CN107727858A - A kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors - Google Patents

A kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors Download PDF

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CN107727858A
CN107727858A CN201710924116.8A CN201710924116A CN107727858A CN 107727858 A CN107727858 A CN 107727858A CN 201710924116 A CN201710924116 A CN 201710924116A CN 107727858 A CN107727858 A CN 107727858A
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王平
裴福彬
李明党
马恩慧
余昊轩
董云会
李月云
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Shandong University of Technology
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Abstract

The invention belongs to new function material and bio-sensing detection technique field, there is provided a kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors.A kind of electrochemical immunosensor is specifically prepared for and applied to the detection of tumor markers antigen as substrate as label, polypyrrole golden nanometer particle using Rh@Pt nanodendrites composites.

Description

A kind of preparation method based on Rh@Pt nanodendrites composite immunosensors and Using
Technical field
The invention belongs to new function material and bio-sensing detection technique field, there is provided one kind is based on Rh@Pt nanometers The preparation method and application of dendrite composite immunosensor.
Background technology
The incidence of disease of tumour is high, and is not easy to discover, and China's case load is quite huge, accounts for the 55% of whole world case load, and swollen The speed of growth and the transfer of knurl is fast, and high risks are produced to the health of the mankind, if but tumour can make a definite diagnosis healing in early stage Rate is still very high.Tumor markers and tumour have close relationship, by detecting containing for tumor markers in human serum Measure to speculate a kind of method for whether suffering from tumour and having become people and being widely recognized as.
Electrochemical immunosensor is widely used for the detection of tumor markers, interlayer type electrochemistry immuno-sensing at present Device combines the immuno analytical method of high specific and highly sensitive electrochemical analysis techniques, have high sensitivity, prepare it is simple, The advantages that detection is quick, cost is cheap, there is weight in fields such as clinical examination, environmental monitoring, food safety control, biological detections The application value wanted.
The Rh@Pt nanodendrites used in the present invention not only have the bimetallic synergy of nucleocapsid shape, also have abundant Edge and corner atom, this causes Rh@Pt nanodendrites to have excellent catalytic.Amination graphene nanometer sheet has There is larger specific surface area, substantial amounts of Rh@Pt nanodendrites can be loaded, while amination graphene also has excellent conduction Property, electronics caused by Rh Pt nanodendrites catalysis reduction hydrogen peroxide can be disperseed, to prevent from causing because electronics is assembled Catalytic reaction slows down.In addition, the introducing of Rh@Pt nanodendrites not only makes the electric conductivity of composite obtain significantly carrying It is high, moreover it is possible to effectively prevent the stacking of graphene.Therefore, Rh@Pt nanodendrites composite can carry as signal amplifier The sensitivity of high sensor.Polypyrrole can accelerate electronics to conduct, form polypyrrole-golden nanometer particle as conducting polymer Not only there is the high conductivity of polypyrrole afterwards, be also provided with good biocompatibility, can be good at immobilized capture antibody, together When golden nanometer particle addition further increase the electric conductivity of polypyrrole.
The content of the invention
The invention provides a kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors, Realize the quantitative detection to tumor markers.
An object of the present invention is to provide a kind of preparation side based on Rh@Pt nanodendrites composite immunosensors Method.
The second object of the present invention is that prepared Rh@Pt nanodendrites composites immunosensors are applied into tumour Specific, the quantitative detection of mark.
Technical scheme, comprise the following steps.
1. a kind of preparation method based on Rh@Pt nanodendrites composite immunosensors, step are as follows：
（1）By a diameter of 3 ~ 5 mm glass-carbon electrode Al2O3Polishing powder is polished, and ultra-pure water, ethanol clean up；
（2）Take 6 μ L, 1 ~ 3 mg/mL polypyrrole-golden nanometer particle modification to arrive electrode surface, dry at room temperature, use is ultrapure Water rinses electrode surface, dries；
（3）Continue 6 μ L, 8 ~ 12 μ g/mL tumor markers capture antibody A b1Electrode surface is added drop-wise to, in 4 DEG C of refrigerators Dry；
（4）Continue 3 μ L, 0.5 ~ 1 wt% bovine serum albumin(BSA) BSA solution being added drop-wise to electrode surface, be 7.4 with pH Phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（5）Be added dropwise 6 μ L, 0.0001 ~ 5 ng/mL a series of various concentrations tumor markers antigen A g solution, be with pH 7.4 phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（6）By 6 μ L, 1 ~ 3 mg/mL Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2- GS/Ab2Solution, drop coating on electrode surface, be placed in 4 DEG C of refrigerators hatch it is molten with the phosphate-buffered that pH is 7.4 after 40 min Liquid cleaning electrode, dry in 4 DEG C of refrigerators, a kind of immunosensor based on Rh@Pt nanodendrites composites is made.
