CN105758916B - A kind of preparation method and application of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation - Google Patents
A kind of preparation method and application of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
The invention discloses a kind of preparation method of the biological immune sensing device for possessing electrogenerated chemiluminescence and the flourishing strategy of optical electro-chemistry dual signal based on function nano material structure, prepared sensor operations are simple, easy to carry, detection is fast, cost is low, quick, the Sensitive Detection to decis available for fields such as daily production and lifes.
Description
Technical field
The present invention relates to a kind of preparation method for the sensor for being used to detect decis, sensor integration electrochemistry
Shine and optical electro-chemistry dual-use function.Belong to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Decis is highest one kind of virulence in chrysanthemum ester insecticide, to the toxic effect of pest up to 100 times of DDT, it is right
40 times of sulphur phosphorus, have and tag and stomach poison function, and action of contace poison is rapid, and it is strong to knock down power, not stifling and systemic action, highly concentrated
There is repellent action to some pests under degree, the lasting period was up to 7~12 days.Decis belongs to the malicious class of poisoning.Skin contact can draw
Irritation is played, red papules occurs；During acute poisoning, the lighter has headache, dizziness, Nausea and vomiting, loss of appetite, weak；Weight
Person is it may also occur that fasciculation and twitch.
At present, the method for detecting decis mainly has chromatography, mass spectrography etc..Such method instrument is valuable, operation is multiple
Miscellaneous, laboratory personnel can just be detected after needing professional training.Therefore, R＆D costs are low, detection is fast, high sensitivity, specificity
Strong decis sensor is of great significance.
Electrochemical biosensor analytical technology increasingly obtains the weight of people due to the advantage such as easy to operate, detection speed is fast
Depending on.The electrochemical biosensor analytical technology for being presently used for detection decis mainly has electrochemistry according to detection means to divide
Three kinds of sensor, electrochemical luminescence sensor and optical electro-chemistry sensor.Wherein, electrochemical luminescence sensor and optical electro-chemistry pass
Sensor has the characteristics that few background signal noise, high sensitivity, testing cost are low relative to electrochemical sensor, in recent years by
More and more researchers are of interest.
Electrochemical luminescence is also referred to as electrogenerated chemiluminescence, and it is special to refer to produce some in electrode surface by electrochemical method
Material, form excitation state between these materials or by electron transmission between other components in system, returned by excitation state
Return to ground state and produce luminescence phenomenon.Electrochemical luminescence sensor is the decorative material by varying electrode surface, with analyzing produce
Raw electrochemical luminescence, in optimal conditions, is realized to analysis according to the associated change of analyte concentration and electrochemical luminescence intensity
The qualitative and quantitative analysis of thing.
Optical electro-chemistry sensor is to cause electron-hole pair to be separated based on additional light source activation Electrophotosensitivmaterial material,
Under suitable potential condition partially, quick transmission of the electronics on electrode, semiconductor and trim and analyte is realized, and formed
Photoelectric current.In optimal conditions, the change of analyte concentration can directly affect the size of photoelectric current, can be according to the change of photoelectric current
Change the qualitative and quantitative analysis realized to analyte.
But since electrochemical luminescence sensor needs external optical signal to catch equipment such as photodiode etc., and photoelectricity
Chemical sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this have impact on the convenient of the two operation to a certain extent
Property, limit them and be more widely applied in actual production, life.Therefore, design, prepare more simple, fast inspection
The electrochemical biosensor analytical technology for surveying decis has highly important practical value.
