CN104880456B - A kind of based on GO/MWCNTs-COOH/Au@CeO2the preparation method and application of the electrochemiluminescence immunosensor built - Google Patents
A kind of based on GO/MWCNTs-COOH/Au@CeO2the preparation method and application of the electrochemiluminescence immunosensor built Download PDFInfo
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Abstract
The invention belongs to nano-functional material, immunoassay and biosensor technique field, it is provided that the preparation method and applications of the electrochemiluminescence immunosensor of the structure of a kind of graphene oxide/carboxylic carbon nano-tube gold-supported doping cerium dioxide nanoparticle.Using graphene oxide/carboxylic carbon nano-tube gold-supported as base material, ceria is as the electrochemiluminescence immunosensor of luminescent material.Early diagnosis and clinical practice aspect to tumor have important practicality.
Description
Technical field
The present invention relates to a kind of based on GO/MWCNTs-COOH/Au@CeO2The preparation method and application of the electrochemiluminescence immunosensor built.Specifically use GO/MWCNTs-COOH/Au as base material and CeO2As luminescent material, prepare a kind of unmarked type electrochemiluminescence immunosensor detecting tumor markers, belong to new function material and bio-sensing detection technique field.
Background technology
Cancer is the general designation of a big class malignant tumor.The sickness rate of tumor is high, and growth and transfer velocity are fast, and the health of the mankind is had harm greatly.Tumor marker be tumor cell produce and release with the metabolite of the forms such as antigen, enzyme, hormone, and can be used for diagnosis and the auxiliary diagnosis of some tumor clinical.Therefore, in clinical research, develop a kind of quick, easy, sensitive detection tumor markers method and cause the extensive concern of people.
The clinical testing procedure of current existing tumor markers is a lot, such as radioimmunoassay, RIA, enzyme immunoassay, chemiluminescence immune assay, Timed resolved fluoroimmunoassay etc..Immunosensor is a kind of biosensor combined with analytical chemistry method by immunological method, is combined by the characteristic between antigen with antibody so that it is has high sensitivity, high selectivity, analyze the advantages such as quick and easy and simple to handle.
Electrochemiluminescence immunosensor have highly sensitive, selectivity good, easy and simple to handle, be prone to miniaturization, can the advantage such as detection analysis continuous, rapid automatized, therefore the present invention is prepared for a kind of based on GO/MWCNTs-COOH/Au@CeO2Electrochemiluminescence immunosensor, it is achieved that the detection to tumor markers.
Graphene oxide and carboxylic carbon nano-tube have the advantages such as specific surface area is big, electric conductivity is excellent, and the water solublity of carboxylic carbon nano-tube is preferable, and it can improve the stability of this electrochemiluminescence immunosensor.Au NPs can improve the electric conductivity of composite, thus improves electron transport ability.Therefore golden nanometer particle is modified by the present invention graphene oxide and carboxylic carbon nano-tube are incorporated in the preparation of immunosensor, utilize its specific surface area big, the features such as electron transmission ability is excellent, thus play the effect strengthening electrochemical luminescence signals.CeO2There is low toxicity, good biocompatibility, the features such as chemical stability is good.Therefore, the present invention utilizes the preferable biocompatibility of Au atom, it is achieved that antibody fixing at electrode surface；By composite GO/MWCNTs-COOH/Au@CeO2Introduce in the preparation of sensor, construct a kind of overdelicate unmarked type electrochemiluminescence immunosensor.CeO2Apply in immunosensor for the first time as electrochemiluminescence material.Composite GO/MWCNTs-COOH/Au@CeO2Good electrochemical luminescence signals can be produced during detection, significantly reduce the detection limit of sensor, can be used for the analysis of Diagnostic Value of Several Serum Tumor Markers.The method has the advantages such as low cost, highly sensitive, specificity good, detection is quick, and preparation process is relatively simple, effectively overcomes the deficiency of current tumor-marker object detecting method.
Summary of the invention
(1) based on composite GO/MWCNTs-COOH/Au@CeO2, construct a kind of without enzyme, quick and sensitive unmarked type electrochemiluminescence immunosensor.
(2) this unmarked type electrochemiluminescence immunosensor is applied to the detection of Diagnostic Value of Several Serum Tumor Markers.
