CN110441361A - A kind of indium sulfide cadmium sulfide is sensitized the 17 beta estradiol aptamer sensor preparation method of optical electro-chemistry of cerium doped titanium dioxide altogether - Google Patents
A kind of indium sulfide cadmium sulfide is sensitized the 17 beta estradiol aptamer sensor preparation method of optical electro-chemistry of cerium doped titanium dioxide altogether Download PDFInfo
- Publication number
- CN110441361A CN110441361A CN201910776014.5A CN201910776014A CN110441361A CN 110441361 A CN110441361 A CN 110441361A CN 201910776014 A CN201910776014 A CN 201910776014A CN 110441361 A CN110441361 A CN 110441361A
- Authority
- CN
- China
- Prior art keywords
- solution
- electrode
- room temperature
- beta estradiol
- beta
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to the preparation methods that a kind of indium sulfide cadmium sulfide is sensitized the 17 beta estradiol aptamer sensor of optical electro-chemistry of cerium doped titanium dioxide altogether, belong to optical electro-chemistry sensor field.The present invention obtains the titanium dioxide of cerium dopping as base material using simple hydro-thermal method and obtains photoelectric current, and the cerium doped titanium dioxide after indium sulfide sensitization, photoelectric conversion efficiency greatly improves, and absorbs optical range and increases.Under the common sensitization of cadmium sulfide, three's conduction band positions step wise reduction is conducive to the fast transfer of electronics, provides ideal photo-signal.It is acted in conjunction with aptamer and 17 beta estradiol specific recognitions, realizes that the highly sensitive detection of 17 beta estradiols, detection are limited to 3.98 fg/mL, this is significant to the analysis detection of 17 beta estradiols.
Description
Technical field
The invention belongs to novel function nanometer material, immunoassay and optical electro-chemistry sensor field, indium sulfide cadmium sulfides
It is sensitized the 17 beta estradiol aptamer sensor preparation method of optical electro-chemistry of cerium doped titanium dioxide altogether.
Background technique
17 beta estradiols are the steroid hormones of a kind of lipophilicity, low molecular weight, be in environment incretion interferent most
One kind of estrogenic activity, it is micro to influence the normal endocrine system of people.17 beta estradiols can by many approach into
Enter into environment, for example, pathology treatment, feed addictive, be not metabolized complete excreta etc., excessive 17 beta estradiol can be with
Food chain is transferred to human body and accumulates in human body, leads to dysplasia, suffers from reproductive disease and the probability of breast cancer etc. increases greatly
Add, irreversible damage is caused to human body.Therefore, establishing has highly sensitive, 17 beta estradiol detection method easy to operate
The concern of researchers is caused.
Currently, the detection method for 17 beta estradiols mainly has gas chromatography, high performance liquid chromatography, electron spray matter
Spectrometry etc..However, there are complicated for operation, extraction process time-consuming, expensive equipment, the uses of poisonous and harmful reagent for these detection methods
The disadvantages of, and can not be solved in the short time.The present invention provides the high photoelectricity of a kind of quick, easy, sensitivity and selectivity
Chemical aptamers sensor detecting method has Always Online" detection, and instrumentation is convenient, and specificity is high, and it is excellent that detection range is wide etc.
Point.Optical electro-chemistry sensing is since it is with independent excitation and transmitting signal, and background signal is low, and detection range is wide, response speed
Fastly, it is easy to the advantages that minimizing, has been widely used in detection.Compared with other detectable substances, endocrine disruption species are usual
With lesser molecular weight, it is not easy to be captured by biological antibody.Aptamer as a kind of chemical antibody, be one section of specific DNA or
RNA sequence can accurately capture object and specifically bind with it.And compared with antibody, aptamer is easier to modify,
Configuration is changeable, and object range that can be detected is wider, has been developed as very potential antibody substitute.It will be photoelectrochemical
Method is combined with the advantage of aptamer, has highly sensitive and easy detection property in terms of detecting small-molecule substance, before
Scape is wide.
