CN104133069A - Preparation method for double-functional mark photo-electrochemical sensor and application - Google Patents
Preparation method for double-functional mark photo-electrochemical sensor and application Download PDFInfo
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- CN104133069A CN104133069A CN201410411550.2A CN201410411550A CN104133069A CN 104133069 A CN104133069 A CN 104133069A CN 201410411550 A CN201410411550 A CN 201410411550A CN 104133069 A CN104133069 A CN 104133069A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/574—Immunoassay; Biospecific binding assay; Materials therefor for cancer
- G01N33/57484—Immunoassay; Biospecific binding assay; Materials therefor for cancer involving compounds serving as markers for tumor, cancer, neoplasia, e.g. cellular determinants, receptors, heat shock/stress proteins, A-protein, oligosaccharides, metabolites
- G01N33/57488—Immunoassay; Biospecific binding assay; Materials therefor for cancer involving compounds serving as markers for tumor, cancer, neoplasia, e.g. cellular determinants, receptors, heat shock/stress proteins, A-protein, oligosaccharides, metabolites involving compounds identifable in body fluids
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/54366—Apparatus specially adapted for solid-phase testing
Abstract
The invention provides a preparation method for a double-functional mark photo-electrochemical sensor and application and belongs to the technical fields of nano-functional materials, clinical analysis, bio-sensing and electrochemistry. A TiO2-CdSe semiconductor compound is prepared based on a ligand principle between TiO2 and carboxyl; a remarkably-enhanced photoelectric conversion effect of the prepared TiO2-CdSe semiconductor compound is displayed on a visible region; a photocurrent value is 10 times as much as that of a single TiO2 photocurrent value; the TiO2-CdSe semiconductor compound has large specific surface area and good biocompatibility and is used for marking a second antibody (Ab2) of CA125 so that a TiO2-CdSe-Ab2 hatched matter is prepared. The difference between the double-functional mark photo-electrochemical sensor and other electrochemical or photo-induced electrochemical sensors is as follows: the TiO2-CdSe semiconductor compound can be used for not only carrying out photoelectric conversion and but also generating Cd2<+>, so that an immunosensor taking the TiO2-CdSe semiconductor compound as a second antibody marker can adopt an electrochemical analysis technology and a photo-induced electrochemical analysis technology to rapidly, sensitively and accurately detect the CA125. The method has certain guiding significance and application value on early diagnosis of cancers.
Description
Technical field
The invention belongs to functionalized nano material, immunoassay and biosensor technique field, be specifically related to based on a kind of difunctional TiO
2preparation and the application of the sandwich type immunosensor that/CdSe semiconductor label builds.
Background technology
Semiconductor material because of its can be with and valence band between there is energy level difference, make it under the exciting of light homenergic, can produce the transition of electronics, thereby present the semiconductive state between conductor and insulator.
TiO
2it is a kind of semiconductor material through aspect application such as the photocatalysis of being everlasting, solar cell and fuel cells.TiO
2the feature with the synthetic and environmentally safe of easy batch.Than block TiO
2, the TiO of nano shape
2have that specific surface area is large, bioaffinity good and be convenient to the advantages such as functionalization.But not enough, TiO
2bandwidth wider (3.2 eV), thus it can only effectively be excited at ultraviolet region, extremely low in the photoelectric transformation efficiency of visible region.For the light transfer characteristic that can show in visible-range, to TiO
2sensitization is the Hot Contents of researcher research always.
CdSe quantum dots (CdSe QDs) is a kind of narrow semiconductor nano material that can be with, and its bandwidth is about 1.7 eV, almost approaches TiO
250% size of bandwidth.Narrow energy gap makes CdSe QDs within the scope of visible region, just can show good photocatalysis and opto-electronic conversion character.In addition, according to correlative study, show, when wide can be with semiconductor and narrow can be with semiconductor mutually compound after, resulting compound can show and be better than the two photoelectric conversion result itself.Therefore say, CdSe is except itself being exactly a kind of good opto-electronic conversion original paper, and it also can be used as TiO
2sensitizer in order to improve TiO
2photoelectric transformation efficiency in visible region.
Photic electrochemical immunosensor is a kind ofly to using luminous energy as excitation energy, and electric signal is as the sensor of detection signal.In sensors with auxiliary electrode were, photo-electric conversion element-semiconductor material is being played the part of irreplaceable effect.Different just because of detection signal and excitation energy mode, make photic electrochemical sensor have high sensitivity.Immuno analytical method is combined with photoelectric detecting technology, can greatly improves the sensitivity that measured object detects, and can reduce detectability.The impact of photosignal semiconductor being produced by measured matter, realizes the quantitative detection to measured matter.Semiconductor nano material has high specific surface area and good bioaffinity, therefore can the more antigen of load, the biomolecule such as antibody, thus further improve the sensitivity detecting.
