CN111766290A - Preparation method and application of biosensor based on three-dimensional titanium carbide-molybdenum disulfide compound - Google Patents
Preparation method and application of biosensor based on three-dimensional titanium carbide-molybdenum disulfide compound Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 56
- 239000010936 titanium Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 12
- 108010036226 antigen CYFRA21.1 Proteins 0.000 claims abstract description 43
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 43
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 13
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- 239000008055 phosphate buffer solution Substances 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000003556 assay Methods 0.000 claims description 5
- 229940098773 bovine serum albumin Drugs 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 239000012086 standard solution Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 4
- 208000002154 non-small cell lung carcinoma Diseases 0.000 abstract description 4
- 208000029729 tumor suppressor gene on chromosome 11 Diseases 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000003550 marker Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- -1 superoxide anion free radical Chemical class 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000013399 early diagnosis Methods 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 4
- 201000010099 disease Diseases 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 208000020816 lung neoplasm Diseases 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 2
- 201000005202 lung cancer Diseases 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 102100033420 Keratin, type I cytoskeletal 19 Human genes 0.000 description 1
- 108010066302 Keratin-19 Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 208000009956 adenocarcinoma Diseases 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 208000003362 bronchogenic carcinoma Diseases 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000011984 electrochemiluminescence immunoassay Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 208000003849 large cell carcinoma Diseases 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010837 poor prognosis Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 208000000649 small cell carcinoma Diseases 0.000 description 1
- 206010041823 squamous cell carcinoma Diseases 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 239000000439 tumor marker Substances 0.000 description 1
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- G—PHYSICS
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- 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
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- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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- G01N27/28—Electrolytic cell components
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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Abstract
The invention relates to a preparation method and application of an immunosensor based on a three-dimensional titanium carbide-molybdenum disulfide compound, belonging to the field of novel nano materials and the technical field of biosensing; the invention prepares the three-dimensional porous titanium carbide-molybdenum disulfide (Ti) by a mixing-drying method for the first time3C2Tx/MoS2) Composite material and method for preparing platinum functionalized three-dimensional Ti by using luminol as reducing agent3C2Tx/MoS2(Lum@Pt/Ti3C2Tx‑MoS2) As a sensorThe substrate firstly provides a preparation method of an immunosensor for the high-sensitivity detection of a non-small cell lung cancer disease marker CYFRA21-1, and Ti3C2Tx/MoS2Has high conductivity, high electrochemical activity, large specific surface area and biocompatibility, and can efficiently catalyze the conversion of dissolved oxygen in water into superoxide anion free radical O2 •−Thereby enhancing luminol and O2 •−The electrochemiluminescence reaction between the two sensors realizes the high-efficiency and stable output of signals, the detection limit of the sensor is as low as 18 pg/mL, the linear range is 50 pg/mL-50 ng/mL, and the sensor has obvious potential application value in the early diagnosis of the non-small cell lung cancer.
Description
Technical Field
The invention belongs to the field of novel nano materials and the technical field of biosensing.
Background
CYFRA21-1 is a soluble fragment of cytokeratin 19, is considered to be a tumor marker mainly used for detecting lung cancer, and has important value particularly for diagnosing non-small cell lung cancer. If unclear annular shadows exist in the lung, the concentration of CYFRA21-1 in serum is higher than 30 ng/mL, the possibility of primary bronchogenic carcinoma is very high, the positive detection rate of various non-small cell lung cancers is 70% -85%, the serum concentration level of CYFRA21-1 is positively correlated with the clinical stage of tumors, the serum concentration level can also be used as an effective index for tracking early relapse after lung cancer surgery and radiotherapy and chemotherapy, the serum high concentration level of CYFRA21-1 indicates that the disease is in the progressive stage and poor prognosis, the marker of successful quality is that the serum concentration of CYFRA21-1 is rapidly reduced, otherwise, the disease is not completely cleared, and the sensitivity of CYFRA21-1 to diagnosis of various lung cancers is sequentially as follows: squamous carcinoma > adenocarcinoma > large cell carcinoma > small cell carcinoma. So far, only several analysis methods such as fluorescence, electrochemical analysis, and chromatography have been developed. Therefore, a simple, rapid and accurate determination method is developed, and the method has important significance for the instant detection of CYFRA 21-1.
