CN103472121B - Sandwich type electrochemical immunosensor for simultaneously detecting markers of cervical cancer - Google Patents
Sandwich type electrochemical immunosensor for simultaneously detecting markers of cervical cancer Download PDFInfo
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Abstract
The invention relates to an electrochemical immunosensor, and in particular relates to a sandwich type electrochemical immunosensor which is constructed by taking Au-hybridized mesoporous carbon CMK-3(Au@CMK-3) and two electronic mediators, namely neutral red and thionine, as second antibody markers, a preparation method of the sandwich type electrochemical immunosensor, and application of the electrochemical immunosensor, which is prepared by the method, to simultaneous detection on markers of a cervical cancer. The electrochemical immunosensor can be used for simultaneously detecting two samples and overcoming the limitation of a single index, plays an important role in further improvement of the early confirming rate of the cervical cancer, and can be popularized to the field of simultaneous detection on tumor markers of other cancers.
Description
Technical field
The present invention relates to a kind of electrochemical immunosensor, more specifically, the present invention relates to a kind of mesoporous carbon CMK-3 (Au@CMK-3) based on Au hydridization and detect at the same time the application in cervical carcinoma mark with dimethyl diaminophenazine chloride and two kinds of electron mediators of thionine as sandwich type electrochemical immunosensor, its preparation method of two anti-labels structures and the electrochemical immunosensor of being prepared by the method respectively.
Background technology
Cervical carcinoma is common female reproductive system malignant tumour, although closely decades, cervical cancer pathogenesis rate obviously declined, annual China cervical carcinoma new cases still reach 13.15 ten thousand, account for 28.8% of world's cervical carcinoma new cases, and present younger trend.As early as possible, find that accurately precancerous lesions of uterine cervix or cervical carcinoma are to reduce the incidence of disease of cervical carcinoma and the key of mortality ratio.And the discovery of tumor markers and application become after diagnostic imaging and pathological diagnosis, one of method that current clinical detection tumour is conventional, and following up a case by regular visits to and result for the treatment of observation for tumour.Method of immunity based on specific recognition effect between Ag-Ab is a kind of important analytical technology that detects tumor markers.Wherein, immunosensor combines high-sensitive sensing technology and high special immune response, have advantages of that real-time output, sensitivity for analysis are high, high specificity, easy to use and cost is low, therefore, immunosensor is widely used in the detection of early diagnosis and tumor markers.
Not ideal enough in view of susceptibility and the specificity of existing tumor markers, in order to improve the clinical value of tumor markers, according to the characteristic of different tumours and unlike signal thing, choose reasonable multiple markers detects simultaneously and just seems very important.Because the analysis efficiency detecting for single tumor markers is not high, in order to shorten analysis time, reduce analytical procedure, improve analysis efficiency, reduce testing cost etc., people start to pay close attention to the research that realizes the high flux electrochemical immunosensor that multiple samples detect simultaneously.The tumor markers of cervical carcinoma has a lot, and wherein topmost two kinds is carcinomebryonic antigen (CEA) and squamous cell cancer associated antigen (SCCA).CEA and two kinds of tumor markerses of SCCA are detected to the limitation that can make up single index simultaneously, the early stage diagnosis rate of further raising cervical carcinoma is had great importance.
CN102980925A discloses a kind of based on dumbbell shape Pt-Fe
3o
4preparation method and the application of the sandwich type electrochemical immunosensor that nano particle builds as two anti-labels, this invention has only realized the detection of single tumor markers.The present invention utilizes the amino of rGO-TEPA and the reaction of the carboxyl generation acid amides of antibody self, rGO-TEPA is used for to fixing primary antibodie, Au@CMK-3 respectively from dimethyl diaminophenazine chloride, two kinds of different electron mediators of thionine as two anti-labels, prepared the sandwich type electrochemical immunosensor that simultaneously detects CEA and two kinds of tumor markerses of SCCA.Test result demonstration, sensitivity, selectivity and the stability of electrochemical immunosensor prepared by said method are high, and based on above-mentioned discovery, inventor has completed the present invention.
Summary of the invention
An object of the present invention is to provide a kind of sandwich type electrochemical immunosensor that simultaneously detects two kinds of marks of cervical carcinoma, described electrochemical immunosensor comprises: working electrode, contrast electrode and to electrode, the basal electrode of described working electrode is glass-carbon electrode, and primary antibodie, bovine serum albumin, Cervical Tumor mark antigen and Au@CMK-3 that rGO-TEPA hatching is modified on its surface successively resist with two of dimethyl diaminophenazine chloride, thionine hatching respectively.