Different from photic galvanochemistry, electrochemical analysis is a kind of electric signal by different way as the analysis and detection technology exciting with detection signal.Electrochemical sensor is a kind of produced a kind of senser element that electrochemical analysis is combined with sensing technology.It detects principle is based on measured matter, to affect the electrochemical signals of electrode system, thereby realizes the quantitative and qualitative analysis to measured matter.Electrochemical sensor is also in recent years emerging sensitive analysis detection technique, and in fields such as life science, bio-science and Surface Sciences, has obtained research widely and application.Nano material is often used in the building process of electrochemical sensor because of its good physics, chemical property.
Tumor markers refers to that tumour cell produces a kind of material of secretion in growth course, and existing of its content and tumour cell is closely related.By detecting tumor markers, can realize the monitoring to tumour clinically, realize the early diagnosis of tumor disease and prevention etc., clinical detection is had to important directive significance.CA125 is a kind of Specific marker of oophoroma.In oophoroma patients serum, CA125 level can be apparently higher than normal value, and chemotherapy and operation responder CA125 level decline very soon, if while having recurrence, CA125 raises can be prior to before clinical symptoms.Therefore realize the rapid and accurate determination of CA125, find in time and understand the state of an illness that clinical detection is had to important directive significance.
The present invention is based on TiO
2and the coordination between carboxyl, has prepared TiO by simple concussion method
2-CdSe semiconductor compound.Prepared TiO
2-CdSe semiconductor compound has shown that in visible region 10 times to TiO
2photocurrent intensity.First by prepared TiO
2-CdSe semiconductor compound, as the two anti-labels of tumor markers CA125, has successfully built the sandwich type immunosensor for Sensitive Detection CA125.
With TiO
2-CdSe is two anti-labels, this sandwich type immunosensor can be used up and send a telegraph the quantitative detection of two kinds of analysis and detection technologies realizations of chemistry and galvanochemistry to CA125.Testing result shows, no matter is electrochemical method or photic electrochemical method, and this sensor all has high sensitivity, low detection limit and the wide range of linearity to the detection of CA125.With prepared TiO
2-CdSe semiconductor compound is the constructed sandwich type immunosensor of the anti-label of CA125 bis-, can expand to other tumor markerses such as the analyzing and testing of CA153, CA199.
Summary of the invention
One of object of the present invention is to provide the TiO that preparation has high-photoelectric transformation efficiency
2the short-cut method of-CdSe heterojunction composite semiconductor.
Two of object of the present invention is by prepared TiO
2-CdSe semiconductor compound is used for building sandwich type immunosensor as the anti-label of CA125 bis-.
Three of object of the present invention is to use galvanochemistry and two kinds of methods of photic galvanochemistry to realize the rapid sensitive of CA125 is detected.
Technical scheme of the present invention, comprises the following steps.
1. the preparation method of a difunctional mark Optical Electro-Chemistry sensor
(1) pre-service of ITO electrode: ito glass is cut to 3 cm * 0.5 cm sizes, use successively liquid detergent, acetone, ethanol and ultrapure water ultrasonic cleaning 30 min, finally with nitrogen, dry up glass, the area that reserves 0.5 cm * 0.5 cm size in one end of ITO electrode with insulating tape is in order to modified biological molecule;
(2) by the ITO electrode after processing in being immersed in the methanol solution that volume fraction is 1% ~ 3% 3-aminopropyl triethoxysilane APTES, lucifuge is soaked 10 ~ 14 h, water rinses electrode, to remove unconjugated APTES molecule;
(3) the 10 μ L gold nano colloidal sols of getting fresh preparation are added drop-wise to electrode surface, in conjunction with CA125 primary antibodie molecule;
(4) 6 μ L, 8 ~ 12 μ g/mL CA125 primary antibodie solution are added drop-wise on electrode, are placed in 4 ℃ of constant temperature refrigerators and hatch 2 h, rinse electrode surface to remove unconjugated primary antibodie molecule;
(5) drip and be coated with BSA solution that 2 μ L, massfraction are 0.5% ~ 1.5% on electrode, be placed in 4 ℃ of Refrigerator stores, dry;
(6) with ultrapure water, clean, dry in the air to moisture state, the CA125 antigenic solution of 6 μ L, 0.05 pg/mL ~ 100 ng/mL variable concentrations is dripped and is applied to electrode surface, make to occur between itself and CA125 primary antibodie specific immune response and continue hatching 2 h, with ultrapure water, rinse to remove unconjugated CA125, dry;
(7) get 6 μ LTiO
2-CdSe-Ab
2two anti-hatching thing solution drip and are applied to electrode surface, and hatching 2 h post-flush electrode surfaces, dry, and make difunctional mark Optical Electro-Chemistry sensor.
