CN111273014B - Photoelectrochemical immunosensor for detecting prostate specific antigen and preparation method thereof - Google Patents
Photoelectrochemical immunosensor for detecting prostate specific antigen and preparation method thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/577—Immunoassay; Biospecific binding assay; Materials therefor involving monoclonal antibodies binding reaction mechanisms characterised by the use of monoclonal antibodies; monoclonal antibodies per se are classified with their corresponding antigens
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/36—Glass electrodes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/574—Immunoassay; Biospecific binding assay; Materials therefor for cancer
- G01N33/57407—Specifically defined cancers
- G01N33/57434—Specifically defined cancers of prostate
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/574—Immunoassay; Biospecific binding assay; Materials therefor for cancer
- G01N33/57484—Immunoassay; Biospecific binding assay; Materials therefor for cancer involving compounds serving as markers for tumor, cancer, neoplasia, e.g. cellular determinants, receptors, heat shock/stress proteins, A-protein, oligosaccharides, metabolites
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Abstract
The invention discloses a photoelectrochemical immunosensor for detecting a prostate specific antigen and a preparation method thereof, wherein the immunosensor is formed by fixing graphite-like carbon nitride/tin disulfide quantum dot nanocomposite on the surface of an FTO glass electrode, fixing an anti-prostate specific antigen monoclonal antibody on the surface of the nanocomposite, wherein the anti-prostate specific antigen monoclonal antibody can perform specific recognition reaction with a target prostate specific antigen, and the exposed end of the target prostate specific antigen can be connected with an anti-prostate specific antigen polyclonal antibody modified with a signal amplification factor. The invention realizes the detection of the prostate specific antigen by the photoelectrochemical immunosensor, and has simple method, high sensitivity and easy operation.
Description
Technical Field
The invention relates to a photoelectrochemical immunosensor for detecting a prostate specific antigen and a preparation method thereof, in particular to a photoelectrochemical immunosensor based on graphite-like carbon nitride/tin disulfide quantum dot nanocomposite modified electrodes.
Background
Graphite-like phase carbon nitride, which is a nonmetallic semiconductor photoelectroactive material, has been developed in recent years due to its excellent photoelectrochemical properties such as: narrow bandwidth (2.7 eV), high visible light absorptivity, good biocompatibility, high chemical and physical stability, environmental friendliness, etc. are receiving extensive attention from various students [ Dong, y.x., cao, j.t., wang, b., ma, s.h., liu, Y.M., appl.Mater.Interfaces,2018,10,3723 ]. Although such materials have many advantages as described above, the high electron-hole recombination rate of the materials themselves still greatly limits their application in the field of photoelectrochemistry. In order to overcome the problems and improve the photoelectric conversion efficiency of the graphite-like phase carbon nitride material, the graphite-like phase carbon nitride material must be subjected to functional modification so that the graphite-like phase carbon nitride material can be better applied to the field of photoelectrochemistry. Tin disulfide quantum dots, a transition metal sulfide, have also been known in recent years for their own unique properties such as: low cost, abundant metal reserves, non-toxicity, and narrow bandwidth (2.0-2.4 eV) have received increasing attention [ Lei, y.m., zhou, j., chai, y.q., zhou, y, yuan, r., anal.chem.,2018,90,12270 ]. Although the tin disulfide quantum dot has certain defects, the combination of the graphite-phase carbon nitride and the tin disulfide quantum dot greatly relieves the defects of the two materials, for example, the electron-hole recombination rate of the graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite is greatly reduced, and the light absorption capacity of the nanocomposite is greatly improved [ Pulipaka, S., koushik, A.K.S., boni, N., deep, M, meduri, P, int.J.hydrogen energy, 2019,44,11584 ].
Photoelectrochemical bioassays are an emerging bioanalytical technology that utilizes light to induce electron transfer processes between analytes, photoactive materials and electrodes. The photoelectrochemical analysis method is widely applied to detection of various biomolecules such as nucleic acid sequences, tumor markers, enzyme activities, cancer cells and the like [ Zhang, g.y., shan, d., dong, h.f., cosnier, s., al-Ghanim, k.a., ahmad, z., mahboob, s, zhang, X.J., anal.Chem.,2018,90,12284 ]. However, the problems of low light energy utilization rate, poor biocompatibility and the like of the traditional photoelectrochemical material limit the application of the photoelectrochemical material in life analysis chemistry, so that searching for a novel photoelectrochemical electrode material with high efficiency, low cost and good biocompatibility is still an important research target for constructing a photoelectrochemical immunosensor.
