CN112147191A - Preparation method of electrochemical luminescence sensor for detecting procalcitonin by using gold cluster modified copper-cobalt material - Google Patents

Preparation method of electrochemical luminescence sensor for detecting procalcitonin by using gold cluster modified copper-cobalt material Download PDF

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CN112147191A
CN112147191A CN202010854094.4A CN202010854094A CN112147191A CN 112147191 A CN112147191 A CN 112147191A CN 202010854094 A CN202010854094 A CN 202010854094A CN 112147191 A CN112147191 A CN 112147191A
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solution
cuco
procalcitonin
electrode
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鞠熀先
贾洪英
魏琴
张勇
范大伟
匡轩
孙旭
王欢
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University of Jinan
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Abstract

The invention relates to a preparation method of an electrochemical luminescence sensor for detecting procalcitonin by using a gold cluster modified copper-cobalt material. The electro-deposition platinum nano particles are used as a substrate material, the gold cluster modified copper-cobalt material is used as a secondary antibody marker and a co-reaction promoter, a co-reaction promoter type signal amplification strategy is adopted, the signal-enhanced ECL sensor is constructed, sensitive detection of procalcitonin in a linear range of 10 fg/mL-50 ng/mL is realized, and the detection limit is 3.41 fg/mL.

Description

Preparation method of electrochemical luminescence sensor for detecting procalcitonin by using gold cluster modified copper-cobalt material
Technical Field
The invention relates to a preparation method of an electrochemical luminescence sensor for detecting procalcitonin by using a gold cluster modified copper-cobalt material. In particular to CuCo2O4As a carrier, gold nanoclusters are loaded on CuCo as luminophors2O4The surface prepares a signal enhancement type electrochemical luminescence sensor for detecting procalcitonin, and belongs to the field of electrochemical luminescence sensors.
Background
Procalcitonin is a protein whose concentration in the plasma increases when humans suffer from severe bacterial, fungal, parasitic infections as well as sepsis and multi-organ failure. Elevated concentrations of procalcitonin are observed in autoimmune, allergic and viral infections. Localized limited bacterial infection, mild infection and chronic inflammation do not result in elevated concentrations. Procalcitonin is a parameter for the diagnosis and monitoring of bacterial inflammatory disease infections. Severe infections are fatal complications for patients with immunosuppression and neutropenia due to chemotherapy or bone marrow transplantation, and fever is caused by a variety of causes during chemotherapy. Fever is usually a symptom of bacterial, viral or fungal infection, but sometimes is a response to the drug during treatment. Fever caused by tumor cell lysis is common, and the origin of fever in most cases remains unclear. Sensitive detection of procalcitonin facilitates a clear diagnosis of systemic infections caused by bacteria and fungi. Even chemotherapy patients can reliably detect and evaluate whether the patients are infected by septicemia or not by procalcitonin. Neutropenic patients often lack the specific symptoms of inflammation. The performance of procalcitonin in immunosuppressed and neutropenic patients is similar to the results observed in non-immunosuppressed patients. Therefore, highly sensitive detection of procalcitonin is very important. The invention provides an electrochemiluminescence immunosensor which is simple and rapid to operate and high in sensitivity and is used for detecting procalcitonin.
Electrochemiluminescence (ECL) combines the characteristics of controllable electrochemical potential and high sensitivity of chemiluminescence, and has been developed into an analysis method with great application potential. As a novel gold nanocluster (AuNCs) material, the gold nanocluster has the advantages of being good in biocompatibility, free of toxic elements such as Cd and Pd, capable of emitting light in multiple colors and adjustable, and the optical properties of traditional quantum dots are superior. The invention synthesizes gold nanoclusters by using methionine and simultaneously utilizes CuCo2O4Large specific surface area, good catalytic performance and the like, and CuCo2O4As a carrier of gold nanoclusters, the nanoclusters are stably supported on the electrode surface in a large amount. In addition, the co-reaction promoter has been widely applied to an electrochemiluminescence signal amplification strategy, and can react with the co-reactant to promote the generation of a luminescence intermediate, so that the excited state number of the luminophor can be increased, and the ECL signal of the luminophor can be enhanced. The invention provides CuCo2O4A large amount of ECL luminophor gold nanoclusters are immobilized, triethanolamine is used as a co-reactant, and CuCo is used as a co-reactant2O4As a co-reaction promoter, a signal-enhanced ECL immunosensor is constructed.
