CN111721821B - Preparation method of foam nickel supported photoelectric cathode material DNA (deoxyribonucleic acid) immunosensor for detecting breast cancer - Google Patents
Preparation method of foam nickel supported photoelectric cathode material DNA (deoxyribonucleic acid) immunosensor for detecting breast cancer Download PDFInfo
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Abstract
The invention relates to a preparation method of a DNA immunosensor for detecting breast cancer based on a foamed nickel-supported photocathode material. Conventional photovoltaicThe chemical electrode mostly adopts an ITO or FTO glass electrode, and the photosensitive material is easy to agglomerate when the electrode is decorated, so that the photoelectric response is weakened. The invention relies on foam nickel with distinct structure as a supporting electrode, and Eu-doped Co3O4Growing in situ on the foamed nickel to obtain a continuously arranged needle-like structure with beautiful appearance, eliminating the possibility of material agglomeration, and simultaneously modifying CuS on the surface of the foamed nickel electrode in a continuous ion layer adsorption mode, wherein the needle-like Eu: Co3O4And a large number of loading sites are provided for the adsorption of CuS, and the response of cathode photocurrent is improved. Meanwhile, the anti-fouling interface is constructed in a soaking mode, the operation process is simple, the modification step of the electrode is simplified, the interference of interference substances is eliminated by the anti-fouling interface, the sensitive detection of the sensor is realized, and the detection limit of the breast cancer DNA reaches 0.3 fM.
Description
Technical Field
The invention relates to a preparation method of a DNA immunosensor for detecting breast cancer based on a foamed nickel-supported photocathode material. Specifically, foam nickel is adopted as a support electrode, and Eu is doped with Co3O4The photocathode material is directly grown on foamed nickel, and then CuS is modified on Eu: Co in a needle-shaped arrangement in an ionic layer adsorption mode3O4In the above, an antifouling interface is constructed by using a soaking modification process, and the photocathode immunosensor for detecting breast cancer DNA is prepared, belonging to the technical field of novel functional materials and biosensing detection.
Background
The breast cancer becomes a major public health problem of the current society, the incidence rate of the breast cancer is always on the rise from the end of the 70 th 20 th century, China is not a high incidence country of the breast cancer, but China is not optimistic, and the increase speed of the incidence rate of the breast cancer in China is 1-2% higher than that of the high incidence country in recent years. The mammary gland is not an important organ for maintaining the life activity of a human body, the in-situ breast cancer is not fatal, but the breast cancer cells lose the characteristics of normal cells, and the cells are loosely connected and easily fall off. Once cancer cells fall off, free cancer cells can be disseminated throughout the body along with blood or lymph fluid to form metastasis, so that life is threatened, and breast cancer becomes a common tumor threatening the physical and mental health of women at present. Early-stage breast cancer often does not have typical symptoms and signs, is not easy to attach importance, and is usually discovered through physical examination or breast cancer screening. Therefore, it is necessary to establish a simple and rapid analysis method for detecting breast cancer markers. At present, there are many electrochemical methods for breast cancer detection, such as the most commonly used imaging methods (linlin, litau, dane pavilion. application of infrared thermal imaging technology in breast cancer detection [ J ] journal of chinese medical physics, 2018 (6)), enzyme-linked immunosorbent assay, chemiluminescence assay, and the like. However, these methods often have the disadvantages of slow detection speed, complex operation, etc. The invention designs a novel photocathode sensor which has the advantages of high analysis speed, simple operation and low detection limit, and the detection limit of the photocathode sensor designed by the invention on breast cancer DNA reaches 0.3 fM.
Co3O4Is a typical p-type semiconductor photosensitive material, is simple to prepare, and has photoactivity under visible light conditions. For Co3O4The most common synthesis methods of (a) are hydrothermal synthesis methods, synthesis of nanoparticle structures, or synthesis of larger-sized cubic or flower-like structures using templates. The invention adopts the foam nickel as the supporting electrode, the foam nickel has excellent conductivity, and the foam nickel is used as the support to support the Co3O4Directly growing on a foam nickel framework to obtain a nano needle-shaped structure which is orderly arranged, solving the problem of agglomeration of materials and being more beneficial to exerting the Co3O4The Eu ions are doped in the synthesis process to synthesize Eu: Co3O4Improving pure Co3O4The band gap defect of (2) improves the photoelectric response. Secondly, the continuous ion layer adsorption mode is adopted to modify CuS to Eu: Co3O4On nickel foam, the photocurrent of the electrode is further increased, which promotes the stability of the sensor construction. An antifouling interface is constructed in a soaking mode in the construction process of the sensor, so that the operation steps are simplified, and the construction of the antifouling interface effectively blocks the dryness of other interfering substancesAnd interference is beneficial to sensitive detection of the sensor.
