CN110068570B - Preparation of electrochemical sensor with instant visual colorimetric display - Google Patents
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Abstract
The invention discloses a preparation method of an electrochemical sensor with instant visual colorimetric display, and relates to the technical field of electrochemical detection. The nickel is prepared by a potential deposition method, wherein the iron oxyhydroxide/bismuth vanadate nano composite material is used as a photoelectric anode, the electropolymerized Prussian blue is used as a photoelectric cathode, the laccase catalyst is prepared as a biological cathode, and an external coil is connected with a portable digital multimeter and a capacitor. Under the specific binding action of the antigen and the antibody, glucose is promoted to generate hydrogen peroxide under the catalysis of glucose oxidase, so that the generation of nickel, namely iron oxyhydroxide/bismuth vanadate photoelectrons is accelerated under illumination, the instantaneous current generated in the process can be read by a digital multimeter, and the change of Prussian blue receiving electrons into Prussian white can be used as synchronous colorimetric display. After the reaction is finished, the Prussian white and the laccase can be connected and can be restored to an initial state to be converted into Prussian blue, and the circulation of the photocathode material provides great convenience for the construction of the sensor.
Description
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to a preparation method of an electrochemical sensor with instant visual colorimetric display.
Background
It is known that cancer cells are variant cells, are the source of cancer, have three characteristics of unlimited proliferation, transformation and easy metastasis, and can be unlimited in proliferation and destroy normal cell tissues. According to the survey of the world health organization in 2018, nearly one sixth of the worldwide deaths are caused by cancer, and the incidence and mortality of cancer is expected to continue to rise in the next 20 years. Tumor markers are considered to be useful indicators in clinical assays to determine the presence or absence of disease or to monitor disease progression. Therefore, in recent years, various analysis methods such as electrochemiluminescence, fluorescence measurement, liquid chromatography, and radioimmunoassay have been proposed, but these methods have disadvantages such as expensive instruments and complicated operations. The photoelectrochemical sensor constructed by the invention realizes rapid and sensitive direct quantitative detection of a target object through a small simple digital multimeter. Due to its low cost equipment, rapid response and attractive potential in future bioanalytics opens up new avenues for sensor development.
In recent years, photosensitive nanomaterials are widely used in biosensors due to their large specific surface area and good light absorption, and can load a large number of signal molecules and accelerate the diffusion rate. The photosensitive nanocomposite is particularly applied to electrochemical analysis due to the advantages of uniform distribution and better conductivity. Among them, the bismuth vanadate nanocomposite supported by iron hydroxide and nickel hydroxide has received much attention in electrochemical applications.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of an electrochemical sensor with instant visual colorimetric display, which is characterized by comprising the following steps:
(1) cutting fluorine-doped tin oxide (FTO) conductive glass into a size of 1 cm multiplied by 5 cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water, performing ultrasonic treatment for 10-20 min, and then drying in an oven at 40-60 ℃ for 30 min;
(2) preparing nickel, namely a ferric oxyhydroxide/bismuth vanadate nano composite material on the surface of conductive glass as a photoelectric anode by using the conductive glass as a substrate and utilizing a potential deposition method;
(3) conducting electric polymerization on the surface of the conductive glass to obtain Prussian blue serving as a photoelectric cathode;
(4) modifying laccase on the surface of the paper base to be used as a biological cathode;
(5) modifying an antigen antibody and glucose oxidase on the surface of the conductive glass;
(6) and (3) connecting the photoelectric anode prepared in the step (2), the electropolymerized photoelectric cathode in the step (3) and the modified laccase biocathode in the step (4) with a capacitor and a digital multimeter through an external lead to construct an electrochemical sensor with instant visual colorimetric display.
The conductive glass is prepared by cutting FTO conductive glass into the size of 1 cm multiplied by 5 cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water for ultrasonic treatment for 10 min, and then placing the treated glass in a 60 ℃ oven for 30 min for drying.