2. TiO
2-CdSe-Ab
2the preparation method of two anti-hatching thing solution
(1) TiO
2the preparation of nano particle
Getting 6 ~ 8 mL butyl titanates is dissolved in 30 mL ethanol, stir, get 10 mL ultrapure waters and under agitation slowly add in solution, room temperature magnetic agitation is reacted 120 min, and this mixed liquor is transferred in autoclave, 200 ℃ of hydro-thermal reaction 10 ~ 12 h, make white solid, centrifuging, and clean respectively 5 times with intermediate water and ethanol, vacuum drying 10 ~ 14 h at 80 ℃, grind and make TiO
2nano particle.
(2) preparation of carboxyl-functional CdSe quantum dot
By 1.0 ~ 1.3 g CdCl
22.5H
2o is dissolved in 40 mL water, adds the mixed liquor of mercaptoacetic acid, with the NaOH of 1 mol/L, regulates pH to 9 ~ 11, adds the NaSeSO of 12 mL, 0.2 mol/L under stirring
3solution, is heated to boiling by reactant oil bath, and 4 h that reflux, finally obtain carboxylated CdSe quantum dot solution;
The mixed liquor of described mercaptoacetic acid is to be made by 50 ~ 60 mL high purity waters and 0.84 mL mercaptoacetic acid blend; The NaSeSO of described 0.2 mol/L
3solution, gets 10 mmol Se and 12 mmol Na
2sO
3add in 50 mL water, reaction 3 h, filtration makes.
(3) TiO
2-CdSe-Ab
2the preparation of two anti-hatching thing solution
Take 3 ~ 5 mg TiO
2be scattered in the carboxylated CdSe quantum dot solution of 4 mL, ultrasonic and stirring reaction 10 ~ 14 h, after question response completes, use ultrapure water centrifuge washing 3 times, make TiO
2-CdSe semiconductor compound; By TiO
2-CdSe semiconductor compound is scattered in 1 mL water, with the carboxyl on 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides EDC/N-N-Hydroxysuccinimide NHS crosslinking chemical activated camplex surface, by the anti-Ab of CA125 bis-of 1 mL, 8 ~ 12 μ g/mL
2add and mix, and shake 12 h in 4 ℃ of isothermal vibration devices, with ultrapure water centrifuge washing, remove unconjugated Ab
2molecule, makes TiO
2-CdSe-Ab
2two anti-hatching thing solution.
3. galvanochemistry and photic electrochemical method realize the quantitative detection to human body CA125
(1) salpeter solution that difunctional mark Optical Electro-Chemistry sensor is placed in 0.3 ~ 0.5 mL, 0.1 mol/L soaks 4 h, makes CdSe quantum dot be decomposed into Cd
2+, joined 3.6 mL, 30 ~ 50 mg/mL Hg
2+pH 4.6 NaAc_HAc buffer solutions in, use three-electrode system, carry out Electrochemical Detection;
Described three electrode saturated calomel electrodes are contrast electrode, and platinum electrode is auxiliary electrode, and glass-carbon electrode is working electrode;
(2) scanning voltage scope is from-0.9 ~-0.6 V, and the electromotive force rank that jump are 4 mV, frequency 25 Hz, amplitude 25 mV;
(3) Cd
2+there is redox reaction and produce signal near-0.7 V, according to the linear relationship between gained strength of current and analyte, drawing curve;
(4) Photoelectric Detection adopts i-t means of testing, and bias voltage is set to 0 V; Every 20 s, carry out switch lamp, record the changing value of switch lamp front and back electric current, according to the antigen of variable concentrations, produce the photoelectricity flow valuves of different sizes, drawing curve;
(5) testing sample solution is replaced to the standard solution of CA125, according to the method for drafting of the working curve of described CA125, detect.
useful achievement of the present invention
(1) based on coordination principle, prepare photoelectricity successful higher than TiO
2tiO
2-CdSe semiconductor composite nano material.Prepared TiO
2-CdSe semiconductor compound has shown that in visible region 10 times to TiO
2photocurrent intensity, thereby significantly improved the sensitivity that sensing system detects, system detectability is reduced.
(2) prepare TiO
2the CA125 bis-of-CdSe compound mark is anti-, builds sandwich type immunosensor and realizes sensitive, the accurately detection to CA125.
(3) different from other galvanochemistry or photic electrochemical sensor, due to TiO
2-CdSe semiconductor compound can carry out opto-electronic conversion, can produce Cd again
2+.Therefore, TiO
2-CdSe semiconductor compound as the immunosensor of two anti-labels can adopt galvanochemistry and two kinds of analytical technologies of photic galvanochemistry realize to CA125 quick, sensitive, accurately detect and the accuracy of the result mutually.