The present invention successfully constructs the optical electro-chemistry aptamer sensor that 17 beta estradiols are detected under excited by visible light.The sensing
Device is using titanium dioxide/indium sulfide/cadmium sulfide of cerium dopping as substrate, and matched conduction band positions and suitable band gap width are significantly
The transfer rate for improving light induced electron generates strong photo-signal.It adds, the aptamer of particular sequence be used to capture 17 β-
Estradiol is simultaneously fixed to electrode surface, causes the variation of photocurrent response and realizes detection.The optical electro-chemistry 17 β-female two
Alcohol aptamer sensor has many advantages, such as that inexpensive, highly sensitive, specificity is good, detection is quick, preparation process is simple, in visible region
Domain realizes the super sensitivity detection of realization pair, effectively overcomes the deficiency of current 17 beta estradiol detection method.
Summary of the invention
The object of the invention first is that using cerous nitrate as cerium source synthesize cerium dopping titanium dioxide be used as light-sensitive material, introducing
New energy level changes electronic transmission path, reduces electron-hole recombination rate.
The second object of the present invention is to successfully using indium sulfide and cadmium sulfide be sensitized jointly the titanium dioxide of cerium dopping as
Base material, three have matched energy level, and conducive to the rapid transfer of light induced electron, photoelectric properties are greatly promoted, and construct photoelectricity
Chemical 17 beta estradiol aptamer sensors.
There is provided a kind of indium sulfide cadmium sulfides to be sensitized the photoelectrochemical of cerium doped titanium dioxide altogether for the third object of the present invention
17 beta estradiol aptamer sensor preparation methods are learned, the super sensitivity detection to 17 beta estradiols is realized.
Technical scheme is as follows:
1. a kind of indium sulfide and cadmium sulfide are sensitized the 17 beta estradiol aptamer sensor of optical electro-chemistry of cerium doped titanium dioxide altogether
Preparation method, which is characterized in that preparation step is as follows:
(a) preparation of cerium doped titanium dioxide:
1 ~ 2 mL tetrabutyl titanate of measurement, which is dissolved in 40 ~ 80 mL ethyl alcohol, obtains solution A；Weigh 1.6 ~ 9.3 mg nitric acid
Cerium hydrate is soluble in water to obtain solution B；Solution A is instilled into solution B dropwise at room temperature, is turned after being vigorously stirred 30 min
Move in reaction kettle, under 160 ~ 180 °C react 12 ~ 24 h be down to room temperature naturally after reaction, with ethyl alcohol and go from
Sub- water cleaning repeatedly, dries under 50 ~ 80 °C, obtains the titania nanoparticles of cerium dopping；
(b) preparation of indium sulfide
It weighs 0.1 ~ 0.2 g inidum chloride and 0.3 ~ 0.4 g Sodium Sulphate Nine Hydroxide ultrasound is dissolved in 50 mL deionized waters simultaneously
And 30 min of magnetic agitation obtains milky white solution and is transferred in 100 mL reaction kettles, under 160 ~ 200 °C react 16 ~
24 h after a large amount of ethanol washings of the yellow solid obtained after being cooled to room temperature, are placed in a vacuum drying oven at 50 ~ 80 °C
Under be dried overnight；
(c) preparation of cadmium sulfide
It takes 0.2 ~ 0.4 g Sodium Sulphate Nine Hydroxide to be dissolved in 10 ~ 30 mL ultrapure waters, 0.2 ~ 0.5 g cadmium acetate is taken to dissolve
In 10 ~ 40 mL ultrapure waters；After mixing by two solution, it is transferred in reaction kettle, hydro-thermal under the conditions of 160 ~ 200 °C
React 20 ~ 24 h；After being cooled to room temperature, products therefrom dehydrated alcohol and ultrapure water are respectively washed 3 times；Under 50 ~ 80 °C
12 ~ 24 h are dried in vacuo, cadmiumsulfide quantum dot is made；
(d) tin indium oxide ITO electrode is cut to the cm size of 2.5 cm × 0.8, it is successively super with acetone, ethyl alcohol and ultrapure water
Sound cleans 30 ~ 40 min, with being dried with nitrogen；
(e) the cerium doped titanium dioxide Ce:TiO for being 5 mg/mL by 8 ~ 10 μ L concentration2In solution modification to ITO electrode, room temperature
Under dry, then in 400 ~ 450 °C of Muffle furnaces calcine 30 ~ 60 min, cooled to room temperature after taking-up；