Technical scheme is as follows:
1. a kind of based on GO/MWCNTs-COOH/Au CeO2The preparation method of the electrochemiluminescence immunosensor built
(1) by the glass-carbon electrode Al of a diameter of 4 mm2O3Polishing powder is polished, and ultra-pure water cleans up；
(2) the GO/MWCNTs-COOH/Au@CeO of 6 L, 2.0 ~ 14.0 mg/mL is taken2Chitosan solution is added drop-wise under electrode surface, room temperature dry；
(3) drip the tumor markers antibody of 6 L, 6 ~ 12 g/mL, ultrapure water electrode surface, 4 DEG C of refrigerators are dried；
(4) drip 3 L, mass fraction be the BSA solution of 1 ~ 2% in order to nonspecific activity site on enclosed-electrode surface, ultrapure water electrode surface, 4 DEG C of refrigerators dry；
(5) drip the tumor markers antigenic solution of a series of variable concentrations of 6 L, 0.05 ~ 100 ng/mL, 4 DEG C of refrigerators are dried, prepare a kind of based on GO/MWCNTs-COOH/Au@CeO2The electrochemiluminescence immunosensor built.
2. the preparation of graphene oxide
By 36 mL, the sulphuric acid of 98% and 4 mL, the phosphoric acid of 85% adds in the there-necked flask of 500 mL, uniform by magnetic stirrer, adds 300 mg graphite powders, stirring；It is slowly added to the potassium permanganate powder of 1.8 g；Under 50 C oil baths, magnetic agitation 12 h, it is cooled to room temperature；Under agitation, pour in 40 mL ice；Add 300 μ L, mass fraction is the hydrogenperoxide steam generator of 30%, and continuously stirred 1 h；With rotating speed 9000 r/min, centrifugation 10 min, remove supernatant；Washing precipitation twice with the hydrochloric acid solution of 0.2 mol/L, absolute ethanol washing precipitates twice, finally precipitates one time with absolute ether washing；12 h it are vacuum dried under 35 C；Because of the splash stronger, easy of the volatility of ether, to be placed in big centrifuge tube when vacuum drying, wrap with filter paper, with antispray；Finally give yellow solid powder, ground with agate mortar, weigh, prepare graphene oxide.
3. GO/MWCNTs-COOH/Au@CeO2Preparation
100 mg graphene oxide powder are dissolved in 100 mL ultra-pure waters, ultrasonic 2 h；Add 100 mg carboxylic carbon nano-tubes, ultrasonic 1 h；Add the Ce (NO of 2.17 g3)3·6H2O, continuously stirred 30 min；Adding the NaOH of 10 mg, making pH value of solution is 10, adds NH in the case of being stirred continuously3·H2O, making pH value of solution is 11；Adding 5mL, mass fraction is the HAuCl of 1%4·4H2O solution, gained suspension is heated to 80 ° of C and maintains 6 h, and the precipitate ultra-pure water obtained and washes of absolute alcohol are washed 3 times by centrifugal treating, and product is dried 12 h in 40 ° of C vacuum drying ovens, calcines 1 h in 300 C tube furnaces.
4.The detection method of Diagnostic Value of Several Serum Tumor Markers
(1) use electrochemical workstation with three-electrode system, saturated Ag/AgCl electrode is reference electrode, platinum electrode is auxiliary electrode, and prepared sensor is working electrode, includes 0.1 mol/L KCl and 20 ~ 140 mmol/L K at the pH 7.5 ~ 8.5 of 10 mL, 50 mmol/L2S2O8PBS buffer solution in test；
(2) with MPI-F Flow Injection Analysis/Chemiluminescence instrument, analyte is detected, is 10 mL at end liquid, pH 8.0 containing 0.1 mol/L KCl and 120 mmol/L K2S2O8PBS buffer solution in be scanned, scanning voltage scope is-2 ~ 0 V, and photomultiplier tube high pressure is 750 V, and sweep speed is 0.1 V s-1；
(3) after peak value tends towards stability, electrochemiluminescence spectrum is recorded.
5.Above-mentioned tumor markers is selected from one of following: CEA, AFP, parathyroid hormone PTH squamous cell related antigen SCCA, people nuclear matrix protein NMP-22, prostate specific antigen PSA, human chorionic gonadotropin HCG, acid phosphatase ACP, human placental lactogen HPL, ovarian cancer CA125, breast cancer susceptibility gene CAl5-3, glycoprotein antigen CA50, CA19-9, CA549, CA72-4, cytokeratin, phosphatization Proteins p53, alkaline phosphatase, NSE NSE, thyroliberin ACTH, growth hormone GH.
The useful achievement of the present invention
(1) GO/MWCNTs-COOH has bigger surface area can increase the Au NPs load capacity on its surface, and then the load capacity of increase antibody, additionally, its electronic conduction ability is excellent, it is incorporated in electrochemiluminescence immunosensor, makes sensor achieve the Sensitive Detection to tumor markers.
