CN106248657A - A kind of based on dendroid Fe2o3the preparation method and application of the Electrochemiluminescsensor sensor of@Au - Google Patents
A kind of based on dendroid Fe2o3the preparation method and application of the Electrochemiluminescsensor sensor of@Au Download PDFInfo
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- CN106248657A CN106248657A CN201610803682.9A CN201610803682A CN106248657A CN 106248657 A CN106248657 A CN 106248657A CN 201610803682 A CN201610803682 A CN 201610803682A CN 106248657 A CN106248657 A CN 106248657A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
Abstract
The present invention relates to a kind of based on dendroid Fe2O3The preparation method and application of the Electrochemiluminescsensor sensor of@Au, belongs to electrochemical luminous sensor field, with tris (bipyridine) ruthenium for electrochemical luminescence signals source, utilizes dendroid Fe2O3Bio-compatibility that@Au is excellent and big specific surface area increase the supported quantity of antibody, use Pd graphene/Fe3O4‑Ru(bpy)3 2+As two anti-labels, according to the difference of electrochemical luminescence signals intensity, it is achieved the detection to liver cancer marker.
Description
Technical field
The present invention relates to a kind of based on dendroid Fe2O3The preparation method and application of the Electrochemiluminescsensor sensor of@Au,
It is specifically related to a kind of tris (bipyridine) ruthenium as luminescent material, utilizes dendroid Fe2O3Bio-compatibility that@Au is excellent and big ratio
Surface area increases the supported quantity of antibody as base material, uses Pd-graphene/Fe3O4-Ru(bpy)3 2+As two anti-labellings
Thing, belongs to electrochemiluminescence detection technique field.
Background technology
In recent years, the sickness rate of hepatocarcinoma remains high, and mortality rate increases year by year, and reason is the discovery to hepatocarcinoma not mostly
Enough in time, during to discovery be later period of hepatocarcinoma and missed optimal treatment time.Found by research in recent years, alpha-fetoprotein
AFP, squamous cell carcinoma antigen SCCA, CEA, carbohydrate antigen CA15-3 etc. can as liver cancer marker, they
The early prevention of hepatocarcinoma and treatment play an important role.The concentration of liver cancer marker in serum is carried out quick, sensitive
Detection has very important clinical value and meaning, it is possible to reduce the mortality rate of hepatocarcinoma to the full extent, extends hepatocarcinoma and suffers from
In the existence time limit of person, strive for more therapy apparatus meeting for patient.
The method being currently used for detecting liver cancer marker is mainly radioimmunoassays and Chemiluminescence immunoassay, but these
Method existence can not the most quickly detect, has radioactive pollution and operate the drawbacks such as complicated, and electrochemical immunosensor
Can overcome these drawbacks well, it is a kind of immunosensor built based on antigen and antibody specificity identification, with
Simple, highly sensitive, detection low, the advantage of fast response time of limit is prepared, it is possible to antigen is carried out the inspection of rapid sensitive by it
Survey.
Summary of the invention
The problem that it is an object of the invention to exist for existing liver cancer marker detection method, it is provided that a kind of simple and quick
Reliably based on dendroid Fe2O3@Au and Pd-graphene/Fe3O4-Ru(bpy)3 2+The preparation of electrochemical luminous sensor
Methods and applications, it is achieved quick, sensitive, special, the efficient detection to liver cancer marker.
Technical scheme is as follows:
1. one kind based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au, it is characterised in that include with
Lower step:
(1) glass-carbon electrode of diameter 4 mm is taken turns doing polishing with 1.0 μm, 0.3 μm, 0.05 μm aluminum oxide polishing powder successively
Process, clean with ultrapure water;
(2) drop coating 6 μ L, concentration are antibody A b of 2 ~ 4 mg/mL1Capture base material Fe2O3@Au/Ab1Solution is to electrode table
Face, 4 ° of C dry;
(3) drip 3 μ L, mass fraction is the bovine serum albumin solution of 1 ~ 3%, with the non-specific work on enclosed-electrode surface
Property site, rinse electrode surface with the phosphate buffered solution solution of pH 7.4,4 ° of C dry;
(4) drip 6 μ L, certain density determinand antigen, hatch 0.5 ~ 2 h under 4 ° of C, by the phosphate-buffered of pH 7.4
Solutions Solution rinses electrode surface, and 4 ° of C dry;
(5) drop coating 6 μ L, concentration are the two anti-Ab of 2 ~ 4 mg/mL2Label Pd-graphene/Fe3O4 -Ru(bpy)3 2+/
Ab2Solution, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, after 4 ° of C dry, prepares a kind of based on branch
Shape Fe2O3The Electrochemiluminescsensor sensor of@Au.