Disclosure of Invention
One of the purposes of the invention is to synthesize AuNCs and coat methionine on the surface of the AuNCs to be used as a reducing agent and a stabilizing agent; during the synthesis of gold nanoclusters, strong and stable ECL signals were obtained by adjusting the concentration of methionine.
The second purpose of the invention is to synthesize hollow spherical CuCo with larger specific surface area2O4And using it as carrier of gold nanocluster, CuCo2O4Has large specific surface area and catalytic performance.
The third purpose of the invention is to synthesize hollow spherical CuCo2O4As co-reaction promoters for gold nanoclusters; CuCo2O4Can promote the action of the triethanolMore active intermediates are generated by amine decomposition, so that the number of excited state luminophores can be increased, and the ECL strength of the quantum dots can be enhanced.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. a preparation method of an electrochemical luminescence sensor for detecting procalcitonin by using a gold cluster modified copper-cobalt material is characterized in that the preparation of the electrochemical immunosensor comprises the following steps:
(1) polishing a glassy carbon electrode with the diameter of 4 mm to a mirror surface by using alumina powder with the diameter of 0.05 mu m, and then washing the polished glassy carbon electrode by using ultrapure water;
(2) carrying out electro-deposition on the treated electrode for 30 s at constant potential of-0.1 to-0.3V by using a constant potential deposition method, and storing at room temperature until the electrode is dried;
(3) continuously dripping 6 mu L of procalcitonin capture antibody standard solution with the concentration of 10 mu g/mL on the surface of the glassy carbon electrode, storing in a refrigerator at 4 ℃ until the solution is dried, and cleaning with ultrapure water;
(4) continuously dripping 3 mu L of bovine serum albumin solution with the mass fraction of 1% to seal the nonspecific active sites, storing in a refrigerator at 4 ℃ until the active sites are dried, and cleaning with ultrapure water;
(5) continuously dripping a series of procalcitonin antigen standard solutions with different concentrations, of which the concentration is 10 fg/mL to 50 ng/mL, on the surface of the electrode, storing the solution in a refrigerator of 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water;
(6) 5-10 mu L of prepared gold nanocluster functionalized hollow spherical CuCo2O4Structure and procalcitonin detection antibody compound AuNCs-CuCo2O4-Ab2Dripping the solution on the surface of an electrode, storing the solution in a refrigerator at 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water to obtain the electrochemical luminescence immunosensor for detecting procalcitonin;
2. the method for preparing the electrochemiluminescence sensor for detecting procalcitonin by using the gold cluster modified copper-cobalt material as claimed in claim 1, wherein the hollow spherical CuCo is2O4The nano material is characterized by comprising the following preparation steps:
(1) preparation of hollow coreSpherical CuCo2O4Nano material
Dissolving 8 mL of glycerol in 40 mL of isopropanol, and stirring to form a transparent colorless solution; adding 6-10 mmol of cobalt nitrate and 14-20 mmol of copper nitrate into the solution until a uniform pink solution is obtained; then the solution is injected into a high-pressure autoclave and reacts for 10 hours at 180 ℃; washing with ultrapure water and ethanol, and drying; to obtain CuCo2O4Calcining a dried CuCo precursor in air at 350 ℃ for 3h, wherein the heating rate is 3 ℃/min;
(2) preparation of aminated hollow spherical CuCo2O4Nano material
To realize hollow spherical CuCo2O4Amination of nanomaterial at 10 mL CuCo2O42 mL aminopropyltriethoxysilane (3%) was added to the solution (2 mg/mL) and stirred at 60 ℃ for 36 h; after centrifugal washing, CuCo covered with abundant amino groups is obtained2O4A nanomaterial;