As a research hotspot which is raised by the interdigitation of various subjects such as biology, chemistry, medicine, electronic technology and the like, the electrochemiluminescence immunoassay is the organic combination of the electrochemiluminescence technology and an immunoassay method, and the prepared immunosensor has the advantages of low cost, good selectivity, high sensitivity, high analysis speed, easiness in automation, miniaturization, integration and the like, and is widely applied to the fields of disease marker analysis, food safety analysis, environmental pollution analysis and the like.
In recent years, molybdenum disulfide (MoS)2) With metal titanium carbide (Ti)3C2TxMXene) nano material is widely concerned by virtue of excellent electrocatalytic activity and high conductivity, and is also applied to a luminol-hydrogen peroxide system. Compared with the biological toxicity of hydrogen peroxide, the dissolved oxygen which has no biological toxicity and is simple and easy to obtain becomes a new environment-friendly coreactant of luminol. In order to further improve the luminous efficiency of a luminol-dissolved oxygen system, the invention firstly prepares a three-dimensional porous nano composite material Ti by a mixing-drying method3C2Tx-MoS2It integrates MoS2With Ti3C2TxThe composite material has the performance advantages of higher conductivity and electrochemical activity, larger specific surface area and more excellent biocompatibility, and can efficiently catalyze the conversion of dissolved oxygen into superoxide anion free radical O2 •−Thereby greatly enhancing the electrochemiluminescence reaction of the luminol-dissolved oxygen system to realize the high-efficiency and stable output of signals.
Disclosure of Invention
One of the tasks of the invention is to provide a three-dimensional porous-based nano composite material Ti for widening the application of luminol-dissolved oxygen system in electrochemiluminescence sensing3C2Tx-MoS2The method for enhancing the electrochemiluminescence reaction between luminol and dissolved oxygen prepares the Lum @ Pt/Ti by an in-situ reduction method3C2Tx-MoS2Nanocomposite as a sensing substrate, Ti3C2Tx-MoS2Has excellent electric conductionThe luminous efficiency of a luminol-dissolved oxygen system can be obviously enhanced due to the sex and the electrocatalytic activity;
the second technical task of the invention is to make up the defects of the existing CYFRA21-1 detection technology and provide a three-dimensional porous Ti-based material3C2Tx-MoS2The electrochemiluminescence immunosensor can be used for rapidly detecting CYFRA21-1, has the advantages of high sensitivity, strong specificity and good reproducibility, and has the detection limit of 18 pg/mL and the linear range of 50 pg/mL-50 ng/mL.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. a preparation method and application of a biosensor based on a three-dimensional titanium carbide-molybdenum disulfide compound are characterized by comprising the following steps:
(1) polishing glassy carbon electrodes with the diameter of 4 mm by using alumina polishing powder with the diameter of 1.0 micron, 0.3 micron and 0.05 micron in sequence, and washing the polished glassy carbon electrodes with ultrapure water;
(2) 6 mu L of Lum @ Pt/Ti with the concentration of 2-4 mg/mL is dripped on the surface of the glassy carbon electrode3C2Tx-MoS2The solution is used as a sensing substrate and is placed at 37 ℃ for airing;
(3) dripping 6 mu L of CYFRA21-1 antibody solution with the concentration of 100 mu g/mL, washing the surface of the electrode by phosphate buffer solution PBS with the pH value of 7.4, and placing the electrode at 4 ℃ for airing;
(4) dropwise adding 3 mu L of bovine serum albumin solution with the mass fraction of 1-3% to seal non-specific active sites on the surface of the electrode, washing the surface of the electrode by phosphate buffer solution PBS with the pH of 7.4, and placing the electrode at 4 ℃ for airing;
(5) dripping 6 mu L of CYFRA21-1 standard solution with a certain concentration, incubating for 0.5-2 h at 37 ℃, washing the surface of the electrode by phosphate buffer solution PBS with pH 7.4, placing the electrode at 4 ℃, airing, and finishing the construction of the sensor.
