Photocatalytic water-volatilization self-powered sensor for detecting lincomycin and preparation method thereof

Abstract

The application belongs to the field of electrochemical detection, and particularly relates to a water-vapor self-powered sensor for lincomycin detection and a preparation method thereof. A glass substrate is used as a substrate, a copper foil tape is used as a positive electrode and a negative electrode, a ZnO nanowire array and Ce-MOF are used as power generation materials to prepare a water-vapor generator, and a lincomycin aptamer is assembled to construct a light-assisted water-vapor self-powered sensor. The power generation material is a composite material of the ZnO nanowire array and the Ce-MOF. The light assistance is combined into the water-vapor self-powered sensor, and the water-vapor self-powered sensor significantly improves the generated electric output under the light assistance. The application widens the application of the ZnO nanowire array and the Ce-MOF in water-vapor induced power generation, and provides a new strategy for electrochemical detection. The constructed light-assisted water-vapor self-powered sensor has a wide detection range, high sensitivity, low detection limit and low detection cost.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of electrochemical detection, and particularly relates to a light-assisted water-driven self-powered sensor for lincomycin detection and a preparation method thereof. BACKGROUND

[0002] Lincomycin (Lincomycin, for short, Lin) is also known as lincomycin hydrochloride and jiemycin. It is a lincomycin amide antibiotic produced by Streptomyces. It has strong bacteriostatic activity. As an antibiotic veterinary drug, it is widely used in poultry farming. The veterinary drug is specifically added to feed or drinking water, and most of the veterinary drug not absorbed by the animal body flows into the surrounding environment, especially the water environment, in the form of the body or metabolites, and antibiotic residues in the water environment are increasingly serious. Unjustified or excessive use of lincomycin can lead to residues in the animal body, which can enter the human body through the food chain and harm human health.

[0003] At present, common methods for detecting lincomycin include enzyme-linked immunosorbent assay and high-performance liquid chromatography. These methods have the disadvantages of expensive instruments and equipment, complex operation, or low sensitivity. Therefore, it is of great significance to develop a convenient and efficient analysis method for detecting the content of lincomycin in water.

[0004] One of the main drawbacks of typical sensors is the need for an external power source or battery, which makes the sensor system more complex. Compared with traditional energy conversion devices, water-driven power generation devices can be applied in various situations without additional input of mechanical energy. Through direct interaction between materials and water, the water-driven power generation device can directly convert heat in the environment into electrical energy output. It is a clean and pollution-free green new energy conversion technology. There is no related report on the establishment of a self-powered sensing platform based on a light-assisted water-driven power generation device for electrochemical detection of lincomycin. SUMMARY

[0005] The present application aims to provide a construction method of a light-assisted water-driven self-powered sensor for sensitive detection of lincomycin, which has the advantages of high sensitivity, low detection limit and wide detection range. A light-assisted water-driven self-powered sensor is constructed based on a ZnO / Ce-MOF composite material for detection of lincomycin. Test results show that the light-assisted water-driven self-powered sensor has high sensitivity and low detection limit.

[0006] The present application provides a light-assisted water-driven self-powered sensor. A glass substrate is used as a substrate, a copper foil tape is used as a positive and negative electrode, a ZnO nanowire array and Ce-MOF are used as power generation materials to prepare a water-driven power generator, and a lincomycin aptamer is assembled to construct the light-assisted water-driven self-powered sensor.

[0007] The present application further provides a preparation method of the light-assisted water-driven self-powered sensor, comprising the following steps:

[0008] (1) Preparation of ZnO nanowire array:

[0009] First, the glass substrate was pre-cleaned with ethanol and deionized water, and ZnO seeds were prepared on the glass substrate before the growth of ZnO nanowires. Zn(CH3COO)2·2H2O was uniformly dissolved in ethanol, and then the solution was dropped onto the glass substrate and naturally dried. The ZnO seed layer formed on the glass substrate was annealed in air at 300-400℃ for 10-30min. Next, Zn(NO3)2·6H2O was uniformly dissolved in deionized water, and NH3·H2O was slowly dropped into the solution. The mixed solution was transferred to the reaction kettle placed in the glass substrate, and incubated at 80-100℃ for 9-15h. After the reaction was completed, the glass substrate was taken out and gently washed with deionized water, and dried at 50-80℃;

[0010] Preferably, the molar concentration of zinc acetate ethanol solution is 0.05mol / L; the molar concentration of zinc nitrate aqueous solution is 0.075mol / L, and the volume ratio of NH3·H2O solution to zinc nitrate aqueous solution is 2.5:38.

