在最优检测条件下,MnOEP-SWNT/FET对0.25%~100%的4-乙基苯酚饱和蒸汽(20 ℃),检出限为0.15%的4-乙基苯酚饱和蒸气(S/N =3),测定不同浓度的相对标准误差低于10%。通过测定实际样本,表明MnOEP-SWNT/FET检测草莓健康植株会存在假阳性,但对感染恶疫霉的草莓植株有较高的检测精度。

关键词: 草莓, 真菌感染检测, 气体传感器, 纳米复合材料, 场效应晶体管, 4-乙基苯酚, 半导体单壁碳纳米管, 场效应传感器

Abstract:

Phytophthora strawberries, as a kind of plant pathogenic fungi, can cause strawberry skin and crown rot without safe and effective treatment, which affect the economic benefits of planting strawberries. Therefore, it is urgent to use low-cost diagnostic methods to achieve early prevention. Strawberry plants infected with Phytophthora cactorum would release a unique organic volatile gas, 4-ethylphenol, with a concentration ranging from 1.12 to 22.56 mg/kg, which could be used as a marker gas for rapid diagnosis of the disease. In this study, semiconducting single-walled carbon nanotubes (SWNT) and field effect sensors (FET) were used to prepare semiconductor field effect gas sensors (SWNT/FET) without selectivity. And then the metal porphyrin MnOEP with high sensitivity and selectivity to 4-ethylphenol was immoblized on the SWNT's surface to obtain MnOEP-SWNT/FET. MnOEP-SWNT/FET has the advantages of low cost, low power consumption, small size, high sensitivity and easy integration, which can effectively overcome the shortcomings of gas chromatography-mass spectrometry, high-performance liquid chromatography and other analytical methods. By comparing the sensitivity and selectivity of different sensors, MnOEP-SWNT/FET is very suitable for real-time monitoring of 4-ethylphenol. The key reasons for the high sensitivity and selectivity are: MnOEP is a macromolecular heterocyclic compound formed by four pyrrole rings connected together by methylene and manganese ion(Mn), each pyrrole ring consists of four carbons and one nitrogen, and all nitrogen atoms inside the ring form a central cavity; the coordination metal ions of MnOEP are in an unsaturated state, gas molecules can interact with the central metal ions through van der Waals force and hydrogen bond at the axial position of MnOEP to change their own optical or electrical properties. MnOEP-SWNT/FET was studied by Raman spectrum, UV spectrum and voltammetry. The physical and chemical properties were analyzed and the detection conditions were optimized to improve the gas sensitivity of MnOEP-SWNT/FET to 4-ethylphenol. Under the optimal detection conditions, MnOEP-SWNT/FET has a good linear relationship with 0.25% ~100% saturated vapor of 4-ethylphenol (20 ℃) and the detection limit is 0.15% saturated vapor of 4-ethylphenol. The relative standard error of different concentrations was less than 10%. By measuring the actual samples, it has high detection accuracy for strawberry plants infected with Phytophthora, but it still exists false positive for healthy strawberry.

Key words: strawberry, detection of fungal infection, gas sensor, nanocomposites, field effect transistor, 4-ethylphenol, semiconducting single-walled carbon nanotubes, field effect sensor

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