A photoelectrochemical sensor is a type of detection device that determines the concentration of an analyte based on the photoelectric conversion characteristics of a substance. The photoelectrochemical detection method has the characteristics of simple equipment, high sensitivity and easiness in miniaturization, has been developed into an analysis method with great application potential, and has wide application prospects in the fields of food, environment, medicine and the like. The application of the working electrode supported by the foamed nickel in the aspect of the photoelectric chemical sensor is not reported. The invention relates to Eu: Co based on foam nickel support3O4The photoelectrochemical antifouling interface sensor for detecting breast cancer DNA under visible light is successfully constructed by the CuS photocathode material. The sensor is Eu: Co supported by foam nickel3O4the-CuS photocathode material is used as a basic photosensitive material and is also used as a working electrode, a dirty interface is constructed in a soaking mode to realize the construction of the sensor, and the high-sensitivity and anti-interference detection on breast cancer DNA is realized. The photoelectric introduction sensor prepared by the invention has the advantages of low cost, high sensitivity, rapid detection, easy preparation and the like, realizes rapid and high-sensitivity detection of breast cancer DNA in a visible light region, and effectively overcomes the defects of the existing breast cancer DNA detection method.
Disclosure of Invention
One purpose of the invention is to adopt the foamed nickel as a working electrode and directly grow the photosensitive material on the foamed nickel so as to realize the optimization of the material appearance and prevent the agglomeration of the material.
Another object of the present invention is to dope Eu with Co3O4In-situ growth on foamed nickel to obtain continuously arranged needle-like structure, and doping Eu to improve Co3O4The photoelectric response of (a).
The third purpose of the invention is to load CuS on Eu: Co by adopting a continuous ion layer adsorption mode3O4Upper, acicular Eu: Co3O4And a large number of sites are provided for the loading of the CuS, and the photoelectric response of the cathode is further improved.
The fourth purpose of the invention is to construct an antifouling interface in a soaking mode to modify the sensor, so that the steps of the modification process are simplified, the antifouling interface also blocks the interference of other interfering substances, and the sensitivity of the sensor is improved.
The fifth purpose of the invention is to use the CuS modified Eu: Co supported by foam nickel3O4As a working electrode, an antifouling interface is constructed in a soaking mode, and the photoelectric cathode sensor with the advantages of interference resistance, high sensitivity and high detection speed is prepared, so that the sensitive detection of breast cancer DNA under the visible light condition is realized.
The technical scheme of the invention is as follows:
1. the preparation method of the DNA immunosensor for detecting breast cancer based on the foamed nickel supported photocathode material is characterized by comprising the following steps:
（1）Eu:Co3O4preparation of foamed nickel
Respectively dissolving 0.3-0.6 g of cobalt nitrate hexahydrate, 0.1-0.3 g of ammonium fluoride, 0.4-0.5 g of urea and 0.05-0.1 g of europium nitrate hexahydrate in 30-60 mL of ultrapure water, and continuously stirring uniformly at room temperature; meanwhile, carrying out ultrasonic treatment on the foamed nickel in 1-3M hydrochloric acid solution for 30 min, cleaning with ultrapure water, and drying; obliquely placing the treated nickel foam into a high-pressure reaction kettle with the size of 50 mL, pouring the mixed solution, carrying out hydrothermal reaction for 8-15 h at the temperature of 100-150 ℃, washing the nickel foam with ultrapure water after the reaction is finished, and naturally drying the nickel foam in the air; finally, calcining the reacted foam nickel at 200-300 ℃ for 1-5 h to obtain Eu-doped Co3O4-a foamed nickel composite;