2. antibody capture base material Fe2O3@Au/Ab1The preparation of solution
(1) potassium ferricyanide solid of 0.05 ~ 0.20 g is dissolved in 5 ~ 50 mL ultra-pure waters, with 0.001 ~ 0.020
The sodium hydroxide solution regulation pH to 10.0 ~ 12.0 of mol/L, continues stirring 1 ~ 15 min, mixed solution is put into high pressure
In reactor, under 60 ~ 150 ° of C, react 6 ~ 24 h, by product centrifugation use nothing under 6000 ~ 8000 rpm
Water-ethanol and ultra-pure water wash three times respectively, put into vacuum drying oven, be dried 2 ~ 5 h, prepare brick-red under 30 ~ 60 ° of C
Dendroid Fe2O3;
(2) chlorauric acid solution that 40 ~ 100 mL, mass fraction are 0.001 ~ 0.010% is boiled, add 1 ~ 3 mL, matter
Amount mark is the trisodium citrate aqueous solution of 0.1 ~ 1.0%, is heated to reflux 5 ~ 20 min, treats that solution colour becomes claret,
Solution is cooled to room temperature, prepares solution of gold nanoparticles, keep in Dark Place under 4 ° of C;
(3) by dendroid Fe of 0.5 ~ 3 mg2O3It is distributed in 1 mL ultra-pure water, adds 0.5 ~ 1.5 mL golden nanometer particle
Solution, at room temperature vibrate 12 ~ 32 h by mixed solution, centrifugation, removes the golden nanometer particle of excess, prepares Fe2O3@
Au, by product Fe2O3@Au is re-dispersed in 1 mL ultra-pure water, prepares base material Fe2O3@Au solution;
(4) it is 2 ~ 4 mg/mL Fe in 1 ~ 3 mL, concentration2O3In@Au solution, add 100 ~ 400 μ L, concentration is 10
Determinand antibody A b of μ g/mL1Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off determinand antibody A b of excess1, will produce
Thing is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares antibody capture base material Fe2O3@Au/Ab1Molten
Liquid, is stored under 4 ° of C standby.
3. two anti-label Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2The preparation of solution
(1) it is in the ultra-pure water that 12 mol/L hydrochloric acid solutions join 5 ~ 30 mL by 0.1 ~ 2 mL, concentration, with backward molten
Liquid adds 0.5 ~ 6.0 g ferric chloride solid and 0.5 ~ 6.0 g ferrous chloride solid, under continuous stirring, will mix
Solution is added dropwise to 100 ~ 500 mL, concentration be 0.5 ~ 5.0 mol/L sodium hydroxide solution in, 4000 ~
Be centrifuged under the rotating speed of 8000 rpm separating, with milli-Q water three times, backward precipitation in add 200 ~ 600 mL, dense
Degree is the hydrochloric acid solution of 0.01 ~ 0.04 mol/L, and under the rotating speed of 6000 ~ 9000 rpm, centrifugation 5 ~ 15min, abandons
Remove supernatant, add ultra-pure water and carry out the ultrasonic Fe obtaining yellow3O4Nano sol;
(2) by 1 ~ 5 mL Fe3O4Nano sol joins 40 ~ 200 mL, concentration is that 1.0 ~ 3.0 mg/mL aoxidize stone
In ink alkene dispersible suspension, under agitation, add 0.10 ~ 0.60 g sodium sulfite solid, under 80 ~ 160 ° of C, react 2
~ 6 h, dialyse one week with ultra-pure water after cooling, the graphene/Fe of freeze-dried rear available 3D structure3O4;
(3) 0.06 ~ 0.20 g tetrachloro-palladium acid sodium solid and 0.06 ~ 0.20 g sodium citrate solid are dissolved in 10 ~ 100
In mL ultra-pure water, add 0.1 ~ 4.0 mL in solution, concentration is 0.005 ~ 0.020 mol/L sodium borohydride solution, holds
Continuous stirring 30 ~ 90 s, prepares the Pd nano-particle solution of black;
(4) by graphene/Fe that 1 ~ 3 mL, concentration are 2 mg/mL3O4The Pd nano-particle solution of solution and 1 ~ 3 mL
Mixing, lucifuge vibration 24 ~ 48 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, with 1 ~ 3 mL, concentration
It is 1 × 10-3 mol/L Ru(bpy)3 2+Solution mixing vibration 24 ~ 48 h, centrifugation abandoning supernatant, it is distributed to 1 mL and surpasses
In pure water, prepare Pd-graphene/Fe3O4-Ru(bpy)3 2+Solution;
(5) it is 2 ~ 4 mg/mL Pd-graphene/Fe in 1 ~ 3 mL, concentration3O4-Ru(bpy)3 2+In solution, add 100
~ 400 μ L, concentration are determinand antibody A b of 10 μ g/mL2Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off excess
Determinand antibody A b2, product is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares two anti-labels
Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2Solution, is stored under 4 ° of C standby.