A further object of the present invention is to provide a kind of preparation method who simultaneously detects two kinds of mark sandwich type electrochemical immunosensors of cervical carcinoma, and transducer sensitivity prepared by described method is high, favorable reproducibility, easy and simple to handle.
Two kinds of marks of described cervical carcinoma are CEA and SCCA.
In order to solve the problems of the technologies described above, the present invention realizes by following measures.
Sandwich type electrochemical immunosensor of the present invention comprises: working electrode, contrast electrode and to electrode, the basal electrode of described working electrode is glass-carbon electrode, and primary antibodie, bovine serum albumin, Cervical Tumor mark antigen and Au@CMK-3 that rGO-TEPA hatching is modified on its surface successively resist with two of dimethyl diaminophenazine chloride, thionine hatching respectively.Described working electrode and contrast electrode, electrode composition sandwich type electrochemical immunosensor is detected to two kinds of tumor markers antigens of cervical carcinoma.Described contrast electrode is saturated calomel electrode, is platinum electrode to electrode.
The preparation method of sandwich type electrochemical immunosensor of the present invention comprises the following steps:
Two anti-(Ab of a, preparation Au@CMK-3 and electron mediator hatching
2) solution;
B, prepare electrochemical immunosensor working electrode;
C, making electrochemical immunosensor working curve.
Wherein, two anti-(Ab of the preparation Au@CMK-3 of step a and electron mediator hatching
2) method of solution, specifically comprise the following steps:
1. Au@CMK-3's is synthetic: the 100 mL solution that contain 0.01g gold chloride are put into flask and are heated to boiling, more dropwise add 1% sodium citrate and keep this temperature 40 min, are cooled to room temperature.In this solution, add mesoporous carbon CMK-3 to stir 4h.Finally centrifugal 20 min under 9000 rotating speeds, centrifugal three times, vacuum drying makes Au@CMK-3;
2. two anti-(Ab of Au@CMK-3 and electron mediator hatching
2) preparation of solution: parallelly take the Au@CMK-3 that 1. two parts of above-mentioned steps are prepared, to add pH be that 7.4 PBS is ultrasonic it is dissolved after, add respectively anti-CEA, the EDC-NHS solution of anti-SCCA is hatched 12 h at 4 DEG C.Then, then correspondence adds 2 mg/mL neutral red solution respectively, 2 mg/mL thionine solution, and hatch 10 h at 4 DEG C, and finally centrifugal 20 min under 6000 rotating speeds, are again scattered in pH and are in 7.4 PBS and obtain two different anti-solution after washing;
3. two part of two anti-solution equal-volume 2. step being prepared is mixed to get two anti-mixed solutions of Au@CMK-3-anti-CEA-dimethyl diaminophenazine chloride and Au@CMK-3-anti-SCCA-thionine.
The method of preparing electrochemical immunosensor working electrode of step b, specifically comprises the following steps:
1. polishing is carried out in glass-carbon electrode surface and make its any surface finish;
2. EDC and NHS (50 mmol/L) join in the primary antibodie solution of 10 μ g/mL SCCA or 10 μ g/mL CEA, and then add respectively 2 mg amination Graphenes, and centrifugal after vibration 4 h, washing, be diluted to original scale with PBS, obtain corresponding rGO-TPEA-Ab
1solution, finally carries out two parts of solution the primary antibodie mixed solution that equal-volume is mixed to get and drips on electrode, and room temperature is dried;
3. the bovine serum albumin solution that is 1% at electrode face finish massfraction again (BSA) is to eliminate the non-specific avtive spot of electrode.Electrode is cleaned with the PBS that pH is 7.4, after drying, drip successively two kinds of tumor markers antigenic solutions of cervical carcinoma of variable concentrations, antigen and antibody are hatched to 30 min in room temperature, ensure that primary antibodie and antigen form half immune complex;
4. two anti-mixed solutions of the Au@CMK-3-anti-CEA-dimethyl diaminophenazine chloride preparing and Au@CMK-3-anti-SCCA-thionine are modified on electrode, dried 4 DEG C of preservations, obtain the working electrode of electrochemical immunosensor.