(f) the indium sulfide In that 6 ~ 8 μ L concentration are 5 ~ 8 mg/mL is successively modified in electrode surface2S3Solution and 6 ~ 8 μ L
Concentration is 5 ~ 8 mg/mL cadmium sulfide CdS solution, and naturally dry at room temperature；
(g) in ITO/Ce:TiO2/In2S34 ~ 6 μ L thioacetic acid of/CdS electrode face finish, naturally dry simultaneously use ultrapure water
It rinses, it is sub- that 10 mg/mL 1- ethyls-(3- dimethylamino third class) carbon two that volume ratio is 1:1 is added dropwise on modified electrode surface
4 ~ 6 μ L of mixed liquor of amine hydrochlorate and 5 mg/mL n-hydroxysuccinimides is for assisting condensation reaction；Ultrapure water
Electrode surface dries in the air naturally at room temperature to wetting film state；
(h) it further modifies the 17 beta estradiol aptamer of amination that 4 ~ 6 μ L concentration are 1 ~ 2 μM and is incubated for 4 under 4 °C
~ 6 h make the amino on aptamer that electrode surface is reacted and be fixed to the carboxyl in thioacetic acid, not with milli-Q water removal
In conjunction with 17 beta estradiol aptamers, dry at room temperature；
(i) modification 3 ~ 5 μ L 6- sulfydryls-hex- 1- alcohol reacts 1 ~ 2 h to close nonspecific binding site at room temperature, uses
Milli-Q water dries at room temperature；
(j) 17 beta estradiol solution of 6 ~ 8 μ L various concentrations are added dropwise, are incubated for 1 ~ 2 h at room temperature, by object and fit
The immune response of body specific recognition is fixed in electrode surface, then 17 extra beta estradiols are cleaned with ultrapure water, 4 °C of ice
It is dried in case, obtains 17 beta estradiol aptamer sensor of optical electro-chemistry；
2. the detection method of optical electro-chemistry sensor is as follows:
(a) standard solution is prepared: preparing 17 beta estradiol standard solution of one group of various concentration including blank standard specimen；
(b) working electrode is modified: using prepared 17 beta estradiol aptamer sensor of optical electro-chemistry as working electrode, by step
In the 17 beta estradiol standard solution difference drop coating to working electrode for the various concentration prepared in a；
(c) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, is modified with step b
Good working electrode forms three-electrode system, is tested in PBS buffer solution；Using i-t means of testing to analyte into
Row detection, setting voltage are 0 V, and 120 s of runing time, optical source wavelength is 400 ~ 450 nm；Detection is to the 17 of various concentration
The photo-current intensity that beta estradiol standard solution generates draws working curve；The 17 beta estradiol standards containing various concentration are molten
The photo-current intensity of liquid is denoted asI i,I iWith 17 beta estradiol concentration of standard solutioncLogarithm between it is linear, drawI i -
logcWorking curve；
(d) detection of 17 beta estradiols: replace 17 β-in step b female with the tap water of laboratory tap to be measured and lake water
Glycol standard solution is detected, according to response photo-current intensity according to the method in step b and cIAnd working curve, it obtains
The content of 17 beta estradiols in sample to be tested；
The PBS buffer solution is that the phosphate-buffered containing 0.1 mol/L ascorbic acid that 10 mL, pH are 5.0 ~ 8.0 is molten
Liquid.
Beneficial achievement of the invention
(1) present invention has successfully synthesized the titanium dioxide nano material of cerium dopping and has introduced in original titanium dioxide band gap
New energy level, greatly reduces electron-hole recombination rate, is conducive to the analysis inspection of 17 beta estradiol aptamer sensor of optical electro-chemistry
It surveys；
(2) present invention successfully synthesizes indium sulfide and cadmiumsulfide quantum dot and carries out to the titanium dioxide nano material of cerium dopping quick
Change, obtains fabulous photoelectric properties, this is that indium sulfide material is used in the preparation of optical electro-chemistry sensor for the first time.Three it
Between good level-density parameter, realize higher incident photon-to-electron conversion efficiency；
(3) present invention successfully constructs 17 β of optical electro-chemistry-female two that a kind of indium sulfide cadmium sulfide is sensitized cerium doped titanium dioxide altogether
Alcohol aptamer sensor, it is easy to operate, signal response range is wide, realize the highly sensitive detection to 17 beta estradiol aptamers.