4. the electrochemical luminous sensor of preparation is for the Electrochemical Detection of testing sample
(1) using the three-electrode system of electrochemical workstation to test, Ag/AgCl electrode is as reference electrode, platinum electrode
For to electrode, prepared electrochemical luminous sensor is working electrode, electrochemical workstation and chemiluminescence detector is connected
Being connected together and the high pressure of photomultiplier tube is set to 800 V, cyclic voltammetry scan potential range is 0 ~ 1.2 V, scanning speed
Rate is 0.1 V/s;
(2) at 10 mL, pH 6.4 ~ 8.4 containing the phosphate buffered solution solution that concentration is 35 ~ 65 mmol/L triethylamines
In, by electrochemical luminescence system, detect the electrochemical luminescence signals intensity that the determinand antigen to variable concentrations produces, draw
Working curve;
(3) testing sample solution replace determinand antigen detect.
5. determinand antigen is selected from one of following liver cancer marker: AFP, squamous cell carcinoma antigen SCCA, cancer
Embryonal antigen CEA, carbohydrate antigen CA15-3.
The useful achievement of the present invention
(1) electrochemical luminous sensor preparation method, with Ru (bpy)3 2+For luminescent material, utilize Ru (bpy)3 2+Good optics
Character, the sensor of structure has higher sensitivity.
(2) with Fe2O3@Au is as antibody capture substrate, Pd-graphene/Fe3O4-Ru(bpy)3 2+As two anti-labellings
Thing, Fe2O3@Au and Pd-graphene/Fe3O4-Ru(bpy)3 2+The advantages such as bio-compatibility is good, and specific surface area is big increase effectively
Add the supported quantity of antibody.
(3) electrochemical luminous sensor prepared by the present invention is for the detection of liver cancer marker, simple to operate, and reaction is fast
Speed, signal response range width, it is possible to achieve simple, quick, sensitive, specific detection.
Embodiment 1 one kinds is based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au
(1) glass-carbon electrode of diameter 4 mm is taken turns doing polishing with 1.0 μm, 0.3 μm, 0.05 μm aluminum oxide polishing powder successively
Process, clean with ultrapure water;
(2) 6 μ L, antibody A b of 2 mg/mL are dripped1Capture base material Fe2O3@Au/Ab1Solution is to electrode surface, and 4 ° of C dry in the air
Dry;
(3) drip 3 μ L, mass fraction is the bovine serum albumin solution of 1%, with the nonspecific activity position on enclosed-electrode surface
Point, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, and 4 ° of C dry;
(4) drip 6 μ L, certain density determinand antigen, under 4 ° of C, hatch 0.5 h, by the phosphate buffered solution of pH 7.4
Solution rinses electrode surface, and 4 ° of C dry;
(5) drip 6 μ L, concentration is the 2 anti-Ab of mg/mL bis-2Label Pd-graphene/Fe3O4-Ru(bpy)3 2+ /Ab2Molten
Liquid, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, after 4 ° of C dry, prepares a kind of based on dendroid
Fe2O3The Electrochemiluminescsensor sensor of@Au.
Embodiment 2 one kinds is based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au
(1) glass-carbon electrode of diameter 4 mm is taken turns doing polishing with 1.0 μm, 0.3 μm, 0.05 μm aluminum oxide polishing powder successively
Process, clean with ultrapure water;
(2) the antibody capture base material Fe of 6 μ L, 3 mg/mL is dripped2O3@Au/Ab1Solution and electrode surface, 4 ° of C dry;
(3) drip 3 μ L, mass fraction is the bovine serum albumin solution of 2%, with the nonspecific activity position on enclosed-electrode surface
Point, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, and 4 ° of C dry;
(4) drip 6 μ L, certain density determinand antigen, under 4 ° of C, hatch 1.5 h, by the phosphate buffered solution of pH 7.4
Solution rinses electrode surface, and 4 ° of C dry;
(5) drip 6 μ L, concentration is the 3 anti-Ab of mg/mL bis-2Label Pd-graphene/Fe3O4-Ru(bpy)3 2+ /Ab2Molten
Liquid, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, after 4 ° of C dry, prepares a kind of based on dendroid
Fe2O3The Electrochemiluminescsensor sensor of@Au.
Embodiment 3 one kinds is based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au
(1) glass-carbon electrode of diameter 4 mm is taken turns doing polishing with 1.0 μm, 0.3 μm, 0.05 μm aluminum oxide polishing powder successively
Process, clean with ultrapure water;
(2) 6 μ L, antibody A b of 4 mg/mL are dripped1Capture base material Fe2O3@Au/Ab1Solution and electrode surface, 4 ° of C dry in the air
Dry;
(3) drip 3 μ L, mass fraction is the bovine serum albumin solution of 3%, with the nonspecific activity position on enclosed-electrode surface
Point, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, and 4 ° of C dry;
(4) dripping 6 μ L, certain density determinand antigen, hatch 2 h under 4 ° of C, the phosphate buffered solution with pH 7.4 is molten
Liquid rinses electrode surface, and 4 ° of C dry;
(5) drip 6 μ L, concentration is the 4 anti-Ab of mg/mL bis-2Label Pd-graphene/Fe3O4-Ru(bpy)3 2+ /Ab2Molten
Liquid, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, after 4 ° of C dry, prepares a kind of based on dendroid
Fe2O3The Electrochemiluminescsensor sensor of@Au.