The content of the invention
It is an object of the invention to provide a kind of decis sensing easy to operate, easy to carry, detection is fast, cost is low
The preparation method of device, prepared sensor, available for fields such as daily production and lifes to the quick, sensitive of decis
Detection.Based on this purpose, the present invention is in same electrolytic cell, and using four electrode systems, i.e. two working electrodes, one to electrode
With a reference electrode, wherein working electrode 1 uses ITO electro-conductive glass, is first modifying nickel phosphate ammonium micro-nano material above
NH4NiPO4With gold nanorods Sol A u NRs as substrate, then electropolymerization luminol, the electrode are sent out as electrochemistry on it
Light working electrode W1, working electrode 2 is using titanium dioxide nanoplate colloidal sol TiO2NSs and decis antibody are repaiied jointly
Decorations, as optical electro-chemistry working electrode W2.When being detected, after adding fixed concentration hydrogen peroxide in electrolytic cell, on W1
Apply step voltage, due to NH4NiPO4The effect and NH of stabilized illumination and increase Au NRs loads4NiPO4With Au NRs'
Concerted catalysis acts on, and luminol and hydroperoxidation, produce electrochemical luminescence, this just equivalent to " turning on light ", works as step voltage
For 0 when, electrochemical luminescence disappear, this just equivalent to " turning off the light ", at the same time applies constant voltage, due to TiO always on W22
NSs can be marked on decis secondary antibody because the luminous excitation that electrochemical luminescence produces causes electron-hole pair to be separated
Horseradish peroxidase HRP catalyzing hydrogen peroxides produce oxygen, hydrogen peroxide is become hole " donor ", thus on W2 must
To photoelectric current, when electrogenerated chemiluminescence disappears, i.e., when " turning off the light ", photoelectric current disappears immediately.Due in fixed concentration of hydrogen peroxide
On the premise of, photoelectric current size and HRP concentration positive correlations, when decis concentration is bigger in measured object, when with an anti-immunity knot
When closing on W2, then immune binding marker has the concentration of the decis secondary antibody of HRP will be bigger, and the photoelectric current of generation is also got over
Greatly, the size of the photoelectric current of generation and decis concentration positive correlation, therefore by recording size i.e. achievable pair of photoelectric current
The detection of decis.
Based on above inventive principle, the concrete technical scheme that the present invention uses is as follows：
1. a kind of preparation method of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation, its feature exist
In preparation process is：
（1）The preparation method of electrochemical luminescence working electrode W1, the W1 are by NH4NiPO4Repaiied jointly with Au NRs
It is prepared on the ITO electro-conductive glass of decorations after electropolymerization luminol, its main feature is that, specific preparation process is：
1）Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4Solution, area coverage for 1 cm ×
1 cm, dries at room temperature；
2）By 1）Obtained working electrode, in NH4NiPO4Surface drop coating Au NRs, area coverage are the cm of 1 cm × 1,
Dry at room temperature；
3）By 2）Obtained working electrode, immerses in electrolyte, immersion area is NH4NiPO4Covered jointly with Au NRs
Area, electrochemical deposition is carried out to working electrode using three-electrode system, takes out working electrode after deposition, it is clear using ultra-pure water
Wash, lucifuge is dried at 4 DEG C, and electrochemical luminescence working electrode W1 is made；
The NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, and the nickel phosphate ammonium micro-nano material is porous
Sheet micro-nano material, the NH4NiPO4Preparation process be：2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g are added in 40mL water
Phosphate, after being completely dissolved, adds 0.15 ~ 0.25 g Nickel Chlorides, 10 ~ 14h is stirred at 30 ~ 45 DEG C, centrifuge, will produce
Product are placed in drying at 50 DEG C, that is, obtain NH4NiPO4；
The ammonium salt is selected from one of following：Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The phosphate is selected from one of following：Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The Au NRs are the aqueous solution of gold nanorods, and the gold nanorods are bar-like gold nanoparticle, length for 20 ~
40 nm；
The electrolyte is the sulfuric acid solution containing luminol, and the concentration of luminol is 1 ~ 10 in the electrolyte
Mmol/L, sulfuric acid concentration are 0.1 ~ 1.0 mol/L；
The three-electrode system, including working electrode, reference electrode and to electrode, the reference electrode is sweet for saturation
Mercury electrode, described is platinum electrode to electrode；
The electrochemical deposition process, for the electrochemical method used for cyclic voltammetry, starting voltage is -0.2 V, eventually
Only voltage is 1.5 V, and it is 100 mv/s to sweep speed, the circle of circulation 20 ~ 30；
（2）The preparation method of optical electro-chemistry working electrode W2, the W2 are by TiO2NSs and decis antibody are total to
With the ITO electro-conductive glass of modification, its main feature is that, specific preparation process is：
1）Using ITO electro-conductive glass as working electrode, in 8 ~ 12 μ L TiO of electrode surface drop coating2NSs, dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained 8 ~ 12 μ L decis antibody of working electrode surface drop coating, it is dry at 4 DEG C, used after dry
Ultra-pure water cleans, dry at 4 DEG C, and optical electro-chemistry working electrode W2 is made；
The TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1 mg/mL, and the titanium dioxide nanoplate is
The titanium dioxide nano-particle of square sheet, the length of side are 60 ~ 80 nm；
The concentration of the decis antibody-solutions is 300 μ g/mL；
（3）The preparation method of decis optical electro-chemistry sensor based on electrochemical luminescence excitation：
1）By in the opposite insertion electrolytic cell of the one side of W1 and W2 conductions, W1 and W2 spacing are the cm of 0.5 cm ~ 1.5；
2）It is to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, is inserted into electrolytic cell, it is common with W1 and W2
Form four electrode systems；
3）It is 1 mmol/L's that NaOH solution that 10 mL pH value are 11 ~ 13 and 0.2 mL concentration are added in electrolytic cell
Hydrogenperoxide steam generator；
4）By 1）~3）Obtained four electrode systems and electrolytic cell are placed in magazine, that is, are made and are swashed based on electrochemical luminescence
The decis optical electro-chemistry sensor of hair.