Polypyrrole-golden nanometer particle, Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh used in 2. Pt/NH2-GS/Ab2The preparation of solution
（1）The preparation of polypyrrole-golden nanometer particle
1. the synthesis of polypyrrole
Take 0.5 ~ 1.5 mL pyrroles to be dispersed in 25 mL, 0.5 ~ 1.5 mol/L hydrochloric acid, obtain the mixing of pyrroles and hydrochloric acid Liquid；The mixed liquor of 10 mL pyrroles and hydrochloric acid is taken, adds 2 mL, 1 mol/L ammonium persulfate under stirring condition, ice bath reaction 4 ~ 6 h, are centrifuged, and drying at room temperature obtains polypyrrole；
2. the synthesis of polypyrrole-golden nanometer particle
Take 1 mL, 0.8 ~ 1.2 wt% chlorauric acid solution to be added in 99 mL ultra-pure waters, be heated to micro-boiling, add 2.5 ML, 0.5 ~ 1.5 wt% sodium citrate solution, after keeping the min of slight boiling condition 15, room temperature is cooled to, obtains golden nanometer particle Dispersion liquid, it is transferred at 4 DEG C and saves backup；By the golden nanometer particle dispersion liquid centrifugation point of the above-mentioned preparations of 20 ~ 30 mL From, it is dispersed in again in 10 mL ultra-pure water, adds 10 mg polypyrroles, 12 h are vibrated in shaken cultivation case, centrifuges, Drying at room temperature, obtain polypyrrole-golden nanometer particle；
（2）It is prepared by Rh@Pt nanodendrites composite
1. the synthesis of Rh@Pt nanodendrites
0.21 g sodium citrates and 0.2 ~ 0.3 g hexadecyltrimethylammonium chlorides is taken to be added in 9 mL ultra-pure waters, stirring 5 Min, sequentially add 0.1 mL, 0.1 mol/L rhodium chloride, 0.9 mL, 0.08 ~ 0.12 mol/L chloroplatinic acid, stirring After 15 min, 1 mL formaldehyde is added, mixed liquor is transferred in autoclave, 40 ~ 60 are reacted under 180 DEG C of condition Min, room temperature is cooled to, centrifuged, freeze-drying, obtain Rh@Pt nanodendrites；
2. Rh@Pt nanodendrites composite synthesizes
Take the concentrated sulfuric acid and 10 mL concentrated phosphoric acids that 0.8 g graphite powders add 90 ~ 98 mL, mass fraction is 98 wt%, stirring 25 After min, 4 ~ 5 g potassium permanganate are added, after stirring 15 min, 45 ~ 60 DEG C is heated to, after reacting 12 h, adds 40 mL ultrapure The ice that water is frozen into, then add 0.5 mL, 20 ~ 30 wt% hydrogen peroxide, centrifuge washing after 20 min is stirred, adds 30 mL ultra-pure waters, 40 min of ultrasound, centrifuge, supernatant is freeze-dried to obtain graphene oxide；0.1 g graphene oxides are taken to be put into small burning In cup, add 40 mL ethylene glycol, 30 min of ultrasound, add 0.8 ~ 1 mL concentrated ammonia liquors, mixture is transferred to autoclave, 180 DEG C 5 h of lower reaction, are cooled to room temperature, centrifuge, at room temperature dry amination graphene；Take 15 mg amination graphenes and 5 ~ 10 mg Rh@Pt nanodendrites are dispersed in 10 mL ultra-pure waters, 1 h of ultrasound, centrifuge Rh@Pt nanodendrites are compound Material；
（3）Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2 -GS/Ab2The preparation of solution
The amination graphene of 1 ~ 4 mg load Rh@Pt nanodendrites is distributed in 1 mL ultra-pure waters, 100 μ L of addition, 80 ~ 120 μ g/mL tumor-marker analyte detection antibody A b2The phosphate that solution and 900 μ L, 50 mmol/L pH are 7.4 Cushioning liquid, 12 h of vibration hatching in 4 DEG C of constant-temperature shaking incubators；At 4 DEG C, 10 min are centrifuged under 6000 rpm rotating speeds, are obtained Lower sediment, add 1 mL, the phosphate buffer solution centrifuge washing that 50 mmol/L pH is 7.4, obtain lower sediment, finally Add 1 mL, the phosphate buffer solution that 50 mmol/L pH is 7.4, Rh@Pt nanodendrites composite tumor-markers are made Analyte detection antibody Rh@Pt/NH2-GS/Ab2Solution, save backup at 4 DEG C.