Prostate cancer is one of the most common malignant tumors in men, and is the fifth leading cause of cancer mortality worldwide. Thus, rapid and accurate detection of early stage prostate cancer is critical to increase overall survival [ Mickert, m.j., farka, z., kostiv, u.,A.,Horák,D.,Skládal,P.,Gorris,H.H.,Anal.Chem.,2019,91,9435]. Prostate specific antigen is a specific disease marker for prostate cancer, produced by prostate cells (normal and patient), widely used in clinical diagnosis, serum prostate specific antigen levels are an important indicator for clinical diagnosis of prostate cancer [ Khan, m.s., ameer, h., ali, a, zhu, w.j., li, x.j., yang, l., wang, h., feng, r.q., wei, q., j.electrotechnical. Chem, 2019,847,113266.]. To date, although various analytical methods for detecting prostate-specific antigens have been developed, such as electrochemiluminescence, electrochemistry, surface plasmon resonance, fluorescence, etc., there are limitations in that sensitivity is limited, operation is complicated, etc. Therefore, developing a simple, rapid and highly sensitive serum prostate specific antigen detection method is of great importance for early clinical diagnosis.
The graphite-like carbon nitride and tin disulfide quantum dots are combined to prepare the graphite-like carbon nitride and tin disulfide quantum dot nanocomposite modified electrode, so that the advantages of the nanocomposite can be fully exerted, the spectrum absorption range is enlarged, the light energy utilization rate is improved, the stability is enhanced, and the electrode is a novel strategy for developing photoelectrochemical immunosensor and has wide application prospects in the fields of immunobiology, clinical diagnosis and the like.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides a photoelectrochemical immunosensor for detecting prostate specific antigen based on graphite-like carbon nitride/tin disulfide quantum dot nanocomposite and a preparation method thereof, so that the photoelectrochemical immunosensor with high photoelectrochemical current and high biocompatibility can realize simple and rapid detection of the prostate specific antigen.
The invention solves the technical problems by adopting the following technical scheme:
the invention firstly discloses a photoelectrochemical immunosensor for detecting prostate specific antigen, which is characterized in that: the photoelectrochemical immunosensor is characterized in that the surface of an FTO glass electrode is covered with a graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite, an anti-prostate specific antigen monoclonal antibody is fixed on the surface of the graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite, and the anti-prostate specific antigen monoclonal antibody can perform specific recognition reaction with a target object prostate specific antigen.
Further, the preparation method of the graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposite comprises the following steps:
calcining melamine powder for 4 hours at 550 ℃, naturally cooling and grinding, weighing 0.5-0.9 g, adding the melamine powder into 150mL of glycol solution, continuously carrying out ultrasonic treatment for 4 hours, centrifuging the obtained dispersion liquid for 15-30 minutes at 6000rpm/min, and centrifugally washing with ultrapure water; adding the obtained centrifugal product into 200mL of ethanol solution, continuously carrying out ultrasonic treatment for 24 hours, centrifuging the obtained dispersion liquid for 20-30 minutes at 9000rpm/min, and centrifugally washing with ultrapure water; dispersing the obtained centrifugal product in 100mL of ultrapure water to obtain graphite-like phase carbon nitride dispersion liquid;
and 2, adding acetic acid into the graphite-like phase carbon nitride dispersion liquid obtained in the step 1 to enable the volume concentration to be 5%, then taking 25mL, adding 0.5841g of tin tetrachloride pentahydrate and 0.2513g of thioacetamide, carrying out ultrasonic treatment for 30min, transferring to a high-pressure reaction kettle to react for 12h at 180 ℃, naturally cooling, centrifuging the obtained mixed liquid for 15min under the condition of 9000rpm/min, repeatedly washing with ultrapure water, and drying the obtained wet solid at 35 ℃ overnight to obtain the graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposite solid.