(4) adopting electrochemical method is 0.1 pg/mL ~ 20 ng/mL to the sensing range of CA125, detects and is limited to 0.02 pg/mL; Adopting photic electrochemical method is 0.05 pg/mL ~ 100 ng/mL to the sensing range of CA125, detects and is limited to 0.01 pg/mL.
Embodiment
embodiment 1the preparation method of difunctional mark Optical Electro-Chemistry sensor
(1) pre-service of ITO electrode: ito glass is cut to 3 cm * 0.5 cm sizes, use successively liquid detergent, acetone, ethanol and ultrapure water ultrasonic cleaning 30 min, finally with nitrogen, dry up glass, the area that reserves 0.5 cm * 0.5 cm size in one end of ITO electrode with insulating tape is in order to modified biological molecule;
(2) by the ITO electrode after processing in being immersed in the methanol solution that volume fraction is 1% 3-aminopropyl triethoxysilane APTES, lucifuge is soaked 10h, water rinses electrode, to remove unconjugated APTES molecule;
(3) the 10 μ L gold nano colloidal sols of getting fresh preparation are added drop-wise to electrode surface, in conjunction with CA125 primary antibodie molecule;
(4) 6 μ L, 8 μ g/mL CA125 primary antibodie solution are added drop-wise on electrode, are placed in 4 ℃ of constant temperature refrigerators and hatch 2 h, rinse electrode surface to remove unconjugated primary antibodie molecule;
(5) drip and be coated with BSA solution that 2 μ L, massfraction are 0.5% on electrode, be placed in 4 ℃ of Refrigerator stores, dry;
(6) with ultrapure water, clean, dry in the air to moisture state, the CA125 antigenic solution of 6 μ L, 0.05 pg/mL ~ 100 ng/mL variable concentrations is dripped and is applied to electrode surface, make to occur between itself and CA125 primary antibodie specific immune response and continue hatching 2 h, with ultrapure water, rinse to remove unconjugated CA125, dry;
(7) get 6 μ LTiO
2-CdSe-Ab
2two anti-hatching thing solution drip and are applied to electrode surface, and hatching 2 h post-flush electrode surfaces, dry, and make difunctional mark Optical Electro-Chemistry sensor.
embodiment 2the preparation method of difunctional mark Optical Electro-Chemistry sensor
(1) pre-service of ITO electrode: ito glass is cut to 3 cm * 0.5 cm sizes, use successively liquid detergent, acetone, ethanol and ultrapure water ultrasonic cleaning 30 min, finally with nitrogen, dry up glass, the area that reserves 0.5 cm * 0.5 cm size in one end of ITO electrode with insulating tape is in order to modified biological molecule;
(2) by the ITO electrode after processing in being immersed in the methanol solution that volume fraction is 2% 3-aminopropyl triethoxysilane APTES, lucifuge is soaked 12 h, water rinses electrode, to remove unconjugated APTES molecule;
(3) the 10 μ L gold nano colloidal sols of getting fresh preparation are added drop-wise to electrode surface, in conjunction with CA125 primary antibodie molecule;
(4) 6 μ L, 10 μ g/mL CA125 primary antibodie solution are added drop-wise on electrode, are placed in 4 ℃ of constant temperature refrigerators and hatch 2 h, rinse electrode surface to remove unconjugated primary antibodie molecule;
(5) drip and be coated with BSA solution that 2 μ L, massfraction are 1.0% on electrode, be placed in 4 ℃ of Refrigerator stores, dry;
(6) with ultrapure water, clean, dry in the air to moisture state, the CA125 antigenic solution of 6 μ L, 0.05 pg/mL ~ 100 ng/mL variable concentrations is dripped and is applied to electrode surface, make to occur between itself and CA125 primary antibodie specific immune response and continue hatching 2 h, with ultrapure water, rinse to remove unconjugated CA125, dry;
(7) get 6 μ LTiO
2-CdSe-Ab
2two anti-hatching thing solution drip and are applied to electrode surface, and hatching 2 h post-flush electrode surfaces, dry, and make difunctional mark Optical Electro-Chemistry sensor.