（2）Eu:Co3O4preparation of foamed nickel-CuS
Dissolving 0.01-0.05 g of copper nitrate trihydrate in 10-50 mL of absolute ethanol, and uniformly stirring at room temperature to obtain a solution A; dissolving 0.01-0.05 g of sodium sulfide nonahydrate in 10-50 mL of absolute ethanol, and uniformly stirring at room temperature to obtain a solution B; mixing the synthesized Eu to Co3O4Soaking foamed nickel in the solution A for 1-2 min, and then adding Eu to Co3O4Foam nickel leachingSoaking in the solution B for 1-2 min, carefully washing the soaked foam nickel with absolute ethyl alcohol, and drying in the air, wherein the soaking process is a cycle, and the cycle is repeated for 2-5 times to obtain the CuS modified Eu: Co3O4-a nickel foam electrode;
(3) preparation of PBS buffer solution
Taking 11.94 g of disodium hydrogen phosphate dodecahydrate, dissolving the disodium hydrogen phosphate dodecahydrate in a 500 mL volumetric flask to prepare an aqueous solution with the concentration of 1/15 mol/L, and taking the aqueous solution as a liquid A; taking 4.54 g of monopotassium phosphate, fixing the volume in a 500 mL volumetric flask, and preparing an aqueous solution with the concentration of 1/15 mol/L as a solution B; mixing the solution A and the solution B in proportion to prepare a series of PBS (phosphate buffer solution) with the pH value of 5.0-8.0;
(4) preparation of photoelectrochemical sensor
1) The obtained CuS modified Eu: Co3O4Soaking the foamed nickel electrode in an aminated polyethylene glycol solution with the concentration of 0.5-2 mg/mL prepared by using a PBS buffer solution with the pH value of 7.4 for 1 hour, and then washing the electrode by using the PBS buffer solution;
2) soaking the electrode obtained in the step 1) in a mixed solution containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride of 1-5 mg/mL and N-hydroxysuccinimide of 5-10 mg/mL for 1 h, and washing the electrode with PBS (phosphate buffer solution);
3) continuously soaking the electrode obtained in the step 2) in a breast cancer DNA solution of 0.001 pM-50 nM prepared by using a PBS buffer solution, washing the electrode by using the PBS buffer solution after soaking for 1 h, and preparing the breast cancer DNA detection immunosensor.
The linear range of the sensor for detecting the breast cancer DNA is 0.001 pM-50 nM, and the detection limit is 0.3 fM.
The chemical reagents required for material synthesis were purchased from reagent stores and were not reprocessed.
Advantageous effects of the invention
(1) The invention successfully dopes Eu with Co by using foamed nickel as a supporting electrode3O4The nano needle array grows on the foamed nickel, and the structure of the photosensitive material is optimized by utilizing the foamed nickelThe agglomeration of materials is reduced, and the doping of Eu improves Co3O4The photoelectric response of (a).
(2) Modifying CuS to Eu: Co by adopting a continuous ion layer adsorption mode3O4In addition, the needle-shaped array structure provides a large specific surface area for loading CuS, and cathode photoelectric current is further improved after modification.
(3) The sensor is constructed in a soaking mode, the constructed antifouling interface can effectively block the interference of other interferents, and in addition, the construction steps of the sensor are simplified through the construction of the antifouling interface, and the operation is simpler.
(4) The photoelectrochemical sensor prepared by the invention is used for detecting breast cancer DNA, is simple to operate, has high detection speed and low detection limit, and can realize simple, quick, high-sensitivity and specific detection. The linear range of the detection of the breast cancer DNA is 0.001 pM-50 nM, and the detection limit is 0.3 fM.
