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

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.