Embodiment 4 antibody capture base material Fe2O3@Au/Ab1The preparation of solution
(1) potassium ferricyanide solid of 0.05 g is dissolved in 10 mL ultra-pure waters, adjusts with the sodium hydroxide solution of 0.001 mol/L
Joint pH to 10.0, continues stirring 5 min, is put into by mixed solution in autoclave, react 8 h, existed by product under 80 ° of C
Centrifugation washing respectively three times with dehydrated alcohol and ultra-pure water under 6000 rpm, puts into vacuum drying oven, is dried under 30 ° of C
2 h, prepare bolarious dendroid Fe2O3;
(2) chlorauric acid solution that 40 mL, mass fraction are 0.001% is boiled, add 1 mL, mass fraction is the lemon of 0.1 %
Lemon acid three sodium water solutions, are heated to reflux 5 min, treat that solution colour becomes claret, solution is cooled to room temperature, prepare gold nano
Particle solution, keeps in Dark Place under 4 ° of C;
(3) by dendroid Fe of 0.5 mg2O3It is distributed in 1 mL ultra-pure water, adds 0.5 mL solution of gold nanoparticles, will be mixed
Close solution at room temperature to vibrate 12 h, centrifugation, remove the golden nanometer particle of excess, prepare Fe2O3@Au, by product Fe2O3@
Au is re-dispersed in 1 mL ultra-pure water, prepares base material Fe2O3@Au solution;
(4) it is 2 mg/mL Fe in 1 mL, concentration2O3In@Au solution, add 100 μ L, concentration is the determinand of 10 μ g/mL
Antibody A b1Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off determinand antibody A b of excess1, product is distributed to 1 mL,
In the phosphate buffered solution solution of pH 7.4, prepare antibody capture base material Fe2O3@Au/Ab1Solution, is stored under 4 ° of C
Standby.
Embodiment 5 antibody capture base material Fe2O3@Au/Ab1The preparation of solution
(1) potassium ferricyanide solid of 0.15 g is dissolved in 25 mL ultra-pure waters, regulates with the sodium hydroxide solution of 0.01 mol/L
PH to 11.0, continues stirring 8 min, is put into by mixed solution in autoclave, react 12 h, existed by product under 120 ° of C
Centrifugation washing respectively three times with dehydrated alcohol and ultra-pure water under 7000 rpm, puts into vacuum drying oven, is dried under 40 ° of C
3 h, prepare bolarious dendroid Fe2O3;
(2) chlorauric acid solution that 80 mL, mass fraction are 0.005% is boiled, add 1.5 mL, mass fraction is the lemon of 0.5%
Lemon acid three sodium water solutions, are heated to reflux 10 min, treat that solution colour becomes claret, solution is cooled to room temperature, prepare Jenner
Rice corpuscles solution, keeps in Dark Place under 4 ° of C;
(3) by dendroid Fe of 1 mg2O3It is distributed in 1 mL ultra-pure water, adds 1 mL solution of gold nanoparticles, will mix molten
Liquid at room temperature vibrates 18 h, centrifugation, removes the golden nanometer particle of excess, prepares Fe2O3@Au, by product Fe2O3@Au weight
Newly it is distributed in 1 mL ultra-pure water, prepares base material Fe2O3@Au solution;
(4) it is 3 mg/mL Fe in 2 mL, concentration2O3In@Au solution, add 200 μ L, concentration is the determinand of 10 μ g/mL
Antibody A b1Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off determinand antibody A b of excess1, product is distributed to 1 mL,
In the phosphate buffered solution solution of pH 7.4, prepare antibody capture base material Fe2O3@Au/Ab1Solution, is stored under 4 ° of C
Standby.