embodiment 3the preparation method of difunctional mark Optical Electro-Chemistry sensor
(1) pre-service of ITO electrode: ito glass is cut to 3 cm * 0.5 cm sizes, use successively liquid detergent, acetone, ethanol and ultrapure water ultrasonic cleaning 30 min, finally with nitrogen, dry up glass, the area that reserves 0.5 cm * 0.5 cm size in one end of ITO electrode with insulating tape is in order to modified biological molecule;
(2) by the ITO electrode after processing in being immersed in the methanol solution that volume fraction is 3% 3-aminopropyl triethoxysilane APTES, lucifuge is soaked 14 h, water rinses electrode, to remove unconjugated APTES molecule;
(3) the 10 μ L gold nano colloidal sols of getting fresh preparation are added drop-wise to electrode surface, in conjunction with CA125 primary antibodie molecule;
(4) 6 μ L, 12 μ g/mL CA125 primary antibodie solution are added drop-wise on electrode, are placed in 4 ℃ of constant temperature refrigerators and hatch 2 h, rinse electrode surface to remove unconjugated primary antibodie molecule;
(5) drip and be coated with BSA solution that 2 μ L, massfraction are 1.5% on electrode, be placed in 4 ℃ of Refrigerator stores, dry;
(6) with ultrapure water, clean, dry in the air to moisture state, the CA125 antigenic solution of 6 μ L, 0.05 pg/mL ~ 100 ng/mL variable concentrations is dripped and is applied to electrode surface, make to occur between itself and CA125 primary antibodie specific immune response and continue hatching 2 h, with ultrapure water, rinse to remove unconjugated CA125, dry;
(7) get 6 μ LTiO
2-CdSe-Ab
2two anti-hatching thing solution drip and are applied to electrode surface, and hatching 2 h post-flush electrode surfaces, dry, and make difunctional mark Optical Electro-Chemistry sensor.
embodiment 4tiO
2the preparation of nano particle
Getting 6 mL butyl titanates is dissolved in 30 mL ethanol, stir, get 10 mL ultrapure waters and under agitation slowly add in solution, room temperature magnetic agitation is reacted 120 min, and this mixed liquor is transferred in autoclave, 200 ℃ of hydro-thermal reaction 10 h, make white solid, centrifuging, and clean respectively 5 times with intermediate water and ethanol, vacuum drying 10 h at 80 ℃, grind and make TiO
2nano particle.
embodiment 5tiO
2the preparation of nano particle
Getting 7 mL butyl titanates is dissolved in 30 mL ethanol, stir, get 10 mL ultrapure waters and under agitation slowly add in solution, room temperature magnetic agitation is reacted 120 min, and this mixed liquor is transferred in autoclave, 200 ℃ of hydro-thermal reaction 11 h, make white solid, centrifuging, and clean respectively 5 times with intermediate water and ethanol, vacuum drying 12 h at 80 ℃, grind and make TiO
2nano particle.
embodiment 6tiO
2the preparation of nano particle
Getting 8 mL butyl titanates is dissolved in 30 mL ethanol, stir, get 10 mL ultrapure waters and under agitation slowly add in solution, room temperature magnetic agitation is reacted 120 min, and this mixed liquor is transferred in autoclave, 200 ℃ of hydro-thermal reaction 12 h, make white solid, centrifuging, and clean respectively 5 times with intermediate water and ethanol, vacuum drying 14 h at 80 ℃, grind and make TiO
2nano particle.
embodiment 7the preparation of carboxyl-functional CdSe quantum dot
By 1.0 gCdCl
22.5H
2o is dissolved in 40mL water, adds the mixed liquor of mercaptoacetic acid, with the NaOH of 1mol/L, regulates pH to 9, adds the NaSeSO of 12mL, 0.2mol/L under stirring
3solution, is heated to boiling by reactant oil bath, and backflow 4h, finally obtains carboxylated CdSe quantum dot solution;
The mixed liquor of described mercaptoacetic acid is to be made by 50 mL high purity waters and the blend of 0.84mL mercaptoacetic acid; The NaSeSO of described 0.2mol/L
3solution, gets 10mmolSe and 12mmolNa
2sO
3add in 50mL water, reaction 3h, filtration makes.
embodiment 8the preparation of carboxyl-functional CdSe quantum dot
By 1.2 gCdCl
22.5H
2o is dissolved in 40mL water, adds the mixed liquor of mercaptoacetic acid, with the NaOH of 1mol/L, regulates pH to 10, adds the NaSeSO of 12mL, 0.2mol/L under stirring
3solution, is heated to boiling by reactant oil bath, and backflow 4h, finally obtains carboxylated CdSe quantum dot solution;
The mixed liquor of described mercaptoacetic acid is to be made by 55 mL high purity waters and the blend of 0.84mL mercaptoacetic acid; The NaSeSO of described 0.2mol/L
3solution, gets 10mmolSe and 12mmolNa
2sO
3add in 50mL water, reaction 3h, filtration makes.
embodiment 9the preparation of carboxyl-functional CdSe quantum dot
By 1.3 gCdCl
22.5H
2o is dissolved in 40mL water, adds the mixed liquor of mercaptoacetic acid, with the NaOH of 1mol/L, regulates pH to 11, adds the NaSeSO of 12mL, 0.2mol/L under stirring
3solution, is heated to boiling by reactant oil bath, and backflow 4h, finally obtains carboxylated CdSe quantum dot solution;
The mixed liquor of described mercaptoacetic acid is to be made by 60 mL high purity waters and the blend of 0.84mL mercaptoacetic acid; The NaSeSO of described 0.2mol/L
3solution, gets 10mmolSe and 12mmolNa
2sO
3add in 50mL water, reaction 3h, filtration makes.