(2) CeO2One step reverts on base material GO/MWCNTs-COOH, composite GO/MWCNTs-COOH/Au@CeO2Prepare relatively simple.CeO2There is strong and stable electrochemical luminescence signals, applied as electrochemiluminescence material for the first time in immunosensor.
(3) use of MWCNTs-COOH, had both utilized its large specific surface area and good electronic conduction ability, can increase again the water solublity of base material so that it is has more stable electrochemical luminescence signals, thus preferably improves the stability of sensor.
(4) chitosan is applied in the middle of the preparation of electrochemical immunosensor, utilizes the filming performance of its excellence, it is therefore prevented that composite GO/MWCNTs-COOH/Au@CeO2Come off from electrode surface, utilize chitosan to have good biocompatibility and hypotoxicity, beneficially antibody fixing at electrode surface simultaneously.
(5) present invention utilizes the immunoreation of antigen, antibody, improves the specificity of detection method.
(6) the electrochemiluminescence immunosensor that prepared by the present invention is for the detection of Diagnostic Value of Several Serum Tumor Markers, response time is short, and detection limit is low, range of linearity width, simple, quick, highly sensitive and specific detection can be realized, to common tumor markers detection limit up to 0.02 ng/mL.
Detailed description of the invention
Embodiment 1 A kind of based on GO/MWCNTs-COOH/Au@CeO2The preparation of electrochemiluminescence immunosensor
(1) by the glass-carbon electrode Al of a diameter of 4 mm2O3Polishing powder is polished, and ultra-pure water cleans up；
(2) the GO/MWCNTs-COOH/Au@CeO of 6 L, 2.0 mg/mL is taken2Chitosan solution is added drop-wise under electrode surface, room temperature dry；
(3) drip the tumor markers antibody of 6 L, 6 g/mL, ultrapure water electrode surface, 4 DEG C of refrigerators are dried；
(4) drip 3 L, mass fraction be the BSA solution of 1 % in order to nonspecific activity site on enclosed-electrode surface, ultrapure water electrode surface, 4 DEG C of refrigerators dry；
(5) drip the tumor markers antigenic solution of a series of variable concentrations of 6 L, 0.05 ~ 100 ng/mL, 4 DEG C of refrigerators are dried, prepare a kind of based on GO/MWCNTs-COOH/Au@CeO2The electrochemiluminescence immunosensor built.
Embodiment 2 A kind of based on GO/MWCNTs-COOH/Au@CeO2The preparation of electrochemiluminescence immunosensor
(1) by the glass-carbon electrode Al of a diameter of 4 mm2O3Polishing powder is polished, and ultra-pure water cleans up；
(2) the GO/MWCNTs-COOH/Au@CeO of 6 L, 8.0 mg/mL is taken2Chitosan solution is added drop-wise under electrode surface, room temperature dry；
(3) drip the tumor markers antibody of 6 L, 10 g/mL, ultrapure water electrode surface, 4 DEG C of refrigerators are dried；
(4) drip 3 L, mass fraction be the BSA solution of 1.5% in order to nonspecific activity site on enclosed-electrode surface, ultrapure water electrode surface, 4 DEG C of refrigerators dry；
(5) drip the tumor markers antigenic solution of a series of variable concentrations of 6 L, 0.05 ~ 100 ng/mL, 4 DEG C of refrigerators are dried, prepare a kind of based on GO/MWCNTs-COOH/Au@CeO2The electrochemiluminescence immunosensor built.
Embodiment 3 A kind of based on GO/MWCNTs-COOH/Au@CeO2The preparation of electrochemiluminescence immunosensor
(1) by the glass-carbon electrode Al of a diameter of 4 mm2O3Polishing powder is polished, and ultra-pure water cleans up；
(2) the GO/MWCNTs-COOH/Au@CeO of 6 L, 14.0 mg/mL is taken2Chitosan solution is added drop-wise under electrode surface, room temperature dry；
(3) drip the tumor markers antibody of 6 L, 12 g/mL, ultrapure water electrode surface, 4 DEG C of refrigerators are dried；
(4) drip 3 L, mass fraction be the BSA solution of 2% in order to nonspecific activity site on enclosed-electrode surface, ultrapure water electrode surface, 4 DEG C of refrigerators dry；
(5) drip the tumor markers antigenic solution of a series of variable concentrations of 6 L, 0.05 ~ 100 ng/mL, 4 DEG C of refrigerators are dried, prepare a kind of based on GO/MWCNTs-COOH/Au@CeO2The electrochemiluminescence immunosensor built.