Embodiment 6 antibody capture base material Fe2O3@Au/Ab1The preparation of solution
(1) potassium ferricyanide solid of 0.19 g is dissolved in 40 mL ultra-pure waters, adjusts with the sodium hydroxide solution of 0.015 mol/L
Joint pH to 12.0, continues stirring 15 min, is put into by mixed solution in autoclave, react 24 h under 140 ° of C, will produce
Product centrifugation washing respectively three times with dehydrated alcohol and ultra-pure water under 8000 rpm, puts into vacuum drying oven, under 50 ° of C
It is dried 4 h, prepares bolarious dendroid Fe2O3;
(2) chlorauric acid solution that 100 mL, mass fraction are 0.010% is boiled, add 2 mL, mass fraction is the lemon of 1.0%
Lemon acid three sodium water solutions, are heated to reflux 15 min, treat that solution colour becomes claret, solution is cooled to room temperature, prepare Jenner
Rice corpuscles solution, keeps in Dark Place under 4 ° of C;
(3) by dendroid Fe of 2 mg2O3It is distributed in 1 mL ultra-pure water, adds 1.5 mL solution of gold nanoparticles, will mixing
Solution at room temperature vibrates 32 h, centrifugation, removes the golden nanometer particle of excess, prepares Fe2O3@Au, by product Fe2O3@Au
It is re-dispersed in 1 mL ultra-pure water, prepares base material Fe2O3@Au solution;
(4) it is 4 mg/mL Fe in 3 mL, concentration2O3In@Au solution, add 400 μ L, concentration is the determinand of 10 μ g/mL
Antibody A b1Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off determinand antibody A b of excess1, product is distributed to 1 mL,
In the phosphate buffered solution solution of pH 7.4, prepare antibody capture base material Fe2O3@Au/Ab1Solution, is stored under 4 ° of C
Standby.
Embodiment 7 two anti-label Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2The preparation of solution
(1) it is in the ultra-pure water that 12 mol/L hydrochloric acid solutions join 13 mL by 0.4 mL, concentration, adds with in backward solution
2.6 g ferric chloride solids and 1.6g ferrous chloride solid, under continuous stirring, be added dropwise to 125 by mixed solution
ML, concentration are in the sodium hydroxide solution of 1.5 mol/L, be centrifuged separating, use ultrapure washing under the rotating speed of 4000 rpm
Wash three times, backward precipitation in add 250 mL, concentration is the hydrochloric acid solution of 0.01 mol/L, under the rotating speed of 6000 rpm from
The heart separates 5 min, abandoning supernatant, adds ultra-pure water and carries out the ultrasonic Fe obtaining yellow3O4Nano sol;
(2) by 2.5 mL Fe3O4Nano sol joins 50 mL, concentration is in 1.5 mg/mL graphene oxide dispersible suspension,
Under agitation, add 0.22 g sodium sulfite solid, under 95 ° of C, react 3 h, dialyse one week with ultra-pure water after cooling, warp
Graphene/Fe is obtained after lyophilization3O4;
(3) 0.07 g tetrachloro-palladium acid sodium solid and 0.07 g sodium citrate solid are dissolved in 20 mL ultra-pure waters, add in solution
Entering 0.6 mL, concentration is 0.01 mol/L sodium borohydride solution, continuously stirred 30 s, prepares the Pd nano-particle solution of black;
(4) by graphene/Fe that 1 mL, concentration are 2 mg/mL3O4The Pd nano-particle solution mixing of solution and 1 mL, keeps away
Light generation 24 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, is 1 × 10 with 1 mL, concentration-3 mol/L Ru
(bpy)3 2+Solution mixing vibration 24h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, prepares Pd-graphene/
Fe3O4-Ru(bpy)3 2+Solution;
(5) it is 2 mg/mL Pd-graphene/Fe in 1 mL, concentration3O4-Ru(bpy)3 2+In solution, add 100 μ L, concentration
It it is determinand antibody A b of 10 μ g/mL2Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off determinand antibody A b of excess2,
Product is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares two anti-label Pd-graphene/Fe3O4-
Ru(bpy)3 2+/Ab2Solution, is stored under 4 ° of C standby.
Embodiment 8 two anti-label Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2The preparation of solution
(1) it is in the ultra-pure water that 12 mol/L hydrochloric acid solutions join 20 mL by 1.5 mL, concentration, adds with in backward solution
3.0 g ferric chloride solids and 4.0 g ferrous chloride solids, under continuous stirring, be added dropwise to 300 by mixed solution
ML, concentration are in the sodium hydroxide solution of 3.0 mol/L, be centrifuged separating, use ultrapure washing under the rotating speed of 6000 rpm
Wash three times, backward precipitation in add 400 mL, concentration is the hydrochloric acid solution of 0.03 mol/L, under the rotating speed of 7000 rpm from
The heart separates 10 min, abandoning supernatant, adds ultra-pure water and carries out the ultrasonic Fe obtaining yellow3O4Nano sol;
(2) by 2 mL Fe3O4Nano sol joins 100 mL, concentration is in 2.0 mg/mL graphene oxide dispersible suspension,
Under agitation, add 0.40 g sodium sulfite solid, under 120 ° of C, react 4 h, dialyse one week with ultra-pure water after cooling, warp
Graphene/Fe is obtained after lyophilization3O4;
(3) 0.15 g tetrachloro-palladium acid sodium solid and 0.15 g sodium citrate solid are dissolved in 80 mL ultra-pure waters, add in solution
Enter 3.0 mL, concentration is 0.015 mol/L sodium borohydride solution, continuously stirred 60 s, prepares the Pd nano-particle solution of black;
(4) by graphene/Fe that 2 mL, concentration are 2 mg/mL3O4The Pd nano-particle solution mixing of solution and 2 mL, keeps away
Light generation 32 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, is 1 × 10 with 2 mL, concentration-3 mol/L Ru
(bpy)3 2+Solution mixing vibration 32 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, prepares Pd-
graphene/Fe3O4-Ru(bpy)3 2+Solution;
(5) it is 3 mg/mL Pd-graphene/Fe in 2 mL, concentration3O4-Ru(bpy)3 2+In solution, add 200 μ L, concentration
It it is determinand antibody A b of 10 μ g/mL2Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off the determinand antibody of excess
Ab2, product is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares two anti-label Pd-graphene/
Fe3O4-Ru(bpy)3 2+/Ab2Solution, is stored under 4 ° of C standby.