Detailed description of the preferred embodiments
EXAMPLE 1 preparation of photoelectrochemical sensor
1. The preparation method of the DNA immunosensor for detecting breast cancer based on the foamed nickel supported photocathode material is characterized by comprising the following steps:
（1）Eu:Co3O4preparation of foamed nickel
Respectively dissolving 0.3 g of cobalt nitrate hexahydrate, 0.1 g of ammonium fluoride, 0.4 g of urea and 0.05 g of europium nitrate hexahydrate in 30 mL of ultrapure water, and continuously stirring uniformly at room temperature; meanwhile, after carrying out ultrasonic treatment on the foamed nickel in 1M hydrochloric acid solution for 30 min, cleaning with ultrapure water and drying; obliquely placing the processed foamed nickel into a high-pressure reaction kettle with the size of 50 mL, pouring the mixed solution, carrying out hydrothermal reaction for 8 hours at 100 ℃, washing the foamed nickel with ultrapure water after the reaction is finished, and naturally drying in the air; finally, calcining the reacted foam nickel at 200 ℃ for 1 h to obtain Eu-doped Co3O4-a foamed nickel composite;
（2）Eu:Co3O4-bulbPreparation of nickel foam-CuS
0.01 g of copper nitrate trihydrate is dissolved in 10 mL of absolute ethyl alcohol and is stirred uniformly at room temperature, and the solution is used as solution A; dissolving 0.01 g of sodium sulfide nonahydrate in 10 mL of absolute ethanol, and uniformly stirring at room temperature to obtain a solution B; mixing the synthesized Eu to Co3O4Soaking foamed nickel in the solution A for 1 min, and adding Eu to Co3O4Soaking the foamed nickel in the solution B for 1 min, carefully washing the soaked foamed nickel with absolute ethyl alcohol, and drying the soaked foamed nickel in the air, wherein the soaking process is a cycle, and the cycle is repeated for 2 times to obtain the CuS modified Eu: Co3O4-a nickel foam electrode;
(3) preparation of PBS buffer solution
Taking 11.94 g of disodium hydrogen phosphate dodecahydrate, dissolving the disodium hydrogen phosphate dodecahydrate in a 500 mL volumetric flask to prepare an aqueous solution with the concentration of 1/15 mol/L, and taking the aqueous solution as a liquid A; taking 4.54 g of monopotassium phosphate, fixing the volume in a 500 mL volumetric flask, and preparing aqueous solution with the concentration of 1/15 mol/L to be used as solution B; mixing the solution A and the solution B in proportion to prepare a series of PBS (phosphate buffer solution) with the pH value of 5.0-8.0;
(4) preparation of photoelectrochemical sensor
1) The obtained CuS modified Eu: Co3O4Soaking the foamed nickel electrode in 0.5 mg/mL aminated polyethylene glycol solution prepared by using PBS buffer solution with pH of 7.4 for 1 h, and then washing the electrode by using PBS buffer solution;
2) soaking the electrode obtained in the step 1) in a mixed solution containing 1 mg/mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 5 mg/mL of N-hydroxysuccinimide, and washing the electrode with a PBS (phosphate buffer solution) after soaking for 1 h;
3) continuously soaking the electrode obtained in the step 2) in a breast cancer DNA solution of 0.001 pM-50 nM prepared by using a PBS buffer solution, washing the electrode by using the PBS buffer solution after soaking for 1 h, and preparing the immunosensor for detecting the breast cancer DNA.
EXAMPLE 2 preparation of photoelectrochemical sensor
1. The preparation method of the DNA immunosensor for detecting breast cancer based on the foamed nickel supported photocathode material is characterized by comprising the following steps:
（1）Eu:Co3O4preparation of foamed nickel
Respectively dissolving 0.5 g of cobalt nitrate hexahydrate, 0.15 g of ammonium fluoride, 0.45 g of urea and 0.08 g of europium nitrate hexahydrate in 40 mL of ultrapure water, and continuously stirring uniformly at room temperature; meanwhile, after carrying out ultrasonic treatment on the foamed nickel in 2M hydrochloric acid solution for 30 min, cleaning with ultrapure water and drying; obliquely placing the processed foamed nickel into a high-pressure reaction kettle with the size of 50 mL, pouring the mixed solution, carrying out hydrothermal reaction for 10 hours at the temperature of 120 ℃, washing the foamed nickel with ultrapure water after the reaction is finished, and naturally drying the foamed nickel in the air; finally, calcining the reacted foam nickel at 250 ℃ for 3 h to obtain Eu-doped Co3O4-a foamed nickel composite;
（2）Eu:Co3O4preparation of foamed nickel-CuS
0.04 g of copper nitrate trihydrate is dissolved in 35 mL of absolute ethyl alcohol and is uniformly stirred at room temperature, and the solution is used as solution A; dissolving 0.04 g of sodium sulfide nonahydrate in 25 mL of absolute ethyl alcohol, and uniformly stirring at room temperature to obtain a solution B; mixing the synthesized Eu to Co3O4Soaking foamed nickel in the solution A for 1 min, and adding Eu to Co3O4Soaking the foamed nickel in the solution B for 1 min, carefully washing the soaked foamed nickel with absolute ethyl alcohol, and drying the soaked foamed nickel in the air, wherein the soaking process is a cycle, and the cycle is repeated for 3 times to obtain the CuS modified Eu: Co3O4-a nickel foam electrode;