embodiment 10tiO
2-CdSe-Ab
2the preparation of two anti-hatching things
Take 3 mg TiO
2be scattered in the carboxylated CdSe quantum dot solution of 4 mL, ultrasonic and stirring reaction 10 ~ 14 h, after question response completes, use ultrapure water centrifuge washing 3 times, make TiO
2-CdSe semiconductor compound; By TiO
2-CdSe semiconductor compound is scattered in 1 mL water, with the carboxyl on 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides EDC/N-N-Hydroxysuccinimide NHS crosslinking chemical activated camplex surface, by the anti-Ab of CA125 bis-of 1 mL, 8 μ g/mL
2add and mix, and shake 12 h in 4 ℃ of isothermal vibration devices, with ultrapure water centrifuge washing, remove unconjugated Ab
2molecule;
Described TiO
2, be the TiO of embodiment 4, embodiment 5 or embodiment 6 preparations
2nano particle.
Described carboxylated CdSe quantum dot solution is the carboxylated CdSe quantum dot solution of embodiment 7, embodiment 8 or embodiment 9 preparations.
embodiment 11tiO
2-CdSe-Ab
2the preparation of two anti-hatching things
Take 4 mg TiO
2be scattered in the carboxylated CdSe quantum dot solution of 4 mL, ultrasonic and stirring reaction 10 ~ 14 h, after question response completes, use ultrapure water centrifuge washing 3 times, make TiO
2-CdSe semiconductor compound; By TiO
2-CdSe semiconductor compound is scattered in 1 mL water, with the carboxyl on 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides EDC/N-N-Hydroxysuccinimide NHS crosslinking chemical activated camplex surface, by the anti-Ab of CA125 bis-of 1 mL, 10 μ g/mL
2add and mix, and shake 12 h in 4 ℃ of isothermal vibration devices, with ultrapure water centrifuge washing, remove unconjugated Ab
2molecule;
Described TiO
2tiO for embodiment 5, embodiment 6 or embodiment 7 preparations
2nano particle.
Described carboxylated CdSe quantum dot solution is the carboxylated CdSe quantum dot solution of embodiment 7, embodiment 8 or embodiment 9 preparations.
embodiment 12tiO
2-CdSe-Ab
2the preparation of two anti-hatching things
Take 5 mg TiO
2be scattered in the carboxylated CdSe quantum dot solution of 4 mL, ultrasonic and stirring reaction 10 ~ 14 h, after question response completes, use ultrapure water centrifuge washing 3 times, make TiO
2-CdSe semiconductor compound; By TiO
2-CdSe semiconductor compound is scattered in 1 mL water, with the carboxyl on 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides EDC/N-N-Hydroxysuccinimide NHS crosslinking chemical activated camplex surface, by the anti-Ab of CA125 bis-of 1 mL, 12 μ g/mL
2add and mix, and shake 12 h in 4 ℃ of isothermal vibration devices, with ultrapure water centrifuge washing, remove unconjugated Ab
2molecule;
Described TiO
2tiO for embodiment 5, embodiment 6 or embodiment 7 preparations
2nano particle.
Described carboxylated CdSe quantum dot solution is the carboxylated CdSe quantum dot solution of embodiment 7, embodiment 8 or embodiment 9 preparations.
embodiment 13two kinds of methods of galvanochemistry and photic galvanochemistry detect CA125
(1) salpeter solution that difunctional mark Optical Electro-Chemistry sensor is placed in 0.3 mL, 0.1 mol/L soaks 4 h, makes CdSe quantum dot be decomposed into Cd
2+, joined 3.6 mL, 30 mg/mL Hg
2+pH 4.6 NaAc_HAc buffer solutions in, use three-electrode system, carry out Electrochemical Detection;
Described three electrode saturated calomel electrodes are contrast electrode, and platinum electrode is auxiliary electrode, and glass-carbon electrode is working electrode;
(2) scanning voltage scope is from-0.9 ~-0.6 V, and the electromotive force rank that jump are 4 mV, frequency 25 Hz, amplitude 25 mV;
(3) Cd
2+there is redox reaction and produce signal near-0.7 V, according to the linear relationship between gained strength of current and analyte, drawing curve;
(4) Photoelectric Detection adopts i-t means of testing, and bias voltage is set to 0 V; Every 20 s, carry out switch lamp, record the changing value of switch lamp front and back electric current, according to the antigen of variable concentrations, produce the photoelectricity flow valuves of different sizes, drawing curve;
(5) testing sample solution is replaced to the standard solution of CA125, according to the method for drafting of the working curve of described CA125, detect;
(6) for the detection of 1# blood serum sample CA125, adopt using standard samples recovery, every kind of sample Parallel testing 7 times, its relative standard deviation is lower than 3.2%, and the recovery is 90.9% ~ 105%, and the preci-sion and accuracy of detection method of the present invention is all satisfactory.