[0011] (2) Preparation of Ce-MOF suspension:

[0012] Ce-MOF powder was added to ethanol and ultrasonically dispersed, 3-(trimethoxysilyl) propylamine (APTMS) was added and stirred for 12-24h to obtain a mixture; the mixture was centrifuged, washed and dried to obtain Ce-MOF with amino functional groups, then anhydrous ethanol and deionized water were added to prepare a turbid liquid with a volume ratio of 1:1, and ultrasonic dispersion was carried out for 20-50min to obtain a uniform Ce-MOF suspension;

[0013] Preferably, the mass concentration of APTMS in the mixture is 4.5%w / v; the concentration of amino-functionalized Ce-MOF suspension is 10mg / ml.

[0014] Further, the preparation method of Ce-MOF: dissolve 1,3,5-benzenetricarboxylic acid (H3BTC) in a mixed solution of water and ethanol to obtain a H3BTC solution; dissolve cerium nitrate (Ce(NO3)3·6H2O) in ultrapure water to obtain a Ce(NO3)3·6H2O solution, the molar ratio of 1,3,5-benzenetricarboxylic acid to cerium nitrate is 1:1; drop the Ce(NO3)3·6H2O solution into the H3BTC solution, and keep it in a 60℃ water bath for 1-2h, after the reaction is completed, centrifuge, wash, collect the white precipitate, and vacuum dry at 50-80℃ to obtain Ce-MOF powder;

[0015] (3) Preparation of ZnO / Ce-MOF composite water-voltaic cell:

[0016] The copper foil tape is used as the electrode, and the upper and lower electrodes are pasted on the ZnO nanowire glass substrate in the shape of "L". The 10 mg·mL -1 Ce-MOF suspension, wherein the suspension is uniformly spread between the two electrodes using deionized water and ethanol 1:1. The prepared device is dried at 50-80℃ for 6-10h;

[0017] Further, the volume of the amino-functionalized Ce-MOF suspension dropped is 100-500μL, preferably 300-400μL; the drop-coating area is 1.5*3.0cm 2 .

[0018] (4) Preparation of aptamer sensor:

[0019] A certain concentration of lincomycin aptamer is dropped on the surface of the water-voltaic cell power generation material prepared in step (3). Natural drying at room temperature obtains an aptamer sensor with selective recognition of lincomycin.

[0020] Among them, the concentration of aptamer is 1μmol / L; the drop-coating amount of aptamer is 20-60μL.

[0021] The nucleotide sequence of lincomycin aptamer is: 5'-CGCG TGAT GTGG TCGATGCGATAC GGTGAGTCGCGC CACG GCTACACA CGTC TCAG CGA-3'.

[0022] The above-mentioned water-voltaic-based self-powered sensor is applied in the detection of lincomycin, and the specific detection steps are as follows:

[0023] S1, prepare a solution containing different concentrations of lincomycin;

[0024] Accurately weigh a certain amount of lincomycin, and prepare a standard solution of 1.0×10 -4 mol / L using deionized water. Dilute the standard solution with deionized water step by step to obtain a series of lincomycin standard solutions with different concentrations, with a concentration range of 1.0×10 -15 mol / L to 1.0×10 -9 mol / L;

[0025] S2, drawing of standard curve:

[0026] Take a series of lincomycin with known concentrations and drop them on the surface of the prepared water-voltaic cell power generation material, and dry naturally at room temperature;

[0027] The copper foil tape is used as the positive and negative electrodes of the electrochemical test, ZnO nanowire array and Ce-MOF are used as power generation materials, and lincomycin aptamer is assembled to form a water-driven self-powered system, deionized water is used as an electrolyte, the current of the xenon lamp light source is controlled to be 20 A, the horizontal distance from the light source outlet to the glass substrate is 10 cm, the short-circuit current response value is measured at a test potential of 0 V, a series of concentration-short-circuit current corresponding relationships are obtained, and then a standard curve of lincomycin is obtained, a linear relationship between the short-circuit current intensity after lincomycin is added and the logarithmic value of the concentration of lincomycin is established, and a corresponding linear regression equation is obtained.