The preparation method of the photoelectrochemical immunosensor for detecting the prostate specific antigen comprises the following steps:
step 1, ultrasonically cleaning an FTO glass electrode by using acetone, water and ethanol in sequence, and then drying overnight at 60 ℃ for later use;
step 2, adding 2mg of graphite-like carbon nitride/tin disulfide quantum dot nanocomposite into 2mL of deionized water, and uniformly dispersing by ultrasonic to obtain nanocomposite dispersion;
step 3, uniformly dripping 30 mu L of the nanocomposite dispersion liquid prepared in the step 2 on the surface of the FTO glass electrode cleaned in the step 1, and airing at room temperature to obtain a graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite modified electrode;
step 4, after the modified electrode prepared in the step 3 is treated by chitosan and glutaraldehyde, 30 mu L of 0.01mg/mL of anti-prostate specific antigen monoclonal antibody is dripped on the surface, the reaction is carried out for 12 to 13 hours at the temperature of 4 ℃, and after the reaction is taken out, the reaction is washed by a PBS buffer solution with the concentration of 10mmol/L, pH of 7.2 to 7.4; then 30 mu L of calf serum protein solution with the mass concentration of 2-3% is dripped, the mixture is blocked for 1-2 hours at 37 ℃, and after the mixture is taken out, the mixture is washed by a PBS buffer solution with the mass concentration of 10mmol/L, pH of 7.2-7.4, and the photoelectrochemical immunosensor for detecting the prostate specific antigen is obtained.
The method for detecting the prostate specific antigen by using the immunosensor comprises the following steps:
step 1, dropwise adding 30 mu L of a prostate specific antigen sample to be detected on the surface of the photoelectrochemical immunosensor for detecting the prostate specific antigen, incubating for 50min at 37 ℃, taking out and flushing with 10mmol/L, pH PBS buffer solution with the concentration of 7.2-7.4;
step 2, dropwise adding 30 mu L of anti-prostate specific antigen polyclonal antibody modified with a signal amplification factor to the surface of the electrode prepared in the step 1, incubating for 70min at 37 ℃, and then taking out and flushing with 10mmol/L, pH PBS buffer solution with the concentration of 7.2-7.4 to obtain an immunosensor electrode to be detected;
and 3, performing photoelectrochemical test on the immunosensor electrode to be tested obtained in the step 2 in a PBS buffer solution containing 0.1mol/L AA and having 0.1mol/L, pH of 7.4 to obtain the photocurrent intensity of the prostate specific antigen sample to be tested, and judging the concentration of the prostate specific antigen sample to be tested by using a standard relation curve of the photocurrent intensity and the concentration of the prostate specific antigen sample.
Further, the anti-prostate specific antigen polyclonal antibody modified with the signal amplification factor is obtained as follows:
step 1, adding 172 mu L of trimercapto propionic acid into 40mL of 20mmol/L cadmium chloride aqueous solution, adjusting the pH of the solution to 11 by 1mol/L sodium hydroxide, then introducing nitrogen gas, stirring for 15min, adding 40mL of 20mmol/L thioacetamide aqueous solution, and stirring uniformly at room temperature; then reacting for 2 hours at 80 ℃, naturally cooling, settling and centrifuging the reaction product with ethanol once, and diluting with pure water to 16mL to obtain a solution of the signal amplification factor cadmium sulfide quantum dot;
step 2, taking 1mL of the solution of the cadmium sulfide quantum dot, activating at room temperature, adding 1mL of 10 mug/mL anti-prostate specific antigen polyclonal antibody into the solution, oscillating for 2 hours at 37 ℃, standing overnight at 4 ℃, then adding 50 mug of 2% by mass concentration calf serum protein solution, and oscillating for 1-2 hours at 37 ℃; and centrifuging the obtained mixed solution for 15min at 4500rpm/min, and fixing the volume of the obtained centrifugal product to 1mL by using PBS buffer solution to obtain the target product.