The making electrochemical immunosensor working curve of step c, step is as follows:
1. by contrast electrode-saturated calomel electrode, to the working electrode exact connect ion of electrode-platinum electrode and above-mentioned preparation on electrochemical workstation;
2. the PBS buffer solution of pH 7.4 (containing 0.1 mol/LKCl as supporting electrolyte), as end liquid, detects working electrode centering red (0.62V) and the response of thionine (0.17V) under different potentials of having modified by differential pulse voltammetry (DPV); According to the relation of the different electron mediator gained current-responsives different tumor markers antigen concentration of standard solution corresponding from it, drawing curve.
Useful achievement of the present invention:
(1) the present inventor is incorporated into rGO-TEPA in the middle of the preparation of electrochemical immunosensor of tumor markers, because rGO-TEPA has larger specific surface area and more amino, so can be by the immobilized more primary antibodie of acid amides effect, thereby sensitivity that has improved sensor.
(2) in preparation method of the present invention, Au@CMK-3 compound substance has the advantage of Au and meso-porous carbon material simultaneously, serve as a mark for immobilized a large amount of electron mediator two anti-, therefore further improved the sensitivity of sensor, thereby realized the high-sensitive amplification detection of the immune molecule of super low concentration.
(3) utilize electronic media body tag two anti-, there is different oxidation-reduction potential by different electron mediators, when can realizing two kinds of tumor markerses of cervical carcinoma, detect.
Electrochemical immunosensor of the present invention has shown good accuracy, stability, reappearance and high sensitivity, and immunoassay detects rapidly, convenient, can be used for clinical analysis.
Brief description of the drawings
Below in conjunction with brief description of the drawings and specific embodiment, the present invention is described in further detail.
Fig. 1 is the SEM photo of Au@CMK-3 of the present invention.
Fig. 2 is the working curve of immunosensor of the present invention to CEA (A) and SCCA (B) mensuration.
Embodiment
The CEA that the present invention uses, SCCA is all purchased from Shanghai Linc-Bio Science Co., Ltd., 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides (EDC), N-hydroxy-succinamide (NHS) is purchased from Shanghai brilliant pure reagent company limited, dimethyl diaminophenazine chloride, thionine is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, rGO-TPEA is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., sodium citrate is purchased from the Shanghai scientific and technological research institute that refines, bovine serum albumin(BSA) (96%-99%) is purchased from Sigma-Aldrich company, potassium dihydrogen phosphate, sodium hydrogen phosphate is all purchased from Tianjin Guang Cheng chemical reagent company limited, except glass-carbon electrode cleans with ultrapure water, what whole experimentation was used is all intermediate waters.
CHI760D electrochemical workstation is purchased from Shanghai Chen Hua Instrument Ltd..
embodiment 1 prepares sandwich type electrochemical immunosensor
(1) prepare two of Au@CMK-3 and electron mediator hatching and resist (Ab
2) solution
Au@CMK-3's is synthetic: the 100 mL solution that contain 0.01g gold chloride are put into flask and are heated to boiling, more dropwise add the sodium citrate of 10 mL 1% and keep this temperature 40 min, are cooled to room temperature.In this solution, add mesoporous carbon CMK-3 to stir 4h.Finally centrifugal 20 min under 9000 rotating speeds, centrifugal three times, vacuum drying makes Au@CMK-3; Fig. 1 is the SEM photo of Au@CMK-3, and as known in the figure, Au nano particle is dispersed in the surface of mesoporous carbon CMK-3;
Two anti-(Ab of Au@CMK-3 and electron mediator hatching
2) preparation of solution: parallelly take the Au@CMK-3 (4 mg) that 1. two parts of above-mentioned steps are prepared, to add pH be that 7.4 PBS is ultrasonic it is dissolved after, add respectively anti-CEA, the EDC-NHS solution of anti-SCCA is hatched 12 h at 4 DEG C.Then, then correspondence adds 2 mg/mL neutral red solution respectively, 2 mg/mL thionine solution, and hatch 10 h at 4 DEG C, and finally centrifugal 20 min under 6000 rotating speeds, are again scattered in pH and are in 7.4 PBS and obtain two different anti-solution after washing;
Above-mentioned two anti-solution equal-volumes are mixed to get to two anti-mixed solutions of Au@CMK-3-anti-CEA-dimethyl diaminophenazine chloride and Au@CMK-3-anti-SCCA-thionine.