embodiment 14two kinds of methods of galvanochemistry and photic galvanochemistry detect CA125
(1) salpeter solution that difunctional mark Optical Electro-Chemistry sensor is placed in 0.4 mL, 0.1 mol/L soaks 4 h, makes CdSe quantum dot be decomposed into Cd
2+, joined 3.6 mL, 40 mg/mL Hg
2+pH 4.6 NaAc_HAc buffer solutions in, use three-electrode system, carry out Electrochemical Detection;
Described three electrode saturated calomel electrodes are contrast electrode, and platinum electrode is auxiliary electrode, and glass-carbon electrode is working electrode;
(2) scanning voltage scope is from-0.9 ~-0.6 V, and the electromotive force rank that jump are 4 mV, frequency 25 Hz, amplitude 25 mV;
(3) Cd
2+there is redox reaction and produce signal near-0.7 V, according to the linear relationship between gained strength of current and analyte, drawing curve;
(4) Photoelectric Detection adopts i-t means of testing, and bias voltage is set to 0 V; Every 20 s, carry out switch lamp, record the changing value of switch lamp front and back electric current, according to the antigen of variable concentrations, produce the photoelectricity flow valuves of different sizes, drawing curve;
(5) adopting electrochemical method is 0.1 pg/mL ~ 20 ng/mL to the sensing range of CA125, detects and is limited to 0.02 pg/mL;
(6) adopting PhotoelectrochemicalMethod Method is 0.05 pg/mL ~ 100 ng/mL to the sensing range of CA125, detects and is limited to 0.01 pg/mL;
(7) testing sample solution is replaced to the standard solution of CA125, according to the method for drafting of the working curve of described CA125, detect;
(8) for the detection of 2# blood serum sample CA125, adopt using standard samples recovery, every kind of sample Parallel testing 7 times, its relative standard deviation is lower than 1.9%, and the recovery is 95.6% ~ 97.6%, and the preci-sion and accuracy of detection method of the present invention is all satisfactory.
embodiment 15two kinds of methods of galvanochemistry and photic galvanochemistry detect CA125
(1) salpeter solution that difunctional mark Optical Electro-Chemistry sensor is placed in 0.5 mL, 0.1 mol/L soaks 4 h, makes CdSe quantum dot be decomposed into Cd
2+, joined 3.6 mL, 50 mg/mL Hg
2+pH 4.6 NaAc_HAc buffer solutions in, use three-electrode system, carry out Electrochemical Detection;
Described three electrode saturated calomel electrodes are contrast electrode, and platinum electrode is auxiliary electrode, and glass-carbon electrode is working electrode;
(2) scanning voltage scope is from-0.9 ~-0.6 V, and the electromotive force rank that jump are 4 mV, frequency 25 Hz, amplitude 25 mV;
(3) Cd
2+there is redox reaction and produce signal near-0.7 V, according to the linear relationship between gained strength of current and analyte, drawing curve;
(4) Photoelectric Detection adopts i-t means of testing, and bias voltage is set to 0 V; Every 20 s, carry out switch lamp, record the changing value of switch lamp front and back electric current, according to the antigen of variable concentrations, produce the photoelectricity flow valuves of different sizes, drawing curve;
(5) for the detection of 3# blood serum sample CA125, adopt using standard samples recovery, every kind of sample Parallel testing 7 times, its relative standard deviation is lower than 1.8%, and the recovery is 95.8% ~ 98.0%, and the preci-sion and accuracy of detection method of the present invention is all satisfactory.
Claims (3)
1. a preparation method for difunctional mark Optical Electro-Chemistry sensor, is characterized in that, comprises the following steps:
(1) pre-service of ITO electrode: ito glass is cut to 3 cm * 0.5 cm sizes, use successively liquid detergent, acetone, ethanol and ultrapure water ultrasonic cleaning 30 min, finally with nitrogen, dry up glass, the area that reserves 0.5 cm * 0.5 cm size in one end of ITO electrode with insulating tape is in order to modified biological molecule;
(2) by the ITO electrode after processing in being immersed in the methanol solution that volume fraction is 1% ~ 3% 3-aminopropyl triethoxysilane APTES, lucifuge is soaked 10 ~ 14 h, water rinses electrode, to remove unconjugated APTES molecule;
(3) the 10 μ L gold nano colloidal sols of getting fresh preparation are added drop-wise to electrode surface, in conjunction with CA125 primary antibodie molecule;
(4) 6 μ L, 8 ~ 12 μ g/mL CA125 primary antibodie solution are added drop-wise on electrode, are placed in 4 ℃ of constant temperature refrigerators and hatch 2 h, rinse electrode surface to remove unconjugated primary antibodie molecule;
(5) drip and be coated with BSA solution that 2 μ L, massfraction are 0.5% ~ 1.5% on electrode, be placed in 4 ℃ of Refrigerator stores, dry;
(6) with ultrapure water, clean, dry in the air to moisture state, the CA125 antigenic solution of 6 μ L, 0.05 pg/mL ~ 100 ng/mL variable concentrations is dripped and is applied to electrode surface, make to occur between itself and CA125 primary antibodie specific immune response and continue hatching 2 h, with ultrapure water, rinse to remove unconjugated CA125, dry;
(7) get 6 μ LTiO
2-CdSe-Ab
2two anti-hatching thing solution drip and are applied to electrode surface, and hatching 2 h post-flush electrode surfaces, dry, and make difunctional mark Optical Electro-Chemistry sensor.