[0028] S3, sample detection, impurity removal of the sample, testing according to step 2 and obtaining a short-circuit current value, the short-circuit current value is calculated by using the linear regression equation obtained in step 2, and the concentration of lincomycin in the sample is obtained.

[0029] As preferred, the reaction time of the water-driven self-powered sensor based on light assistance is 20 min.

[0030] The beneficial effects of the present application are:

[0031] The ZnO nanowire array and Ce-MOF composite prepared as power generation materials successfully establish an electrochemical sensing platform, and an electrochemical detection method of lincomycin is established, and the characteristics and advantages are as follows:

[0032] (1) In the present application, ZnO nanowire array and Ce-MOF are used as power generation materials to prepare a water-driven device. Ordinary glass is used as a substrate material, ZnO nanowire array has a high surface potential and abundant capillary channels to meet the movement of water molecules in the evaporation driven channel, and is supplemented by Ce-MOF material with excellent hydrophilicity. In the preparation of the water-driven self-powered sensor, light assistance significantly improves the current signal, and the addition of aptamer enables the sensor to specifically detect lincomycin.

[0033] (2) Compared with the traditional detection method, the water-driven electrochemical detection method proposed in the present application has the characteristics of simple and flexible operation, simple instrument and equipment, high sensitivity, wide linear range, low detection limit, low detection cost and the like. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a brief flow chart of the preparation of the sensor in the present application and the detection of lincomycin;

[0035] Figure 2 is the current signal measured by the battery with different Ce-MOF drop amounts;

[0036] Figure 3This is a short-circuit current graph for different concentrations of lincomycin. The lincomycin concentrations are listed from top to bottom according to the peak value of the curve: (a) 1×10⁻⁶ -15 mol / L, (b) 1×10 -14 mol / L, (c) 1×10 -13 mol / L, (d) 1×10 -12 mol / L, (e) 1×10 -11 mol / L, (f) 1×10 -10 mol / L, (g) 1×10 -9 mol / L;

[0037] Figure 4 It is a standard curve of short-circuit current after the addition of lincomycin versus the logarithm of lincomycin concentration. Detailed Implementation

[0038] The present invention will be further described in detail below with reference to the embodiments.

[0039] Example 1

[0040] like Figure 1 As shown, the self-powered water-volt sensor uses copper foil tape as positive and negative electrodes, ZnO nanowire array and Ce-MOF as power generation materials to prepare a water-volt generator, and lincomycin aptamers are assembled to form a self-powered system for lincomycin detection.

[0041] The fabrication method of a self-powered water-based photovoltaic sensor includes the following steps:

[0042] (1) Fabrication of ZnO nanowire arrays:

[0043] First, use ethanol and deionized water to disinfect the glass substrate (3.8*2.5cm). 2 Before ZnO nanowire growth, ZnO seed crystals were prepared on a glass substrate after pre-cleaning. Zn(CH3COO)2·2H2O (0.11 g) was uniformly dissolved in ethanol (10 mL), and then 100 μL of the solution was dropped onto the glass substrate and allowed to air dry. The ZnO seed layer formed on the glass substrate was annealed in air at 350 °C for 20 min. Next, Zn(NO3)2·6H2O (0.85 g) was uniformly dissolved in deionized water (38 mL), and NH3·H2O (2.5 mL) with a purity of 25%–28% was slowly added dropwise to the solution. The mixed solution was transferred to a reaction vessel containing the glass substrate and kept at 83 °C for 12 h. After the reaction was completed, the glass substrate was removed, gently rinsed with deionized water, and dried at 60 °C.