3. the gold cluster-modified spherical CuCo of claim 12O4Preparation method of electrochemical luminescence sensor for detecting procalcitonin, and hollow spherical CuCo2O4And gold nanoclusters, characterized in that the preparation steps are as follows:
(1) preparation of AuNCs
Methionine (4 mL of 0.1M) and sodium hydroxide (0.6 mL of 0.5M) were added to an aqueous solution of chloroauric acid (0.4 mL of 20 mg/mL); the pale yellow color of the mixture rapidly faded away to form the Au (III) -methionine complex; the mixed solution was incubated at 37 ℃ for 10 h to give a pale yellow solution. Then adding sulfuric acid aqueous solution (0.5 mL, 1M) to precipitate AuNCs; after centrifugation, the gold nanoclusters are collected and washed three times with sulfuric acid solution (5 mL, 0.1M); dissolving the gold nanoclusters in 1.4% ammonia water solution, incubating at 70 ℃ to obtain AuNCs solution with high luminous intensity, and storing at 4 ℃ in the dark for later use;
(2) preparing AuNCs functionalized hollow spherical CuCo2O4
1.0-3.0 mg of aminated CuCo2O4Mixing with 4-6 mL of gold nanoclusters, adding glutaraldehyde solution, incubating for 8 hours at room temperature, centrifuging, dispersing into 2 mL of phosphate buffer solution with the pH of 7.4, adding 1 mL of procalcitonin detection antibody with the concentration of 10 mu g/mL, mixing, and incubating for 12 hours at 4 ℃ to obtain AuNCs-CuCo2O4-Ab2A complex;
4. the series of 10 fg/mL to 50 ng/mL of the procalcitonin standard solutions of claim 1, which is obtained by diluting 1 mg/mL of procalcitonin solution available from tsinggis biotechnology limited of Nanjing with a phosphate buffer solution;
5. the assay of procalcitonin according to claim 1, characterized by the following steps:
(1) connecting an Ag/AgCl electrode serving as a reference electrode, a platinum wire electrode serving as a counter electrode and the prepared electrochemical luminescence sensor serving as a working electrode in a cassette of a chemiluminescence detector, and connecting an electrochemical workstation with the chemiluminescence detector together;
(2) the parameters of the chemiluminescence detector are set, the high voltage of the photomultiplier is set to be 600-800V, and the scanning speed is set to be 0.1V/s;
(3) setting parameters of an electrochemical workstation, wherein the range of a cyclic voltammetry scanning potential is 0V-1.2V, and the scanning rate is set to be 0.1V/s;
(4) using 10 mL of 0.1mol/L phosphate buffer solution containing 0.1mol/L triethanolamine as a co-reactant, and detecting the intensity of an electrochemiluminescence signal generated by procalcitonin with different concentrations by an electrochemiluminescence method; the pH value of the phosphate buffer solution is 7.4, and the phosphate buffer solution is prepared by 0.1mol/L disodium hydrogen phosphate and 0.1mol/L potassium dihydrogen phosphate;
(5) and drawing a working curve according to the linear relation between the obtained electrochemical luminescence intensity value and the logarithm of the concentration of the procalcitonin antibody.
Advantageous results of the invention
(1) Compared with the traditional quantum dots, the AuNCs has the characteristics of environmental friendliness, strong biocompatibility, high luminous intensity and the like; methionine wraps the gold nanocluster, wherein the methionine can be used as a reducing agent and a stabilizing agent, so that the luminous intensity and stability of the quantum dots are enhanced, and the quantum yield of the gold nanocluster is improved; the quantum dot has strong and stable ECL properties and is used as an ECL luminophor in an ECL system for the first time.
(2) Hollow spherical CuCo2O4Having a large specific surface area to make CuCo2O4The gold nanoclusters are loaded in a large amount by proper sizes, and the ECL strength can be well enhanced.
(3) The third purpose of the invention is to synthesize hollow spherical CuCo2O4As co-reaction promoters for gold nanoclusters; CuCo2O4Can promote the decomposition of triethanolamine to generate more active intermediates, thereby improving the number of excited state luminophors and enhancing the ECL strength of the quantum dots.