(3) preparation of PBS buffer solution
Taking 11.94 g of disodium hydrogen phosphate dodecahydrate, dissolving the disodium hydrogen phosphate dodecahydrate in a 500 mL volumetric flask to prepare an aqueous solution with the concentration of 1/15 mol/L, and taking the aqueous solution as a liquid A; taking 4.54 g of monopotassium phosphate, fixing the volume in a 500 mL volumetric flask, and preparing an aqueous solution with the concentration of 1/15 mol/L as a solution B; mixing the solution A and the solution B in proportion to prepare a series of PBS (phosphate buffer solution) with the pH value of 5.0-8.0;
(4) preparation of photoelectrochemical sensor
1) The obtained CuS modified Eu: Co3O4Soaking the foamed nickel electrode in an aminated polyethylene glycol solution with the concentration of 1 mg/mL prepared by using a PBS buffer solution with the pH value of 7.4 for 1 hour, and then washing the electrode by using the PBS buffer solution;
2) soaking the electrode obtained in the step 1) in a mixed solution containing 2 mg/mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 5 mg/mL of N-hydroxysuccinimide, and washing the electrode with a PBS (phosphate buffer solution) after soaking for 1 h;
3) continuously soaking the electrode obtained in the step 2) in a breast cancer DNA solution of 0.001 pM-50 nM prepared by a PBS buffer solution, and cleaning the electrode by the PBS buffer solution after soaking for 1 h to prepare the breast cancer DNA detection immunosensor.
EXAMPLE 3 preparation of photoelectrochemical sensor
1. The preparation method of the DNA immunosensor for detecting breast cancer based on the foamed nickel supported photocathode material is characterized by comprising the following steps:
（1）Eu:Co3O4preparation of foamed nickel
Respectively dissolving 0.6 g of cobalt nitrate hexahydrate, 0.3 g of ammonium fluoride, 0.5 g of urea and 0.1 g of europium nitrate hexahydrate in 60 mL of ultrapure water, and continuously stirring uniformly at room temperature; meanwhile, after carrying out ultrasonic treatment on the foamed nickel in a 3M hydrochloric acid solution for 30 min, cleaning with ultrapure water and drying; obliquely placing the processed foamed nickel into a high-pressure reaction kettle with the size of 50 mL, pouring the mixed solution, carrying out hydrothermal reaction for 15 h at the temperature of 150 ℃, washing the foamed nickel with ultrapure water after the reaction is finished, and naturally drying the foamed nickel in the air; finally, calcining the reacted foam nickel at 300 ℃ for 5 hours to obtain Eu-doped Co3O4-a foamed nickel composite;
（2）Eu:Co3O4preparation of foamed nickel-CuS
0.05 g of copper nitrate trihydrate solution was takenDissolving in 50 mL of absolute ethyl alcohol, and uniformly stirring at room temperature to obtain a solution A; dissolving 0.05 g of sodium sulfide nonahydrate in 50 mL of absolute ethanol, and uniformly stirring at room temperature to obtain a solution B; mixing the synthesized Eu to Co3O4Soaking foamed nickel in the solution A for 2 min, and adding Eu to Co3O4Soaking the foamed nickel in the solution B for 2 min, carefully washing the soaked foamed nickel with absolute ethyl alcohol, and drying the soaked foamed nickel in the air, wherein the soaking process is a cycle, and the cycle is repeated for 5 times to obtain the CuS modified Eu: Co3O4-a nickel foam electrode;
(3) preparation of PBS buffer solution
Taking 11.94 g of disodium hydrogen phosphate dodecahydrate, dissolving the disodium hydrogen phosphate dodecahydrate in a 500 mL volumetric flask to prepare an aqueous solution with the concentration of 1/15 mol/L, and taking the aqueous solution as a liquid A; taking 4.54 g of monopotassium phosphate, fixing the volume in a 500 mL volumetric flask, and preparing an aqueous solution with the concentration of 1/15 mol/L as a solution B; mixing the solution A and the solution B in proportion to prepare a series of PBS (phosphate buffer solution) with the pH value of 5.0-8.0;
(4) preparation of photoelectrochemical sensor
1) The obtained CuS modified Eu: Co3O4Soaking the foamed nickel electrode in an aminated polyethylene glycol solution with the concentration of 2 mg/mL prepared by using a PBS buffer solution with the pH value of 7.4 for 1 hour, and then washing the electrode by using the PBS buffer solution;
2) soaking the electrode obtained in the step 1) in a mixed solution containing 5 mg/mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 10 mg/mL of N-hydroxysuccinimide, and washing the electrode by using a PBS buffer solution after soaking for 1 h;
3) continuously soaking the electrode obtained in the step 2) in a breast cancer DNA solution of 0.001 pM-50 nM prepared by a PBS buffer solution, and cleaning the electrode by the PBS buffer solution after soaking for 1 h to prepare the breast cancer DNA detection immunosensor.