Embodiment 9 two anti-label Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2The preparation of solution
(1) it is in the ultra-pure water that 12 mol/L hydrochloric acid solutions join 30 mL by 2 mL, concentration, adds with in backward solution
6.0 g ferric chloride solids and 6.0 g ferrous chloride solids, under continuous stirring, be added dropwise to 500 by mixed solution
ML, concentration are in the sodium hydroxide solution of 5.0 mol/L, be centrifuged separating, use ultrapure washing under the rotating speed of 8000 rpm
Wash three times, backward precipitation in add 600 mL, concentration is the hydrochloric acid solution of 0.04 mol/L, under the rotating speed of 9000 rpm from
The heart separates 15 min, abandoning supernatant, adds ultra-pure water and carries out the ultrasonic Fe obtaining yellow3O4Nano sol;
(2) by 5 mL Fe3O4Nano sol joins 200 mL, concentration is in 3.0 mg/mL graphene oxide dispersible suspension,
Under agitation, add 0.60 g sodium sulfite solid, under 160 ° of C, react 6 h, dialyse one week with ultra-pure water after cooling, warp
Graphene/Fe is obtained after lyophilization3O4;
(3) 0.20 g tetrachloro-palladium acid sodium solid and 0.20 g sodium citrate solid are dissolved in 100 mL ultra-pure waters, in solution
Adding 4.0 mL, concentration is 0.020 mol/L sodium borohydride solution, continuously stirred 90 s, and the Pd nanoparticle preparing black is molten
Liquid;
(4) by graphene/Fe that 3 mL, concentration are 2 mg/mL3O4The Pd nano-particle solution mixing of solution and 3 mL, keeps away
Light generation 48 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, is 1 × 10 with 3 mL, concentration-3 Mol/L's
Ru(bpy)3 2+Solution mixing vibration 48 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, prepares Pd-
graphene/Fe3O4-Ru(bpy)3 2+Solution;
(5) it is 4 mg/mL Pd-graphene/Fe in 3 mL, concentration3O4-Ru(bpy)3 2+In solution, add 400 μ L, concentration
It it is determinand antibody A b of 10 μ g/mL2Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off the determinand antibody of excess
Ab2, product is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares two anti-label Pd-graphene/
Fe3O4-Ru(bpy)3 2+/Ab2Solution, is stored under 4 ° of C standby.
The detection of embodiment 10 AFP
(1) using the three-electrode system of electrochemical workstation to test, Ag/AgCl electrode is as reference electrode, platinum electrode
For to electrode, prepared electrochemical luminous sensor is working electrode, electrochemical workstation and chemiluminescence detector is connected
Being connected together and the high pressure of photomultiplier tube is set to 800 V, cyclic voltammetry scan potential range is 0 ~ 1.2 V, scanning speed
Rate is 0.1 V/s;
(2) at 10 mL, pH 6.4 ~ 8.4 containing the phosphate buffered solution solution that concentration is 35 ~ 65 mmol/L triethylamines
In, by electrochemical luminescence system, detect the electrochemical luminescence signals that the squamous cell carcinoma antigen SCCA to variable concentrations produces
Intensity, drawing curve, recording the range of linearity is 0.001 pg/mL ~ 1 ng/mL, and detection is limited to 0.29 fg/mL;
(3) AFP is replaced to detect testing sample solution.
The detection of embodiment 11 squamous cell carcinoma antigen SCCA
(1) using the three-electrode system of electrochemical workstation to test, Ag/AgCl electrode is as reference electrode, platinum electrode
For to electrode, prepared electrochemical luminous sensor is working electrode, electrochemical workstation and chemiluminescence detector is connected
Being connected together and the high pressure of photomultiplier tube is set to 800 V, cyclic voltammetry scan potential range is 0 ~ 1.2 V, scanning speed
Rate is 0.1 V/s;
(2) at 10 mL, pH 6.4 ~ 8.4 containing the phosphate buffered solution solution that concentration is 35 ~ 65 mmol/L triethylamines
In, by electrochemical luminescence system, detect the electrochemical luminescence signals that the squamous cell carcinoma antigen SCCA to variable concentrations produces
Intensity, drawing curve, recording the range of linearity is 0.001 pg/mL ~ 1 ng/mL, and detection is limited to 0.29 fg/mL;
(3) testing sample solution replace squamous cell carcinoma antigen SCCA detect.