The preparation process of the nickel-iron oxyhydroxide/bismuth vanadate nanocomposite comprises the following steps: 0.3638 g of bismuth nitrate (Bi (NO))3) 6.6404 g of potassium iodide (KI) is dissolved in 100 mL of ultrapure water, the pH value of the solution is adjusted to 1.2 by concentrated hydrochloric acid, then 45 mL of ethanol solution containing 1.4592 g of p-benzoquinone is added, the solution is stirred for 30 min to be fully dissolved and mixed, then the FTO conductive glass treated in the step (1) is inserted into the mixed solution, the constant potential deposition method is adopted to deposit for 10 s at-0.3V, then the deposition is carried out for 600 s at-0.1V, the FTO conductive glass is taken out and dried at normal temperature, the conductive glass is continuously immersed into 5 mL of dimethyl sulfoxide solution containing 0.5301 g of vanadyl acetylacetonate to be kept for 60 s, then the conductive glass is transferred into a muffle furnace at 120 ℃, the annealing temperature is firstly increased to 280 ℃, the heating rate is 1 ℃/min, then is increased to 450 ℃, the heating rate is 2 ℃/min, then the bismuth vanadate electrode is kept for 1 h at 450 ℃, the obtained bismuth vanadate electrode is immersed for 5min in 0.05M of sodium hydroxide solution, taking out and washing with ultrapure water for three times, finally inserting the obtained FTO conductive glass into 2 mL of a urea mixed solution of 30mM ferric trichloride and 25 mL of 30mM nickel dichloride, placing the FTO conductive glass in an oil bath at 100 ℃ for keeping for 1 h, and washing with ultrapure water for three times after the reaction is finished to obtain the nickel-iron oxyhydroxide/bismuth vanadate photoelectric anode material.
The preparation process of the invention for electropolymerizing prussian blue on the surface of conductive glass as a photocathode comprises the following steps: immersing FTO conductive glass into ethanol with a volume ratio of 1: sodium hydroxide (1M), followed by rinsing with ultrapure water, drying with nitrogen gas, and inserting FTO conductive glass into 0.1M KCl, 0.1M HCl, 2.5 mM K3[Fe(CN)6]And 2.5 mM FeCl3And (3) depositing for 600 s in the mixed solution by adopting a constant potential deposition method, wherein the deposition potential is 0.4V, and rinsing with ultrapure water for three times after the reaction is finished to obtain the Prussian blue-light cathode material.
The preparation process of the invention for modifying laccase on the surface of conductive glass as a biological cathode comprises the following steps: dissolving carbon nanotubes in 4.0 mL of 1% diallyl dimethyl ammonium chloride (0.02M sodium chloride), performing ultrasonic treatment for 30 min, centrifuging at 15000 rpm for 10 min, placing the obtained mixed solution in 3 mL of 10 mM gold nanoparticles, stirring for 24 h, centrifuging at 8000 rpm for 10 min to dissolve the precipitate in water to a concentration of 1 mg/mL, uniformly coating the precipitate on a 1 cm × 5 cm paper chip, drying at 37 ℃ for 2 h, immersing the obtained paper chip in 6 mM dopamine solution (0.1M PBS, pH 8.5) for 3 h, taking out, rinsing with ultrapure water three times, immersing in 50 μ L of 30 mg/mL laccase PBS solution (pH 7.4) again, and keeping at 4 ℃ for 12 h to obtain the laccase biocathode material.
The process for modifying the antigen antibody and the glucose oxidase on the surface of the conductive glass comprises the following steps: firstly, 4% (v/v) 3-Mercaptotoluene (MPTS)/ethanol is dripped into treated FTO conductive glass for natural drying, then N- (4-maleiniferyl butyl hydroxyl) succinimide)/dimethyl sulfoxide is dripped on the surface of the FTO conductive glass, and 10 mu L of 20 mu g/mL carcinoembryonic antibody 1 (AbAb Ab) is dried1) Dropping into the surface, reacting at room temperature for 50 min, dropping Phosphate Buffer Solution (PBS) and 1% Bovine Serum Albumin (BSA) to prevent nonspecific binding sites, dropping 10 μ L of carcinoembryonic antigen with different concentrations onto FTO surface, reacting for 40 min, washing with PBS, and mixing with glucose oxidase and carcinoembryonic antibody 2 (GOx-AuNP-Ab) connected with synthesized gold nanoparticles2Specifically, the pH value of the prepared gold nanoparticles is adjusted to about 8.5 by ammonium carbonate, and then 200 mu L of 0.5 mg/mL GOx and 50 mu L of 0.5 mg/mL Ab are added2Respectively dropping the mixture into 5 mL of gold nanoparticle solution, oscillating the solution at room temperature for 2 h, then adding 100 mu L of 1.0 wt% polyethylene glycol, reacting the mixture at 4 ℃ for 12 h, finally centrifuging the mixture at 14000 rmp for 15min, and obtaining a precipitate GOx-AuNP-Ab2Dispersed in a PBS solution containing 1.0 wt% BSA and 0.1% sodium azide at pH 7.4, stored at 4 ℃ until use) was added dropwise thereto for reaction for 45 min, and finally washed with PBS (pH 7.4).
