CN105784685B - A kind of preparation method and application of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry - Google Patents
A kind of preparation method and application of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry Download PDFInfo
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Abstract
The preparation method for having electrogenerated chemiluminescence and the flourishing tactful biological immune sensing device of optical electro-chemistry dual signal based on function nano material structure that the invention discloses a kind of, prepared sensor operations are simple, easy to carry, detection is fast, at low cost, can be used for quick, the Sensitive Detection to ethinyloestradiol in the fields such as daily production and life.
Description
Technical field
The present invention relates to a kind of preparation method for detecting the sensor of ethinyloestradiol, the electroluminescent chemistry of the sensor integration
It shines and optical electro-chemistry dual function.Belong to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Environmental estrogens refer to after one kind enters body, with the synthesis, release of normal endocrine substance, fortune in interfering bodies
The processes such as defeated, combination, metabolism activate or inhibit the function of internal system, maintain organism stability and regulation and control to make to destroy
Compound, environmental estrogens type is various, including artificial-synthetic compound and natural plant estrogen, is distributed widely in certainly
In right boundary.Female ethinyloestradiol is a kind of steroid synthetic estrogen.Currently, detection ethinyloestradiol method mainly have chromatography,
Mass spectrography etc..Such method instrument is valuable, complicated for operation, and laboratory personnel can just be detected after needing professional training.Therefore, it grinds
Send out at low cost, detection is fast, high sensitivity, high specificity ethinyloestradiol sensor is of great significance.
Electrochemical biosensor analytical technology increasingly obtains the weight of people due to the advantages such as easy to operate, detection speed is fast
Depending on.The electrochemical biosensor analytical technology for being presently used for detection ethinyloestradiol has electrochemistry biography according to detection means to divide mainly
Three kinds of sensor, Electrochemiluminescsensor sensor and optical electro-chemistry sensor.Wherein, Electrochemiluminescsensor sensor and optical electro-chemistry
Sensor has the characteristics that few background signal noise, high sensitivity, testing cost are low, in recent years relative to electrochemical sensor
It is of interest by more and more researchers.
Electrogenerated chemiluminescence is also referred to as electrochemical luminescence, refers to that generate some in electrode surface by electrochemical method special
Substance, form excitation state between these substances or by electron transmission between other components in system, returned by excitation state
Luminescence phenomenon is generated to ground state.Electrochemiluminescsensor sensor is the decorative material by changing electrode surface, with analysis produce
Raw electrochemical luminescence is realized according to the associated change of analyte concentration and electrochemical luminescence intensity to analysis in optimal conditions
The qualitative and quantitative analysis of object.
Optical electro-chemistry sensor is to cause electron-hole pair to be detached 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 variation of analyte concentration will have a direct impact on 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 Electrochemiluminescsensor sensor needs external optical signal to capture equipment such as photodiode etc., and light
Electrochemical sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this affects the convenient of the two operation to a certain extent
Property, it limits them and is more widely applied in actual production, life.Therefore, it designs, prepare more simple, fast inspection
The electrochemical biosensor analytical technology for surveying hydrogen peroxide has highly important practical value.
Invention content
The purpose of the present invention is to provide a kind of ethinyloestradiol sensors easy to operate, easy to carry, detection is fast, at low cost
Preparation method, prepared sensor can be used for quick, the Sensitive Detection to ethinyloestradiol in the fields such as daily production and life.
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 and one
A reference electrode, wherein working electrode 1 using gold@nickel palladium nanometer rods Sol A u@NiPd NRs and electropolymerization luminol jointly into
Row modification, as electrogenerated chemiluminescence working electrode W1, working electrode 2 is using titanium dioxide nanoplate colloidal sol TiO2NSs and alkynes
Female alcohol antibody is modified jointly, as optical electro-chemistry working electrode W2.When being detected, fixed concentration is added in electrolytic cell
After hydrogen peroxide, apply step voltage on W1, due to the catalytic action of Au@NiPd NRs, luminol and hydroperoxidation,
Electrogenerated chemiluminescence is generated, this is just equivalent to " turning on light ", and when step voltage is 0, electrogenerated chemiluminescence disappears, this is just equivalent to
" turning off the light "；At the same time apply constant voltage always on W2, due to TiO2NSs can be because of the hair that electrogenerated chemiluminescence generates
Light excitation causes electron-hole pair to be detached, and the horseradish peroxidase HRP on ethinyloestradiol secondary antibody is marked to be catalyzed peroxidating
Hydrogen generates oxygen, and hydrogen peroxide is made to become hole " donor ", to obtaining photoelectric current on W2, when electrogenerated chemiluminescence disappears,
When " turning off the light ", photoelectric current disappears immediately.Due under the premise of fixed concentration of hydrogen peroxide, photoelectric current size and HRP concentration
Positive correlation, when ethinyloestradiol concentration is bigger in measured object, when being attached on W2 with an anti-immunity, then immune binding marker has HRP
The concentration of ethinyloestradiol secondary antibody will be bigger, the photoelectric current of generation is also bigger, therefore passes through the size for recording photoelectric current
Realize the detection to ethinyloestradiol.