The detection of embodiment 12 CEA
(1) using the three-electrode system of electrochemical workstation to test, Ag/AgCl electrode is as reference electrode, platinum electrode
For to electrode, prepared electrochemical luminous sensor is working electrode, electrochemical workstation and chemiluminescence detector is connected
Being connected together and the high pressure of photomultiplier tube is set to 800 V, cyclic voltammetry scan potential range is 0 ~ 1.2 V, scanning speed
Rate is 0.1 V/s;
(2) at 10 mL, pH 6.4 ~ 8.4 containing the phosphate buffered solution solution that concentration is 35 ~ 65 mmol/L triethylamines
In, by electrochemical luminescence system, detect the electrochemical luminescence signals intensity that the CEA to variable concentrations produces, paint
Working curve processed, recording the range of linearity is 0.001 pg/mL ~ 1 ng/mL, and detection is limited to 0.29 fg/mL;
(3) CEA is replaced to detect testing sample solution.
Claims (5)
1. one kind based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au, it is characterised in that include following
Step:
(1) glass-carbon electrode of diameter 4 mm is taken turns doing polishing with 1.0 μm, 0.3 μm, 0.05 μm aluminum oxide polishing powder successively
Process, clean with ultrapure water;
(2) drop coating 6 μ L, concentration are antibody A b of 2 ~ 4 mg/mL1Capture base material Fe2O3@Au/Ab1Solution is to electrode table
Face, 4 ° of C dry;
(3) drip 3 μ L, mass fraction is the bovine serum albumin solution of 1 ~ 3%, with the non-specific work on enclosed-electrode surface
Property site, rinse electrode surface with the phosphate buffered solution solution of pH 7.4,4 ° of C dry;
(4) drip 6 μ L, certain density determinand antigen, hatch 0.5 ~ 2 h under 4 ° of C, by the phosphate-buffered of pH 7.4
Solutions Solution rinses electrode surface, and 4 ° of C dry;
(5) drop coating 6 μ L, concentration are the two anti-Ab of 2 ~ 4 mg/mL2Label Pd-graphene/Fe3O4 -Ru(bpy)3 2+/
Ab2Solution, rinses electrode surface with the phosphate buffered solution solution of pH 7.4, after 4 ° of C dry, prepares a kind of based on branch
Shape Fe2O3The Electrochemiluminescsensor sensor of@Au.
2. as claimed in claim 1 a kind of based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au, its
It is characterised by, described antibody capture base material Fe2O3@Au/Ab1Solution preparation step is as follows:
(1) potassium ferricyanide solid of 0.05 ~ 0.20 g is dissolved in 5 ~ 50 mL ultra-pure waters, with 0.001 ~ 0.020
The sodium hydroxide solution regulation pH to 10.0 ~ 12.0 of mol/L, continues stirring 1 ~ 15 min, mixed solution is put into high pressure
In reactor, under 60 ~ 150 ° of C, react 6 ~ 24 h, by product centrifugation use nothing under 6000 ~ 8000 rpm
Water-ethanol and ultra-pure water wash three times respectively, put into vacuum drying oven, be dried 2 ~ 5 h, prepare brick-red under 30 ~ 60 ° of C
Dendroid Fe2O3;
(2) chlorauric acid solution that 40 ~ 100 mL, mass fraction are 0.001 ~ 0.010% is boiled, add 1 ~ 3 mL, matter
Amount mark is the trisodium citrate aqueous solution of 0.1 ~ 1.0%, is heated to reflux 5 ~ 20 min, treats that solution colour becomes claret,
Solution is cooled to room temperature, prepares solution of gold nanoparticles, keep in Dark Place under 4 ° of C;
(3) by dendroid Fe of 0.5 ~ 3 mg2O3It is distributed in 1 mL ultra-pure water, adds 0.5 ~ 1.5 mL golden nanometer particle
Solution, at room temperature vibrate 12 ~ 32 h by mixed solution, centrifugation, removes the golden nanometer particle of excess, prepares Fe2O3@
Au, by product Fe2O3@Au is re-dispersed in 1 mL ultra-pure water, prepares base material Fe2O3@Au solution;
(4) it is 2 ~ 4 mg/mL Fe in 1 ~ 3 mL, concentration2O3In@Au solution, add 100 ~ 400 μ L, concentration is 10 μ
Determinand antibody A b of g/mL1Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off determinand antibody A b of excess1, will produce
Thing is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares antibody capture base material Fe2O3@Au/Ab1Molten
Liquid, is stored under 4 ° of C standby.