2. The preparation method and application of the biosensor based on the three-dimensional titanium carbide-molybdenum disulfide compound as claimed in claim 1, wherein the Lum @ Pt/Ti3C2Tx-MoS2Solutions ofThe preparation method comprises the following steps:
firstly, Ti with the mass concentration of 1.5-3.5 mg/mL is prepared3C2TxA nanosheet solution prepared by mixing the nanosheet solution with 1.5-3.5 mg/mL of MoS2Mixing the two solutions, carrying out ultrasonic treatment for 0.5-2 h under the protection of argon to form a uniformly dispersed mixed solution, and freeze-drying the mixed solution for 12-36 h to obtain a final product Ti3C2Tx-MoS2A complex;
weighing 50-80 mg of Ti3C2Tx-MoS2Dissolving a nano material in 25-40 mL of ultrapure water, adding a chloroplatinic acid solution with the volume of 3-6 mL and the concentration of 10mmol/L for ultrasonic treatment for 5-20 min, then adding a luminol solution with the concentration of 5-10 mL and the concentration of 1mmol/L, oscillating for 0.5-2 h, carrying out aging treatment for 2-3 h, carrying out centrifugal separation on solids in the solution, and carrying out vacuum drying at 70-90 ℃ for 12 h to obtain Lum @ Pt/Ti3C2Tx-MoS2And (3) a solid.
3. The electrochemiluminescence sensor prepared by the preparation method of claim 1 is used for detecting the concentration of CYFRA 21-1.
4. The assay of CYFRA21-1 concentration according to claim 4, wherein the procedure is as follows:
(1) setting parameters: the high voltage of a photomultiplier of the ultra-weak electrochemiluminescence instrument is set to be 600V, the cyclic volt-ampere scanning potential range of the electrochemical workstation is set to be 0-0.6V, and the scanning rate is set to be 0.1V/s;
(2) and (3) testing: introducing high-purity oxygen for 0.5-2 h into the electrolyte to improve the concentration of dissolved oxygen, taking a silver/silver chloride electrode as a reference electrode and a platinum wire electrode as a counter electrode, taking the sensor prepared by the method as a working electrode, performing electrochemiluminescence test in 10 mL of phosphate buffer solution to obtain corresponding electrochemiluminescence signal intensity when incubating CYFRA21-1 with different concentrations, and drawing a working curve, wherein the detection limit is 20 pg/mL, and the linear range is 50 pg/mL-50 ng/mL;
(3) and testing a sensor for incubating the actual sample of the CYFRA21-1 with unknown concentration, bringing the test sample into a working curve according to the signal intensity, and calculating to obtain the concentration of the CYFRA21-1 in the reagent sample.