[0044] (2) Preparation of Ce-MOF:

[0045] Ce-MOF powder was obtained by dissolving 0.105 g of trimesic acid (H3BTC) in a mixed solution of 5 mL of water and ethanol to obtain an H3BTC solution; dissolving 0.217 g of cerium nitrate (Ce(NO3)3·6H2O) in 5 mL of ultrapure water to obtain a Ce(NO3)3·6H2O solution, the molar ratio of trimesic acid to cerium nitrate being 1:1; adding the Ce(NO3)3·6H2O solution dropwise into the H3BTC solution, keeping it in a 60°C water bath for 1 h, after the reaction was completed, centrifuging, washing, collecting the white precipitate, and drying it under vacuum at 60°C to obtain Ce-MOF powder; adding 200 mg of Ce-MOF powder to 25 mL of ethanol and ultrasonically dispersing it, adding 1.05 mL of 3-(trimethoxysilyl)propylamine (APTMS, analytical pure, 97%) and stirring for 24 h, centrifuging, washing, and drying the mixture to obtain Ce-MOF with amino functional groups, adding 20 mL of a turbid solution of anhydrous ethanol and deionized water in a volume ratio of 1:1 to it, ultrasonically dispersing it for 30 min to obtain a uniform Ce-MOF suspension with a concentration of 10 mg·mL -1 .

[0046] (3) Preparation of ZnO / Ce-MOF composite water-voltaic cell:

[0047] A copper foil tape was used as an electrode, and the upper and lower electrodes were pasted on the ZnO nanowire glass substrate in the shape of "L". 10 mg·mL -1 Ce-MOF suspension was added dropwise between the upper and lower electrodes, and the suspension was uniformly spread between the two electrodes using deionized water and ethanol at a ratio of 1:1. The prepared device was dried at 60°C for 8 h;

[0048] The amount of Ce-MOF suspension drop-coated was 100 μL, 200 μL, 300 μL, 400 μL, and 500 μL.

[0049] The current signals measured by comparing the batteries with different amounts of Ce-MOF drop-coated are shown in Figure 2 It can be seen from Figure 2 that the current signal is the strongest when the amount of Ce-MOF drop-coated is 300 μL.

[0050] (4) Preparation of aptamer sensor:

[0051] 20 μL of lincomycin aptamer with a concentration of 1 μmol / L was added dropwise to the water-voltaic cell power generation material with a drop-coated amount of 300 μL prepared in step (3). It was naturally dried at room temperature to obtain an aptamer sensor with selective recognition for lincomycin.

[0052] The above-mentioned water-voltaic self-powered sensor based on light assistance is applied in the detection of lincomycin, and the nucleotide sequence of the lincomycin aptamer is as follows:

[0053] Adaptor: 5'-CGCG TGAT GTGG TCGA TGCG ATAC GGTG AGTC GCGC CACGGCTACACACGTC TCAG CGA-3'.

[0054] (5) Drawing of standard curve:

[0055] Lincomycin solution was prepared, a certain mass of lincomycin was accurately weighed, and deionized water was used to prepare 1.0×10 -4 mol / L standard solution. The standard solution was gradually diluted with deionized water to obtain a series of lincomycin standard solutions with different concentrations.

[0056] In the light-assisted water-volt self-powered sensor, copper foil tape was used as the positive and negative electrodes, ZnO nanowire array and Ce-MOF were used as power generation materials, and lincomycin aptamer was assembled to form a self-powered system for lincomycin detection. The incubation time of the self-powered aptamer sensor was 20 min, deionized water was used as the electrolyte, the current of the xenon lamp light source was controlled to be 20 A, the horizontal distance from the light source outlet to the glass substrate was 10 cm, and the short-circuit current response value was measured at a test potential of 0 V, as shown in Figure 2 Fig. 2, wherein the concentrations of lincomycin from top to bottom according to the peak height of the curve are:

[0057] (a) 1×10 -15 mol / L, (b) 1×10 -14 mol / L, (c) 1×10 -13 mol / L, (d) 1×10 -12 mol / L, (e) 1×10 -11 mol / L, (f) 1×10 -10 mol / L, (g) 1×10 -9 mol / L