3. as claimed in claim 1 a kind of based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au, its
It is characterised by, described two anti-label Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2Solution preparation step is as follows:
(1) it is in the ultra-pure water that 12 mol/L hydrochloric acid solutions join 5 ~ 30 mL by 0.1 ~ 2 mL, concentration, with backward molten
Liquid adds 0.5 ~ 6.0 g ferric chloride solid and 0.5 ~ 6.0 g ferrous chloride solid, under continuous stirring, will mix
Solution is added dropwise to 100 ~ 500 mL, concentration be 0.5 ~ 5.0 mol/L sodium hydroxide solution in, 4000 ~
Be centrifuged under the rotating speed of 8000 rpm separating, with milli-Q water three times, backward precipitation in add 200 ~ 600 mL, dense
Degree is the hydrochloric acid solution of 0.01 ~ 0.04 mol/L, and under the rotating speed of 6000 ~ 9000 rpm, centrifugation 5 ~ 15min, abandons
Remove supernatant, add ultra-pure water and carry out the ultrasonic Fe obtaining yellow3O4Nano sol;
(2) by 1 ~ 5 mL Fe3O4Nano sol joins 40 ~ 200 mL, concentration is 1.0 ~ 3.0 mg/mL graphite oxides
In alkene dispersible suspension, under agitation, add 0.10 ~ 0.60 g sodium sulfite solid, under 80 ~ 160 ° of C react 2 ~
6 h, dialyse one week with ultra-pure water after cooling, freeze-dried rear available graphene/Fe3O4;
(3) 0.06 ~ 0.20 g tetrachloro-palladium acid sodium solid and 0.06 ~ 0.20 g sodium citrate solid are dissolved in 10 ~ 100
In mL ultra-pure water, add 0.1 ~ 4.0 mL in solution, concentration is 0.005 ~ 0.020 mol/L sodium borohydride solution, holds
Continuous stirring 30 ~ 90 s, prepares the Pd nano-particle solution of black;
(4) by graphene/Fe that 1 ~ 3 mL, concentration are 2 mg/mL3O4The Pd nano-particle solution of solution and 1 ~ 3 mL
Mixing, lucifuge vibration 24 ~ 48 h, centrifugation abandoning supernatant, it is distributed in 1 mL ultra-pure water, with 1 ~ 3 mL, concentration
It is 1 × 10-3 The Ru (bpy) of mol/L3 2+Solution mixing vibration 24 ~ 48 h, centrifugation abandoning supernatant, it is distributed to 1 mL
In ultra-pure water, prepare Pd-graphene/Fe3O4-Ru(bpy)3 2+Solution;
(5) it is 2 ~ 4 mg/mL Pd-graphene/Fe in 1 ~ 3 mL, concentration3O4-Ru(bpy)3 2+In solution, add 100
~ 400 μ L, concentration are determinand antibody A b of 10 μ g/mL2Solution, under 4 ° of C, vibration hatching 24 h, are centrifuged off excess
Determinand antibody A b2, product is distributed in the phosphate buffered solution solution of 1 mL, pH 7.4, prepares two anti-labels
Pd-graphene/Fe3O4-Ru(bpy)3 2+/Ab2Solution, is stored under 4 ° of C standby.
4. the one that as claimed in claim 1 prepared by preparation method is based on dendroid Fe2O3The Electrochemiluminescsensor sensor of@Au
Detection for testing sample, it is characterised in that the Electrochemiluminescsensor sensor of described preparation is for the electrification of testing sample
Detecting step is as follows:
(1) using the three-electrode system of electrochemical workstation to test, Ag/AgCl electrode is as reference electrode, platinum electrode
For to electrode, prepared electrochemical luminous sensor is working electrode, electrochemical workstation and chemiluminescence detector is connected
Being connected together, the high pressure of photomultiplier tube is set to 800 V, cyclic voltammetry scan potential range is 0 ~ 1.2 V, scanning speed
Rate is 0.1 V/s;
(2) at 10 mL, pH 6.4 ~ 8.4 containing the phosphate buffered solution solution that concentration is 35 ~ 65 mmol/L triethylamines
In, by electrochemical luminescence system, detect the electrochemical luminescence signals intensity that the determinand antigen to variable concentrations produces, draw
Working curve;
(3) testing sample solution replace determinand antigen detect.
5. as claimed in claim 1 a kind of based on dendroid Fe2O3The preparation method of the Electrochemiluminescsensor sensor of@Au, its
Being characterised by, described determinand antigen is one of selected from following liver cancer marker: AFP, squamous cell carcinoma antigen SCCA,
CEA, carbohydrate antigen CA15-3.
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