Advantageous results of the invention
(1) The invention firstly provides a Ti-based alloy3C2Tx-MoS2Method for promoting electrochemiluminescence performance of luminol-dissolved oxygen system, Ti3C2Tx-MoS2Has more excellent electrochemical activity and can efficiently catalyze the dissolved oxygen O in the electrolyte2Conversion to superoxide anion radical O2 •−Thereby greatly enhancing luminol and O2 •−The electrochemiluminescence reaction between the two is beneficial to further application and research of the luminol-dissolved oxygen system in the field of electrochemiluminescence;
(2) the invention is based on Ti3C2Tx-MoS2Promoting luminol-dissolved oxygen electrochemiluminescence principle and providing a precise and reliable immunosensing technology. The method solves the problems of complex operation, low sensitivity and poor reproducibility of the existing electrochemical detection technology, has the detection limit of 18 pg/mL and the linear range of 50 pg/mL-50 ng/mL when being applied to the sample detection of CYFRA21-1, and has the advantages of high response speed, high sensitivity, good reproducibility, simplicity in preparation, low cost and environmental friendliness.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
Embodiment 1. a preparation method and application based on three-dimensional titanium carbide-molybdenum disulfide compound biosensor, which is characterized by comprising the following steps:
1. a preparation method and application of a biosensor based on a three-dimensional titanium carbide-molybdenum disulfide compound are characterized by comprising the following steps:
(1) polishing glassy carbon electrodes with the diameter of 4 mm by using alumina polishing powder with the diameter of 1.0 micron, 0.3 micron and 0.05 micron in sequence, and washing the polished glassy carbon electrodes with ultrapure water;
(2) 6 mu L of Lum @ Pt/Ti with the concentration of 2 mg/mL is dripped on the surface of the glassy carbon electrode3C2Tx-MoS2The solution is used as a sensing substrate and is placed at 37 ℃ for airing;
(3) dripping 6 mu L of CYFRA21-1 antibody solution with the concentration of 100 mu g/mL, washing the surface of the electrode by phosphate buffer solution PBS with the pH value of 7.4, and placing the electrode at 4 ℃ for airing;
(4) dropwise adding 3 mu L of bovine serum albumin solution with the mass fraction of 1% to seal the nonspecific active sites on the surface of the electrode, washing the surface of the electrode with phosphate buffer solution PBS with the pH of 7.4, and placing the electrode at 4 ℃ for airing;
(5) dripping 6 mu L of CYFRA21-1 standard solution with a certain concentration, incubating for 0.5-2 h at 37 ℃, washing the surface of the electrode by phosphate buffer solution PBS with pH 7.4, placing the electrode at 4 ℃, airing, and finishing the construction of the sensor.
Embodiment 2. a preparation method and application based on three-dimensional titanium carbide-molybdenum disulfide compound biosensor, which is characterized by comprising the following steps:
(1) polishing glassy carbon electrodes with the diameter of 4 mm by using alumina polishing powder with the diameter of 1.0 micron, 0.3 micron and 0.05 micron in sequence, and washing the polished glassy carbon electrodes with ultrapure water;
(2) 6 mu L of Lum @ Pt/Ti with the concentration of 3 mg/mL is dripped on the surface of the glassy carbon electrode3C2Tx-MoS2The solution is used as a sensing substrate and is placed at 37 ℃ for airing;
(3) dripping 6 mu L of CYFRA21-1 antibody solution with the concentration of 100 mu g/mL, washing the surface of the electrode by phosphate buffer solution PBS with the pH value of 7.4, and placing the electrode at 4 ℃ for airing;
(4) dropwise adding 3 mu L of 2% bovine serum albumin solution to seal the nonspecific active sites on the surface of the electrode, washing the surface of the electrode with phosphate buffer solution PBS (pH 7.4), and airing at 4 ℃;
(5) dripping 6 mu L of CYFRA21-1 standard solution with a certain concentration, incubating for 0.5-2 h at 37 ℃, washing the surface of the electrode by phosphate buffer solution PBS with pH 7.4, placing the electrode at 4 ℃, airing, and finishing the construction of the sensor.
