CN109738641A - A kind of preparation method and application without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide - Google Patents
A kind of preparation method and application without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide Download PDFInfo
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- CN109738641A CN109738641A CN201910057354.2A CN201910057354A CN109738641A CN 109738641 A CN109738641 A CN 109738641A CN 201910057354 A CN201910057354 A CN 201910057354A CN 109738641 A CN109738641 A CN 109738641A
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Abstract
The invention belongs to novel nanocomposite materials, immunoassay and biosensor technique fields for abstract of description, the present invention relates to a kind of preparation method and applications without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide, based on Supported Pt Nanoparticles palladium nano cubic molybdenum disulfide composite material building without enzyme electrochemical immunosensor, for quantitative detection breast cancer tumour marker content, with high specificity, high sensitivity, detection limits low advantage, has important scientific meaning and application value to the early diagnosis of breast cancer.
Description
Technical field
The invention belongs to novel nanocomposite materials, immunoassay and biosensor technique fields, provide one kind and are based on
The preparation method of the unmarked type electrochemical immunosensor of platinum palladium functionalization molybdenum disulfide is applied to breast cancer tumour marker
Detection.
Background technique
Breast cancer has become first of female malignant morbidity, and the death rate occupies women the 5th.Carcinomebryonic antigen
(CEA), carbohydrate antigen 125 (CA-125) all can serve as the cancer markers of breast cancer, for breast cancer in medical diagnosis
It is of great significance.
Biological enzyme specificity is good, but saves difficult, easy inactivation, therefore the advantage without enzyme electrochemical immunosensor
It highlights, and is widely used in the detection of virus marker object or tumor markers.Unmarked type electrochemistry immuno-sensing
Device have many advantages, such as specificity it is good, easy to operate, easily prepared, medicine context of detection have important value.
MoS2Nanometer sheet has big specific surface area, can be with payload PtPd nano cubic；PtPd nano cubic has very
Good catalytic performance and electric conductivity, can be easily in conjunction with antibody；Platinum palladium functionalization molybdenum disulfide detects antibody marker energy
It is enough further to realize to measurement signal amplification, improve the sensitivity of breast cancer tumour marker detection.
Summary of the invention
The present invention provides a kind of systems without enzyme electrochemical immunosensor of unmarked type platinum palladium functionalization molybdenum disulfide
Preparation Method and application realize the super sensitivity detection to breast cancer tumour marker antigen.
An object of the present invention be to provide it is a kind of based on platinum palladium functionalization molybdenum disulfide without enzyme electrochemistry immuno-sensing
The preparation method of device.
The second object of the present invention is to by a kind of prepared unmarked type platinum palladium functionalization molybdenum disulfide without enzyme electrification
Learn the detection that immunosensor is used for breast cancer tumour marker antigen.
Technical solution of the present invention, comprising the following steps:
1. a kind of preparation method without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide, steps are as follows:
(1) the glass-carbon electrode Al for being 3.0 ~ 5.0 mm by diameter2O3Polishing powder is polished to mirror surface, ultrasonic in dehydrated alcohol
It cleans up；
(2) the platinum palladium functionalization molybdenum disulfide nano particle dispersion of 6.0 μ L, 0.5 ~ 2.0 mg/mL are added drop-wise to electrode table
Face, ultrapure water dry at room temperature；
(3) the breast cancer tumour marker antibody of 6.0 μ L, 5 ~ 15 μ g/mL are added drop-wise to electrode surface, the phosphate of pH=7.0
Buffer rinses electrode surface, drying in 4 DEG C of refrigerators；
(4) continue the bovine serum albumen solution of 3.0 μ L, 1 ~ 2 mg/mL being added drop-wise to electrode surface, to enclosed-electrode surface
Upper nonspecific activity site, the phosphate buffer of pH=7.0 rinse electrode surface, dry in 4 DEG C of refrigerators；
(5) continue a series of breast cancer tumour marker that various concentrations of 6.0 μ L, the ng/mL of 10 fg/mL ~ 200 are added dropwise
Antigenic solution is rinsed with the phosphate buffer of pH=7.0, dry in 4 DEG C of refrigerators, is made a kind of and is based on the functionalization curing of platinum palladium
Molybdenum without enzyme electrochemical immunosensor.