The working process of the electrochemical sensor comprises the following steps: connecting the constructed photoelectric anode and cathode with a capacitor and a digital multimeter through leads, inserting FTO which generates antigen-antibody immunoreaction, dripping 110 mu L of PBS solution (50 mM, PH = 6.0) containing 4 mM glucose into a left reaction tank, generating hydrogen peroxide under the action of glucose oxidase, further promoting the photoelectric anode to generate electrons and holes under the irradiation of a xenon lamp, realizing the conversion of light energy to electric energy, directly observing the current generated in the process through the digital multimeter, transmitting the electrons generated by the photoelectric anode to the cathode through leads, reducing Prussian blue into Prussian white, realizing instant visual colorimetric display, connecting the Prussian white with a laccase biocathode in a right reaction tank after the reaction is finished, acquiring electrons from the Prussian white in the process of laccase biocatalytic oxygen reduction, so that the Prussian white is oxidized and restored to an initial state and becomes Prussian blue, and the Prussian blue is repeatedly used as a synchronous visual analysis electrode to provide a qualitative result for detecting the carcinoembryonic antigen.
The invention has the beneficial effects that:
(1) the nickel-iron oxyhydroxide/bismuth vanadate nano composite material synthesized by the experiment has larger specific surface area and is beneficial to expanding the absorption of light.
(2) The Prussian blue-light electric cathode is constructed, so that the sensor can realize instant visual colorimetric display besides quantitative detection of a digital multimeter.
(3) The constructed laccase biocathode realizes the recycling of the Prussian blue cathode material, so that the operation is simpler and more convenient.
(4) The photoelectrochemistry analysis device can greatly reduce background signals and improve the detection sensitivity when being used for detecting the target object.
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The invention is described in further detail below with reference to the accompanying drawings and the specific embodiments, and fig. 1 is a schematic diagram of the electrochemical sensor with instant visualization colorimetric display.
Detailed Description
Example 1: construction of electrochemical sensors with instantaneous visual colorimetric display
(1) Cutting FTO conductive glass into a size of 1 cm multiplied by cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water, performing ultrasonic treatment for 10 min, and then drying in an oven at 60 ℃ for 30 min.
(2) 0.3638 g of bismuth nitrate (Bi (NO))3) 6.6404 g of potassium iodide (KI) is dissolved in 100 mL of secondary water, the pH value of the solution is adjusted to 1.2 by concentrated hydrochloric acid, then 45 mL of ethanol solution containing 1.4592 g of p-benzoquinone is added, the solution is stirred for 30 min to be fully dissolved and mixed, then the FTO conductive glass treated in the step (1) is inserted into the mixed solution, the FTO conductive glass is deposited for 10 s at-0.3V by adopting a constant potential deposition method, then deposited for 600 s at-0.1V, taken out and dried at normal temperature, the conductive glass is continuously immersed into 5 mL of dimethyl sulfoxide solution containing 0.5301 g of vanadyl acetylacetonate for 60 s, then transferred into a muffle furnace at 120 ℃, the annealing temperature is firstly increased to 280 ℃, the temperature increasing rate is 1 ℃/min, then increased to 450 ℃, the temperature increasing rate is 2 ℃/min, then kept for 1 h at 450 ℃, the obtained bismuth vanadate electrode is immersed for 5min in 0.05M of sodium hydroxide solution, taking out and washing with ultrapure water for three times, finally inserting the obtained FTO conductive glass into 2 mL of a urea mixed solution of 30mM ferric trichloride and 25 mL of 30mM nickel dichloride, placing the FTO conductive glass in an oil bath at 100 ℃ for keeping for 1 h, and washing with ultrapure water for three times after the reaction is finished to obtain the nickel-iron oxyhydroxide/bismuth vanadate photoelectric anode material.
(3) Immersing FTO conductive glass into ethanol with a volume ratio of 1: sodium hydroxide (1M), followed by a second rinse with water, nitrogen drying, and inserting FTO conductive glass into 0.1M KCl, 0.1M HCl, 2.5 mM K3[Fe(CN)6]And 2.5 mM FeCl3And (3) depositing for 600 s in the mixed solution by adopting a constant potential deposition method, wherein the deposition potential is 0.4V, and rinsing with ultrapure water for three times after the reaction is finished to obtain the Prussian blue-light cathode material.