2. the detection applied to hydrogen peroxide of decis optical electro-chemistry sensor of the present invention, its main feature is that
Specifically detection method is：
（1）Be added dropwise the decis standard solution of 10 μ L various concentrations on W2, after hatching 30 min, decis with
Decis antibody on W2 carries out immune combination, after flushing, then the bromine cyanogen of 10 μ L horseradish peroxidases HRP marks is added dropwise
Chrysanthemum ester secondary antibody, after hatching 30 min, decis secondary antibody and the decis of HRP marks carry out immune combination, after flushing, are made
W2 to be measured；
（2）Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1
For 0 v, step voltage is 0.7 ~ 0.9 v, and snap time is 10 ~ 30 s；Meanwhile the m- current methods when being used on W2 to be measured
Constant voltage is applied to W2 to be measured, voltage is 0 ~ 0.6 v；Electric current on W2 to be measured can with the increase of decis concentration phase
It should increase, according to the relation between gained electric current increment value and decis concentration, drawing curve；
（3）Decis solution to be measured is replaced to the standard solution of decis, according to（1）With（2）The bromine cyanogen chrysanthemum
Ester detection method is detected, and show that decis to be measured is molten with the working curve drawn according to obtained electric current increment value
The concentration of liquid；
The concentration of the decis secondary antibody of the HRP marks is 300 μ g/mL.
The useful achievement of the present invention
（1）Decis optical electro-chemistry sensor of the present invention is prepared simply, easy to operate, is set without external auxiliary
It is standby, using the micromation of detection device, portability, and realize to the quick, sensitive of hydrogen peroxide, high selectivity detection, tool
There is wide market development prospect；
（2）The present invention realizes electroluminescentization first in same electrolytic cell using four electrode systems detection decis
Learn the signal amplification strategy difunctional with optical electro-chemistry that shines.With the increase of decis concentration in electrolytic cell, modify in W2
On HRP mark decis secondary antibody will increase, also mean that HRP to hydrogen peroxide catalyzed raising.Consequently, it is possible to
On the one hand so that electrogenerated chemiluminescence intensity is linearly increasing, the photoelectricity cleanliness increase excited；On the other hand, hydrogen peroxide
As electron donor so that photoelectricity cleanliness increases in optical electro-chemistry reaction.Therefore, two kinds of electrogenerated chemiluminescence and optical electro-chemistry
Method reacts, interacts jointly in same electrolytic cell, under same electrochemical workstation, realizes and detects electricity to decis
The dual amplification of signal, drastically increases detection sensitivity and detection limit, has important scientific meaning and application value.