Further, the standard relation curve is to obtain the photocurrent intensity corresponding to each concentration of the prostate-specific antigen sample by performing photoelectrochemistry test on the immunosensor to be tested prepared by the prostate-specific antigen samples with the concentrations of 10fg/mL, 100fg/mL, 1pg/mL, 10pg/mL, 100pg/mL, 1ng/mL and 10ng/mL, and as shown in fig. 1, each line corresponds to the concentration from left to right: 10fg/mL, 100fg/mL, 1pg/mL, 10pg/mL, 100pg/mL, 1ng/mL, and 10ng/mL; and then fitting the obtained values of the concentration of the prostate specific antigen sample on the abscissa and the photocurrent intensity on the ordinate. As shown in fig. 1, the standard relationship is I (μa) = 2.5405+0.4768log C PSA /fg·mL -1 . Detection shows that the concentration of the current prostate specific antigen sample is in the range of 10fg/mL to 10ng/mL, the photocurrent intensity is increased along with the increase of the concentration of the prostate specific antigen sample, the photocurrent intensity is in linear relation with the concentration, and the detection limit reaches 1.3 fg.mL -1 。
The photoelectrochemical test is a three-electrode system with the immunosensor as a working electrode, a Pt electrode as a counter electrode and a saturated silver chloride electrode as a reference electrode, a 250W xenon lamp as a light source, the wavelength range of 280-1000nm, the applied voltage of 0V, and the CHI660D electrochemical workstation used for recording current change.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention realizes the detection of the prostate specific antigen by the photoelectrochemical immunosensor, and has the advantages of simple method, wide detection range, high sensitivity and easy operation;
2. the detection method of the prostate specific antigen has the advantages of small sample amount and low detection cost;
3. the photoelectrochemical immunosensor is prepared from the graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite, and has high photoelectrochemical current, good biocompatibility and excellent stability.
Drawings
FIG. 1 shows the results of the photoelectrochemical conversion test of prostate specific antigen standard samples of the present invention at concentrations of 10fg/mL, 100fg/mL, 1pg/mL, 10pg/mL, 100pg/mL, 1ng/mL and 10ng/mL, respectively, with the inset being a standard relationship curve.
FIG. 2 shows the results of Transmission Electron Microscope (TEM) characterization of graphite-like phase carbon nitride in the present invention.
FIG. 3 is a Transmission Electron Microscope (TEM) characterization of graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposites of the present invention.
FIG. 4 is a High Resolution Transmission Electron Microscope (HRTEM) characterization result of graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposite materials according to the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. The following is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
The preparation method of the graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposite used in the following examples comprises the following steps:
calcining melamine powder for 4 hours at 550 ℃, naturally cooling and grinding, weighing 0.5-0.9 g, adding the melamine powder into 150mL of glycol solution, continuously carrying out ultrasonic treatment for 4 hours, centrifuging the obtained dispersion liquid for 15-30 minutes at 6000rpm/min, and centrifugally washing with ultrapure water; adding the obtained centrifugal product into 200mL of ethanol solution, continuously carrying out ultrasonic treatment for 24 hours, centrifuging the obtained dispersion liquid for 20-30 minutes at 9000rpm/min, and centrifugally washing with ultrapure water; dispersing the obtained centrifugal product in 100mL of ultrapure water to obtain graphite-like phase carbon nitride dispersion liquid;
step 2, adding acetic acid into the graphite-like phase carbon nitride dispersion liquid obtained in the step 1 to enable the volume concentration of the graphite-like phase carbon nitride dispersion liquid to be 5%; taking 25mL of the solution, adding 0.5841g of tin tetrachloride pentahydrate and 0.2513g of thioacetamide, carrying out ultrasonic treatment for 30min, transferring to a high-pressure reaction kettle for reaction at 180 ℃ for 12h, naturally cooling, centrifuging the obtained mixed solution for 15min under the condition of 9000rpm/min, repeatedly washing with ultrapure water, and drying the obtained wet solid at 35 ℃ overnight to obtain the graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite solid.
The 10mmol/L, pH PBS buffer solution of 7.2-7.4 used in the following examples was purchased from Shanghai Biotechnology engineering services Co., ltd;
the PBS buffer solution containing 0.1mol/L AA (ascorbic acid) and having a 0.1mol/L, pH of 7.4 was prepared as follows: 1.1496g of Na is weighed 2 HPO 4 、0.2964g NaH 2 PO 4 ·2H 2 O, 0.8g NaCl, 1.7613g AA, 100mL of an aqueous solution was prepared.