(2) prepare electrochemical immunosensor working electrode
1. be the alundum (Al2O3) burnishing powder polishing of 1.0,0.3,0.05 μ m for the glass-carbon electrode of 4 mm by diameter, ethanol ultrasonic cleaning, rinse well with ultrapure water again, then electrode is placed in to 0.05 mol/L potassium ferricyanide solution, in-0.2 ~ 0.6 V scanning, make poor 110 mV that are less than of spike potential, with ultrapure water cleaning electrode surface, dry up;
2. EDC and NHS (50 mmol/L) join in the primary antibodie solution of 10 μ g/mL SCCA or 10 μ g/mL CEA, and then add respectively 2 mg amination Graphenes, and centrifugal after vibration 4 h, washing, be diluted to original scale with PBS, obtain corresponding rGO-TPEA-Ab
1solution, finally carries out two parts of solution primary antibodie mixed solution that equal-volume is mixed to get and gets 6 μ L and drip on electrode, and room temperature is dried;
3. the bovine serum albumin solution (BSA) that is 1% at electrode face finish 6 μ L massfractions is again to eliminate the non-specific avtive spot of electrode.The PBS solution that is 7.4 with pH cleans electrode, after drying, drip successively the SCCA antigenic solution of 6 μ L variable concentrations and the CEA antigenic solution of 6 μ L variable concentrations, antigen and antibody are hatched to 30 min in room temperature, ensure that primary antibodie and antigen form half immune complex;
4. two anti-mixed solutions of 6 μ L Au@CMK-3-anti-CEA-dimethyl diaminophenazine chlorides and Au@CMK-3-anti-SCCA-thionine are modified on electrode, dried 4 DEG C of preservations, obtain the working electrode of electrochemical immunosensor.
(3) make electrochemical immunosensor working curve
Open electrochemical workstation, by contrast electrode-saturated calomel electrode, to the working electrode exact connect ion of electrode-platinum electrode and above-mentioned preparation on electrochemical workstation;
The PBS buffer solution of 10 mL pH 7.4 as end liquid, detects working electrode centering red (0.62V) and the response of thionine (0.17V) under different potentials of having modified at (containing 0.1 mol/LKCl as supporting electrolyte) by differential pulse voltammetry (DPV); According to the relation of the different electron mediator gained current-responsives different tumor markers antigen concentration of standard solution corresponding from it, drawing curve.
when embodiment 2 Cervical Tumor mark, detect: SCCA and CEA
Prepare electrochemical immunosensor according to the step described in embodiment 1, adopt this electrochemical immunosensor Cervical Tumor mark shown in detection table 1 simultaneously, its detection technique index is in table 1.
The detection technique index of table 1 Cervical Tumor mark
From table 1 detection technique index result, electrochemical immunosensor prepared by the present invention detects for Cervical Tumor mark time, and its range of linearity is wide, and detectability is low, and method is highly sensitive.
in embodiment 3 human serums, detect when Cervical Tumor mark
The concentration of preparation CEA antigen is followed successively by 0.05,1.0,5.0, the concentration of 10,15,20 ng/mL and SCCA antigen is followed successively by 0.03,1.0,5.0,10,15,20 ng/mL, draw and obtain relevant work curve according to embodiment 1, respectively as shown in Figure 2 A and 2 B, for human serum CEA and SCCA time, detect.Get fresh serum sample, after centrifuging, get supernatant, with the content that determines CEA and SCCA in human serum after PBS buffer solution dilution.Then in human serum, add certain density CEA and SCCA standard solution, carry out recovery testu, the alluvial obtaining by mensuration and the radiometer of addition calculate the average recovery rate of CEA and SCCA in sample, and testing result is in table 2.
The testing result of Cervical Tumor mark in table 2 human serum
In upper table
nfor the number of times of replicate determination.
From table 2 testing result, the relative standard deviation of result (RSD) is less than 5.0%, and average recovery rate is 96.0 ~ 104%, when showing the present invention for human serum Cervical Tumor mark, detects, and the precision of method is high, and result accurately and reliably.