(4) Dissolving carbon nanotubes in 4.0 mL of 1% diallyl dimethyl ammonium chloride (0.02M sodium chloride), performing ultrasonic treatment for 30 min, centrifuging at 15000 rpm for 10 min, placing the obtained mixed solution in 3 mL of 10 mM gold nanoparticles, stirring for 24 h, centrifuging at 8000 rpm for 10 min to dissolve the precipitate in water to a concentration of 1 mg/mL, uniformly coating the precipitate on a 1 cm × 5 cm paper chip, drying at 37 ℃ for 2 h, immersing the obtained paper chip in 6 mM dopamine solution (0.1M PBS, pH 8.5) for 3 h, taking out, rinsing with ultrapure water three times, immersing in 50 μ L of 30 mg/mL laccase PBS solution (pH 7.4) again, and keeping at 4 ℃ for 12 h to obtain the laccase biocathode material.
(5) Firstly, 4% (v/v) 3-Mercaptotoluene (MPTS)/ethanol is dripped into treated FTO conductive glass for natural drying, then N- (4-maleiniferyl butyl hydroxyl) succinimide)/dimethyl sulfoxide is dripped on the surface of the FTO conductive glass, and 10 mu L of 20 mu g/mL carcinoembryonic antibody 1 (AbAb Ab) is dried1) Dropping into the surface, reacting at room temperature for 50 min, dropping Phosphate Buffer Solution (PBS) and 1% Bovine Serum Albumin (BSA) to prevent nonspecific binding sites, dropping 10 μ L of carcinoembryonic antigen with different concentrations onto FTO surface, reacting for 40 min, washing with PBS, and mixing with glucose oxidase and carcinoembryonic antibody 2 (GOx-AuNP-Ab) connected with synthesized gold nanoparticles2Specifically, the pH value of the prepared gold nanoparticles is adjusted to about 8.5 by ammonium carbonate, and then 200 mu L of 0.5 mg/mL GOx and 50 mu L of 0.5 mg/mL Ab are added2Respectively dropping the mixture into 5 mL of gold nanoparticle solution, oscillating the solution at room temperature for 2 h, then adding 100 mu L of 1.0 wt% polyethylene glycol, reacting the mixture at 4 ℃ for 12 h, finally centrifuging the mixture at 14000 rmp for 15min, and obtaining a precipitate GOx-AuNP-Ab2Dispersed in a PBS solution containing 1.0 wt% BSA and 0.1% sodium azide and having a pH of 7.4, stored at 4 ℃ for later use) was added dropwise thereto for reaction for 45 min, and finally washed with PBS (pH 7.4), to obtain conductive glass modified with an antigen antibody and glucose oxidase.
(6) Connecting the constructed photoelectric anode and cathode with a capacitor and a digital multimeter through leads, inserting FTO which generates antigen-antibody immunoreaction, dripping 110 mu L of PBS solution (50 mM, PH = 6.0) containing 4 mM glucose into a left reaction tank, generating hydrogen peroxide under the action of glucose oxidase, further promoting the photoelectric anode to generate electrons and holes under the irradiation of a xenon lamp, realizing the conversion of light energy to electric energy, directly observing the current generated in the process through the digital multimeter, transmitting the electrons generated by the photoelectric anode to the cathode through leads, reducing Prussian blue into Prussian white, realizing instant visual colorimetric display, connecting the Prussian white with a laccase biocathode in a right reaction tank after the reaction is finished, acquiring electrons from the Prussian white in the process of laccase biocatalytic oxygen reduction, so that the Prussian white is oxidized and restored to an initial state and becomes Prussian blue, and the Prussian blue is repeatedly used as a synchronous visual analysis electrode to provide a qualitative result for detecting the carcinoembryonic antigen.