The preparation of 1 cerium doped titanium dioxide of case study on implementation
It measures 1 mL tetrabutyl titanate and is dissolved in 40 mL ethyl alcohol and obtain solution A；It is soluble in water to weigh 9.3 mg cerous nitrate hydrates
Obtain solution B；Solution A is instilled into solution B dropwise at room temperature, is transferred in reaction kettle after being vigorously stirred 30 min, 180
12 h are reacted under °C.After reaction, it is down to room temperature naturally, is cleaned repeatedly with ethyl alcohol and deionized water, dries, obtain under 80 °C
To the titania nanoparticles of cerium dopping.
The preparation of 2 cerium doped titanium dioxide of case study on implementation
It measures 1 mL tetrabutyl titanate and is dissolved in 40 mL ethyl alcohol and obtain solution A；It is soluble in water to weigh 3.1 mg cerous nitrate hydrates
Obtain solution B；Solution A is instilled into solution B dropwise at room temperature, is transferred in reaction kettle after being vigorously stirred 30 min, 180
12 h are reacted under °C.After reaction, it is down to room temperature naturally, is cleaned repeatedly with ethyl alcohol and deionized water, dries, obtain under 80 °C
To the titania nanoparticles of cerium dopping.
The preparation of 3 cerium doped titanium dioxide of case study on implementation
It measures 1 mL tetrabutyl titanate and is dissolved in 40 mL ethyl alcohol and obtain solution A；It is soluble in water to weigh 1.6 mg cerous nitrate hydrates
Obtain solution B；Solution A is instilled into solution B dropwise at room temperature, is transferred in reaction kettle after being vigorously stirred 30 min, 180
12 h are reacted under °C.After reaction, it is down to room temperature naturally, is cleaned repeatedly with ethyl alcohol and deionized water, dries, obtain under 80 °C
To the titania nanoparticles of cerium dopping.
The preparation of 4 indium sulfide of case study on implementation
It weighs 0.1106 g inidum chloride and 0.3603 g Sodium Sulphate Nine Hydroxide ultrasound is dissolved in 50 mL deionized waters and magnetic force
It stirs 30 min to obtain milky white solution and be transferred in 100 mL reaction kettles, 16 h is reacted under 180 °C.It is cooled to room temperature
After a large amount of ethanol washings of the yellow solid obtained afterwards, it is placed in a vacuum drying oven and is dried overnight under 50 °C.
The preparation of 5 cadmium sulfide of case study on implementation
It weighs 0.3 g Sodium Sulphate Nine Hydroxide to be dissolved in 10 mL ultrapure waters, 0.4 g cadmium acetate is taken to be dissolved in 10 mL ultrapure waters
In；After mixing by two solution, it is transferred in reaction kettle, 20 h of hydro-thermal reaction under the conditions of 160 °C；After being cooled to room temperature, institute
It obtains product dehydrated alcohol and ultrapure water respectively washs 3 times；It is dried in vacuo 12 h under 40 °C, cadmiumsulfide quantum dot is made.