Claims (3)
1. a sandwich type electrochemical immunosensor, described electrochemical immunosensor comprises: working electrode, contrast electrode and to electrode, the basal electrode of described working electrode is glass-carbon electrode, primary antibodie, bovine serum albumin, Cervical Tumor mark antigen and Au@CMK-3 that rGO-TEPA hatching is modified on its surface successively resist with two of dimethyl diaminophenazine chloride, thionine hatching respectively, described contrast electrode is saturated calomel electrode, and described is platinum electrode to electrode;
It is characterized in that, described preparation method comprises the following steps:
Two anti-(Ab of a, preparation Au@CMK-3 and electron mediator hatching
2) solution;
B, prepare electrochemical immunosensor working electrode;
C, making electrochemical immunosensor working curve;
Wherein, step a prepares two anti-(Ab of Au@CMK-3 and electron mediator hatching
2) concrete steps of solution are as follows:
1. Au@CMK-3's is synthetic: the 100 mL solution that contain 0.01g gold chloride are put into flask and are heated to boiling, dropwise add again 1% sodium citrate and keep this temperature 40 min, be cooled to room temperature, in this solution, add mesoporous carbon CMK-3 to stir 4h, finally centrifugal 20 min under 9000 rotating speeds, centrifugal three times, vacuum drying makes Au@CMK-3;
2. two anti-(Ab of Au@CMK-3 and electron mediator hatching
2) preparation of solution: parallelly take the Au@CMK-3 that 1. two parts of above-mentioned steps are prepared, to add pH be that 7.4 PBS is ultrasonic it is dissolved after, add respectively anti-CEA, the EDC-NHS solution of anti-SCCA, at 4 DEG C, hatch 12 h, and then correspondence adds 2 mg/mL neutral red solution, 2 mg/mL thionine solution respectively, and at 4 DEG C, hatch 10 h, finally centrifugal 20 min under 6000 rotating speeds, are again scattered in pH and are in 7.4 PBS and obtain two different anti-solution after washing;
3. two part of two anti-solution equal-volume 2. step being prepared is mixed to get two anti-mixed solutions of Au@CMK-3-anti-CEA-dimethyl diaminophenazine chloride and Au@CMK-3-anti-SCCA-thionine;
The concrete steps that step b prepares electrochemical immunosensor working electrode are as follows:
1. polishing is carried out in glass-carbon electrode surface and make its any surface finish;
2. EDC and NHS, its concentration is 50 mmol/L, joins in the primary antibodie solution of 10 μ g/mL SCCA or 10 μ g/mL CEA, and then add respectively 2 mg amination Graphenes, and centrifugal after vibration 4 h, washing, be diluted to original scale with PBS, obtain corresponding rGO-TPEA-Ab
1solution, finally carries out two parts of solution the primary antibodie mixed solution that equal-volume is mixed to get and drips on electrode, and room temperature is dried;
3. the bovine serum albumin solution that is 1% at electrode face finish massfraction again (BSA) is to eliminate the non-specific avtive spot of electrode, electrode is cleaned with the PBS that pH is 7.4, after drying, drip successively two kinds of tumor markers antigenic solutions of cervical carcinoma of variable concentrations, antigen and antibody are hatched to 30 min in room temperature, ensure that primary antibodie and antigen form half immune complex;
4. two anti-mixed solutions of the Au@CMK-3-anti-CEA-dimethyl diaminophenazine chloride preparing and Au@CMK-3-anti-SCCA-thionine are modified on electrode, dried 4 DEG C of preservations, obtain the working electrode of electrochemical immunosensor;
The concrete steps that step c makes electrochemical immunosensor working curve are as follows:
1. by contrast electrode-saturated calomel electrode, to the working electrode exact connect ion of electrode-platinum electrode and above-mentioned preparation on electrochemical workstation;
2. the PBS buffer solution of pH 7.4 is as end liquid, described buffer solution contains 0.1 mol/L KCl as supporting electrolyte, detect the red and response of thionine under different potentials of the working electrode centering of having modified by differential pulse voltammetry (DPV), be respectively-0.62V of the current potential that described dimethyl diaminophenazine chloride and thionine are corresponding and-0.17V; According to the relation of the different electron mediator gained current-responsives different tumor markers antigen concentration of standard solution corresponding from it, drawing curve.
2. sandwich type electrochemical immunosensor as claimed in claim 1 detects the purposes in Cervical Tumor mark at the same time.
3. purposes claimed in claim 2, wherein, described Cervical Tumor mark is SCCA and CEA.
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