[0058] The electrodes modified with lincomycin with different concentrations were tested, wherein the concentrations of lincomycin (1.0×10 -15 mol / L, 1.0×10 -14 mol / L, 1.0×10 -13 mol / L, 1.0×10 -12 mol / L, 1.0×10 -11 mol / L, 1.0×10 -10 mol / L, 1.0×10 -9mol / L, with deionized water as electrolyte, the current of xenon lamp light source was controlled at 20 A, the horizontal distance from light source outlet to glass substrate was 10 cm, the short-circuit current response value was measured at 0 V test potential; then the linear relationship between short-circuit current after adding lincomycin and the logarithmic value of lincomycin concentration was established, and the corresponding linear regression equation was I (nA) = -28.94573logC (mol / L) - 159.49211, the correlation coefficient (R) was 0.98107; the detection range of linear regression equation was 1.0 x 10 -15 ~ 1.0 x 10 -9 mol / L, and the lowest detection limit was 2.19 x 10 -16 mol / L.

[0059] (6), sample detection:

[0060] A certain amount of filtered wastewater was taken to prepare lincomycin solution, which was used for electrochemical detection, and the lincomycin concentration in the sample to be detected was calculated according to the linear regression equation corresponding to the above step (5), and the results are shown in Table 1.

[0061] Comparative Example 1

[0062] (1), preparation of ZnO nanowire array water-activated cell:

[0063] The glass substrate was ultrasonically cleaned in deionized water and ethanol for half an hour, then washed with deionized water for several times and dried in an oven for use; before the growth of ZnO nanowires, ZnO seeds were prepared on the glass substrate. Zn (CH3COO) 2·2H2O (0.11 g) was uniformly dissolved in ethanol (10 mL), and then the solution was dropped onto the glass substrate and naturally dried. The ZnO seed layer formed on the glass substrate was annealed in air at 300-400 ℃ for 10-30 min. Next, Zn (NO3) 2·6H2O (0.85 g) was uniformly dissolved in deionized water (38 mL), and NH3·H2O (2.5 mL) was slowly dropped into the solution. The mixed solution was transferred to the reaction kettle placed in the glass substrate, and incubated at 80-100 ℃ for 9-15 h. After the reaction was completed, the glass substrate was taken out, gently washed with deionized water, and dried at 50-80 ℃; copper foil tape was used as positive and negative electrodes, and the water-activated cell device was obtained after drying.

[0064] (2), preparation of standard curve:

[0065] With glass substrate as substrate, copper foil tape as positive and negative electrodes, and ZnO nanowires as power generation material, a self-powered system was formed for lincomycin detection, and the detection method was the same as in the embodiment.

[0066] Comparative Example 2:

[0067] (1) Preparation of Ce-MOF water-voltage battery

[0068] The glass substrate was cleaned in deionized water and ethanol for half an hour, respectively, and then washed with deionized water for several times and dried in an oven; the trimesic acid (H3BTC) was dissolved in a mixed solution of water and ethanol to obtain a H3BTC solution; the cerium nitrate (Ce(NO3)3·6H2O) was dissolved in ultrapure water to obtain a Ce(NO3)3·6H2O solution, and the molar ratio of trimesic acid to cerium nitrate was 1:1; the Ce(NO3)3·6H2O solution was added dropwise into the H3BTC solution, and kept in a 60°C water bath for 1-2h, after the reaction was completed, centrifugation, washing, and collection of white precipitate, vacuum drying at 50-80°C, to obtain Ce-MOF powder; the Ce-MOF powder was added to ethanol and ultrasonically dispersed, 3-(trimethoxysilyl) propylamine (APTMS) was added and stirred for 12-24h, and the mixture was centrifuged, washed, and dried to obtain Ce-MOF with amino functional groups, and then anhydrous ethanol and deionized water were mixed in a volume ratio of 1:1 to prepare a turbid liquid, and the Ce-MOF suspension was obtained by ultrasonic dispersion for 20-50min.

[0069] The copper foil tape was used as the positive and negative electrodes of the "L" shape, 300μL of the Ce-MOF suspension material was dropped between the upper and lower electrodes by using a pipette, and the water-voltage battery device was obtained after drying.

[0070] (2) Drawing of standard curve:

[0071] The glass substrate was used as the substrate, the copper foil tape was used as the positive and negative electrodes, and the Ce-MOF was used as the power generation material to form a self-powered system for lincomycin detection, and the detection method was the same as in the embodiment.

