A S-La based 0.3 Ni 0.7 CuO 2.5 Method for detecting zearalanol based on polyhedron of multi-metal oxides

Abstract

The present invention belongs to the technical field of preparation of sensing interfaces for detecting environmental pollutants such as zearalanol, and specifically relates to a sulfur-doped multimetal oxide S-La 0.3 Ni 0.7 CuO 2.5 Preparation method of polyhedron and its application in the detection of zearalanol. The ultrasensitive detection of zearalanol described in the present invention is achieved by constructing an electrochemical sensor. 0.3 Ni 0.7 CuO 2.5+x polyhedron, and then use chemical vapor deposition to dope non-metallic sulfur to obtain sulfur-doped multi-metal oxide S-La 0.3 Ni 0.7 CuO 2.5 Polyhedron. As a sensing substrate material, S‑La 0.3 Ni 0.7 CuO 2.5 The electron-hole recombination rate can be effectively reduced and the utilization rate of light can be improved. 0.3 Ni 0.7 CuO 2.5 Photoelectrochemical sensing strategy based on multi-metal oxide polyhedrons improves the detection signal intensity and sensitivity of the sensor. The detection range of zearalanol is 0.1 pg·mL ‑1 ~100 ng·mL ‑1 , the detection limit was 38 fg·mL ‑1 The patent of this invention solves the problem that the traditional zearalanol detection method cannot accurately detect low concentrations. This technology will provide a strong basis for future environmental and food analytical chemistry.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of electrode materials for zearalanol detection, and particularly relates to an electrode material based on S-La 0.3 Ni 0.7 CuO 2.5 Preparation method and application of electrode materials of multi-metal oxide polyhedron zearalanol photoelectrochemical sensor. Background Art

[0002] Zearalenol, also known as "right-cyclotetradecanol", with the trade name "Hu Da Zhuang", is a reduction product of zearalenone, a secondary metabolite produced by corn gibberella during its growth process. It belongs to the class of non-steroidal anabolic hormones of the rasololide class. Zearalenol is an ideal embedded weight gain agent, which mainly acts directly or indirectly on the pituitary gland and pancreas to increase the levels of growth hormone and insulin in the body, promote the synthesis of body protein, and improve feed utilization, thereby promoting weight gain. In animal husbandry, it is widely used as a feed additive for ruminants to increase their growth rate and feed conversion rate. However, due to its certain harmfulness to mammals, including significant effects on the reproductive system, the European Union banned the use of hormone drugs such as zearalenol in livestock and poultry farming in 1998. China also clearly stipulated in 2002 that zearalenol is prohibited for all food animals and must not be detected in all edible animals. In addition, zearalanol and its metabolites have the biological activity of estrogen-like substances, which may cause disorders in the function of human sex hormones, affect the normal development of secondary sexual characteristics, and may cause cancer under external conditions. Therefore, all countries have strengthened the detection and monitoring of zearalanol residues in animal products.

[0003] Photoelectrochemical immunoassay is an analytical method that combines photoelectrochemical technology with the principle of immune response. Its basic principle is to use the electron-hole pairs generated by the photoactive material after absorbing energy under illumination conditions to form photocurrent or photovoltage through the transfer of electrons. When an immune response occurs, it will indirectly or directly change the electrical signal originally generated by the photoactive material. By monitoring the changes in these electrical signals, the quantitative determination of the target substance can be achieved. Photoelectrochemical immunoassay technology combines the sensitivity of photoelectrochemical technology with the high specificity of immune response, providing a new analytical method for biomedicine, environmental monitoring and other fields. This technology can detect trace substances with high sensitivity and accuracy. At the same time, due to the high specificity of immune response, this technology can selectively detect target substances and avoid interference from other substances. In the biomedical field, photoelectrochemical immunoassay technology can be used to detect biomarkers, disease-related antigens or antibodies, etc., providing an important basis for the early diagnosis and treatment of diseases. In addition, this technology can also be used in environmental monitoring to monitor harmful substances or pollutants in the environment, providing technical support for environmental protection and pollution control.