(4) The fourth purpose of the invention is to design a signal enhancement type ECL sensor by a co-reaction promoting agent type ECL amplification strategy, realize high selectivity and high sensitivity detection of procalcitonin within the concentration range of 10 fg/mL-50 ng/mL according to the linear relation of the antigen concentration and the final ECL signal, and the detection limit is as low as 3.2 fg. mL-1。
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Embodiment 1 a method for preparing an electrochemical luminescence sensor for detecting procalcitonin by using a gold cluster modified copper-cobalt material, which is characterized in that the preparation of the electrochemical immunosensor comprises the following steps:
(1) polishing a glassy carbon electrode with the diameter of 4 mm to a mirror surface by using alumina powder with the diameter of 0.05 mu m, and then washing the polished glassy carbon electrode by using ultrapure water;
(2) performing electro-deposition of platinum nanoparticles on the treated electrode for 30 s at constant potential of-0.1V by using a constant potential deposition method, and storing at room temperature until the electrode is dried;
(3) continuously dripping 6 mu L of procalcitonin capture antibody standard solution with the concentration of 10 mu g/mL on the surface of the glassy carbon electrode, storing in a refrigerator at 4 ℃ until the solution is dried, and cleaning with ultrapure water;
(4) continuously dripping 3 mu L of bovine serum albumin solution with the mass fraction of 1% to seal the nonspecific active sites, storing in a refrigerator at 4 ℃ until the active sites are dried, and cleaning with ultrapure water;
(5) continuously dripping a series of procalcitonin antigen standard solutions with different concentrations, of which the concentration is 10 fg/mL to 50 ng/mL, on the surface of the electrode, storing the solution in a refrigerator of 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water;
(6) 5-10 mu L of prepared gold nanocluster functionalized hollow spherical CuCo2O4Structure and procalcitonin detection antibody compound AuNCs-CuCo2O4-Ab2And (3) dripping the solution on the surface of an electrode, storing the solution in a refrigerator at 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water to obtain the electrochemical luminescence immunosensor for detecting procalcitonin.
Embodiment 2 a method for preparing an electrochemical luminescence sensor for detecting procalcitonin by using a gold cluster modified copper-cobalt material, which is characterized in that the preparation of the electrochemical immunosensor comprises the following steps:
(1) polishing a glassy carbon electrode with the diameter of 4 mm to a mirror surface by using alumina powder with the diameter of 0.05 mu m, and then washing the polished glassy carbon electrode by using ultrapure water;
(2) performing electro-deposition of platinum nanoparticles on the treated electrode for 30 s at constant potential of-0.2V by using a constant potential deposition method, and storing at room temperature until the electrode is dried;
(3) continuously dripping 6 mu L of procalcitonin capture antibody standard solution with the concentration of 10 mu g/mL on the surface of the glassy carbon electrode, storing in a refrigerator at 4 ℃ until the solution is dried, and cleaning with ultrapure water;
(4) continuously dripping 3 mu L of bovine serum albumin solution with the mass fraction of 1% to seal the nonspecific active sites, storing in a refrigerator at 4 ℃ until the active sites are dried, and cleaning with ultrapure water;
(5) continuously dripping a series of procalcitonin antigen standard solutions with different concentrations, of which the concentration is 10 fg/mL to 50 ng/mL, on the surface of the electrode, storing the solution in a refrigerator of 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water;
(6) functionalizing 5-10 mu L of prepared gold nanoclusterHollow spherical CuCo2O4Structure and procalcitonin detection antibody compound AuNCs-CuCo2O4-Ab2And (3) dripping the solution on the surface of an electrode, storing the solution in a refrigerator at 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water to obtain the electrochemical luminescence immunosensor for detecting procalcitonin.
Embodiment 3 a method for preparing an electrochemical luminescence sensor for detecting procalcitonin by using a gold cluster modified copper-cobalt material, which is characterized in that the preparation of the electrochemical immunosensor comprises the following steps:
(1) polishing a glassy carbon electrode with the diameter of 4 mm to a mirror surface by using alumina powder with the diameter of 0.05 mu m, and then washing the polished glassy carbon electrode by using ultrapure water;
(2) electrodepositing the treated electrode for 30 seconds by using a constant potential deposition method under the constant potential of-0.1 to-0.3V, and storing at room temperature until the electrode is dried;
(3) continuously dripping 6 mu L of procalcitonin capture antibody standard solution with the concentration of 10 mu g/mL on the surface of the glassy carbon electrode, storing in a refrigerator at 4 ℃ until the solution is dried, and cleaning with ultrapure water;
(4) continuously dripping 3 mu L of bovine serum albumin solution with the mass fraction of 1% to seal the nonspecific active sites, storing in a refrigerator at 4 ℃ until the active sites are dried, and cleaning with ultrapure water;
(5) continuously dripping a series of procalcitonin antigen standard solutions with different concentrations, of which the concentration is 10 fg/mL to 50 ng/mL, on the surface of the electrode, storing the solution in a refrigerator of 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water;
(6) 5-10 mu L of prepared gold nanocluster functionalized hollow spherical CuCo2O4Structure and procalcitonin detection antibody compound AuNCs-CuCo2O4-Ab2And (3) dripping the solution on the surface of an electrode, storing the solution in a refrigerator at 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water to obtain the electrochemical luminescence immunosensor for detecting procalcitonin.