Claims (7)
1. A method for preparing an electrochemical sensor with an instantaneous visual colorimetric display, characterized in that the method comprises the following steps:
(1) cutting fluorine-doped tin oxide (FTO) conductive glass into a size of 1 cm multiplied by 5 cm, sequentially adding acetone, absolute ethyl alcohol and ultrapure water, carrying out ultrasonic treatment for 10-20 min, and then putting the treated glass into a 40-60 ℃ drying oven for 30 min for drying;
(2) preparing nickel, namely a ferric oxyhydroxide/bismuth vanadate nano composite material on the surface of conductive glass as a photoelectric anode by using the conductive glass as a substrate and utilizing a potential deposition method;
(3) conducting electric polymerization on the surface of the conductive glass to obtain Prussian blue serving as a photoelectric cathode;
(4) modifying laccase on the surface of the paper base to be used as a biological cathode;
(5) modifying an antigen antibody and glucose oxidase on the surface of the conductive glass;
(6) and (3) connecting the photoelectric anode prepared in the step (2), the electropolymerized photoelectric cathode in the step (3) and the laccase biocathode modified in the step (4) with a capacitor and a digital multimeter through an external lead to construct an electrochemical sensor with instant visual colorimetric display.
2. The method of claim 1, wherein the electrochemical sensor with real-time visual colorimetric display comprises: in the step (1), the FTO conductive glass is cut into the size of 1 cm multiplied by 5 cm, and then is sequentially put into acetone, absolute ethyl alcohol and ultrapure water for ultrasonic treatment for 10 min and then is put into a 60 ℃ drying oven for 30 min for drying.
3. The method for preparing the electrochemical sensor with the instant visual colorimetric display as claimed in claim 1, wherein the preparation of the nickel-iron oxyhydroxide/bismuth vanadate nanocomposite material is characterized in that: 0.3638 g of bismuth nitrate (Bi (NO))3) 6.6404 g of potassium iodide (KI) is dissolved in 100 mL of ultrapure water, the pH of the solution is adjusted to 1.2 by concentrated hydrochloric acid, then 45 mL of ethanol solution containing 1.4592 g of p-benzoquinone is added, the solution is stirred for 30 min to be fully dissolved and mixed, then the FTO conductive glass treated in the step (1) is inserted into the mixed solution, the solution is deposited for 10 s at-0.3V by a constant potential deposition method, then the solution is deposited for 600 s at-0.1V, the solution is taken out and dried at normal temperature, the conductive glass is continuously immersed in 5 mL of dimethyl sulfoxide solution containing 0.5301 g of vanadyl acetylacetonate to be kept for 60 s, then the solution is transferred to a 120-degree muffle furnace, the annealing temperature is firstly increased to 280 degrees, the temperature rise rate is 1 degree C/min, then is increased to 450 degrees C, the temperature rise rate is 2 degrees C/min, and then the solution is kept for 1 h at 450 degrees C, and soaking the obtained bismuth vanadate electrode in 0.05M sodium hydroxide solution for 5min, taking out and washing the bismuth vanadate electrode with ultrapure water for three times, finally inserting the obtained FTO conductive glass into 2 mL of a mixed solution of 30mM ferric trichloride and 25 mL of 30mM nickel dichloride urea, placing the FTO conductive glass in an oil bath at 100 ℃ for 1 h, and washing the FTO conductive glass with ultrapure water for three times after the reaction is finished to obtain the nickel-iron oxyhydroxide/bismuth vanadate photoelectric anode material.
4. The method for preparing an electrochemical sensor with instant visual colorimetric display according to claim 1, comprising electropolymerizing prussian blue on the surface of conductive glass as a photocathode, wherein: immersing FTO conductive glass into ethanol with the concentration of 1M and the volume ratio of 1: in sodium hydroxide solution, followed by rinsing with ultrapure water, drying with nitrogen gas, and inserting FTO conductive glass containing 0.1M KCl, 0.1M HCl, 2.5 mM K3[Fe(CN)6]And 2.5 mM FeCl3In the mixed solution, depositing for 600 s by adopting a constant potential deposition method, wherein the deposition potential is 0.4V, and washing with ultrapure water for three times after the reaction is finished to obtain the Prussian blue-light cathode material.
5. The method for preparing an electrochemical sensor with instant visual colorimetric display as claimed in claim 1, wherein laccase is modified on the surface of conductive glass as a biocathode, which is characterized in that: firstly, 0.0024 g of carbon nano tube is dissolved in 4.0 mL of 1 percent diallyl dimethyl ammonium chloride solution, simultaneously adding 0.0046 g of sodium chloride, performing ultrasonic treatment for 30 min, centrifuging at 15000 rpm for 10 min, placing the obtained mixed solution in 3 mL of 10 mM gold nanoparticles, stirring for 24 h, centrifuging at 8000 rpm for 10 min to dissolve the precipitate in water to a concentration of 1 mg/mL, uniformly coating on a paper chip of 1 cm × 5 cm, drying at 37 ℃ for 2 h, dissolving a proper amount of dopamine in PBS (pH 8.5 and 0.1M) to obtain a dopamine solution with the concentration of 6 mM, then immersing the paper chip in the dopamine solution, and after 3 h, taking out and washing with ultrapure water for three times, immersing in a PBS solution containing 50 mu L of 30 mg/mL laccase and having a pH of 7.4 again, and keeping at 4 ℃ for 12 h to obtain the laccase biocathode material.