Based on the above inventive principle, the specific technical solution that the present invention uses is as follows：
1. a kind of preparation method of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry, special
Point is that preparation process is：
（1）The preparation method of electrogenerated chemiluminescence working electrode W1, the W1 are by Au@NiPd NRs and electropolymerization Shandong
The ITO electro-conductive glass that minot is modified jointly, its main feature is that, specific preparation process is：
1）Using ITO electro-conductive glass as working electrode, in electrode surface drop coating Au@NiPd NRs, area coverage be 1 cm ×
1 cm, dries at room temperature；
2）By 1）Obtained working electrode immerses in electrolyte, immerses the area that area is covered by Au@NiPd NRs,
Electrochemical deposition is carried out to working electrode using three-electrode system, working electrode is taken out after deposition, is cleaned using ultra-pure water, 4 DEG C
Under be protected from light drying, electrogenerated chemiluminescence working electrode W1 is made；
The Au@NiPd NRs be nucleocapsid rod-like nano material aqueous solution, the nucleocapsid it is rodlike
Nano material is using gold nanorods as core, and Ni-Pd alloy nano-particle is the rod-like nano material of shell, and the gold nanorods are
Rodlike gold nanoparticle, length are 20 ~ 40 nm；
The electrolyte is the sulfuric acid solution containing luminol, a concentration of the 1 ~ 10 of luminol 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 be saturated it is sweet
Mercury electrode, described is platinum electrode to electrode；
The electrochemical deposition process, the electrochemical method used is cyclic voltammetry, and starting voltage is -0.2 V, eventually
Only voltage is 1.5 V, and it is 100 mv/s, 20 ~ 30 circle of cycle to sweep speed；
（2）The preparation method of optical electro-chemistry working electrode W2, the W2 are by TiO2NSs and ethinyloestradiol antibody are common
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 ethinyloestradiol antibody-solutions of working electrode surface drop coating, it is dry at 4 DEG C, after dry
It is 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 rectangular sheet, the length of side are 60 ~ 80 nm；
A concentration of 300 μ g/mL of the ethinyloestradiol antibody-solutions；
（3）Preparation method based on the difunctional ethinyloestradiol sensor of electrogenerated chemiluminescence and optical electro-chemistry：
1）By in the opposite insertion electrolytic cell of the one side of W1 and W2 conductions, W1 is the cm of 0.5 cm ~ 1.5 with W2 spacing；
2）It is to be inserted into electrolytic cell to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, it is common with W1 and W2
Form four electrode systems；
3）NaOH solution and 0.2 mL a concentration of 1 mmol/L that 9.8 mL pH value are 11 ~ 13 are added in electrolytic cell
Hydrogenperoxide steam generator；
4）By 1）~3）Obtained four electrode system and electrolytic cell are placed in magazine, are obtained based on electrogenerated chemiluminescence
The ethinyloestradiol sensor difunctional with optical electro-chemistry.
2. the detection applied to ethinyloestradiol of ethinyloestradiol sensor of the present invention, its main feature is that specific detection side
Method is：
（1）The ethinyloestradiol standard solution of 10 μ L various concentrations is added dropwise on W2, after hatching 30 min, on ethinyloestradiol and W2
Ethinyloestradiol antibody carry out immune combination, after flushing, then the ethinyloestradiol secondary antibody of 10 μ L horseradish peroxidases HRP labels is added dropwise,
After hatching 30 min, ethinyloestradiol secondary antibody and the ethinyloestradiol of HRP labels carry out immune combination, and after flushing, W2 to be measured is made；
（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 be corresponding with the increase of ethinyloestradiol concentration
Increase, according to the relationship between gained electric current increment value and ethinyloestradiol concentration, drawing curve；
（3）The standard solution that ethinyloestradiol solution to be measured is replaced to ethinyloestradiol, according to（1）With（2）The ethinyloestradiol detection
Method is detected, and the dense of ethinyloestradiol solution to be measured is obtained with the working curve drawn according to obtained electric current increment value
Degree；
A concentration of 300 μ g/mL of the ethinyloestradiol secondary antibody of the HRP labels.