Example 4 preparation of gold nanocluster functionalized hollow spherical CuCo2O4
(1) Preparation of hollow spherical CuCo2O4Nano material
1) Preparation of hollow spherical CuCo2O4Nano material
Dissolving 8 mL of glycerol in 40 mL of isopropanol, and stirring to form a transparent colorless solution; adding 6 mmol of cobalt nitrate and 14 mmol of copper nitrate into the solution until a uniform pink solution is obtained; the solution was then injected into an autoclave and reacted at 180 ℃ for 10 hours. Washing with ultrapure water and ethanol, and drying; to obtain CuCo2O4Calcining a dried CuCo precursor in air at 350 ℃ for 3h, wherein the heating rate is 3 ℃/min;
2) preparation of aminated hollow spherical CuCo2O4Nano material
To realize hollow spherical CuCo2O4Amination of nanomaterial at 10 mL CuCo2O4To the solution (2 mg/mL) was added 2 mL aminopropyltriethoxysilane (3%) and stirred at 60 ℃ for 36 h. After centrifugal washing, CuCo covered with abundant amino groups is obtained2O4Nano material
(2) Preparation of gold nanoclusters
Methionine (4 mL of 0.1M) and sodium hydroxide (0.6 mL of 0.5M) were added to an aqueous solution of chloroauric acid (0.4 mL of 20 mg/mL); the pale yellow color of the mixture rapidly faded away to form the Au (III) -methionine complex; incubating the mixed solution at 37 ℃ for 10 h to obtain a light yellow solution; then adding sulfuric acid aqueous solution (0.5 mL, 1M) to precipitate AuNCs; after centrifugation, the gold nanoclusters are collected and washed three times with sulfuric acid solution (5 mL, 0.1M); dissolving the gold nanoclusters in 1.4% ammonia water solution, incubating at 70 ℃ to obtain AuNCs solution with high luminous intensity, and storing at 4 ℃ in the dark for later use;
(3) preparing AuNCs functionalized hollow spherical CuCo2O4
1.0 mg of aminated CuCo2O4Mixing with 4 mL of gold nanoclusters, adding glutaraldehyde solution, incubating for 8 hours at room temperature, centrifuging, dispersing into 2 mL of phosphate buffer solution with the pH of 7.4, adding 1 mL of procalcitonin detection antibody of 10 mu g/mL, mixing, and incubating for 12 hours at 4 ℃ to obtain AuNCs-CuCo2O4-Ab2And (c) a complex.