3. the detection of tumor markers
（1）Tested using electrochemical workstation with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is Auxiliary electrode, prepared sensor are working electrode, are delayed in 10 mL, 50 mmol/L the pH phosphate for being 5.3 ~ 8.0 Rush in solution and tested；
（2）Used time, m- current method detected to analyte, and input voltage is -0.4 V, the s of sampling interval 0.1, run time 400 s；
（3）After background current tends towards stability, the pH every 50 s to 10 mL, 50 mmol/L is molten for 7.4 phosphate-buffered 10 μ L, 5 mol/L hydrogen peroxide solution, record current change are injected in liquid.
Tumor markers described above is selected from one of following：AFP、CEA、PSA.
Raw materials of the present invention can be bought in chemical reagents corporation or biopharmaceutical company.
The useful achievement of the present invention
（1）Present invention uses polypyrrole-golden nanometer particle, polypyrrole is cheap, has excellent electric conductivity, can speed up Electronics shifts, and golden nanometer particle can further improve the electric conductivity of polypyrrole, while flake is presented in polypyrrole, have larger Specific surface area, more golden nanometer particle can be loaded, this causes polypyrrole-golden nanometer particle not only to have excellent conduction Property, good biocompatibility is also provided with, while the addition of golden nanometer particle also increases dispersiveness of the polypyrrole in water；
（2）Graphite can be prevented as detection antibody labeling thing, Rh@Pt nanodendrites using Rh@Pt nanodendrites composite The stacking of alkene, dispersiveness of the graphene in water is improved, Rh@Pt nanodendrites have more edge and turning in addition, increase Specific surface area, has a more avtive spot, is capable of the reduction of preferably catalyzing hydrogen peroxide, while based between platinum-ammonia Effect Rh@Pt nanodendrites can be good at immobilized antibody, realize amplification electrochemical signals effect, so as to improve pass The sensitivity of sensor, reduces test limit；
（3）It is a kind of based on detection of the Rh@Pt nanodendrites composite immunosensors to tumor markers, its range of linearity 0.0001 ~ 5 ng/mL, minimum 0.033 pg/mL of test limit, show a kind of based on the immune biography of Rh@Pt nanodendrites composite Sensor can reach the purpose of quantitative detection.
Embodiment
Now the present invention is further illustrated by embodiment, but not limited to this.
A kind of preparation based on Rh@Pt nanodendrites composite immunosensors of embodiment 1
（1）By a diameter of 3 mm glass-carbon electrode Al2O3Polishing powder is polished, and ultra-pure water, ethanol clean up；
（2）Take 6 μ L, 1 mg/mL polypyrrole-golden nanometer particle modification to arrive electrode surface, dry, rushed with ultra-pure water at room temperature Electrode surface is washed, is dried；
（3）Continue 6 μ L, 8 μ g/mL tumor markers capture antibody A b1Electrode surface is added drop-wise to, is dried in 4 DEG C of refrigerators；
（4）Continue 3 μ L, 0.5 wt% bovine serum albumin(BSA) BSA solution being added drop-wise to electrode surface, with the phosphoric acid that pH is 7.4 Salt buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（5）Be added dropwise 6 μ L, 0.0001 ~ 5 ng/mL a series of various concentrations tumor markers antigen A g solution, be with pH 7.4 phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（6）By 6 μ L, 1 mg/mL Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2-GS/ Ab2Solution, drop coating on electrode surface, be placed in 4 DEG C of refrigerators hatch it is clear with the phosphate buffer solution that pH is 7.4 after 40 min Electrode is washed, is dried in 4 DEG C of refrigerators, one kind is made and is based on Rh@Pt nanodendrites composite immunosensors.
A kind of preparation based on Rh@Pt nanodendrites composite immunosensors of embodiment 2
（1）By a diameter of 4 mm glass-carbon electrode Al2O3Polishing powder is polished, and ultra-pure water, ethanol clean up；
（2）Take 6 μ L, 2 mg/mL polypyrrole-golden nanometer particle modification to arrive electrode surface, dry, rushed with ultra-pure water at room temperature Electrode surface is washed, is dried；
（3）Continue 6 μ L, 10 μ g/mL tumor markers capture antibody A b1Electrode surface is added drop-wise to, is done in 4 DEG C of refrigerators It is dry；
（4）Continue 3 μ L, 0.8 wt% bovine serum albumin(BSA) BSA solution being added drop-wise to electrode surface, with the phosphoric acid that pH is 7.4 Salt buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（5）Be added dropwise 6 μ L, 0.0001 ~ 5 ng/mL a series of various concentrations tumor markers antigen A g solution, be with pH 7.4 phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（6）By 6 μ L, 2 mg/mL Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2-GS/ Ab2Solution, drop coating on electrode surface, be placed in 4 DEG C of refrigerators hatch it is clear with the phosphate buffer solution that pH is 7.4 after 40 min Electrode is washed, is dried in 4 DEG C of refrigerators, one kind is made and is based on Rh@Pt nanodendrites composite immunosensors.