The useful achievement of the present invention
（1）Ethinyloestradiol sensor of the present invention is prepared simply, easy to operate, is not necessarily to external accessory, is utilized inspection
The micromation of measurement equipment, portability, and quick, sensitive, the highly selective detection to ethinyloestradiol is realized, it has a vast market
Development prospect；
（2）The present invention detects ethinyloestradiol in same electrolytic cell using four electrode systems for the first time, and realizes electroluminescent chemistry
It shines and the difunctional signal amplification strategy of optical electro-chemistry.With the increase of ethinyloestradiol concentration in electrolytic cell, modify on W2
The ethinyloestradiol secondary antibody of HRP labels will increase, and also mean that HRP to hydrogen peroxide catalyzed raising.Thus, a side
Face so that electrogenerated chemiluminescence intensity is linearly increasing, and the photoelectricity cleanliness excited increases；On the other hand, hydrogen peroxide conduct
Electron donor so that photoelectricity cleanliness increases in optical electro-chemistry reaction.Therefore, two methods of electrogenerated chemiluminescence and optical electro-chemistry
It reacts, interact jointly in same electrolytic cell, under same electrochemical workstation, realize and electric signal is detected to ethinyloestradiol
Dual amplification greatly improves detection sensitivity and detection limit, has important scientific meaning and application value.
Specific implementation mode
A kind of ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry of embodiment 1, it is specific to make
It is for step：
（1）The preparation of electrogenerated chemiluminescence working electrode W1：
1）Using ITO electro-conductive glass as working electrode, in electrode surface drop coating Au@NiPd NRs, area coverage be 1 cm ×
1 cm, dries at room temperature；
2）By 1）Obtained working electrode immerses in electrolyte, immerses the area that area is covered by Au@NiPd NRs,
Electrochemical deposition is carried out to working electrode using three-electrode system, working electrode is taken out after deposition, is cleaned using ultra-pure water, 4 DEG C
Under be protected from light drying, electrogenerated chemiluminescence working electrode W1 is made；
The Au@NiPd NRs be nucleocapsid rod-like nano material aqueous solution, the nucleocapsid it is rodlike
Nano material is using gold nanorods as core, and Ni-Pd alloy nano-particle is the rod-like nano material of shell, and the gold nanorods are
Rodlike gold nanoparticle, length are 20 nm；
The electrolyte is the sulfuric acid solution containing luminol, a concentration of the 1 of luminol 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 be saturated it is sweet
Mercury electrode, described is platinum electrode to electrode；
The electrochemical deposition process, the electrochemical method used is cyclic voltammetry, and starting voltage is -0.2V, eventually
Only voltage is 1.5V, and it is 100mv/s, 20 circle of cycle to sweep speed.
（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 ethinyloestradiol antibody-solutions 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 rectangular sheet, the length of side are 60 ~ 80 nm；
A concentration of 300 μ g/mL of the ethinyloestradiol antibody-solutions；
（3）Preparation method based on the difunctional ethinyloestradiol sensor of electrogenerated chemiluminescence and optical electro-chemistry：
1）It 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 be inserted into electrolytic cell to electrode CE by reference electrode RE, platinum electrode of Ag/AgCl, it is common with W1 and W2
Form four electrode systems；
3）The peroxide of NaOH solution and a concentration of 1 mmol/L of 0.2 mL that 10 mL pH value are 11 is added in electrolytic cell
Change hydrogen solution；
4）By 1）~3）Obtained four electrode system and electrolytic cell are placed in magazine, are obtained based on electrogenerated chemiluminescence
The ethinyloestradiol sensor difunctional with optical electro-chemistry.
A kind of ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry of embodiment 2, it is specific to make
It is for step：
（1）The preparation of electrogenerated chemiluminescence working electrode W1：
For preparation process with the preparation process of W1 in embodiment 1, difference is that the length of gold nanorods is 30 nm, electrolysis
A concentration of 5 mmol/L of luminol in liquid, sulfuric acid concentration are that 0.5 mol/L is followed when cyclic voltammetry carries out electrochemical deposition
Ring 25 encloses.