Example 1
This example first prepared a photoelectrochemical immunosensor for detection of prostate specific antigen as follows:
step 1, ultrasonically cleaning an FTO glass electrode sequentially by using acetone, water and ethanol, and then drying at 60 ℃ overnight for standby, wherein the effective working area is 45mm 2 ；
Step 2, adding 2mg of graphite-like carbon nitride/tin disulfide quantum dot nanocomposite into 2mL of deionized water, and uniformly dispersing by ultrasonic to obtain nanocomposite dispersion;
step 3, uniformly dripping 30 mu L of the nanocomposite dispersion liquid prepared in the step 2 on the surface of the FTO glass electrode cleaned in the step 1, and airing at room temperature to obtain a graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite modified electrode;
step 4, dropwise adding 10 mu L of chitosan solution with the mass concentration of 0.1% on the surface of the modified electrode prepared in the step 3, naturally airing, flushing with ultrapure water, drying, dropwise adding 30 mu L of glutaraldehyde solution with the mass concentration of 5% on the surface, keeping for thirty minutes, flushing with ultrapure water, and drying; then 30 mu L of anti-prostate specific antigen monoclonal antibody with the concentration of 0.01mg/mL is dripped on the surface, the reaction is carried out for 12 hours at the temperature of 4 ℃, and the mixture is taken out and washed by PBS buffer solution with the concentration of 10mmol/L, pH of 7.2-7.4; then 30 mu L of calf serum protein solution with the mass concentration of 2% is dripped, the mixture is blocked for 1 hour at 37 ℃, and after the mixture is taken out, the mixture is washed by a PBS buffer solution with the mass concentration of 10mmol/L, pH of 7.2-7.4, and the photoelectrochemical immunosensor for detecting the prostate specific antigen is obtained.
With the immunosensor of this embodiment, the method for detecting prostate-specific antigen is as follows:
step 1, dropwise adding 30 mu L of a prostate specific antigen sample to be detected on the surface of a photoelectrochemical immunosensor for detecting the prostate specific antigen, incubating for 50min at 37 ℃, taking out and flushing with 10mmol/L, pH of PBS buffer solution with the concentration of 7.2-7.4;
step 2, dropwise adding 30 mu L of anti-prostate specific antigen polyclonal antibody modified with a signal amplification factor to the surface of the electrode prepared in the step 1, incubating for 70min at 37 ℃, and then taking out and flushing with 10mmol/L, pH PBS buffer solution with the concentration of 7.2-7.4 to obtain an immunosensor electrode to be detected;
and 3, performing photoelectrochemical test on the immunosensor electrode to be tested obtained in the step 2 in a PBS buffer solution containing 0.1mol/L AA and having 0.1mol/L, pH of 7.4 to obtain the photocurrent intensity of the prostate specific antigen sample to be tested, and judging the concentration of the prostate specific antigen sample to be tested by using a standard relation curve of the photocurrent intensity and the concentration of the prostate specific antigen sample.
The preparation method of the anti-prostate specific antigen polyclonal antibody modified with the signal amplification factor comprises the following steps:
step 1, adding 172 mu L of trimercapto propionic acid into 40mL of 20mmol/L cadmium chloride aqueous solution, adjusting the pH of the solution to 11 by 1mol/L sodium hydroxide, then introducing nitrogen gas, stirring for 15min, adding 40mL of 20mmol/L thioacetamide aqueous solution, and stirring uniformly at room temperature; then reacting for 2 hours at 80 ℃, naturally cooling, settling and centrifuging the reaction product with ethanol once, and diluting with pure water to 16mL to obtain a solution of the signal amplification factor cadmium sulfide quantum dot;
step 2, taking 1mL of a solution of cadmium sulfide quantum dots, adding 200 mu L of a mixed solution of 10mg/mL of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 5mg/mL of N-hydroxysuccinimide, activating for 1h at room temperature, adding 1mL of 10 mu g/mL of an anti-prostate-specific antigen polyclonal antibody, oscillating for 2h at 37 ℃, standing overnight at 4 ℃, adding 50 mu L of a 2% mass concentration calf serum protein solution, and oscillating for 1h at 37 ℃; and centrifuging the obtained mixed solution for 15min at 4500rpm/min, and fixing the volume of the obtained centrifugal product to 1mL by using PBS buffer solution to obtain the target product.
To verify the feasibility of the method of this example, samples of the prostate specific antigen to be tested having known concentrations of 10fg/mL, 100fg/mL, 1pg/mL, 10pg/mL, 100pg/mL, 1ng/mL and 10ng/mL were taken, and the immunosensor of this example was used to detect and calculate the concentrations of each sample, respectively, in the above-described manner, of 10.3fg/mL, 96.1fg/mL, 0.9874pg/mL, 10.65pg/mL, 94.62pg/mL, 0.9333ng/mL and 12.51ng/mL, respectively, and it was found that the immunosensor prepared has rapid, sensitive, accurate and efficient detection of the target prostate specific antigen.