A kind of preparation based on Rh@Pt nanodendrites composite immunosensors of embodiment 3
（1）By a diameter of 5 mm glass-carbon electrode Al2O3Polishing powder is polished, and ultra-pure water, ethanol clean up；
（2）Take 6 μ L, 3 mg/mL polypyrrole-golden nanometer particle modification to arrive electrode surface, dry, rushed with ultra-pure water at room temperature Electrode surface is washed, is dried；
（3）Continue 6 μ L, 12 μ g/mL tumor markers capture antibody A b1Electrode surface is added drop-wise to, is done in 4 DEG C of refrigerators It is dry；
（4）Continue 3 μ L, 1 wt% bovine serum albumin(BSA) BSA solution being added drop-wise to electrode surface, with the phosphate that pH is 7.4 Cushioning liquid rinses electrode surface, is dried in 4 DEG C of refrigerators；
（5）Be added dropwise 6 μ L, 0.0001 ~ 5 ng/mL a series of various concentrations tumor markers antigen A g solution, be with pH 7.4 phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（6）By 6 μ L, 3 mg/mL Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2-GS/ Ab2Solution, drop coating on electrode surface, be placed in 4 DEG C of refrigerators hatch it is clear with the phosphate buffer solution that pH is 7.4 after 40 min Electrode is washed, is dried in 4 DEG C of refrigerators, one kind is made and is based on Rh@Pt nanodendrites composite immunosensors.
The preparation of 4 polypyrroles of embodiment-golden nanometer particle
（1）The synthesis of polypyrrole
Take 0.5 mL pyrroles to be dispersed in 25 mL, 0.5 mol/L hydrochloric acid, obtain the mixed liquor of pyrroles and hydrochloric acid；Take 10 mL pyrroles The mixed liquor with hydrochloric acid is coughed up, 2 mL, 1 mol/L ammonium persulfate solution are added under stirring condition, ice bath reacts 4 h, centrifugation point From drying at room temperature obtains polypyrrole；
（2）The preparation of golden nanometer particle dispersion liquid
Take 1 mL, 0.8 wt% chlorauric acid solution to be added in 99 mL ultra-pure waters, be heated to micro-boiling, add 2.5 mL, 0.5 Wt% sodium citrate solution, after keeping the min of slight boiling condition 15, room temperature is cooled to, obtains golden nanometer particle dispersion liquid, by its turn Move on at 4 DEG C and save backup；
（3）The synthesis of polypyrrole-golden nanometer particle
The golden nanometer particle dispersion liquid of the above-mentioned preparations of 20 mL is centrifuged, is dispersed in again in 10 mL ultra-pure water, is added 10 mg polypyrroles, 12 h are vibrated in shaken cultivation case, centrifuge, drying at room temperature, obtain polypyrrole-golden nanometer particle.
The preparation of 5 polypyrroles of embodiment-golden nanometer particle
（1）The synthesis of polypyrrole
Take 1 mL pyrroles to be dispersed in 25 mL, 1 mol/L hydrochloric acid, obtain the mixed liquor of pyrroles and hydrochloric acid；Take 10 mL pyrroles and The mixed liquor of hydrochloric acid, 2 mL, 1 mol/L ammonium persulfate solution are added under stirring condition, ice bath reacts 5 h, centrifuges, room Temperature is dried to obtain polypyrrole；
（2）The preparation of golden nanometer particle dispersion liquid
Take 1 mL, 1 wt% chlorauric acid solution to be added in 99 mL ultra-pure waters, be heated to micro-boiling, add 2.5 mL, 1 wt% Sodium citrate solution, after keeping the min of slight boiling condition 15, room temperature is cooled to, obtains golden nanometer particle dispersion liquid, is transferred into 4 Saved backup at DEG C；
（3）The synthesis of polypyrrole-golden nanometer particle
The golden nanometer particle dispersion liquid of the above-mentioned preparations of 25 mL is centrifuged, is dispersed in again in 10 mL ultra-pure water, is added 10 mg polypyrroles, 12 h are vibrated in shaken cultivation case, centrifuge, drying at room temperature, obtain polypyrrole-golden nanometer particle.