Embodiment 4 Electrochemiluminescence immunosensor is for the detection of CEA
(1) use electrochemical workstation with three-electrode system, saturated Ag/AgCl electrode is reference electrode, and platinum electrode is auxiliary electrode, and prepared sensor is working electrode, at 10 mL, pH 7.5 ~ 8.5 containing 0.1 mol/L KCl and 20 ~ 140 mmol/L K2S2O8PBS buffer solution in test；
(2) with MPI-F Flow Injection Analysis/Chemiluminescence instrument, analyte is detected, is 10 mL at end liquid, pH 8.0 containing 0.1 mol/L KCl and 120 mmol/L K2S2O8PBS buffer solution in be scanned, scanning voltage scope is-2 ~ 0 V, and photomultiplier tube high pressure is 750 V, and sweep speed is 0.1 V s-1；
(3) after peak value tends towards stability, electrochemiluminescence spectrum is recorded.
(4) according to the linear relationship between gained electrochemiluminescence intensity and CEA concentration, drawing curve, recording the range of linearity is 0.05 ~ 100 ng/mL, and detection is limited to 0.02 ng/mL.
Embodiment 5 Electrochemiluminescence immunosensor is for the detection of AFP
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and AFP concentration, drawing curve, recording the range of linearity is 0.04 ~ 110 ng/mL, and detection is limited to 0.02 ng/mL.
Embodiment 6 Electrochemiluminescence immunosensor is for the detection of ovarian cancer CA125
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and ovarian cancer CA125 concentration, drawing curve, recording the range of linearity is 0.04 ~ 100 ng/mL, and detection is limited to 0.02 ng/mL.
Embodiment 7 Electrochemiluminescence immunosensor is for the detection of squamous cell related antigen SCCA
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and squamous cell related antigen SCCA concentration, drawing curve, recording the range of linearity is 0.06 ~ 100 ng/mL, and detection is limited to 0.03 ng/mL.
Embodiment 8 Electrochemiluminescence immunosensor is for the detection of prostate specific antigen PSA
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and prostate specific antigen PSA concentration, drawing curve, recording the range of linearity is 0.05 ~ 110 ng/mL, and detection is limited to 0.02 ng/mL.
Embodiment 9 Electrochemiluminescence immunosensor is for the detection of people nuclear matrix protein NMP-22
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and people's nuclear matrix protein NMP-22 concentration, drawing curve, recording the range of linearity is 0.04 ~ 120 ng/mL, and detection is limited to 0.02 ng/mL.
Embodiment 10 Electrochemiluminescence immunosensor is for the detection of breast cancer susceptibility gene CAl5-3
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and breast cancer susceptibility gene CAl5-3 concentration, drawing curve, recording the range of linearity is 0.03 ~ 100 ng/mL, and detection is limited to 0.01 ng/mL.
Embodiment 11 Electrochemiluminescence immunosensor is for the detection of glycoprotein antigen CA50
Operating according to embodiment 4, according to the linear relationship between gained electrochemiluminescence intensity and glycoprotein antigen CA50 concentration, drawing curve, recording the range of linearity is 0.05 ~ 100 ng/mL, and detection is limited to 0.02 ng/mL.