Embodiment
A kind of decis optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 1, it is specific to prepare step
Suddenly it is：
（1）The preparation of electrochemical luminescence working electrode W1：
1）Using ITO electro-conductive glass as working electrode, in electrode surface drop coating NH4NiPO4Solution, area coverage for 1 cm ×
1 cm, dries at room temperature；
2）By 1）Obtained working electrode, in NH4NiPO4Surface drop coating Au NRs, area coverage are the cm of 1 cm × 1,
Dry at room temperature；
3）By 2）Obtained working electrode, immerses in electrolyte, immersion area is NH4NiPO4Covered jointly with Au NRs
Area, electrochemical deposition is carried out to working electrode using three-electrode system, takes out working electrode after deposition, it is clear using ultra-pure water
Wash, lucifuge is dried at 4 DEG C, and electrochemical luminescence working electrode W1 is made；
The NH4NiPO4Solution is nickel phosphate ammonium micro-nano material aqueous solution, the preparation of the nickel phosphate ammonium micro-nano material
Step is：2.0 ~ 4.0 g ammonium salts and 0.15 ~ 0.25 g phosphate are added in 40mL water, after being completely dissolved, addition 0.15 ~
0.25 g Nickel Chlorides, stir 10 ~ 14h at 30 ~ 45 DEG C, centrifuge, and product is placed in drying at 50 DEG C, that is, is obtained
NH4NiPO4；
The ammonium salt is selected from one of following：Ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The phosphate is selected from one of following：Ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；
The Au NRs are the aqueous solution of gold nanorods, and the gold nanorods are bar-like gold nanoparticle, length 20
nm；
The electrolyte is the sulfuric acid solution containing luminol, and the concentration of luminol is 1 in the electrolyte
Mmol/L, sulfuric acid concentration are 0.1 mol/L；
The three-electrode system, including working electrode, reference electrode and to electrode, the reference electrode is sweet for saturation
Mercury electrode, described is platinum electrode to electrode；
The electrochemical deposition process, for the electrochemical method used for cyclic voltammetry, starting voltage is -0.2 V, eventually
Only voltage is 1.5 V, and it is 100 mv/s to sweep speed, the circle of circulation 20 ~ 30.
（2）The preparation of optical electro-chemistry working electrode W2：
1）Using ITO electro-conductive glass as working electrode, in 8 μ L TiO of electrode surface drop coating2NSs, dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained 8 μ L decis antibody-solutions of working electrode surface drop coating, it is dry at 4 DEG C, after dry
Cleaned with ultra-pure water, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
The TiO2NSs is the aqueous solution of the titanium dioxide nanoplate of 1 mg/mL, and the titanium dioxide nanoplate is
The titanium dioxide nano-particle of square sheet, the length of side are 60 ~ 80 nm；
The concentration of the decis antibody-solutions is 300 μ g/mL；
（3）The preparation method of decis optical electro-chemistry sensor based on electrochemical luminescence excitation：
1）Will（1）The W1 of middle preparation and（2）The W2 of middle preparation is inserted into electrolytic cell face to face, and W1 is 0.5 with W2 spacing
cm；
2）It is to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, is inserted into electrolytic cell, it is common with W1 and W2
Form four electrode systems；
3）The NaOH solution that 10 mL pH value are 11 and the peroxide that 0.2 mL concentration is 1 mmol/L are added in electrolytic cell
Change hydrogen solution；
4）By 1）~3）Obtained four electrode systems and electrolytic cell are placed in magazine, that is, are made and are swashed based on electrochemical luminescence
The decis optical electro-chemistry sensor of hair.
A kind of decis optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 2, it is specific to prepare step
Suddenly it is：
（1）The preparation of electrochemical luminescence working electrode W1：
With the preparation process of W1 in embodiment 1, difference is preparation process：The preparation process of nickel phosphate ammonium micro-nano material
Middle ammonium salt addition is 0.3 g, and phosphate addition is 0.20 g, and Nickel Chloride addition is 0.20 g, whipping temp and when
Between be respectively 38 DEG C and 12 h；The length of gold nanorods is 30 nm；The concentration of luminol is 5 mmol/L in electrolyte, sulfuric acid
Concentration is 0.5 mol/L；When cyclic voltammetry carries out electrochemical deposition, the circle of circulation 25.
（2）The preparation of optical electro-chemistry working electrode W2：
1）Using ITO electro-conductive glass as working electrode, in 10 μ L TiO of electrode surface drop coating2NSs, dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained 10 μ L decis antibody-solutions of working electrode surface drop coating, it is dry at 4 DEG C, after dry
Cleaned with ultra-pure water, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
Remaining preparation process with W2 in embodiment 1.
（3）The preparation method of decis optical electro-chemistry sensor based on electrochemical luminescence excitation：
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0 cm, and the NaOH added in electrolytic cell is molten
The pH value of liquid is 12.
A kind of decis optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 3, it is specific to prepare step
Suddenly it is：
（1）The preparation of electrogenerated chemiluminescence working electrode W1：
With the preparation process of W1 in embodiment 1, difference is preparation process：The preparation process of nickel phosphate ammonium micro-nano material
Middle ammonium salt addition is 0.4 g, and phosphate addition is 0.25 g, and Nickel Chloride addition is 0.25 g, whipping temp and when
Between be respectively 45 DEG C and 14 h；The length of gold nanorods is 40 nm；The concentration of luminol is 10 mmol/L in electrolyte, sulphur
Acid concentration is 1.0 mol/L；When cyclic voltammetry carries out electrochemical deposition, the circle of circulation 30.