2. a kind of preparation method without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide, the phase
The preparation of material is closed, steps are as follows:
(1) preparation of PtPd nano cubic
At room temperature, by 20 mmol/L chlorine platinum of the 20 mmol/L chlorine palladium acid solutions of 0.5 ~ 1.5 mL and 0.5 ~ 1.5 mL
Acid solution is added in 20 ~ 60 mL ethylene glycol containing polyvinylpyrrolidone (160 ~ 480 mg), is added into mixture
Mixture, is heated to 150 DEG C in oil bath, is vigorously stirred next time by the 5 mol/L potassium iodide aqueous solutions for entering 110 ~ 330 μ L
60 min are flowed, cooled to room temperature is collected by centrifugation to obtain the moisture of PtPd nano cubic nanoparticle in 5000 rpm of revolving speed
Dissipate system；
(2) MoS2The preparation of nanometer sheet
By the Na of 0.25 ~ 0.75 g2MoO4·2H2O is dissolved in 25 ~ 75 mL water, is ultrasonically treated 10 min, when mixture becomes
It is clear bright, the L-cysteine and 50 ~ 150 mL water of 0.5 ~ 1.5 g are added into solution, obtained precursor solution is turned
Move on in 100 ~ 300 mL stainless steel autoclaves, seal and in 200 DEG C of 36 h of holding, be cooled to room temperature, in revolving speed 10000
It is centrifuged 15 min under rpm and collects MoS2Nanometer sheet dispersion liquid；
(3) preparation of platinum palladium functionalization molybdenum disulfide nano particle
The MoS prepared to 20.0 mg2The PtPd nano cubic dispersion liquid of the mL of 5.0 mL ~ 15.0 preparation is added in nanometer sheet
(1.0 mg/mL), then by mixture 1 h of ultrasound, after centrifugation, black precipitate is dried at room temperature for, then, by 20.0 mg
Black powder is redispersed in 5.0 mL buffer solutions (pH=7.4).
3. a kind of preparation without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide is used for breast cancer
The detection of tumor markers antigen, steps are as follows:
(1) electrochemical workstation is used, is tested under three-electrode system, using saturated calomel electrode as reference electrode, with platinum
Silk electrode is to electrode, includes that 5.0 mmol/L hydrogen peroxide are molten in 10 mL using prepared immunosensor as working electrode
It is tested in 5.18 ~ 8.25 phosphate buffer solution of pH of liquid；
(2) used time m- current method detects analyte, and input voltage is -0.4 V, 0.1 s of sampling interval, runing time
400 s, every 50 s to 10 mL, 50 mmol/L the phosphate buffer solution of pH=7.0 in inject the mistake of 10 μ L, 5 mol/L
Hydrogen peroxide solution, record current variation；
(3) working curve method is utilized, the concentration of breast cancer tumour marker antigen in sample to be tested is obtained.
Beneficial achievement of the invention
(1) present invention is prepared for PtPd nano cubic, and with monometallic catalytic phase ratio, two-metal alloy nanoparticle, which has, is preferably urged
Change ability, can effectively increase electron transmission efficiency, improve sensitivity, while PtPd has good biocompatibility, can be with
Effectively combined with antibody.MoS2Nanometer sheet has biggish specific surface area and excellent catalytic performance.With horseradish mistake
The PtPd nano cubic and MoS of peroxidase activity2After nanometer sheet combines, the electric conductivity of material is effectively enhanced, by this
Synergistic effect and multiple amplification reduce the detection limit of sensor；
(2) it is a kind of based on platinum palladium functionalization molybdenum disulfide without enzyme electrochemical immunosensor to breast cancer tumour marker antigen
Detection, be the ng/mL of 10 fg/mL ~ 200 to breast cancer tumour marker antigen detection range, lowest detection lower limit is
3.3 fg/mL show that a kind of prepared unmarked type platinum palladium functionalization molybdenum disulfide can be with without enzyme electrochemical immunosensor
Accurate quantification detects breast cancer tumour marker antigen.
Specific embodiment
Now the present invention is further illustrated by specific embodiment, but not limited to this.