（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 ethinyloestradiol antibody-solutions of working electrode surface drop coating, it is dry at 4 DEG C, after dry
It is 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）Preparation method based on the difunctional ethinyloestradiol sensor of electrogenerated chemiluminescence and optical electro-chemistry：
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0 cm, and the NaOH being added in electrolytic cell is molten
The pH value of liquid is 12.
A kind of ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry of embodiment 3, it is specific to make
It is for step：
（1）The preparation of electrogenerated chemiluminescence working electrode W1：
For preparation process with the preparation process of W1 in embodiment 1, difference is that the length of gold nanorods is 40 nm, electrolysis
A concentration of 10 mmol/L of luminol in liquid, sulfuric acid concentration are that 1.0 mol/L are followed when cyclic voltammetry carries out electrochemical deposition
Ring 30 encloses.
（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 ethinyloestradiol antibody-solutions 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；
Remaining preparation process with W2 in embodiment 1；
（3）Preparation method based on the difunctional ethinyloestradiol sensor of electrogenerated chemiluminescence and optical electro-chemistry：
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5 cm, and the NaOH being added in electrolytic cell is molten
The pH value of liquid is 13.
A kind of application of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry of embodiment 4
Embodiment 1 prepare a kind of ethinyloestradiol sensor application difunctional based on electrogenerated chemiluminescence and optical electro-chemistry in
The detection of ethinyloestradiol, detecting step are：
（1）The ethinyloestradiol standard solution of 10 μ L various concentrations is added dropwise on W2, after hatching 30 min, on ethinyloestradiol and W2
Ethinyloestradiol antibody carry out immune combination, after flushing, then the ethinyloestradiol secondary antibody of 10 μ L horseradish peroxidases HRP labels is added dropwise,
After hatching 30 min, ethinyloestradiol secondary antibody and the ethinyloestradiol of HRP labels carry out immune combination, and after flushing, W2 to be measured is made；
（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 when being used on W2 to be measured 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 ethinyloestradiol concentration, according to institute
Obtain the relationship between electric current increment value and ethinyloestradiol concentration, drawing curve；
（3）The standard solution that ethinyloestradiol solution to be measured is replaced to ethinyloestradiol, according to（1）With（2）The ethinyloestradiol detection
Method is detected, and the dense of ethinyloestradiol solution to be measured is obtained with the working curve drawn according to obtained electric current increment value
Degree；
A concentration of 300 μ g/mL of the ethinyloestradiol secondary antibody of the HRP labels.
A kind of application of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry of embodiment 5
Embodiment 2 prepare a kind of ethinyloestradiol sensor application difunctional based on electrogenerated chemiluminescence and optical electro-chemistry in
The detection of ethinyloestradiol, 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
It surveys W2 and applies constant voltage, voltage is 0.3 v；Electric current on W2 to be measured can accordingly increase with the increase of ethinyloestradiol concentration,
According to the relationship between gained electric current increment value and ethinyloestradiol concentration, drawing curve.
A kind of application of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry of embodiment 6
Embodiment 3 prepare a kind of ethinyloestradiol sensor application difunctional based on electrogenerated chemiluminescence and optical electro-chemistry in
The detection of ethinyloestradiol, 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
It surveys W2 and applies constant voltage, voltage is 0.6 v；Electric current on W2 to be measured can accordingly increase with the increase of ethinyloestradiol concentration,
According to the relationship between gained electric current increment value and ethinyloestradiol concentration, drawing curve.
Ethinyloestradiol sensor prepared by 7 embodiment 1-3 of embodiment, is applied to according to the detecting step of embodiment 4-6
There is excellent detection result, detection to be limited to 10 pmol/L for the detection of ethinyloestradiol.
Claims (5)
1. a kind of preparation method of the ethinyloestradiol sensor difunctional based on electrogenerated chemiluminescence and optical electro-chemistry, feature exist
In the ITO electro-conductive glass modified jointly using golden@nickel palladium nanometer rods Sol A u@NiPd NRs and electropolymerization luminol is as electricity
Cause chemiluminescence working electrode W1, titanium dioxide nanoplate colloidal sol TiO2The ITO that NSs and ethinyloestradiol antibody are modified jointly is conductive
Glass is used as reference electrode RE, platinum electrode to electrode CE as optical electro-chemistry working electrode W2, Ag/AgCl electrode, will
Four electrodes, which are inserted into jointly in same electrolytic cell, forms four electrode systems, and four electrode system obtained is placed in magazine, that is, is made
It obtains based on the difunctional ethinyloestradiol sensor of electrogenerated chemiluminescence and optical electro-chemistry.