（2）The preparation of optical electro-chemistry working electrode W2：
1）Using ITO electro-conductive glass as working electrode, in 12 μ L TiO of electrode surface drop coating2NSs, dries at room temperature；
2）By 1）In obtained working electrode be put into Muffle furnace, made annealing treatment at 450 DEG C, handle postcooling
To room temperature；
3）By 2）In obtained 12 μ L decis antibody-solutions of working electrode surface drop coating, it is dry at 4 DEG C, after dry
Cleaned with ultra-pure water, it is dry at 4 DEG C, optical electro-chemistry working electrode W2 is made；
Remaining preparation process with W2 in embodiment 1.
（3）The preparation method of decis optical electro-chemistry sensor based on electrochemical luminescence excitation：
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5 cm, and the NaOH added in electrolytic cell is molten
The pH value of liquid is 13.
A kind of application of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 4
A kind of decis optical electro-chemistry sensor application based on electrochemical luminescence excitation prepared by embodiment 1 is in bromine cyanogen
The detection of chrysanthemum ester, its detecting step are：
（1）Be added dropwise the decis standard solution of 10 μ L various concentrations on W2, after hatching 30 min, decis with
Decis antibody on W2 carries out immune combination, after flushing, then the bromine cyanogen of 10 μ L horseradish peroxidases HRP marks is added dropwise
Chrysanthemum ester secondary antibody, after hatching 30 min, decis secondary antibody and the decis of HRP marks carry out immune combination, after flushing, are made
W2 to be measured；
（2）Using electrochemical workstation, step voltage, initial voltage are applied to W1 using the method for step voltage on W1
For 0 v, step voltage is 0.7 v, and snap time is 10 s；Meanwhile on W2 to be measured use when m- current methods to W2 to be measured
Apply constant voltage, voltage is 0 v；Electric current on W2 to be measured can accordingly increase with the increase of decis concentration, according to
Relation between gained electric current increment value and decis concentration, drawing curve；
（3）Decis solution to be measured is replaced to the standard solution of decis, according to（1）With（2）The bromine cyanogen chrysanthemum
Ester detection method is detected, and show that decis to be measured is molten with the working curve drawn according to obtained electric current increment value
The concentration of liquid；
The concentration of the decis secondary antibody of the HRP marks is 300 μ g/mL.
A kind of application of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 5
A kind of decis optical electro-chemistry sensor application based on electrochemical luminescence excitation prepared by embodiment 2 is in bromine cyanogen
The detection of chrysanthemum ester, its detecting step is in addition to following steps, remaining step is the same as embodiment 4：
Step（2）Using electrochemical workstation, step voltage is applied to W1 using the method for step voltage on W1, initially
Voltage is 0 v, and step voltage is 0.8 v, and snap time is 20 s；Meanwhile m- current methods are treated when being used on W2 to be measured
Survey W2 and apply constant voltage, voltage is 0.3 v；Electric current on W2 to be measured can accordingly increase with the increase of decis concentration
Greatly, according to the relation between gained electric current increment value and decis concentration, drawing curve.
A kind of application of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation of embodiment 6
A kind of decis optical electro-chemistry sensor application based on electrochemical luminescence excitation prepared by embodiment 3 is in bromine cyanogen
The detection of chrysanthemum ester, its detecting step is in addition to following steps, remaining step is the same as embodiment 4：
Step（2）Using electrochemical workstation, step voltage is applied to W1 using the method for step voltage on W1, initially
Voltage is 0 v, and step voltage is 0.9 v, and snap time is 30 s；Meanwhile m- current methods are treated when being used on W2 to be measured
Survey W2 and apply constant voltage, voltage is 0.6 v；Electric current on W2 to be measured can accordingly increase with the increase of decis concentration
Greatly, according to the relation between gained electric current increment value and decis concentration, drawing curve.
Decis optical electro-chemistry sensor prepared by 7 embodiment 1-3 of embodiment, according to the detection of embodiment 4-6
Step is applied to the detection of decis, has excellent detection result, and detection is limited to 20 pmol/L.