[0072] Table 1 shows the determination results of lincomycin in water samples

[0073]

[0074]

[0075] As shown in Table 1, the sample was detected in parallel for 3 times, the relative standard deviation was less than 5%, and the recovery rate was 96%-101%. The above results show that the sensors prepared by ZnO / glass or Ce-MOF / glass alone cannot detect lincomycin, and the present application is feasible for detecting lincomycin in wastewater.

[0076] The above merely describes preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make equivalent replacements or changes to the technical solutions and concepts of the present application within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A photo-assisted water-volatilization self-powered sensor, characterized in that, The water-voltaic generator is prepared by taking a glass substrate as a substrate, taking a copper foil tape as positive and negative electrodes, and taking ZnO nanowire arrays and Ce-MOF as power generation materials, and a lincomycin aptamer is assembled to construct a light-assisted water-voltaic self-powered sensor; The preparation method of the light-assisted water-voltaic self-powered sensor comprises the following steps: (1) Preparation of ZnO nanowire arrays: Zinc acetate ethanol solution is dropped onto a pre-cleaned glass substrate, and after natural drying to form a ZnO seed layer on the glass substrate, annealing at 300-400 DEG C in air for 10-30 min to obtain a ZnO crystal seed / glass substrate; NH3·H2O solution is added dropwise in zinc nitrate aqueous solution to obtain a mixed solution; the mixed solution is transferred to a reaction kettle containing the ZnO crystal seed / glass substrate, and incubated at 80-100 DEG C for 9-15 h; after taking out and washing, drying at 50-80 DEG C, ZnO nanowire arrays are obtained; (2) Preparation of amino-functionalized Ce-MOF suspension: Ce-MOF powder is ultrasonically dispersed in ethanol, 3-(trimethoxysilyl) propylamine is added and stirred for 12-24 h to obtain a mixture, the mixture is centrifuged, washed and dried to obtain amino-functionalized Ce-MOF; the amino-functionalized Ce-MOF is prepared into a turbid liquid with a volume ratio of 1:1 of anhydrous ethanol and deionized water, and ultrasonically dispersed for 20-50 min to obtain a uniform amino-functionalized Ce-MOF suspension; (3) Preparation of water-voltaic cell: The copper foil tape is used as electrodes, and the upper and lower electrodes are pasted into "L" shape on the ZnO nanowire glass substrate, and the amino-functionalized Ce-MOF suspension of step (2) is dropped between the upper and lower electrodes with a pipette to make it evenly spread between the two electrodes; the prepared device is dried at 50-80 DEG C for 6-10 h; (4) Preparation of aptamer sensor: Lincomycin aptamer is dropped on the surface of the water-voltaic cell device prepared in step (3), and naturally dried at room temperature to obtain an aptamer sensor with selective recognition for lincomycin.

2. A method of fabricating a photo-assisted water-volatge self-powered sensor as claimed in claim 1, characterized in that, The preparation method comprises the following steps: (1) Preparation of ZnO nanowire arrays: Zinc acetate ethanol solution is dropped onto a pre-cleaned glass substrate, and after natural drying to form a ZnO seed layer on the glass substrate, annealing at 300-400 DEG C in air for 10-30 min to obtain a ZnO crystal seed / glass substrate; NH3·H2O solution is added dropwise in zinc nitrate aqueous solution to obtain a mixed solution; the mixed solution is transferred to a reaction kettle containing the ZnO crystal seed / glass substrate, and incubated at 80-100 DEG C for 9-15 h; after taking out and washing, drying at 50-80 DEG C, ZnO nanowire arrays are obtained; (2) Preparation of amino-functionalized Ce-MOF suspension: Ce-MOF powder is ultrasonically dispersed in ethanol, 3-(trimethoxysilyl) propylamine is added and stirred for 12-24 h to obtain a mixture, the mixture is centrifuged, washed and dried to obtain amino-functionalized Ce-MOF; the amino-functionalized Ce-MOF is prepared into a turbid liquid with a volume ratio of 1:1 of anhydrous ethanol and deionized water, and ultrasonically dispersed for 20-50 min to obtain a uniform amino-functionalized Ce-MOF suspension; (3) Preparation of water-logged battery: The copper foil tape was used as the electrode, and the upper and lower electrodes were pasted on the ZnO nanowire glass substrate in the shape of "L". The amino-functionalized Ce-MOF suspension prepared in step (2) was added dropwise between the upper and lower electrodes by using a pipette gun to make it evenly spread between the two electrodes. The prepared device was dried at 50-80℃ for 6-10h; (4) Preparation of aptamer sensor: The lincomycin aptamer was added dropwise on the surface of the water-logged battery device prepared in step (3), and it was naturally dried at room temperature to obtain an aptamer sensor with selective recognition for lincomycin; The nucleotide sequence of the lincomycin aptamer is: 5'-CGCG TGAT GTGG TCGA TGCG ATAC GGTGAGTC GCGC CACG GCTA CACA CGTC TCAG CGA-3'.