6. The method for preparing an electrochemical sensor with instant visual colorimetric display as claimed in claim 1, wherein the modification of antigen antibody and glucose oxidase is carried out on the surface of conductive glass, which is characterized in that: firstly, 4% (v/v) 3-Mercaptotoluene (MPTS)/ethanol is dripped into treated FTO conductive glass for natural drying, then N- (4-maleiniferyl butyl hydroxyl) succinimide)/dimethyl sulfoxide is dripped on the surface of the FTO conductive glass, and 10 mu L of 20 mu g/mL carcinoembryonic antibody 1 (AbAb Ab) is dried1) Dropping into the surface, reacting at room temperature for 50 min, dropping Phosphate Buffer Solution (PBS) and 1% Bovine Serum Albumin (BSA) to prevent nonspecific binding sites, dropping 10 μ L of carcinoembryonic antigen with different concentrations onto FTO surface, reacting for 40 min, washing with PBS, and mixing with glucose oxidase and carcinoembryonic antibody 2 complex (GOx-AuNP-Ab) connected with synthesized gold nanoparticles2) The reaction was added dropwise thereto for 45 min, and finally washed with PBS buffer pH 7.4, in which GOx-AuNP-Ab2The preparation method of the compound comprises the steps of firstly adjusting the pH of the prepared gold nanoparticles to about 8.5 by using ammonium carbonate, and then adjusting 200 mu L of 0.5 mg/mL GOx and 50 mu L of 0.5 mg/mL Ab25 mL of gold nanoparticle solution was added dropwise to each solutionOscillating the solution at room temperature for 2 h, then adding 100 mu L1.0 wt% polyethylene glycol, reacting at 4 ℃ for 12 h, and finally centrifuging the mixture at 14000 rmp for 15min to obtain precipitate GOx-AuNP-Ab2Dispersed in PBS solution containing 1.0 wt% BSA and 0.1% sodium azide and having pH of 7.4, and stored at 4 ℃ for later use.
7. The method of claim 1, wherein the electrochemical sensor with real-time visual colorimetric display comprises: connecting the constructed photoelectric anode and cathode with a capacitor and a digital multimeter through leads, inserting FTO which generates antigen-antibody immunoreaction, adding 10 mL PBS solution containing 4 mM glucose and having pH of 7.4 into the left reaction cell, generating hydrogen peroxide under the action of glucose oxidase, further promoting the photoelectric anode to generate electrons and holes under the irradiation of a xenon lamp, realizing the conversion of light energy to electric energy, directly observing the current generated in the process through the digital multimeter, transmitting the electrons generated by the photoelectric anode to the cathode through leads, reducing Prussian blue into Prussian white, realizing instant visual colorimetric display, connecting the Prussian white with the biological cathode of laccase in the right reaction cell after the reaction is finished, acquiring electrons from the Prussian white in the process of laccase biological catalytic oxygen reduction, thereby leading the Prussian white to be oxidized into Prussian blue in an initial state, therefore, the Prussian blue as a photocathode can be recycled, and a synchronous visual result is provided for qualitative detection of carcinoembryonic antigen.
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| CN110907512A (en) * | 2019-12-18 | 2020-03-24 | 济南大学 | Construction method of visual paper-based biological cathode photoelectrochemical sensor |
| CN111001410B (en) * | 2019-12-25 | 2022-07-26 | 扬州大学 | Preparation of semiconductor bismuth vanadate-iron oxyhydroxide nanoenzyme and method for detecting hydrogen peroxide |
| CN111721821B (en) * | 2020-05-28 | 2022-07-08 | 济南大学 | Preparation method of foam nickel supported photoelectric cathode material DNA (deoxyribonucleic acid) immunosensor for detecting breast cancer |
| CN112919496B (en) * | 2021-01-28 | 2022-03-29 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN113029962B (en) * | 2021-03-03 | 2024-03-12 | 贵阳学通仪器仪表有限公司 | Reaction tank colorimetric device for high-precision water quality detector and manufacturing method thereof |
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