The preparation of 6 polypyrroles of embodiment-golden nanometer particle
（1）The synthesis of polypyrrole
Take 1.5 mL pyrroles to be dispersed in 25 mL, 1.5 mol/L hydrochloric acid, obtain the mixed liquor of pyrroles and hydrochloric acid；Take 10 mL pyrroles The mixed liquor with hydrochloric acid is coughed up, 2 mL, 1 mol/L ammonium persulfate solution are added under stirring condition, ice bath reacts 6 h, centrifugation point From drying at room temperature obtains polypyrrole；
（2）The preparation of golden nanometer particle dispersion liquid
Take 1 mL, 1.2 wt% chlorauric acid solution to be added in 99 mL ultra-pure waters, be heated to micro-boiling, add 2.5 mL, 1.5 Wt% sodium citrate solution, after keeping the min of slight boiling condition 15, room temperature is cooled to, obtains golden nanometer particle dispersion liquid, by its turn Move on at 4 DEG C and save backup；
（3）The synthesis of polypyrrole-golden nanometer particle
The golden nanometer particle dispersion liquid of the above-mentioned preparations of 30 mL is centrifuged, is dispersed in again in 10 mL ultra-pure water, is added 10 mg polypyrroles, 12 h are vibrated in shaken cultivation case, centrifuge, drying at room temperature, obtain polypyrrole-golden nanometer particle.
Embodiment 7Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2-GS/Ab2The system of solution It is standby
（1）The synthesis of Rh@Pt nanodendrites
Take 0.21 g sodium citrates and 0.2 g hexadecyltrimethylammonium chlorides to be added in 9 mL ultra-pure waters, stir 5 min, 0.1 mL, 0.1 mol/L rhodium chloride are sequentially added, 0.9 mL, 0.08 mol/L chloroplatinic acid, after stirring 15 min, is added Enter 1 mL formaldehyde, mixed liquor is transferred in autoclave, 40 min are reacted under 180 DEG C of condition, are cooled to room temperature, from The heart separates, and freeze-drying, obtains Rh@Pt nanodendrites；
（2）The synthesis of amination graphene
Take 0.8 g graphite powders to add 90 mL, the 98 wt% concentrated sulfuric acid and 10 mL concentrated phosphoric acids, after stirring 25 min, add 4 g Gao Meng Sour potassium, after stirring 15 min, it is heated to 45 DEG C, after reacting 12 h, the ice that adds 40 mL ultra-pure waters to be frozen into, then add 0.5 mL, 20 Wt% hydrogen peroxide, centrifuge washing after 20 min is stirred, add 30 mL ultra-pure waters, 40 min of ultrasound, centrifuge, supernatant is cold Jelly is dried to obtain graphene oxide；Take 0.1 g graphene oxides to be put into small beaker, add 40 mL ethylene glycol, 30 min of ultrasound, Add 0.8 mL concentrated ammonia liquors, mixture is transferred to autoclave, 5 h are reacted at 180 DEG C, are cooled to room temperature, centrifuge, room temperature Lower dry amination graphene；
（3）Rh@Pt nanodendrites composite synthesizes
15 mg amination graphenes and 5 mg Rh@Pt nanodendrites are taken to be dispersed in 10 mL ultra-pure waters, 1 h of ultrasound, centrifugation Separate to obtain Rh@Pt nanodendrites composites；
（4）Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2 -GS/Ab2The preparation of solution
1 mg Rh@Pt nanodendrites composites are distributed in 1 mL ultra-pure waters, add 100 μ L, 80 μ g/mL tumour Marker detection antibody A b2The phosphate buffer solution that solution and 900 μ L, 50 mmol/L pH are 7.4,4 DEG C of constant temperature oscillations 12 h of vibration hatching in incubator；At 4 DEG C, 10 min are centrifuged under 6000 rpm rotating speeds, obtain lower sediment, add 1 mL, 50 Mmol/L pH is 7.4 phosphate buffer solution centrifuge washing, obtains lower sediment, is eventually adding 1 mL, 50 mmol/L pH For 7.4 phosphate buffer solution, Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH are made2- GS/Ab2Solution, save backup at 4 DEG C.