[0004] Polymetallic oxides have shown unique properties and application potential in the field of photoelectrochemistry. This type of material has a variety of molecular structures and adjustable energy band gaps, which makes them play an important role in the process of photoelectric energy conversion. First, as electron acceptors and photogenerated charge transport media, polymetallic oxides can effectively capture photogenerated electrons in semiconductor materials, thereby promoting charge separation and transport. This feature gives polymetallic oxides significant advantages in applications such as solar cells and photoelectrochemistry. Secondly, polymetallic oxides have unique light absorption characteristics. They can show strong light absorption capabilities in the visible and ultraviolet regions, thereby improving the photoelectric conversion efficiency. By regulating the material structure and chemical composition, the light absorption performance of polymetallic oxides can be further optimized to meet the needs of different application fields. In addition, polymetallic oxides also have excellent chemical stability and thermal stability. This enables them to maintain stable photoelectrochemical properties in harsh environments such as high temperature and high humidity, thereby broadening their application fields.

[0005] The photoelectrochemical properties of multi-metal oxides combined with the advantages of photoelectrochemical immunoassay technology provide a powerful tool for the ultrasensitive detection of zearalanol. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the defects of the prior art and provide a 0.3 Ni 0.7 CuO 2.5The invention discloses a method for preparing a photoelectrochemical sensing platform using multi-metal oxide polyhedrons for detecting zearalanol, which improves the photocurrent signal of the sensor, improves the detection sensitivity, and improves the stability of the photoelectric sensing platform.

[0007] The S-La of the present invention 0.3 Ni 0.7 CuO 2.5 The preparation method of multi-metal oxide polyhedron and its application in zearalanol detection include the following steps: 1. S-La 0.3 Ni 0.7 CuO 2.5 Preparation (1) One-step preparation of La 0.3 Ni 0.7 CuO 2.5+x Nano polyhedron Weigh LaCl3, Ni(NO3)2·6H2O, Cu(NO3)2, and urea in the ratio of (1.0~3.0) g: (0.3~5.5) g: (2.0~10.0) g: (5.0~25.0) g using an electronic balance, and prepare a solution with 1000 mL of ethylene glycol; weigh 0.1~100 mg of octadecyltrimethylammonium bromide into the above solution, ultrasonicate the solution for 30 min at room temperature, and then place it in a polytetrafluoroethylene-lined autoclave and react at 100~180°C for 10~100 h; LaCl3 can be obtained. 0.3 Ni 0.7 CuO 2.5+x Nanopolyhedron; (2) Sulfur-doped multimetal oxide S-La 0.3 Ni 0.7 CuO 2.5 Preparation of polyhedrons The La 0.3 Ni 0.7 CuO 2.5+x The nanopolyhedron was placed downstream of the tube furnace, and 1.0-5.0 g of sublimated sulfur was placed upstream. In a nitrogen atmosphere, it was heated from room temperature to 600-1200 °C and kept warm for 15-60 min to obtain S-La. 0.3 Ni 0.7 CuO 2.5 ; (3) Amide-doped polymetallic oxide polyhedron S-La 0.3 Ni 0.7 CuO 2.5 Preparation of -NH2 20 mg of S-La 0.3 Ni 0.7 CuO2.5 5 mL of 3-aminopropyltriethoxysilane was dispersed in 20-300 mL of ethanol solution, ultrasonically treated for 20-60 min, and then kept at 60-120 ° C for 2-4 h. The amino-functionalized S-La was obtained by centrifugation, washing and drying. 0.3 Ni 0.7 CuO 2.5 -NH2 polyhedron.

[0008] 2. Based on S-La 0.3 Ni 0.7 CuO 2.5 Preparation method of photoelectrochemical sensor of multi-metal oxide polyhedron (1) 10 mg of S-La 0.3 Ni 0.7 CuO 2.5 -NH2 was dispersed in 10~50 mL of distilled water and ultrasonically dispersed for 1 h to form a dispersion; (2) 6~20 μL of the above dispersion was modified on the ITO electrode and dried at room temperature to form a film; (3) Add 1~20 µL of 5% glutaraldehyde solution and 1~5 µg / mL zearalanol antibody solution Ab in sequence; (4) Add 3 µL of 0.5-2% BSA solution, wash with ultrapure water, and dry in a refrigerator at 4°C; (5) 6~10 µL, 0.1 pg·mL -1 ~100 ng·mL -1 A series of zearalan alcohol antigen solutions Ag with different concentrations were prepared, rinsed with ultrapure water, and dried in a 4°C refrigerator to obtain a sensor for microcystin.