Example 5 preparation of gold nanocluster functionalized hollow spherical CuCo2O4
(1) Preparation of hollow spherical CuCo2O4Nano material
1) Preparation of hollow spherical CuCo2O4Nano material
Dissolving 8 mL of glycerol in 40 mL of isopropanol, and stirring to form a transparent colorless solution; adding 8 mmol of cobalt nitrate and 16 mmol of copper nitrate into the solution until a uniform pink solution is obtained; then the solution is injected into a high-pressure autoclave and reacts for 10 hours at 180 ℃; washing with ultrapure water and ethanol, and drying; to obtain CuCo2O4Calcining a dried CuCo precursor in air at 350 ℃ for 3h, wherein the heating rate is 3 ℃/min;
2) preparation of aminated hollow spherical CuCo2O4Nano material
To realize hollow spherical CuCo2O4Amination of nanomaterial at 10 mL CuCo2O42 mL aminopropyltriethoxysilane (3%) was added to the solution (2 mg/mL) and stirred at 60 ℃ for 36 h; after centrifugal washing, CuCo covered with abundant amino groups is obtained2O4A nanomaterial;
(2) preparation of gold nanoclusters
Methionine (4 mL of 0.1M) and sodium hydroxide (0.6 mL of 0.5M) were added to an aqueous solution of chloroauric acid (0.4 mL of 20 mg/mL); the pale yellow color of the mixture rapidly faded away to form the Au (III) -methionine complex; incubating the mixed solution at 37 ℃ for 10 h to obtain a light yellow solution; then adding sulfuric acid aqueous solution (0.5 mL, 1M) to precipitate AuNCs; after centrifugation, the gold nanoclusters are collected and washed three times with sulfuric acid solution (5 mL, 0.1M); dissolving the gold nanoclusters in 1.4% ammonia water solution, incubating at 70 ℃ to obtain AuNCs solution with high luminous intensity, and storing at 4 ℃ in the dark for later use;
(2) preparing AuNCs functionalized hollow spherical CuCo2O4
2.0 mg of aminated CuCo2O4Mixing with 5 mL of gold nanoclusters, adding glutaraldehyde solution, incubating for 8 hours at room temperature, centrifuging, dispersing into 2 mL of phosphate buffer solution with the pH of 7.4, adding 1 mL of procalcitonin detection antibody of 10 mu g/mL, mixing, and incubating for 12 hours at 4 ℃ to obtain AuNCs-CuCo2O4-Ab2And (c) a complex.
Example 6 preparation of gold nanocluster functionalized hollow spherical CuCo2O4
(1) Preparation of hollow spherical CuCo2O4Nano material
1) Preparation of hollow spherical CuCo2O4Nano material
Dissolving 8 mL of glycerol in 40 mL of isopropanol, and stirring to form a transparent colorless solution; adding 10 mmol of cobalt nitrate and 20 mmol of copper nitrate into the solution until a uniform pink solution is obtained; then the solution is injected into a high-pressure autoclave and reacts for 10 hours at 180 ℃; washing with ultrapure water and ethanol, and drying; to obtain CuCo2O4Calcining a dried CuCo precursor in air at 350 ℃ for 3h, wherein the heating rate is 3 ℃/min;
2) preparation of aminated hollow spherical CuCo2O4Nano material
To realize hollow spherical CuCo2O4Amination of nanomaterial at 10 mL CuCo2O4To the solution (2 mg/mL) was added 2 mL aminopropyltriethoxysilane (3%) and stirred at 60 ℃ for 36 h. After centrifugal washing, CuCo covered with abundant amino groups is obtained2O4Nano material
(2) Preparation of gold nanoclusters
Methionine (4 mL of 0.1M) and sodium hydroxide (0.6 mL of 0.5M) were added to an aqueous solution of chloroauric acid (0.4 mL of 20 mg/mL); the pale yellow color of the mixture rapidly faded away to form the Au (III) -methionine complex; incubating the mixed solution at 37 ℃ for 10 h to obtain a light yellow solution; then adding sulfuric acid aqueous solution (0.5 mL, 1M) to precipitate AuNCs; after centrifugation, the gold nanoclusters are collected and washed three times with sulfuric acid solution (5 mL, 0.1M); dissolving the gold nanoclusters in 1.4% ammonia water solution, incubating at 70 ℃ to obtain AuNCs solution with high luminous intensity, and storing at 4 ℃ in the dark for later use;
(3) preparing AuNCs functionalized hollow spherical CuCo2O4
3.0 mg of aminated CuCo2O4Mixing with 6 mL of gold nanoclusters, adding glutaraldehyde solution, incubating for 8 hours at room temperature, centrifuging, dispersing into 2 mL of phosphate buffer solution with the pH of 7.4, adding 1 mL of procalcitonin detection antibody of 10 mu g/mL, mixing, and incubating for 12 hours at 4 ℃ to obtain AuNCs-CuCo2O4-Ab2And (c) a complex.