Embodiment 8Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2-GS/Ab2The system of solution It is standby
（1）The synthesis of Rh@Pt nanodendrites
Take 0.21 g sodium citrates and 0.25 g hexadecyltrimethylammonium chlorides to be added in 9 mL ultra-pure waters, stir 5 min, 0.1 mL, 0.1 mol/L rhodium chloride are sequentially added, 0.9 mL, 0.1 mol/L chloroplatinic acid, after stirring 15 min, is added 1 mL formaldehyde, mixed liquor is transferred in autoclave, and 50 min are reacted under 180 DEG C of condition, is cooled to room temperature, centrifugation Separation, freeze-drying, obtains Rh@Pt nanodendrites；
（2）The synthesis of amination graphene
Take 0.8 g graphite powders to add 90 ~ 98 mL, the 98 wt% concentrated sulfuric acid and 10 mL concentrated phosphoric acids, after stirring 25 min, add 4.5 g potassium permanganate, after stirring 15 min, it is heated to 50 DEG C, after reacting 12 h, the ice that adds 40 mL ultra-pure waters to be frozen into, then add 0.5 mL, 25 wt% hydrogen peroxide, centrifuge washing after 20 min is stirred, adds 30 mL ultra-pure waters, 40 min of ultrasound, centrifuge, Supernatant is freeze-dried to obtain graphene oxide；Take 0.1 g graphene oxides to be put into small beaker, add 40 mL ethylene glycol, surpass The min of sound 30, add 0.9 mL concentrated ammonia liquors, mixture is transferred to autoclave, 5 h are reacted at 180 DEG C, are cooled to room temperature, centrifuge Separation, at room temperature dry amination graphene；
（3）Rh@Pt nanodendrites composite synthesizes
15 mg amination graphenes and 8 mg Rh@Pt nanodendrites are taken to be dispersed in 10 mL ultra-pure waters, 1 h of ultrasound, centrifugation Separate to obtain Rh@Pt nanodendrites composites；
（4）Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2 -GS/Ab2The preparation of solution
2 mg Rh@Pt nanodendrites composites are distributed in 1 mL ultra-pure waters, add 100 μ L, 100 μ g/mL it is swollen Tumor markers detection antibody A b2The phosphate buffer solution that solution and 900 μ L, 50 mmol/L pH are 7.4,4 DEG C of constant temperature shake Swing 12 h of vibration hatching in incubator；At 4 DEG C, 10 min are centrifuged under 6000 rpm rotating speeds, obtain lower sediment, add 1 mL, 50 mmol/L pH is 7.4 phosphate buffer solution centrifuge washing, obtains lower sediment, is eventually adding 1 mL, 50 mmol/L PH be 7.4 phosphate buffer solution, Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/ are made NH2-GS/Ab2Solution, save backup at 4 DEG C.
Embodiment 9Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2-GS/Ab2The system of solution It is standby
（1）The synthesis of Rh@Pt nanodendrites
Take 0.21 g sodium citrates and 0.3 g hexadecyltrimethylammonium chlorides to be added in 9 mL ultra-pure waters, stir 5 min, 0.1 mL, 0.1 mol/L rhodium chloride are sequentially added, 0.9 mL, 0.12 mol/L chloroplatinic acid, after stirring 15 min, is added Enter 1 mL formaldehyde, mixed liquor is transferred in autoclave, 60 min are reacted under 180 DEG C of condition, are cooled to room temperature, from The heart separates, and freeze-drying, obtains Rh@Pt nanodendrites；
（2）The synthesis of amination graphene
Take 0.8 g graphite powders to add 98 mL, the 98 wt% concentrated sulfuric acid and 10 mL concentrated phosphoric acids, after stirring 25 min, add 5 g Gao Meng Sour potassium, after stirring 15 min, it is heated to 60 DEG C, after reacting 12 h, the ice that adds 40 mL ultra-pure waters to be frozen into, then add 0.5 mL, 30 Wt% hydrogen peroxide, centrifuge washing after 20 min is stirred, add 30 mL ultra-pure waters, 40 min of ultrasound, centrifuge, supernatant is cold Jelly is dried to obtain graphene oxide；Take 0.1 g graphene oxides to be put into small beaker, add 40 mL ethylene glycol, 30 min of ultrasound, Add 1 mL concentrated ammonia liquors, mixture is transferred to autoclave, 5 h are reacted at 180 DEG C, are cooled to room temperature, centrifuge, at room temperature Dry amination graphene；
（3）Rh@Pt nanodendrites composite synthesizes
15 mg amination graphenes and 10 mg Rh@Pt nanodendrites are taken to be dispersed in 10 mL ultra-pure waters, 1 h of ultrasound, centrifugation Separate to obtain Rh@Pt nanodendrites composites；
（4）Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/NH2 -GS/Ab2The preparation of solution
4 mg Rh@Pt nanodendrites composites are distributed in 1 mL ultra-pure waters, add 100 μ L, 120 μ g/mL it is swollen Tumor markers detection antibody A b2The phosphate buffer solution that solution and 900 μ L, 50 mmol/L pH are 7.4,4 DEG C of constant temperature shake Swing 12 h of vibration hatching in incubator；At 4 DEG C, 10 min are centrifuged under 6000 rpm rotating speeds, obtain lower sediment, add 1 mL, 50 mmol/L pH is 7.4 phosphate buffer solution centrifuge washing, obtains lower sediment, is eventually adding 1 mL, 50 mmol/L PH be 7.4 phosphate buffer solution, Rh Pt nanodendrites composite tumor-marker analyte detection antibody Rh Pt/ are made NH2-GS/Ab2Solution, save backup at 4 DEG C.