[0009] 3. Based on S-La 0.3 Ni 0.7 CuO 2.5 Photoelectrochemical sensor based on multi-metal oxide polyhedron for detection of zearalanol (1) The test was carried out using an electrochemical workstation with a three-electrode system, with the Ag / AgCl electrode as the reference electrode, the Pt electrode as the auxiliary electrode, and the prepared zearalanol sensor as the working electrode. The test was carried out in a 0.01-0.5 mol / L PBS buffer solution with a pH of 5.0-8.0. (2) The zearalanol was detected by the time-current method, with the voltage set to -0.2~0.2V, the running time to 40-80s, and the wavelength of the light source to 380~550nm; (3) After the electrodes are placed, turn on the light source for 20 s every 20 s, record the photocurrent, and draw a working curve.

[0010] The photoelectrochemical immunoassay adopted by the present invention is an analytical method that combines photoelectrochemical technology with the principle of immune reaction. The electron-hole pairs generated by the photoactive material after absorbing energy are used to form a photocurrent or photovoltage through the transfer of electrons. When an immune reaction occurs, the electrical signal originally generated by the photoactive material will be indirectly or directly changed. By monitoring the changes in these electrical signals, the quantitative determination of the target substance can be achieved. Due to the high specificity of the immune reaction, this technology can selectively detect the target substance and avoid interference from other substances.

[0011] The multi-metal oxides prepared by the present invention exhibit unique molecular structures and adjustable energy band gaps in the field of photoelectrochemistry. As electron acceptors and photogenerated charge transport media, multi-metal oxides can effectively capture photogenerated electrons in semiconductor materials, thereby promoting charge separation and transport. This feature gives multi-metal oxides significant advantages in applications such as solar cells and photoelectrochemistry. Secondly, multi-metal oxides have unique light absorption characteristics. They can exhibit strong light absorption capabilities in the visible and ultraviolet regions, thereby improving the photoelectric conversion efficiency. By regulating the material structure and chemical composition, the light absorption performance of multi-metal oxides can be further optimized to meet the needs of different application fields. In addition, multi-metal oxides also have excellent chemical stability and thermal stability. This enables them to maintain stable photoelectrochemical properties in harsh environments such as high temperature and high humidity, thereby broadening their application fields.

[0012] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention prepared S-La for the first time 0.3 Ni 0.7 CuO 2.5 Multi-metal oxide polyhedrons with excellent magneto-optical properties and good biocompatibility.

[0013] (2) S-La prepared by the present invention 0.3 Ni 0.7 CuO 2.5 Multi-metal oxide polyhedral electrode materials can effectively capture photogenerated electrons in semiconductor materials, thereby promoting charge separation and transmission and improving the stability of the photoelectric sensing platform.

[0014] (3) S-La prepared by the present invention 0.3 Ni 0.7 CuO 2.5 Polymetallic oxide polyhedral electrode materials, due to their unique polyhedral structure, have unique light absorption characteristics and can exhibit strong light absorption capabilities in the visible and ultraviolet light regions, thereby improving the photoelectric conversion efficiency.

[0015] (4) S-La prepared by the present invention 0.3 Ni 0.7 CuO 2.5 Polyhedral electrode materials of multi-metal oxides, due to the doping of non-metallic sulfur, can effectively capture photogenerated electrons in semiconductor materials, thereby promoting the separation and transport of charges.