Embodiment 3. a preparation method and application based on three-dimensional titanium carbide-molybdenum disulfide compound biosensor, which is characterized by comprising the following steps:
(1) polishing glassy carbon electrodes with the diameter of 4 mm by using alumina polishing powder with the diameter of 1.0 micron, 0.3 micron and 0.05 micron in sequence, and washing the polished glassy carbon electrodes with ultrapure water;
(2) 6 mu L of Lum @ Pt/Ti with the concentration of 4 mg/mL is dripped on the surface of the glassy carbon electrode3C2Tx-MoS2The solution is used as a sensing substrate and is placed at 37 ℃ for airing;
(3) dripping 6 mu L of CYFRA21-1 antibody solution with the concentration of 100 mu g/mL, washing the surface of the electrode by phosphate buffer solution PBS with the pH value of 7.4, and placing the electrode at 4 ℃ for airing;
(4) dropwise adding 3 mu L of bovine serum albumin solution with the mass fraction of 3% to seal the nonspecific active sites on the surface of the electrode, washing the surface of the electrode with phosphate buffer solution PBS with the pH of 7.4, and placing the electrode at 4 ℃ for airing;
(5) dripping 6 mu L of CYFRA21-1 standard solution with a certain concentration, incubating for 0.5-2 h at 37 ℃, washing the surface of the electrode by phosphate buffer solution PBS with pH 7.4, placing the electrode at 4 ℃, airing, and finishing the construction of the sensor.
Example 4. the Lum @ Pt/Ti3C2Tx-MoS2The solution is prepared by the following steps:
first, Ti was prepared at a mass concentration of 1.5 mg/mL3C2TxNanosheet solution, mixing it with 1.5 mg/mL MoS2Mixing the two solutions, carrying out ultrasonic treatment for 0.5 h under the protection of argon gas to form a uniformly dispersed mixed solution, and freeze-drying the mixed solution for 12 h to obtain a final product Ti3C2Tx-MoS2A complex;
weighing 50 mg of Ti3C2Tx-MoS2Dissolving the nanometer material in 25 mL of ultrapure water, adding a chloroplatinic acid solution with the volume of 3 mL and the concentration of 10mmol/L for ultrasonic treatment for 5 min, and then adding 5 mL of the chloroplatinic acid solution with the concentration of 5 mLIs a 1mmol/L luminol solution, is vibrated for 0.5 h, is aged for 2 h, is subjected to centrifugal separation on solids in the solution, and is dried in vacuum at 70 ℃ for 12 h to obtain Lum @ Pt/Ti3C2Tx-MoS2And (3) a solid.
Example 5 the Lum @ Pt/Ti3C2Tx-MoS2The solution is prepared by the following steps:
first, Ti was prepared at a mass concentration of 3.5 mg/mL3C2TxNanosheet solution, mixing it with 3.5 mg/mL of MoS2Mixing the two solutions, carrying out ultrasonic treatment for 2 h under the protection of argon gas to form a uniformly dispersed mixed solution, and freeze-drying the mixed solution for 36 h to obtain a final product Ti3C2Tx-MoS2A complex;
weighing 80 mg of Ti3C2Tx-MoS2Dissolving the nano material in 40 mL of ultrapure water, adding a chloroplatinic acid solution with the volume of 6mL and the concentration of 10mmol/L for ultrasonic treatment for 20 min, then adding a luminol solution with the concentration of 1mmol/L of 10 mL, oscillating for 2 h, carrying out aging treatment for 3 h, carrying out centrifugal separation on solids in the solution, and carrying out vacuum drying at 90 ℃ for 12 h to obtain Lum @ Pt/Ti3C2Tx-MoS2And (3) a solid.
Example 6 the Lum @ Pt/Ti3C2Tx-MoS2The solution is prepared by the following steps:
first, Ti was prepared at a mass concentration of 2.5 mg/mL3C2TxNanosheet solution, mixing it with 2.5 mg/mL of MoS2Mixing the two solutions, carrying out ultrasonic treatment for 1.5 h under the protection of argon gas to form a uniformly dispersed mixed solution, and freeze-drying the mixed solution for 12-36 h to obtain a final product Ti3C2Tx-MoS2A complex;
60 mg of Ti was weighed3C2Tx-MoS2Dissolving the nanometer material in 30 mL of ultrapure water, adding a chloroplatinic acid solution with the volume of 5 mL and the concentration of 10mmol/L for ultrasonic treatment for 15 min, and then carrying out ultrasonic treatmentAdding 8 mL of luminol solution with the concentration of 1mmol/L, shaking for 1.4 h, aging for 2.5 h, centrifugally separating the solid in the solution, and drying in vacuum at 80 ℃ for 12 h to obtain Lum @ Pt/Ti3C2Tx-MoS2And (3) a solid.