A kind of preparation method without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide of embodiment 1
(1) the glass-carbon electrode Al for being 3.0 mm by diameter2O3Polishing powder is polished to mirror surface, is cleaned by ultrasonic in dehydrated alcohol dry
Only；
(2) the platinum palladium functionalization molybdenum disulfide dispersant liquid drop of 6.0 μ L, 0.5 mg/mL are added to electrode surface, ultrapure water,
It dries at room temperature；
(3) the breast cancer tumour marker antibody of 6.0 μ L, 5.0 μ g/mL are added drop-wise to electrode surface, the phosphate of pH=7.0 is slow
Fliud flushing rinses electrode surface, drying in 4 DEG C of refrigerators；
(4) continue the bovine serum albumen solution of 3.0 μ L, 1.0 mg/mL being added drop-wise to electrode surface, to enclosed-electrode surface
Upper nonspecific activity site, the phosphate buffer of pH=7.0 rinse electrode surface, dry in 4 DEG C of refrigerators；
(5) continue a series of breast cancer tumour marker that various concentrations of 6.0 μ L, the ng/mL of 10 fg/mL ~ 200 are added dropwise
Antigenic solution is rinsed with the phosphate buffer of pH=7.0, dry in 4 DEG C of refrigerators, is made a kind of and is based on the functionalization curing of platinum palladium
Molybdenum without enzyme electrochemical immunosensor.
A kind of preparation method without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide of embodiment 2
(1) the glass-carbon electrode Al for being 4.0 mm by diameter2O3Polishing powder is polished to mirror surface, is cleaned by ultrasonic in dehydrated alcohol dry
Only；
(2) the platinum palladium functionalization molybdenum disulfide nano particle dispersion of 6.0 μ L, 1.0 mg/mL are added drop-wise to electrode surface, surpassed
Pure water rinsing is dried at room temperature；
(3) the breast cancer tumour marker antibody of 6.0 μ L, 10.0 μ g/mL are added drop-wise to electrode surface, the phosphate of pH=7.0 is slow
Fliud flushing rinses electrode surface, drying in 4 DEG C of refrigerators；
(4) continue the bovine serum albumen solution of 3.0 μ L, 1.5 mg/mL being added drop-wise to electrode surface, to enclosed-electrode surface
Upper nonspecific activity site, the phosphate buffer of pH=7.0 rinse electrode surface, dry in 4 DEG C of refrigerators；
(5) continue a series of breast cancer tumour marker that various concentrations of 6.0 μ L, the ng/mL of 10 fg/mL ~ 200 are added dropwise
Antigenic solution is rinsed with the phosphate buffer of pH=7.0, dry in 4 DEG C of refrigerators, is made a kind of and is based on the functionalization curing of platinum palladium
Molybdenum without enzyme electrochemical immunosensor.
A kind of preparation method without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide of embodiment 3
(1) the glass-carbon electrode Al for being 5.0 mm by diameter2O3Polishing powder is polished to mirror surface, is cleaned by ultrasonic in dehydrated alcohol dry
Only；
(2) the platinum palladium functionalization molybdenum disulfide nano particle dispersion of 6.0 μ L, 2.0 mg/mL are added drop-wise to electrode surface, surpassed
Pure water rinsing is dried at room temperature；
(3) the breast cancer tumour marker antibody of 6.0 μ L, 15.0 μ g/mL are added drop-wise to electrode surface, the phosphate of pH=7.0 is slow
Fliud flushing rinses electrode surface, drying in 4 DEG C of refrigerators；
(4) continue the bovine serum albumen solution of 3.0 μ L, 2.0 mg/mL being added drop-wise to electrode surface, to enclosed-electrode surface
Upper nonspecific activity site, the phosphate buffer of pH=7.0 rinse electrode surface, dry in 4 DEG C of refrigerators；
(5) continue a series of breast cancer tumour marker that various concentrations of 6.0 μ L, the ng/mL of 10 fg/mL ~ 200 are added dropwise
Antigenic solution is rinsed with the phosphate buffer of pH=7.0, dry in 4 DEG C of refrigerators, is made a kind of and is based on the functionalization curing of platinum palladium
Molybdenum without enzyme electrochemical immunosensor.