Example 7 detection of Procalcitonin
(1) Connecting an Ag/AgCl electrode serving as a reference electrode, a platinum wire electrode serving as a counter electrode and the prepared electrochemical luminescence sensor serving as a working electrode in a cassette of a chemiluminescence detector, and connecting an electrochemical workstation with the chemiluminescence detector together;
(2) the parameters of the chemiluminescence detector are set, the high voltage of the photomultiplier is set to 600V, and the scanning speed is set to 0.1V/s;
(3) setting parameters of an electrochemical workstation, wherein the range of a cyclic voltammetry scanning potential is 0V-1.2V, and the scanning rate is set to be 0.1V/s;
(4) using 10 mL of 0.1mol/L phosphate buffer solution containing 0.1mol/L triethanolamine as a co-reactant, and detecting the intensity of an electrochemiluminescence signal generated by procalcitonin with different concentrations by an electrochemiluminescence method; the pH value of the phosphate buffer solution is 7.4, and the phosphate buffer solution is prepared by 0.1mol/L disodium hydrogen phosphate and 0.1mol/L potassium dihydrogen phosphate;
(5) and drawing a working curve according to the linear relation between the obtained electrochemical luminescence intensity value and the logarithm of the concentration of the procalcitonin antibody.
Example 8 detection of Procalcitonin
(1) Connecting an Ag/AgCl electrode serving as a reference electrode, a platinum wire electrode serving as a counter electrode and the prepared electrochemical luminescence sensor serving as a working electrode in a cassette of a chemiluminescence detector, and connecting an electrochemical workstation with the chemiluminescence detector together;
(2) the parameters of the chemiluminescence detector are set, the high voltage of the photomultiplier is set to 800V, and the scanning speed is set to 0.1V/s;
(3) setting parameters of an electrochemical workstation, wherein the range of a cyclic voltammetry scanning potential is 0V-1.2V, and the scanning rate is set to be 0.1V/s;
(4) using 10 mL of 0.1mol/L phosphate buffer solution containing 0.1mol/L triethanolamine as a co-reactant, and detecting the intensity of an electrochemiluminescence signal generated by procalcitonin with different concentrations by an electrochemiluminescence method; the pH value of the phosphate buffer solution is 7.4, and the phosphate buffer solution is prepared by 0.1mol/L disodium hydrogen phosphate and 0.1mol/L potassium dihydrogen phosphate;
(5) and drawing a working curve according to the linear relation between the obtained electrochemical luminescence intensity value and the logarithm of the concentration of the procalcitonin antibody. Example 9
The procalcitonin antigen solution is detected by applying the sensors constructed in the embodiments 1 and 2 according to the detection methods of the embodiments 7 and 8, and the linear detection range of the sensor is 10 fg/mL-50 ng/mL, and the detection limit is 3.4 fg/mL.

Claims (5)

1. A method for preparing an electrochemical luminescence sensor for detecting procalcitonin by using a copper-cobalt material,
the method is characterized in that the preparation of the electrochemical immunosensor comprises the following steps:
(1) polishing a glassy carbon electrode with the diameter of 4 mm to a mirror surface by using alumina powder with the diameter of 0.05 mu m, and then washing the polished glassy carbon electrode by using ultrapure water;
(2) carrying out electro-deposition on the treated electrode for 30 s at constant potential of-0.1 to-0.3V by using a constant potential deposition method, and storing at room temperature until the electrode is dried;
(3) continuously dripping 6 mu L of procalcitonin capture antibody standard solution with the concentration of 10 mu g/mL on the surface of the glassy carbon electrode, storing in a refrigerator at 4 ℃ until the solution is dried, and cleaning with ultrapure water;
(4) continuously dripping 3 mu L of bovine serum albumin solution with the mass fraction of 1% to seal the nonspecific active sites, storing in a refrigerator at 4 ℃ until the active sites are dried, and cleaning with ultrapure water;
(5) continuously dripping a series of procalcitonin antigen standard solutions with different concentrations, of which the concentration is 10 fg/mL to 50 ng/mL, on the surface of the electrode, storing the solution in a refrigerator of 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water;
(6) preparing 5-10 μ L of gold nanocluster (AuNCs) functionalized copper cobalt material (CuCo)2O4) Structure and procalcitonin detection antibody compound AuNCs-CuCo2O4-Ab2And (3) dripping the solution on the surface of an electrode, storing the solution in a refrigerator at 4 ℃ until the solution is dried, and cleaning the solution with ultrapure water to obtain the electrochemical luminescence immunosensor for detecting procalcitonin.