[0016] (5) The photoelectrochemical zearalanol sensor constructed by the present invention has the advantages of low cost, high sensitivity, high selectivity, rapid detection, and easy preparation, and achieves the purpose of rapid ultrasensitive detection of zearalanol under visible light conditions. The linear range of zearalanol detection in the present invention is 0.1 pg·mL -1 ~100 ng·mL -1 , the detection limit was 38 fg·mL -1 . BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 La prepared in step (1) of Example 1 0.3 Ni 0.7 CuO 2.5+X SEM images of polyhedrons of multimetal oxides; Figure 2 S-La prepared in step (1) of Example 1 0.3 Ni 0.7 CuO 2.5 Transmission electron microscopy images of polyhedrons of multimetal oxides; Figure 3 is a stability diagram of the zearalanol photoelectrochemical sensor prepared in Example 2; Figure 4 This is a reproducibility diagram of the zearalanol photoelectrochemical sensor prepared in Example 2; Figure 5 This is a diagram showing the linear range of detection of zearalanol by the sensor prepared in Example 3. DETAILED DESCRIPTION

[0018] The present invention will be further described below in conjunction with specific embodiments. Example

[0019] The S-La 0.3 Ni 0.7 CuO 2.5 The preparation comprises the following steps: (1) One-step preparation of La 0.3 Ni 0.7 CuO 2.5+x Nano polyhedron LaCl3, Ni(NO3)2·6H2O, Cu(NO3)2, and urea were weighed in the proportion of 1.0 g:0.3 g:2.0 g:5.0 g using an electronic balance, and then prepared into a solution with 1000 mL of ethylene glycol; 0.5 mg of octadecyltrimethylammonium bromide was weighed into the above solution, and the solution was ultrasonicated for 30 min at room temperature, and then placed in a polytetrafluoroethylene-lined autoclave for reaction at 140 °C for 20 h; LaCl3 was obtained. 0.3 Ni 0.7 CuO 2.5+x Nanopolyhedron; (2) Sulfur-doped multimetal oxide S-La 0.3 Ni 0.7 CuO 2.5 Preparation of polyhedrons The La 0.3 Ni 0.7 CuO 2.5+x The nanopolyhedron was placed downstream of the tube furnace, and 3.0 g of sublimated sulfur was placed upstream. In a nitrogen atmosphere, it was heated from room temperature to 800 °C and kept at this temperature for 30 min to obtain S-La. 0.3 Ni 0.7 CuO 2.5 ; (3) Amide-doped polymetallic oxide polyhedron S-La 0.3 Ni 0.7 CuO 2.5 Preparation of -NH2 20 mg of S-La 0.3 Ni 0.7 CuO 2.5 5 mL of 3-aminopropyltriethoxysilane was dispersed in 1300 mL of ethanol solution, ultrasonicated for 20 min, and then kept at 100 °C for 2 h. The amino-functionalized S-La was obtained by centrifugation, washing, and drying. 0.3 Ni 0.7 CuO 2.5 -NH2 polyhedron. Example

[0020] The S-La 0.3 Ni 0.7 CuO 2.5 The preparation method of the multi-metal oxide polyhedron zearalanol sensor comprises the following steps: (1) 10 mg of S-La 0.3 Ni 0.7 CuO 2.5 -NH2 was dispersed in 30 mL of distilled water and ultrasonically dispersed for 1 h to form a dispersion; (2) 6 μL of the above dispersion was applied to the ITO electrode and dried at room temperature to form a film; (3) Add 10 µL of 5% glutaraldehyde solution and 1 µg / mL zearalanol antibody solution Ab in sequence; (4) Add 3 µL of 0.5% BSA solution, wash with ultrapure water, and dry in a refrigerator at 4°C; (5) 6 µL, 0.1 pg mL -1 ~100 ng·mL -1 A series of zearalan alcohol antigen solutions Ag with different concentrations were prepared, rinsed with ultrapure water, and dried in a 4°C refrigerator to obtain a sensor for microcystin. Example

[0021] The S-La 0.3 Ni 0.7 CuO 2.5 The detection of zearalanol by the multi-metal oxide polyhedron sensor includes the following steps: (1) The test was carried out using an electrochemical workstation with a three-electrode system, with the Ag / AgCl electrode as the reference electrode, the Pt electrode as the auxiliary electrode, and the prepared zearalanol sensor as the working electrode. The test was carried out in a 0.05 mol / L PBS buffer solution with a pH of 7.0. (2) The zearalanol was detected by the time-current method, with the voltage set to -0.2 V, the running time to 60 s, and the light source wavelength to 450 nm; (3) After the electrodes are placed, turn on the light source for 20 s every 20 s, record the photocurrent, and draw a working curve.