Claims (3)
1. one kind based on GO/MWCNTs-COOH/Au CeO2The preparation method of electrochemiluminescence immunosensor built, it is characterised in that include following step:
(1) preparation of graphene oxide
By 36 mL, the sulphuric acid of 98% and 4 mL, the phosphoric acid of 85% adds in the there-necked flask of 500 mL, uniform by magnetic stirrer, adds 300 mg graphite powders, stirring；It is slowly added to the potassium permanganate powder of 1.8 g；Under 50 C oil baths, magnetic agitation 12 h, it is cooled to room temperature；Under agitation, pour in 40 mL ice；Add 300 μ L, mass fraction is the hydrogenperoxide steam generator of 30%, and continuously stirred 1 h；With rotating speed 9000 r/min, centrifugation 10 min, remove supernatant；Washing precipitation twice with the hydrochloric acid solution of 0.2 mol/L, absolute ethanol washing precipitates twice, finally precipitates one time with absolute ether washing；12 h it are vacuum dried under 35 C；Because of the splash stronger, easy of the volatility of ether, to be placed in big centrifuge tube when vacuum drying, wrap with filter paper, with antispray；Finally give yellow solid powder, ground with agate mortar, weigh, prepare graphene oxide；
(2) GO/MWCNTs-COOH/Au@CeO2Preparation
100 mg graphene oxide powder are dissolved in 100 mL ultra-pure waters, ultrasonic 2 h；Add 100 mg carboxylic carbon nano-tubes, ultrasonic 1 h；Add the Ce (NO of 2.17 g3)3·6H2O, continuously stirred 30 min；Adding the NaOH of 10 mg, making pH value of solution is 10, adds NH in the case of being stirred continuously3·H2O, making pH value of solution is 11；Adding 5mL, mass fraction is the HAuCl of 1%4·4H2O solution, gained suspension is heated to 80 ° of C and maintains 6 h, and the precipitate ultra-pure water obtained and washes of absolute alcohol are washed 3 times by centrifugal treating, and product is dried 12 h in 40 ° of C vacuum drying ovens, calcines 1 h in 300 C tube furnaces；
(3) preparation method of electrochemiluminescence immunosensor
1) by the glass-carbon electrode Al of a diameter of 4 mm2O3Polishing powder is polished, and ultra-pure water cleans up；
2) the GO/MWCNTs-COOH/Au@CeO of 6 L, 2.0 ~ 14.0 mg/mL is taken2Chitosan solution is added drop-wise under electrode surface, room temperature dry；
3) drip the tumor markers antibody of 6 L, 6 ~ 12 g/mL, ultrapure water electrode surface, 4 DEG C of refrigerators are dried；
4) drip 3 L, mass fraction be the BSA solution of 1 ~ 2% in order to nonspecific activity site on enclosed-electrode surface, ultrapure water electrode surface, 4 DEG C of refrigerators dry；
5) drip the tumor markers antigenic solution of a series of variable concentrations of 6 L, 0.05 ~ 100 ng/mL, 4 DEG C of refrigerators are dried, prepare a kind of based on GO/MWCNTs-COOH/Au@CeO2The electrochemiluminescence immunosensor built.
One the most according to claim 1 is based on GO/MWCNTs-COOH/Au@CeO2The preparation method of the electrochemiluminescence immunosensor built, described tumor markers is selected from one of following: CEA, AFP, parathyroid hormone PTH squamous cell related antigen SCCA, people nuclear matrix protein NMP-22, prostate specific antigen PSA, human chorionic gonadotropin HCG, acid phosphatase ACP, human placental lactogen HPL, ovarian cancer CA125, breast cancer susceptibility gene CAl5-3, glycoprotein antigen CA50, CA19-9, CA549, CA72-4, cytokeratin, phosphatization Proteins p53, alkaline phosphatase, NSE NSE, thyroliberin ACTH, growth hormone GH.
3. the sensor that prepared by preparation method as claimed in claim 1 is for the detection method of Diagnostic Value of Several Serum Tumor Markers, it is characterised in that step is as follows:
(1) using electrochemical workstation to test with three-electrode system, saturated Ag/AgCl electrode is reference electrode, and platinum electrode is auxiliary electrode, and prepared sensor is working electrode；0.1 mol/L KCl and 20 ~ 140 mmol/L K is included at the pH 7.5 ~ 8.5 of 10 mL, 50 mmol/L2S2O8PBS buffer solution in test；
(2) with MPI-F Flow Injection Analysis/Chemiluminescence instrument, analyte is detected, is 10 mL at end liquid, pH 8.0 containing 0.1 mol/L KCl and 120 mmol/L K2S2O8PBS buffer solution in be scanned, scanning voltage scope is-2 ~ 0 V, and photomultiplier tube high pressure is 750 V, and sweep speed is 0.1 V s-1；
(3) after peak value tends towards stability, electrochemiluminescence spectrum is recorded.
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Inventor after: Wei Qin Inventor after: Wu Dan Inventor after: Yan Tao Inventor after: Li Yueyun Inventor after: Li Jianxiu Inventor after: Ma Hongmin Inventor after: Pang Xuehui Inventor after: Wang Xiaodong Inventor after: Du Bin Inventor after: Fan Dawei Inventor after: Cao Wei Inventor after: Hu Lihua Inventor before: Li Jianxiu Inventor before: Wu Dan Inventor before: Yan Tao Inventor before: Li Yueyun Inventor before: Wei Qin Inventor before: Ma Hongmin Inventor before: Pang Xuehui Inventor before: Wang Xiaodong Inventor before: Du Bin Inventor before: Fan Dawei Inventor before: Cao Wei Inventor before: Hu Lihua |
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