Example 2
In the embodiment, the reaction at the temperature of 4 ℃ in the step 4 of the preparation method of the photoelectrochemical immunosensor in the embodiment 1 is changed to be 13 hours, the rest condition steps are the same as those in the embodiment 1, the appearance and the properties of the obtained immunosensor are similar to those of the immunosensor obtained in the embodiment 1, and similar immunodetection results are obtained through detection of the same prostate specific antigen sample.
Example 3
In this example, the "calf serum protein solution with the mass concentration of 2% in the step 4 of the preparation method of the photoelectrochemical immunosensor in example 1" is changed into the "calf serum protein solution with the mass concentration of 3%, the rest of the condition steps are the same as those in example 1, the appearance and the properties of the obtained immunosensor are similar to those of the immunosensor obtained in example 1, and similar immune detection results are obtained through detection of the same prostate specific antigen sample to be detected.
Example 4
In the embodiment, the process for preparing the photoelectrochemical immunosensor in step 4 of the method for preparing the photoelectrochemical immunosensor is changed from '37 ℃ for 1 hour' to '37 ℃ for 2 hours', the rest condition steps are the same as those in the embodiment 1, the appearance and the properties of the obtained immunosensor are similar to those of the immunosensor obtained in the embodiment 1, and similar immune detection results are obtained through detection of the same prostate specific antigen sample to be detected.
Example 5
In this example, 50 μl of 2% concentration calf serum protein solution by mass is added in step 2 of the preparation method of the anti-prostate specific antigen polyclonal antibody modified with the signal amplification factor in example 1, and the shaking is carried out for 1h at 37 ℃ instead of 2 hours, and the rest of the conditions are the same as those in example 1, so that the appearance and properties of the immunosensor obtained in example 1 are similar, and similar immunodetection results are obtained by detecting the same prostate specific antigen sample to be detected.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (4)
1. A photoelectrochemical immunosensor for detecting a prostate-specific antigen, characterized in that: the photoelectrochemical immunosensor is characterized in that the surface of an FTO glass electrode is covered with a graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite, and an anti-prostate specific antigen monoclonal antibody is fixed on the surface of the graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite; the anti-prostate specific antigen monoclonal antibody can perform specific recognition reaction with a target prostate specific antigen;
dropwise adding a prostate specific antigen sample to be detected on the surface of the photoelectrochemical immunosensor, incubating, dropwise adding an anti-prostate specific antigen polyclonal antibody modified with a signal amplification factor, incubating again, and connecting the exposed end of the prostate specific antigen to be detected with the anti-prostate specific antigen polyclonal antibody modified with the signal amplification factor in a recognition way to obtain an immunosensor electrode to be detected;
performing photoelectrochemical test on the immunosensor electrode to be tested to obtain the photocurrent intensity of the prostate specific antigen sample to be tested, and judging the concentration of the prostate specific antigen sample to be tested by using a standard relation curve of the photocurrent intensity and the concentration of the prostate specific antigen sample;
the preparation method of the graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposite comprises the following steps:
calcining melamine powder for 4 hours at 550 ℃, naturally cooling and grinding, weighing 0.5-0.9 g, adding the melamine powder into 150mL of glycol solution, continuously carrying out ultrasonic treatment for 4 hours, centrifuging the obtained dispersion liquid for 15-30 minutes at 6000rpm/min, and centrifugally washing with ultrapure water; adding the obtained centrifugal product into 200mL of ethanol solution, continuously carrying out ultrasonic treatment for 24 hours, centrifuging the obtained dispersion liquid for 20-30 minutes at 9000rpm/min, and centrifugally washing with ultrapure water; dispersing the obtained centrifugal product in 100mL of ultrapure water to obtain graphite-like phase carbon nitride dispersion liquid;