Claims (1)
1. The preparation method of the DNA immunosensor for detecting breast cancer based on the foamed nickel supported photocathode material is characterized by comprising the following steps:
（1）Eu:Co3O4preparation of foamed nickel
Respectively dissolving 0.3-0.6 g of cobalt nitrate hexahydrate, 0.1-0.3 g of ammonium fluoride, 0.4-0.5 g of urea and 0.05-0.1 g of europium nitrate hexahydrate in 30-60 mL of ultrapure water, and continuously stirring uniformly at room temperature; meanwhile, carrying out ultrasonic treatment on the foamed nickel in 1-3M hydrochloric acid solution for 30 min, cleaning with ultrapure water, and drying; obliquely placing the processed foam nickel into a high-pressure reaction kettle with the size of 50 mL, pouring the mixed solution, carrying out hydrothermal reaction for 8-15 h at the temperature of 100-150 ℃, washing the foam nickel with ultrapure water after the reaction is finished, and naturally drying in the air; finally, calcining the reacted foam nickel at 200-300 ℃ for 1-5 h to obtain Eu-doped Co3O4-a foamed nickel composite;
（2）Eu:Co3O4preparation of foamed nickel-CuS
Dissolving 0.01-0.05 g of copper nitrate trihydrate in 10-50 mL of absolute ethanol, and uniformly stirring at room temperature to obtain a solution A; dissolving 0.01-0.05 g of sodium sulfide nonahydrate in 10-50 mL of absolute ethanol, and uniformly stirring at room temperature to obtain a solution B; mixing the synthesized Eu to Co3O4Soaking foamed nickel in the solution A for 1-2 min, and then adding Eu: Co3O4Soaking the foamed nickel into the solution B for 1-2 min, carefully washing the soaked foamed nickel with absolute ethyl alcohol, and then drying the soaked foamed nickel, wherein the soaking process is a cycle, and the cycle is repeated for 2-5 times to obtain the CuS modified Eu: Co3O4-a nickel foam electrode;
(3) preparation of PBS buffer solution
Taking 11.94 g of disodium hydrogen phosphate dodecahydrate, dissolving the disodium hydrogen phosphate dodecahydrate in a 500 mL volumetric flask to prepare an aqueous solution with the concentration of 1/15 mol/L, and taking the aqueous solution as a liquid A; taking 4.54 g of monopotassium phosphate, fixing the volume in a 500 mL volumetric flask, and preparing an aqueous solution with the concentration of 1/15 mol/L as a solution B; mixing the solution A and the solution B in proportion to prepare a series of PBS (phosphate buffer solution) with the pH value of 5.0-8.0;
(4) preparation of photoelectrochemical sensor
1) The obtained CuS modified Eu: Co3O4Soaking the foamed nickel electrode in an aminated polyethylene glycol solution with the concentration of 0.5-2 mg/mL prepared by using a PBS buffer solution with the pH value of 7.4 for 1 hour, and then washing the electrode by using the PBS buffer solution;
2) soaking the electrode obtained in the step 1) in a mixed solution containing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride of 1-5 mg/mL and N-hydroxysuccinimide of 5-10 mg/mL for 1 h, and washing the electrode with PBS (phosphate buffer solution);
3) continuously soaking the electrode obtained in the step 2) in a breast cancer DNA solution of 0.001 pM-50 nM prepared by a PBS buffer solution, and cleaning the electrode by the PBS buffer solution after soaking for 1 h to prepare the breast cancer DNA detection immunosensor.
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