2. the preparation method of a kind of difunctional mark Optical Electro-Chemistry sensor as claimed in claim 1, is characterized in that, described TiO
2-CdSe-Ab
2two anti-hatching thing solution, preparation process is as follows:
(1) TiO
2the preparation of nano particle
Getting 6 ~ 8 mL butyl titanates is dissolved in 30 mL ethanol, stir, get 10 mL ultrapure waters and under agitation slowly add in solution, room temperature magnetic agitation is reacted 120 min, and this mixed liquor is transferred in autoclave, 200 ℃ of hydro-thermal reaction 10 ~ 12 h, make white solid, centrifuging, and clean respectively 5 times with intermediate water and ethanol, vacuum drying 10 ~ 14 h at 80 ℃, grind and make TiO
2nano particle;
(2) preparation of carboxyl-functional CdSe quantum dot
By 1.0 ~ 1.3 g CdCl
22.5H
2o is dissolved in 40 mL water, adds the mixed liquor of mercaptoacetic acid, with the NaOH of 1 mol/L, regulates pH to 9 ~ 11, adds the NaSeSO of 12 mL, 0.2 mol/L under stirring
3solution, is heated to boiling by reactant oil bath, and 4 h that reflux, finally obtain carboxylated CdSe quantum dot solution;
The mixed liquor of described mercaptoacetic acid is to be made by 50 ~ 60 mL high purity waters and 0.84 mL mercaptoacetic acid blend; The NaSeSO of described 0.2 mol/L
3solution, gets 10 mmol Se and 12 mmol Na
2sO
3add in 50 mL water, reaction 3 h, filtration makes;
(3) TiO
2-CdSe-Ab
2the preparation of two anti-hatching thing solution
Take 3 ~ 5 mg TiO
2be scattered in the carboxylated CdSe quantum dot solution of 4 mL, ultrasonic and stirring reaction 10 ~ 14 h, after question response completes, use ultrapure water centrifuge washing 3 times, make TiO
2-CdSe semiconductor compound; By TiO
2-CdSe semiconductor compound is scattered in 1 mL water, with the carboxyl on 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides EDC/N-N-Hydroxysuccinimide NHS crosslinking chemical activated camplex surface, by the anti-Ab of CA125 bis-of 1 mL, 8 ~ 12 μ g/mL
2add and mix, and shake 12 h in 4 ℃ of isothermal vibration devices, with ultrapure water centrifuge washing, remove unconjugated Ab
2molecule, makes TiO
2-CdSe-Ab
2two anti-hatching thing solution.
3. the difunctional mark Optical Electro-Chemistry sensor that prepared by preparation method as claimed in claim 1, is characterized in that, uses galvanochemistry and photic electrochemical method to realize the quantitative detection to human body CA125, and step is as follows:
(1) salpeter solution that difunctional mark Optical Electro-Chemistry sensor is placed in 0.3 ~ 0.5 mL, 0.1 mol/L soaks 4 h, makes CdSe quantum dot be decomposed into Cd
2+, joined 3.6 mL, 30 ~ 50 mg/mL Hg
2+pH 4.6 NaAc_HAc buffer solutions in, use three-electrode system, carry out Electrochemical Detection;
Described three electrode saturated calomel electrodes are contrast electrode, and platinum electrode is auxiliary electrode, and glass-carbon electrode is working electrode;
(2) scanning voltage scope is from-0.9 ~-0.6 V, and the electromotive force rank that jump are 4 mV, frequency 25 Hz, amplitude 25 mV;
(3) Cd
2+there is redox reaction and produce signal near-0.7 V, according to the linear relationship between gained strength of current and analyte, drawing curve;
(4) Photoelectric Detection adopts i-t means of testing, and bias voltage is set to 0 V; Every 20 s, carry out switch lamp, record the changing value of switch lamp front and back electric current, according to the antigen of variable concentrations, produce the photoelectricity flow valuves of different sizes, drawing curve;
(5) testing sample solution is replaced to the standard solution of CA125, according to the method for drafting of the working curve of described CA125, detect.
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