2. preparation method according to claim 1, which is characterized in that the Au@NiPd NRs are the stick of nucleocapsid
The rod-like nano material of the aqueous solution of shape nano material, the nucleocapsid is the Ni-Pd alloy nanoparticle using gold nanorods as core
Son is the rod-like nano material of shell, and the gold nanorods are bar-like gold nanoparticle, and length is 20 ~ 40 nm.
3. preparation method according to claim 1, which is characterized in that the titanium dioxide nanoplate colloidal sol TiO2 NSs
For the aqueous solution of titanium dioxide nanoplate, the titanium dioxide nanoplate is the titanium dioxide nano-particle of rectangular sheet, the length of side
For 60 ~ 80 nm.
4. preparation method according to claim 1, which is characterized in that the one side of W1 and W2 conductions is inserted into electrolytic cell relatively
In, W1 is the cm of 0.5 cm ~ 1.5 with W2 spacing.
5. the application of ethinyloestradiol sensor prepared by preparation method according to claim 1, which is characterized in that the alkynes
In the detection of ethinyloestradiol, detecting step is female alcohol sensor application：
（1）Ethinyloestradiol solution to be measured is added dropwise on W2, the ethinyloestradiol antibody on ethinyloestradiol and W2 in ethinyloestradiol solution to be measured
After immune combination, remaining substance is rinsed out, then the ethinyloestradiol secondary antibody that horseradish peroxidase HRP is marked is added dropwise and carries out immune knot
It closes, the ethinyloestradiol secondary antibody of extra HRP labels is rinsed out in conjunction with 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 ethinyloestradiol in ethinyloestradiol solution to be measured and accordingly increase, and be obtained according to gained electric current increment value to be measured
The concentration of ethinyloestradiol in ethinyloestradiol solution.
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| CN107356640A (en) * | 2017-07-10 | 2017-11-17 | 山东利源康赛环境咨询有限责任公司 | A kind of optical electro-chemistry ethinyloestradiol immunosensor and its preparation and application based on two-dimentional multi-element metal composite nano materials |
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| CN117645416B (en) * | 2024-01-29 | 2024-04-02 | 潍坊市环境科学研究设计院有限公司 | Preparation method of electrode material based on environmental estrogen for magnetic separation strategy and application of electrode material |
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| CN104132981A (en) * | 2014-07-20 | 2014-11-05 | 济南大学 | Preparation method and use of Cu2S-labelled estrogen immunosensor |
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2016
- 2016-03-16 CN CN201610148503.2A patent/CN105784685B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102323323A (en) * | 2011-07-12 | 2012-01-18 | 南京医科大学 | Preparation method for 17 beta-estradiol molecular imprinting film electrochemical sensor |
| CN103940867A (en) * | 2014-04-11 | 2014-07-23 | 同济大学 | Method for preparing photoelectric adapter sensor for detecting 17beta-estradiol |
| CN104132981A (en) * | 2014-07-20 | 2014-11-05 | 济南大学 | Preparation method and use of Cu2S-labelled estrogen immunosensor |
Non-Patent Citations (1)
| Title |
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| Electrochemiluminescence induced photoelectrochemistry for sensing of the DNA based on DNA-linked CdS NPs superstructure with intercalator molecules;Yingshu Guo 等;《Chem.Commun.》;20101126;第47卷;第1595页倒数第1段及1596页第1段，图1 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107356640A (en) * | 2017-07-10 | 2017-11-17 | 山东利源康赛环境咨询有限责任公司 | A kind of optical electro-chemistry ethinyloestradiol immunosensor and its preparation and application based on two-dimentional multi-element metal composite nano materials |
| CN107356640B (en) * | 2017-07-10 | 2019-08-27 | 山东利源康赛环境咨询有限责任公司 | A kind of optical electro-chemistry ethinyloestradiol immunosensor and its preparation and application based on two-dimentional multi-element metal composite nano materials |
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| CN105784685A (en) | 2016-07-20 |
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