Example 7. assay for CYFRA21-1 concentration, characterized by the following procedure:
(1) setting parameters: the high voltage of a photomultiplier of the ultra-weak electrochemiluminescence instrument is set to be 600V, the cyclic volt-ampere scanning potential range of the electrochemical workstation is set to be 0-0.6V, and the scanning rate is set to be 0.1V/s;
(2) and (3) testing: introducing high-purity oxygen for 0.5 h into the electrolyte to improve the concentration of dissolved oxygen, taking a silver/silver chloride electrode as a reference electrode and a platinum wire electrode as a counter electrode, taking the sensor prepared by the method as a working electrode, carrying out electrochemiluminescence test in 10 mL of phosphate buffer solution to obtain corresponding electrochemiluminescence signal intensity when incubating CYFRA21-1 with different concentrations, and drawing a working curve, wherein the detection limit is 20 pg/mL, and the linear range is 50 pg/mL-50 ng/mL;
(3) and testing a sensor for incubating the actual sample of the CYFRA21-1 with unknown concentration, bringing the test sample into a working curve according to the signal intensity, and calculating to obtain the concentration of the CYFRA21-1 in the reagent sample.
Example 8. assay for CYFRA21-1 concentration, characterized by the following steps:
(1) setting parameters: the high voltage of a photomultiplier of the ultra-weak electrochemiluminescence instrument is set to be 600V, the cyclic volt-ampere scanning potential range of the electrochemical workstation is set to be 0-0.6V, and the scanning rate is set to be 0.1V/s;
(2) and (3) testing: introducing high-purity oxygen for 1 h into the electrolyte to improve the concentration of dissolved oxygen, taking a silver/silver chloride electrode as a reference electrode and a platinum wire electrode as a counter electrode, taking the sensor prepared by the method as a working electrode, and carrying out electrochemiluminescence test in 10 mL of phosphate buffer solution to obtain corresponding electrochemiluminescence signal intensity when incubating CYFRA21-1 with different concentrations, and drawing a working curve, wherein the detection limit is 20 pg/mL, and the linear range is 50 pg/mL-50 ng/mL;
(3) and testing a sensor for incubating the actual sample of the CYFRA21-1 with unknown concentration, bringing the test sample into a working curve according to the signal intensity, and calculating to obtain the concentration of the CYFRA21-1 in the reagent sample.
Example 9. assay for CYFRA21-1 concentration, characterized by the following procedure:
(1) setting parameters: the high voltage of a photomultiplier of the ultra-weak electrochemiluminescence instrument is set to be 600V, the cyclic volt-ampere scanning potential range of the electrochemical workstation is set to be 0-0.6V, and the scanning rate is set to be 0.1V/s;
(2) and (3) testing: introducing high-purity oxygen for 2 hours into the electrolyte to improve the concentration of dissolved oxygen, taking a silver/silver chloride electrode as a reference electrode and a platinum wire electrode as a counter electrode, taking the sensor prepared by the method as a working electrode, and carrying out electrochemiluminescence test in 10 mL of phosphate buffer solution to obtain corresponding electrochemiluminescence signal intensity when incubating CYFRA21-1 with different concentrations, and drawing a working curve, wherein the detection limit is 20 pg/mL, and the linear range is 50 pg/mL-50 ng/mL;
(3) and testing a sensor for incubating the actual sample of the CYFRA21-1 with unknown concentration, bringing the test sample into a working curve according to the signal intensity, and calculating to obtain the concentration of the CYFRA21-1 in the reagent sample.