Claims

1. A S-La 0.3 Ni 0.7 CuO 2.5 Preparation method of multi-metal oxide polyhedron and its application in zearalanol detection, the S-La 0.3 Ni 0.7 CuO 2.5 Preparation, characterized in that: The following steps are involved: (1) One-step preparation of La 0.3 Ni 0.7 CuO 2.5+x Nano polyhedron Use an electronic balance to weigh LaCl3, Ni(NO3)2·6H2O, Cu(NO3)2, and urea in the ratio of (1.0~3.0) g: (0.3~5.5) g: (2.0~10.0) g: (5.0~25.0) g, and use 1000 mL of ethylene glycol to prepare a solution; weigh 0.1~100 mg of octadecyltrimethylammonium bromide into the above solution, ultrasonicate the solution for 30 min at room temperature, and then place it in a polytetrafluoroethylene-lined high-pressure reactor and react at 100~180℃ for 10~100 h; LaCl3 can be obtained. 0.3 Ni 0.7 CuO 2.5+x Nanopolyhedron; (2) Sulfur-doped multimetal oxides S-La 0.3 Ni 0.7 CuO 2.5 Preparation of polyhedrons The La 0.3 Ni 0.7 CuO 2.5+x The nanopolyhedron was placed downstream of the tube furnace, and 1.0-5.0 g of sublimated sulfur was placed upstream. In a nitrogen atmosphere, it was heated from room temperature to 600-1200 °C and kept warm for 15-60 min to obtain S-La. 0.3 Ni 0.7 CuO 2.5 ; Sulfur amide doped polyhedron S-La in polymetallic oxides 0.3 Ni 0.7 CuO 2.5 Preparation of -NH2 20 mg of S-La 0.3 Ni 0.7 CuO 2.5 5 mL of 3-aminopropyltriethoxysilane was dispersed in 20-300 mL of ethanol solution, ultrasonically treated for 20-60 min, and then kept at 60-120 °C for 2-4 h. The amino-functionalized S-La was obtained by centrifugation, washing and drying. 0.3 Ni 0.7 CuO 2.5 -NH2 polyhedron.

2. A S-La 0.3 Ni 0.7 CuO 2.5 The preparation method of multi-metal oxide polyhedron and its application in the detection of zearalanol, the preparation method of the photoelectrochemical sensor is characterized in that: The following steps are involved: (1) 10 mg of S-La 0.3 Ni 0.7 CuO 2.5 -NH2 was dispersed in 10-50 mL of distilled water and ultrasonically dispersed for 1 h to form a dispersion; (2) 6~20 μL of the above dispersion was modified on the ITO electrode and dried at room temperature to form a film; (3) Add 1~20 µL of 5% glutaraldehyde solution and 1~5 µg / mL zearalanol antibody solution Ab in sequence; (4) Add 3 µL of 0.5-2% BSA solution, wash with ultrapure water, and dry in a refrigerator at 4°C; (5) 6~10 µL, 0.1 pg·mL -1 ~100 ng·mL -1 A series of zearalan alcohol antigen solutions Ag with different concentrations were prepared, rinsed with ultrapure water, and dried in a 4°C refrigerator to obtain a sensor for microcystin.

3. A S-La 0.3 Ni 0.7 CuO 2.5 A preparation method of a multi-metal oxide polyhedron and its application in the detection of zearalanol, wherein the detection of zearalanol is characterized in that: The following steps are involved: (1) The test was carried out using an electrochemical workstation with a three-electrode system, with the Ag / AgCl electrode as the reference electrode, the Pt electrode as the auxiliary electrode, and the prepared zearalanol sensor as the working electrode. The test was carried out in a 0.01-0.5 mol / L PBS buffer solution with a pH of 5.0-8.

0. (2) The zearalanol was detected by the time-current method, with the voltage set to -0.2~0.2V, the running time to 40-80s, and the wavelength of the light source to 380~550nm; (3) After the electrodes are placed, turn on the light source every 20 seconds for 20 seconds, record the photocurrent, and draw a working curve.

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