3. The method of claim 2, wherein the method further comprises: In step (1), the molar concentration of zinc acetate ethanol solution is 0.05mol / L; the molar concentration of zinc nitrate aqueous solution is 0.075mol / L, and the volume ratio of NH3·H2O solution to zinc nitrate aqueous solution is 2.5:

38.

4. The method for preparing a photovoltaic self-powered sensor according to claim 2, characterized in that, In step (2), the mass concentration of 3-(trimethoxysilyl)propylamine in the mixture is 4.5% w / v; and the concentration of the amino-functionalized Ce-MOF suspension is 10mg / ml.

5. The method for preparing a photovoltaic self-powered sensor according to claim 2, characterized in that, In step (2), the preparation method of Ce-MOF is as follows: dissolve trimesic acid in a mixed solution of water and ethanol to obtain a H3BTC solution; dissolve cerium nitrate in ultrapure water to obtain a Ce(NO3)3·6H2O solution; add the Ce(NO3)3·6H2O solution dropwise into the H3BTC solution, keep it in a 60℃ water bath for 1-2h, after the reaction is completed, centrifuge, wash, collect the white precipitate, and vacuum dry at 50-80℃ to obtain Ce-MOF powder; wherein the molar ratio of trimesic acid to cerium nitrate is 1:

1. In step (4), the concentration of lincomycin aptamer is 1μmol / L; and the volume of the added lincomycin aptamer solution is 20-60μL.

6. The method for preparing a photovoltaic self-powered sensor according to claim 2, characterized in that, In step (3), the volume of the amino-functionalized Ce-MOF suspension dropped is 100-500 μL, and the drop-casting area is 1.5*3.0 cm 2 .

7. The method for preparing a photovoltaic self-powered sensor according to claim 2, characterized in that, The steps for detecting lincomycin are as follows:

8. Use of the water-voltagic self-powered sensor according to claim 1 for the detection of lincomycin by electrochemical methods, characterized by, S1, prepare a solution containing different concentrations of lincomycin; S2, draw a standard curve: Accurately weigh lincomycin, and prepare 1.0×10 -4 mol / L standard solution with deionized water. Dilute the standard solution with deionized water to obtain lincomycin standard solutions with different concentrations, and the concentration range is 1.0×10 -15 mol / L~1.0×10 -9 mol / L. Take a series of lincomycin with known concentration and drop it on the surface of the prepared water-logged battery power generation material, and dry it naturally at room temperature; Use deionized water as electrolyte, control the current of xenon lamp light source to be 20A, the horizontal distance from the light source outlet to the glass substrate is 10cm, measure the response value of short-circuit current at a test potential of 0V, obtain a series of concentration-short-circuit current corresponding relationship, and then obtain the standard curve of lincomycin, establish the linear relationship between the short-circuit current intensity after adding lincomycin and the logarithmic value of lincomycin concentration, and obtain the corresponding linear regression equation; S3, actual sample detection: The actual sample detection is pretreated, and the calculation is carried out according to the linear regression equation in step S2. In step S2, the binding time of aptamer and lincomycin is 10-60min.

9. Use of the photo-assisted water-volte self-powered sensor according to claim 8 for the detection of lincomycin by electrochemical method, characterized by, ​

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