The preparation of PtPd nano cubic described in embodiment 4
At room temperature, 20 mmol/L platinum acid chloride solutions of the 20 mmol/L chlorine palladium acid solutions of 0.5 mL and 0.5 mL are added to
In the 20 mL ethylene glycol containing polyvinylpyrrolidone (160 mg), the 5 mol/L potassium iodide of 110 μ L are added into mixture
Mixture is heated to 150 DEG C by aqueous solution in oil bath, is vigorously stirred 60 min of lower reflux, and cooled to room temperature is turning
5000 rpm of speed are collected by centrifugation to obtain the aqueous dispersion of PtPd nano cubic nanoparticle.
The preparation of PtPd nano cubic described in embodiment 5
At room temperature, 20 mmol/L platinum acid chloride solutions of the 20 mmol/L chlorine palladium acid solutions of 1.0 mL and 1.0 mL are added to
In the 40 mL ethylene glycol containing polyvinylpyrrolidone (320 mg), the 5 mol/L potassium iodide of 220 μ L are added into mixture
Mixture is heated to 150 DEG C by aqueous solution in oil bath, is vigorously stirred 60 min of lower reflux, and cooled to room temperature is turning
5000 rpm of speed are collected by centrifugation to obtain the aqueous dispersion of PtPd nano cubic nanoparticle.
The preparation of PtPd nano cubic described in embodiment 6
At room temperature, 20 mmol/L platinum acid chloride solutions of the 20 mmol/L chlorine palladium acid solutions of 1.5 mL and 1.5 mL are added to
In the 60 mL ethylene glycol containing polyvinylpyrrolidone (480 mg), the 5 mol/L potassium iodide of 330 μ L are added into mixture
Mixture is heated to 150 DEG C by aqueous solution in oil bath, is vigorously stirred 60 min of lower reflux, and cooled to room temperature is turning
5000 rpm of speed are collected by centrifugation to obtain the aqueous dispersion of PtPd nano cubic nanoparticle.
The preparation of platinum palladium functionalization molybdenum disulfide nano dispersion liquid described in embodiment 7
① MoS2The preparation of nanometer sheet
By the Na of 0.25 g2MoO4·2H2O is dissolved in 25 mL water, is ultrasonically treated 10 min, when mixture becomes clear bright, Xiang Rong
The L-cysteine and 50 mL water of 0.5 g are added in liquid, obtained precursor solution is transferred to 100 mL stainless steel autoclaves
In, seal and in 200 DEG C of 36 h of holdings, be cooled to room temperature, be centrifuged at 10000 rpm of revolving speed 15 min collection MoS2Nanometer
Piece dispersion liquid；
2. the preparation of platinum palladium functionalization molybdenum disulfide nano particle
The MoS prepared to 20.0 mg2The PtPd nano cubic dispersion liquid (1.0 mg/mL) of 5.0 mL preparation is added in nanometer sheet, so
Afterwards by mixture 1 h of ultrasound, after centrifugation, black precipitate is dried at room temperature for, then, by 20.0 mg black powder redisperses
In 5.0 mL buffer solutions (pH=7.4).
The preparation of platinum palladium functionalization molybdenum disulfide nano dispersion liquid described in embodiment 8
① MoS2The preparation of nanometer sheet
By the Na of 0.50 g2MoO4·2H2O is dissolved in 50 mL water, is ultrasonically treated 10 min, when mixture becomes clear bright, Xiang Rong
The L-cysteine and 100 mL water of 1.0 g are added in liquid, obtained precursor solution is transferred to 200 mL stainless steel autoclaves
In, seal and in 200 DEG C of 36 h of holdings, be cooled to room temperature, be centrifuged at 10000 rpm of revolving speed 15 min collection MoS2Nanometer
Piece dispersion liquid；
2. the preparation of platinum palladium functionalization molybdenum disulfide nano particle
The MoS prepared to 20.0 mg2The PtPd nano cubic dispersion liquid (1.0 mg/mL) of 10.0 mL preparation is added in nanometer sheet,
Then by mixture 1 h of ultrasound, after centrifugation, black precipitate is dried at room temperature for, and then, 20.0 mg black powders are divided again
It is dispersed in 5.0 mL buffer solutions (pH=7.4).