Claims (4)
1. A preparation method and application of a biosensor based on a three-dimensional titanium carbide-molybdenum disulfide compound are characterized by comprising the following steps:
(1) polishing glassy carbon electrodes with the diameter of 4 mm by using alumina polishing powder with the diameter of 1.0 micron, 0.3 micron and 0.05 micron in sequence, and washing the polished glassy carbon electrodes with ultrapure water;
(2) 6 mu L of Lum @ Pt/Ti with the concentration of 2-4 mg/mL is dripped on the surface of the glassy carbon electrode3C2Tx-MoS2The solution is used as a sensing substrate and is placed at 37 ℃ for airing;
(3) dripping 6 mu L of CYFRA21-1 antibody solution with the concentration of 100 mu g/mL, washing the surface of the electrode by phosphate buffer solution PBS with the pH value of 7.4, and placing the electrode at 4 ℃ for airing;
(4) dropwise adding 3 mu L of bovine serum albumin solution with the mass fraction of 1-3% to seal non-specific active sites on the surface of the electrode, washing the surface of the electrode by phosphate buffer solution PBS with the pH of 7.4, and placing the electrode at 4 ℃ for airing;
(5) dripping 6 mu L of CYFRA21-1 standard solution with a certain concentration, incubating for 0.5-2 h at 37 ℃, washing the surface of the electrode by phosphate buffer solution PBS with pH 7.4, placing the electrode at 4 ℃, airing, and finishing the construction of the sensor.
2. The preparation method and application of the biosensor based on the three-dimensional titanium carbide-molybdenum disulfide compound as claimed in claim 1, wherein the Lum @ Pt/Ti3C2Tx-MoS2The solution is prepared by the following steps:
firstly, Ti with the mass concentration of 1.5-3.5 mg/mL is prepared3C2TxA nanosheet solution prepared by mixing the nanosheet solution with 1.5-3.5 mg/mL of MoS2Mixing the two solutions, carrying out ultrasonic treatment for 0.5-2 h under the protection of argon to form a uniformly dispersed mixed solution, and freeze-drying the mixed solution for 12-36 h to obtain a final product Ti3C2Tx-MoS2A complex;
weighing 50-80 mg of Ti3C2Tx-MoS2Dissolving a nano material in 25-40 mL of ultrapure water, adding a chloroplatinic acid solution with the volume of 3-6 mL and the concentration of 10mmol/L for ultrasonic treatment for 5-20 min, then adding a luminol solution with the concentration of 5-10 mL and the concentration of 1mmol/L, oscillating for 0.5-2 h, carrying out aging treatment for 2-3 h, carrying out centrifugal separation on solids in the solution, and carrying out vacuum drying at 70-90 ℃ for 12 h to obtain Lum @ Pt/Ti3C2Tx-MoS2And (3) a solid.
3. The electrochemiluminescence sensor prepared by the preparation method of claim 1 is used for detecting the concentration of CYFRA 21-1.
4. The assay of CYFRA21-1 concentration according to claim 4, wherein the procedure is as follows:
(1) setting parameters: the high voltage of a photomultiplier of the ultra-weak electrochemiluminescence instrument is set to be 600V, the cyclic volt-ampere scanning potential range of the electrochemical workstation is set to be 0-0.6V, and the scanning rate is set to be 0.1V/s;
(2) and (3) testing: introducing high-purity oxygen for 0.5-2 h into the electrolyte to improve the concentration of dissolved oxygen, taking a silver/silver chloride electrode as a reference electrode and a platinum wire electrode as a counter electrode, taking the sensor prepared by the method as a working electrode, performing electrochemiluminescence test in 10 mL of phosphate buffer solution to obtain corresponding electrochemiluminescence signal intensity when incubating CYFRA21-1 with different concentrations, and drawing a working curve, wherein the detection limit is 20 pg/mL, and the linear range is 50 pg/mL-50 ng/mL;
(3) and testing a sensor for incubating the actual sample of the CYFRA21-1 with unknown concentration, bringing the test sample into a working curve according to the signal intensity, and calculating to obtain the concentration of the CYFRA21-1 in the reagent sample.
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