The tumor markers AFP of embodiment 10 detection
（1）Tested using electrochemical workstation with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is Auxiliary electrode, prepared sensor are working electrode, the phosphate buffer solution for being 5.3 in 10 mL, 50 mmol/L pH In tested；
（2）Used time, m- current method detected to analyte, and input voltage is -0.4 V, the s of sampling interval 0.1, run time 400 s；
（3）After background current tends towards stability, the pH every 50 s to 10 mL, 50 mmol/L is molten for 7.4 phosphate-buffered 10 μ L, 5 mol/L hydrogen peroxide solution, record current change are injected in liquid；
（4）According to the linear relationship between gained current strength and AFP concentration, drawing curve, measuring the range of linearity is 0.0001 ~ 5 ng/mL, detection are limited to 0.033 pg/mL.
The tumor markers CEA of embodiment 11 detection
CEA in sample is detected according to the method for embodiment 10, its range of linearity is 0.001 ~ 5 ng/mL, test limit For 0.3 pg/mL.
The tumor markers PSA of embodiment 12 detection
PSA in sample is detected according to the method for embodiment 10, its range of linearity is 0.0005 ~ 5 ng/mL, test limit For 0.1 pg/mL.

Claims (5)

1. a kind of preparation method based on Rh@Pt nanodendrites composite immunosensors, it is characterised in that step is as follows：
（1）By a diameter of 3 ~ 5 mm glass-carbon electrode Al2O3Polishing powder is polished, and ultra-pure water, ethanol clean up；
（2）Take 6 μ L, 1 ~ 3 mg/mL polypyrrole-golden nanometer particle modification to arrive electrode surface, dry at room temperature, use is ultrapure Water rinses electrode surface, dries；
（3）Continue 6 μ L, 8 ~ 12 μ g/mL tumor markers capture antibody A b1Electrode surface is added drop-wise to, in 4 DEG C of refrigerators Dry；
（4）Continue 3 μ L, 0.5 ~ 1 wt% bovine serum albumin(BSA) BSA solution being added drop-wise to electrode surface, be 7.4 with pH Phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（5）Be added dropwise 6 μ L, 0.0001 ~ 5 ng/mL a series of various concentrations tumor markers antigen A g solution, be with pH 7.4 phosphate buffer solution rinses electrode surface, is dried in 4 DEG C of refrigerators；
（6）By 6 μ L, the tumor-marker analyte detection antibody Rh Pt/NH of 1 ~ 3 mg/mL Rh Pt nanodendrites composites2- GS/Ab2Solution, drop coating on electrode surface, be placed in 4 DEG C of refrigerators hatch it is molten with the phosphate-buffered that pH is 7.4 after 40 min Liquid cleaning electrode, dry in 4 DEG C of refrigerators, one kind is made and is based on Rh@Pt nanodendrites composite immunosensors.
2. a kind of preparation method based on Rh@Pt nanodendrites composite immunosensors as claimed in claim 1, described The preparation of polypyrrole-golden nanometer particle, step are as follows：
（1）The synthesis of polypyrrole
Take 0.5 ~ 1.5 mL pyrroles to be dispersed in 25 mL, 0.5 ~ 1.5 mol/L hydrochloric acid, obtain the mixing of pyrroles and hydrochloric acid Liquid；The mixed liquor of 10 mL pyrroles and hydrochloric acid is taken, 2 mL, 1 mol/L ammonium persulfate solution are added under stirring condition, ice bath is anti- 4 ~ 6 h are answered, are centrifuged, drying at room temperature obtains polypyrrole；
（2）The preparation of golden nanometer particle dispersion liquid
Take 1 mL, 0.8 ~ 1.2 wt% chlorauric acid solution to be added in 99 mL ultra-pure waters, be heated to micro-boiling, add 2.5 ML, 0.5 ~ 1.5 wt% sodium citrate solution, after keeping the min of slight boiling condition 15, room temperature is cooled to, obtains golden nanometer particle Dispersion liquid, it is transferred at 4 DEG C and saves backup；
（3）The synthesis of polypyrrole-golden nanometer particle
The golden nanometer particle dispersion liquid of the above-mentioned preparations of 20 ~ 30 mL is centrifuged, is dispersed in again in 10 mL ultra-pure water, 10 mg polypyrroles are added, 12 h are vibrated in shaken cultivation case, centrifuges, drying at room temperature, obtains polypyrrole-golden nanometer particle.