The preparation of platinum palladium functionalization molybdenum disulfide nano dispersion liquid described in embodiment 9
① MoS2The preparation of nanometer sheet
By the Na of 0.75 g2MoO4·2H2O is dissolved in 75 mL water, is ultrasonically treated 10 min, when mixture becomes clear bright, Xiang Rong
The L-cysteine and 150 mL water of 1.5 g are added in liquid, obtained precursor solution is transferred to 300 mL stainless steel autoclaves
In, it by sealing and in 200 DEG C of 36 h of holding, is cooled to room temperature, 15 min is centrifuged at 10000 rpm of revolving speed and collect MoS2It receives
Rice piece dispersion liquid；
2. the preparation of platinum palladium functionalization molybdenum disulfide nano particle
The MoS prepared to 20.0 mg2The PtPd nano cubic dispersion liquid (1.0 mg/mL) of 15.0 mL preparation is added in nanometer sheet,
Then by mixture 1 h of ultrasound, after centrifugation, black precipitate is dried at room temperature for, and then, 20.0 mg black powders are divided again
It is dispersed in 5.0 mL buffer solutions (pH=7.4).
Described in embodiment 10 based on platinum palladium functionalization molybdenum disulfide without enzyme electrochemical immunosensor to mammary gland cancerous swelling
The detection of tumor markers
(1) it is tested using electrochemical workstation with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is
Auxiliary electrode, prepared sensor is working electrode, in 5.18 ~ 8.25 phosphate-buffered of pH of 10 mL, 50 mmol/L
It is tested in solution；
(2) used time m- current method detects analyte, and input voltage is -0.4 V, 0.1 s of sampling interval, runing time
400 s, every 50 s to 10 mL, 50 mmol/L the phosphate buffer solution of pH=7.0 in inject the mistake of 10 μ L, 5 mol/L
Hydrogen peroxide solution, record current variation；
(3) utilize working curve method, obtain the immunosensor to the linear detection range of carcinomebryonic antigen be 10 fg/mL ~
200 ng/mL, detection are limited to 3.3 fg/mL.
The detection of carbohydrate antigen 125 (CA-125):
Drawing curve step carries out sample point to carbohydrate antigen 125 with embodiment 10, according to the method for drawing working curve
Analysis, measuring its range of linearity is the ng/mL of 0.45 pg/mL ~ 100, and detection is limited to 0.15 pg/mL.
Claims (5)
1. a kind of preparation method and application without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide
A kind of preparation method without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide, which is characterized in that packet
Include following steps:
(1) preparation of platinum palladium functionalization molybdenum disulfide nano particle: the PtPd nano cubic and MoS that will be prepared separately2Nanometer sheet knot
It closes；
(2) construct unmarked type platinum palladium functionalization molybdenum disulfide without enzyme electrochemical immunosensor, measure breast cancer tumour mark
Will object content draws working curve.
2. it is according to claim 1 it is a kind of detection breast cancer tumour marker without enzyme electrochemical immunosensor and its system
Preparation Method, it is characterised in that: preparing for platinum palladium functionalization molybdenum disulfide nano particle described in step (1) is specific as follows:
1. the preparation of PtPd nano cubic
At room temperature, by 20 mmol/L chlorine platinum of the 20 mmol/L chlorine palladium acid solutions of 0.5 ~ 1.5 mL and 0.5 ~ 1.5 mL
Acid solution is added in 20 ~ 60 mL ethylene glycol containing polyvinylpyrrolidone (160 ~ 480 mg), is added into mixture
Mixture, is heated to 150 DEG C in oil bath, is vigorously stirred next time by the 5 mol/L potassium iodide aqueous solutions for entering 110 ~ 330 μ L
60 min are flowed, cooled to room temperature is collected by centrifugation to obtain the moisture of PtPd nano cubic nanoparticle in 5000 rpm of revolving speed
Dissipate system；
② MoS2The preparation of nanometer sheet
By the Na of 0.25 ~ 0.75 g2MoO4·2H2O is dissolved in 25 ~ 75 mL water, is ultrasonically treated 10 min, when mixture becomes
It is clear bright, the L-cysteine and 50 ~ 150 mL water of 0.5 ~ 1.5 g are added into solution, obtained precursor solution is turned
It moves on in 100 ~ 300 mL stainless steel autoclaves, by sealing and in 200 DEG C of 36 h of holding, is cooled to room temperature, in revolving speed
It is centrifuged 15 min under 10000 rpm and collects MoS2Nanometer sheet dispersion liquid；
3. the preparation of platinum palladium functionalization molybdenum disulfide nano particle
The MoS prepared to 20.0 mg2The PtPd nano cubic dispersion liquid (1.0 of the mL of 5.0 mL ~ 15.0 preparation is added in nanometer sheet
Mg/mL), then by mixture 1 h of ultrasound, after centrifugation, black precipitate is dried at room temperature for, then, by 20.0 mg black powder
End is redispersed in 5.0 mL buffer solutions (pH=7.4).