step 2, adding acetic acid into the graphite-like phase carbon nitride dispersion liquid obtained in the step 1 to enable the volume concentration to be 5%, then taking 25mL, adding 0.5841g of tin tetrachloride pentahydrate and 0.2513g of thioacetamide, carrying out ultrasonic treatment for 30min, transferring to a high-pressure reaction kettle to react for 12h at 180 ℃, naturally cooling, centrifuging the obtained mixed liquid for 15min under the condition of 9000rpm/min, repeatedly washing with ultrapure water, and drying the obtained wet solid at 35 ℃ overnight to obtain the graphite-like phase carbon nitride/tin disulfide quantum dot nanocomposite solid;
the anti-prostate specific antigen polyclonal antibody modified with the signal amplification factor is obtained by the following method:
step 1, adding 172 mu L of trimercapto propionic acid into 40mL of 20mmol/L cadmium chloride aqueous solution, adjusting the pH of the solution to 11 by 1mol/L sodium hydroxide, then introducing nitrogen gas, stirring for 15min, adding 40mL of 20mmol/L thioacetamide aqueous solution, and stirring uniformly at room temperature; then reacting for 2 hours at 80 ℃, naturally cooling, settling and centrifuging the reaction product with ethanol once, and diluting with pure water to 16mL to obtain a solution of the signal amplification factor cadmium sulfide quantum dot;
step 2, taking 1mL of the solution of the cadmium sulfide quantum dot, activating at room temperature, adding 1mL of 10 mug/mL anti-prostate specific antigen polyclonal antibody into the solution, oscillating for 2 hours at 37 ℃, standing overnight at 4 ℃, then adding 50 mug of 2% by mass concentration calf serum protein solution, and oscillating for 1-2 hours at 37 ℃; and centrifuging the obtained mixed solution for 15min at 4500rpm/min, and fixing the volume of the obtained centrifugal product to 1mL by using PBS buffer solution to obtain the target product.
2. A photoelectrochemical immunosensor for detecting a prostate-specific antigen as recited in claim 1, wherein: the incubation is carried out for 50min at 37 ℃, and then taken out and washed by a PBS buffer solution with the concentration of 10mmol/L, pH of 7.2-7.4;
the re-incubation was performed at 37℃for 70min, then removed and rinsed with 10mmol/L, pH of 7.2-7.4 PBS buffer.
3. A photoelectrochemical immunosensor for detecting a prostate-specific antigen as recited in claim 1, wherein: the standard relation curve is obtained by performing photoelectrochemical test on an immunosensor electrode to be tested prepared by using prostate-specific antigen samples with concentrations of 10fg/mL, 100fg/mL, 1pg/mL, 10pg/mL, 100pg/mL, 1ng/mL and 10ng/mL respectively, obtaining photocurrent intensities corresponding to the prostate-specific antigen samples with each concentration, and then performing fitting by using the logarithmic value of the concentration of the prostate-specific antigen sample as an abscissa and the photocurrent intensity as an ordinate.
4. A method of manufacturing a photoelectrochemical immunosensor for detecting a prostate specific antigen as claimed in any one of claims 1 to 3, characterised in that it is carried out according to the following steps:
step 1, ultrasonically cleaning an FTO glass electrode by using acetone, water and ethanol in sequence, and then drying overnight at 60 ℃ for later use;
step 2, adding 2mg of graphite-like carbon nitride/tin disulfide quantum dot nanocomposite into 2mL of deionized water, and uniformly dispersing by ultrasonic to obtain nanocomposite dispersion;
step 3, uniformly dripping 30 mu L of the nanocomposite dispersion liquid prepared in the step 2 on the surface of the FTO glass electrode cleaned in the step 1, and airing at room temperature to obtain a graphite-phase carbon nitride/tin disulfide quantum dot nanocomposite modified electrode;
step 4, after the modified electrode prepared in the step 3 is treated by chitosan and glutaraldehyde, 30 mu L of 0.01mg/mL of anti-prostate specific antigen monoclonal antibody is dripped on the surface, the reaction is carried out for 12 to 13 hours at the temperature of 4 ℃, and after the reaction is taken out, the reaction is washed by a PBS buffer solution with the concentration of 10mmol/L, pH of 7.2 to 7.4; then 30 mu L of calf serum protein solution with the mass concentration of 2-3% is dripped, the mixture is blocked for 1-2 hours at 37 ℃, and after the mixture is taken out, the mixture is washed by a PBS buffer solution with the mass concentration of 10mmol/L, pH of 7.2-7.4, and the photoelectrochemical immunosensor for detecting the prostate specific antigen is obtained.
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