Claims (6)
1. a kind of preparation method of the decis optical electro-chemistry sensor based on electrochemical luminescence excitation, it is characterised in that adopt
With nickel phosphate ammonium micro-nano material NH4NiPO4Electropolymerization Shandong on the ITO electro-conductive glass modified jointly with gold nanorods Sol A u NRs
Electrochemical luminescence working electrode W1, titanium dioxide nanoplate colloidal sol TiO are used as after minot2NSs and decis antibody are repaiied jointly
The ITO electro-conductive glass of decorations is as optical electro-chemistry working electrode W2, Ag/AgCl electrode as reference electrode RE, platinum electrode conduct
To electrode CE, four electrodes are inserted into same electrolytic cell jointly and form four electrode systems, obtained four electrode system is placed in
In magazine, that is, the decis optical electro-chemistry sensor based on electrochemical luminescence excitation is made.
2. the preparation side of the decis optical electro-chemistry sensor according to claim 1 based on electrochemical luminescence excitation
Method, it is characterised in that the nickel phosphate ammonium micro-nano material NH4NiPO4For porous flake micro-nano material.
3. the preparation side of the decis optical electro-chemistry sensor according to claim 1 based on electrochemical luminescence excitation
Method, it is characterised in that the gold nanorods Sol A u NRs are the aqueous solution of gold nanorods, and the gold nanorods are bar-like gold
Nano-particle, length are 20 ~ 40 nm.
4. the preparation side of the decis optical electro-chemistry sensor according to claim 1 based on electrochemical luminescence excitation
Method, it is characterised in that the titanium dioxide nanoplate colloidal sol TiO2NSs be titanium dioxide nanoplate aqueous solution, described two
TiOx nano piece is the titanium dioxide nano-particle of square sheet, and the length of side is 60 ~ 80 nm.
5. the preparation side of the decis optical electro-chemistry sensor according to claim 1 based on electrochemical luminescence excitation
Method, it is characterised in that by the opposite insertion electrolytic cell of the one side of W1 and W2 conductions, W1 and W2 spacing are the cm of 0.5 cm ~ 1.5.
6. decis optical electro-chemistry sensor prepared by preparation method according to claim 1, it is characterised in that described
Decis optical electro-chemistry sensor application be in the detection of decis, detecting step：
（1）Decis solution to be measured is added dropwise on W2, the bromine cyanogen on decis and W2 in decis solution to be measured
Chrysanthemum ester antibody mediated immunity combine after, rinse out remaining material, then be added dropwise horseradish peroxidase HRP mark decis secondary antibody into
Row is immune to be combined, and the decis secondary antibody of unnecessary HRP marks is rinsed out with reference to after, W2 to be measured is made；
（2）Using electrochemical workstation, in the electrolyte containing fixed concentration hydrogen peroxide, using step voltage on W1
Method applies step voltage to W1, and initial voltage is 0 v, and step voltage is 0.7 ~ 0.9 v, and snap time is 10 ~ 30 s；Together
When, when being used on W2 to be measured, m- current methods apply constant voltage to W2 to be measured, and voltage is 0 ~ 0.6 v；Electricity on W2 to be measured
Stream can increase with the concentration of decis in decis solution to be measured and accordingly increase, and be drawn according to gained electric current increment value
The concentration of decis in decis solution to be measured.
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| CN103675061A (en) * | 2013-12-16 | 2014-03-26 | 南京市第二医院 | Anatase type TiO2 nano particle based pH sensor and pH value detection method |
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| JPH0384089A (en) * | 1989-08-29 | 1991-04-09 | Idemitsu Kosan Co Ltd | Electro-chemiluminescence element |
| CA2413596A1 (en) * | 2000-06-28 | 2002-01-03 | Joyce Driscoll | Cell lines and cell-based assays for identification of androgen receptor modulators |
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| CN103675061A (en) * | 2013-12-16 | 2014-03-26 | 南京市第二医院 | Anatase type TiO2 nano particle based pH sensor and pH value detection method |
| CN104911629A (en) * | 2015-06-29 | 2015-09-16 | 江苏大学 | Synthesis method of composite electrode |
| CN105044180A (en) * | 2015-06-29 | 2015-11-11 | 江苏大学 | Preparation method and application of heterojunction photoelectrode |
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| Title |
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| Yingshu Guo et al..Electrochemiluminescence induced photoelectrochemistry for sensing of the DNA based on DNA-linked CdS NPs superstructure with intercalator molecules.《Chem. Commun.》.2010,第47卷1595-1597. * |
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