3. it is according to claim 1 it is a kind of detection breast cancer tumour marker without enzyme electrochemical immunosensor and its system
Preparation Method, it is characterised in that: building described in step (2) is specific as follows without enzyme electrochemical immunosensor:
(1) the glass-carbon electrode Al for being 3.0 ~ 5.0 mm by diameter2O3Polishing powder is polished to mirror surface, ultrasonic in dehydrated alcohol
It cleans up；
(2) the platinum palladium functionalization molybdenum disulfide nano particle dispersion of 6.0 μ L, 0.5 ~ 2.0 mg/mL are added drop-wise to electrode table
Face, ultrapure water dry at room temperature；
(3) the breast cancer tumour marker antibody of 6.0 μ L, 5 ~ 15 μ g/mL are added drop-wise to electrode surface, the phosphate of pH=7.0
Buffer rinses electrode surface, drying in 4.0 DEG C of refrigerators；
(4) continue the bovine serum albumen solution of 3.0 μ L, 1 ~ 2 mg/mL being added drop-wise to electrode surface, to enclosed-electrode surface
Upper nonspecific activity site, the phosphate buffer of pH=7.0 rinse electrode surface, dry in 4.0 DEG C of refrigerators；
(5) continue a series of breast cancer tumour marker that various concentrations of 6.0 μ L, the ng/mL of 0.1 pg/mL ~ 200 are added dropwise
Antigenic solution is rinsed with the phosphate buffer of pH=7.0, dry in 4.0 DEG C of refrigerators, and a kind of unmarked type electrification of no enzyme is made
Learn immunosensor.
4. it is according to claim 1 it is a kind of detection breast cancer tumour marker without enzyme electrochemical immunosensor and its system
Preparation Method, it is characterised in that: measurement breast cancer tumour marker antigen described in step (2) draws working curve, specifically such as
Under:
1. preparing the breast cancer tumour mark of various concentration using the phosphate buffer solution of the pH=7.0 of 10 mL, 50 mmol/L
The breast cancer tumour marker antigenic solution of 6 μ L various concentrations is distinguished drop coating to electrode surface, reaction by will object antigenic solution
0.5 ~ 2 h is connected in electrochemical workstation after drying, electrode is dipped in the phosphate buffer solution of pH=7.0 respectively
The variation of its redox current is measured, after background current tends towards stability, every 50 s to pH=7.0 of 10 mL, 50 mmol/L
The hydrogenperoxide steam generator of 10 μ L, 5 mol/L, record current variation are injected in phosphate buffer solution；
2. it is in a linear relationship according to gained current differential and breast cancer tumour marker antigen concentration, draw working curve；
3. utilizing working curve method, the concentration of breast cancer tumour marker antigen in sample to be tested is obtained.
5. a kind of preparation without enzyme electrochemical immunosensor based on platinum palladium functionalization molybdenum disulfide as described in claim 1
The sensor of method preparation, the measurement for breast cancer tumour marker antigen, which is characterized in that the tumor markers are selected from
It is one of following: carcinomebryonic antigen (CEA), carbohydrate antigen 125 (CA-125).
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| CN113447547B (en) * | 2021-05-28 | 2022-11-11 | 天津大学 | Prostate cancer tumor marker detection method based on molybdenum disulfide/nano platinum-coated gold triangle/polydopamine |
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