2. The method for preparing the electrochemiluminescence sensor for detecting procalcitonin by using the gold cluster modified copper-cobalt material as claimed in claim 1, wherein the hollow spherical CuCo is2O4The nano material is characterized by comprising the following preparation steps:
(1) preparation of hollow spherical CuCo2O4Nano material
Dissolving 8 mL of glycerol in 40 mL of isopropanol, and stirring to form a transparent colorless solution; adding 6-10 mmol of cobalt nitrate and 14-20 mmol of copper nitrate into the solution until a uniform pink solution is obtained; then the solution is injected into a high-pressure autoclave and reacts for 10 hours at 180 ℃; washing with ultrapure water and ethanol, and drying; to obtain CuCo2O4Calcining a dried CuCo precursor in air at 350 ℃ for 3h, wherein the heating rate is 3 ℃/min;
(2) preparation of aminated hollow spherical CuCo2O4Nano material
To realize hollow spherical CuCo2O4Amination of nanomaterial at 10 mL CuCo2O42 mL aminopropyltriethoxysilane (3%) was added to the solution (2 mg/mL) and stirred at 60 ℃ for 36 h; after centrifugal washing, CuCo covered with abundant amino groups is obtained2O4And (3) nano materials.
3. The method of claim 1, wherein the gold cluster modified copper cobalt material detection is performedPreparation method of procalcitonin electrochemiluminescence sensor, and hollow spherical CuCo2O4And gold nanoclusters, characterized in that the preparation steps are as follows:
(1) preparation of gold nanoclusters
Methionine (4 mL of 0.1M) and sodium hydroxide (0.6 mL of 0.5M) were added to an aqueous solution of chloroauric acid (0.4 mL of 20 mg/mL); the pale yellow color of the mixture rapidly faded away to form the Au (III) -methionine complex; incubating the mixed solution at 37 ℃ for 10 h to obtain a light yellow solution, and then adding a sulfuric acid aqueous solution (0.5 mL, 1M) to precipitate AuNCs; after centrifugation, the gold nanoclusters are collected and washed three times with sulfuric acid solution (5 mL, 0.1M); dissolving the gold nanoclusters in 1.4% ammonia water solution, incubating at 70 ℃ to obtain AuNCs solution with high luminous intensity, and storing at 4 ℃ in the dark for later use;
(2) preparing AuNCs functionalized hollow spherical CuCo2O4
1.0-3.0 mg of aminated CuCo2O4Mixing with 4-6 mL of gold nanoclusters, adding glutaraldehyde solution, incubating for 8 hours at room temperature, centrifuging, dispersing into 2 mL of phosphate buffer solution with the pH of 7.4, adding 1 mL of procalcitonin detection antibody with the concentration of 10 mu g/mL, mixing, and incubating for 12 hours at 4 ℃ to obtain AuNCs-CuCo2O4-Ab2And (c) a complex.
4. The series of 10 fg/mL-50 ng/mL procalcitonin standard solutions according to claim 1, which is obtained by diluting 1 mg/mL procalcitonin solution obtained from bioscience GmbH of King of Nanjing with phosphate buffered saline.
5. The assay of procalcitonin according to claim 1, characterized by the following steps:
(1) connecting an Ag/AgCl electrode serving as a reference electrode, a platinum wire electrode serving as a counter electrode and the prepared electrochemical luminescence sensor serving as a working electrode in a cassette of a chemiluminescence detector, and connecting an electrochemical workstation with the chemiluminescence detector together;
(2) the parameters of the chemiluminescence detector are set, the high voltage of the photomultiplier is set to be 600-800V, and the scanning speed is set to be 0.1V/s;
(3) setting parameters of an electrochemical workstation, wherein the range of a cyclic voltammetry scanning potential is 0V-1.2V, and the scanning rate is set to be 0.1V/s;
(4) using 10 mL of 0.1mol/L phosphate buffer solution containing 0.1mol/L triethanolamine as a co-reactant, and detecting the intensity of an electrochemiluminescence signal generated by procalcitonin with different concentrations by an electrochemiluminescence method; the pH value of the phosphate buffer solution is 7.4, and the phosphate buffer solution is prepared by 0.1mol/L disodium hydrogen phosphate and 0.1mol/L potassium dihydrogen phosphate;
(5) and drawing a working curve according to the linear relation between the obtained electrochemical luminescence intensity value and the logarithm of the concentration of the procalcitonin antibody.
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