3. a kind of preparation method based on Rh@Pt nanodendrites composite immunosensors as claimed in claim 1, described The tumor-marker analyte detection antibody Rh Pt/NH of Rh Pt nanodendrites composites2-GS/Ab2The preparation of solution, step are as follows：
（1）The synthesis of Rh@Pt nanodendrites
0.21 g sodium citrates and 0.2 ~ 0.3 g hexadecyltrimethylammonium chlorides is taken to be added in 9 mL ultra-pure waters, stirring 5 Min, sequentially add 0.1 mL, 0.1 mol/L rhodium chloride, 0.9 mL, 0.08 ~ 0.12 mol/L chloroplatinic acid, stirring After 15 min, 1 mL formaldehyde is added, mixed liquor is transferred in autoclave, 40 ~ 60 are reacted under 180 DEG C of condition Min, room temperature is cooled to, centrifuged, freeze-drying, obtain Rh@Pt nanodendrites；
（2）The synthesis of amination graphene
Take 0.8 g graphite powders to add 90 ~ 98 mL, the 98 wt% concentrated sulfuric acid and 10 mL concentrated phosphoric acids, after stirring 25 min, add 4 ~ 5 g potassium permanganate, after stirring 15 min, it is heated to 45 ~ 60 DEG C, after reacting 12 h, the ice that adds 40 mL ultra-pure waters to be frozen into, Again plus 0.5 mL, 20 ~ 30 wt% hydrogen peroxide, centrifuge washing after 20 min is stirred, adds 30 mL ultra-pure waters, 40 min of ultrasound, Centrifuge, supernatant is freeze-dried to obtain graphene oxide；Take 0.1 g graphene oxides to be put into small beaker, add 40 mL Ethylene glycol, 30 min of ultrasound, adds 0.8 ~ 1 mL concentrated ammonia liquors, and mixture is transferred into autoclave, 5 h are reacted at 180 DEG C, cold But room temperature is arrived, is centrifuged, at room temperature dry amination graphene；
（3）The synthesis of Rh@Pt nanodendrites composites
15 mg amination graphenes and 5 ~ 10 mg Rh@Pt nanodendrites are taken to be dispersed in 10 mL ultra-pure waters, 1 h of ultrasound, Centrifuge to obtain Rh@Pt nanodendrites composites；
（4）The tumor-marker analyte detection antibody Rh Pt/NH of Rh Pt nanodendrites composites2 -GS/Ab2The preparation of solution
1 ~ 4 mg Rh@Pt nanodendrites composites are distributed in 1 mL ultra-pure waters, add 100 μ L, 80 ~ 120 μ G/mL tumor-marker analyte detection antibody A b2The phosphate buffer solution that solution and 900 μ L, 50 mmol/L pH are 7.4,4 12 h of vibration hatching in DEG C constant-temperature shaking incubator；At 4 DEG C, 10 min are centrifuged under 6000 rpm rotating speeds, lower sediment is obtained, adds Enter 1 mL, the phosphate buffer solution centrifuge washing that 50 mmol/L pH is 7.4, obtain lower sediment, be eventually adding 1 mL, 50 Mmol/L pH is 7.4 phosphate buffer solution, and the tumor-marker analyte detection antibody of Rh Pt nanodendrites composites is made Rh@Pt/NH2-GS/Ab2Solution, save backup at 4 DEG C.
4. a kind of immunosensor preparation method based on Rh@Pt nanodendrites composites as claimed in claim 1, made Standby immunosensor is used for the detection of tumor markers, and detecting step is as follows：
（1）Tested using electrochemical workstation with three-electrode system, saturated calomel electrode is reference electrode, and platinum electrode is Auxiliary electrode, prepared sensor are working electrode, are delayed in 10 mL, 50 mmol/L the pH phosphate for being 5.3 ~ 8.0 Rush in solution and tested；
（2）Used time, m- current method detected to analyte, and input voltage is -0.4 V, the s of sampling interval 0.1, run time 400 s；
（3）After background current tends towards stability, the pH every 50 s to 10 mL, 50 mmol/L is molten for 7.4 phosphate-buffered 10 μ L, 5 mol/L hydrogen peroxide solution, record current change are injected in liquid.
5. according to the tumor markers described in claim 1,2,3, it is characterised in that the tumor markers be selected from it is following it One：AFP、CEA、PSA.
CN201710924116.8A 2017-09-30 2017-09-30 A kind of preparation method and application based on Rh@Pt nanodendrites composite material immunosensor Expired - Fee Related CN107727858B (en)

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