The preparation of 6 optical electro-chemistry of case study on implementation, 17 beta estradiol aptamer sensor
(a) tin indium oxide ITO electrode is cut to the cm size of 2.5 cm × 0.8, it is successively super with acetone, ethyl alcohol and ultrapure water
Sound cleans 30 min, with being dried with nitrogen；
(b) the cerium doped titanium dioxide solution that 10 μ L concentration are 5 mg/mL is modified onto ITO electrode.It dries at room temperature, so
30 min, cooled to room temperature after taking-up are calcined in 450 °C of Muffle furnaces afterwards；
(c) successively modifying the indium sulfide aqueous solution that 6 μ L concentration are 5 mg/mL and 6 μ L concentration in electrode surface is 5 mg/mL sulphur
Cadmium solution, and naturally dry at room temperature, obtain ITO/Ce:TiO2/In2S3/ CdS electrode；
(d) in ITO/Ce:TiO2/In2S34 μ L thioacetic acid of/CdS electrode face finish, naturally dry and with ultrapure water,
10 mg/mL 1- ethyls-(3- dimethylamino third class) carbodiimide hydrochloride that volume ratio is 1:1 is added dropwise on modified electrode surface
The 6 μ L of mixed liquor of salt and 5 mg/mL n-hydroxysuccinimides is for assisting condensation reaction；Ultrapure water electrode surface,
It is dried in the air naturally at room temperature to wetting film state；
(e) the 17 beta estradiol aptamer of amination that 6 μ L concentration are 1 μM is further modified in electrode surface and be incubated under 4 °C
4 h make the amino on aptamer that electrode surface is reacted and be fixed to the carboxyl in thioacetic acid, are not tied with milli-Q water removal
The 17 beta estradiol aptamers closed, dry at room temperature；
(f) 3 μ L6- sulfydryl of electrode face finish-hex- 1- alcohol reacts 1 h to close nonspecific binding site at room temperature, uses
Milli-Q water dries at room temperature；
(g) 17 beta estradiol solution of 6 μ L various concentrations are added dropwise in electrode surface, are incubated for 1 h at room temperature, by object and fit
The immune response of body specific recognition is fixed in electrode surface, then 17 extra beta estradiols are cleaned with ultrapure water, 4 °C of ice
It is dried in case, obtains 17 beta estradiol aptamer sensor of optical electro-chemistry.
The preparation of 7 optical electro-chemistry of case study on implementation, 17 beta estradiol aptamer sensor:
(a) tin indium oxide ITO electrode is cut to the cm size of 2.5 cm × 0.8, it is successively super with acetone, ethyl alcohol and ultrapure water
Sound cleans 30 min, with being dried with nitrogen；
(b) the cerium doped titanium dioxide solution that 10 μ L concentration are 5 mg/mL is modified onto ITO electrode.It dries at room temperature, so
60 min are calcined in 400 °C of Muffle furnaces afterwards, cooled to room temperature after taking-up obtains ITO/Ce:TiO2Electrode；
(c) electrode surface successively modifies the indium sulfide aqueous solution and vulcanization cadmium solution that 6 μ L concentration are 5 mg/mL, and in room temperature
Lower naturally dry, obtains ITO/Ce:TiO2/In2S3/ CdS electrode；
(d) in ITO/Ce:TiO2/In2S34 μ L thioacetic acid of/CdS electrode face finish, naturally dry and with ultrapure water,
10 mg/mL 1- ethyls-(3- dimethylamino third class) carbodiimide hydrochloride that volume ratio is 1:1 is added dropwise on modified electrode surface
The 6 μ L of mixed liquor of salt and 5 mg/mL n-hydroxysuccinimides is for assisting condensation reaction；Ultrapure water electrode surface,
It is dried in the air naturally at room temperature to wetting film state；
(e) electrode surface further modify 6 μ L concentration be 1 μM 17 beta estradiol aptamer of amination and be incubated for 4 under 4 °C
H makes the amino on aptamer that electrode surface is reacted and be fixed to the carboxyl in thioacetic acid, is removed with milli-Q water unbonded
17 beta estradiol aptamers, dry at room temperature；
(f) 3 μ L6- sulfydryl of electrode face finish-hex- 1- alcohol reacts 1 h to close nonspecific binding site at room temperature, uses
Milli-Q water dries at room temperature；
(g) 17 beta estradiol solution of 6 μ L various concentrations are added dropwise in electrode surface, are incubated for 1 h at room temperature, by object and fit
The immune response of body specific recognition is fixed in electrode surface, then 17 extra beta estradiols are cleaned with ultrapure water, 4 °C of ice
It is dried in case, obtains 17 beta estradiol aptamer sensor of optical electro-chemistry.
The preparation of 8 optical electro-chemistry of case study on implementation, 17 beta estradiol aptamer sensor
(a) tin indium oxide ITO electrode is cut to the cm size of 2.5 cm × 0.8, it is successively super with acetone, ethyl alcohol and ultrapure water
Sound cleans 30 min, with being dried with nitrogen；
(b) the cerium doped titanium dioxide solution that 10 μ L concentration are 5 mg/mL is modified onto ITO electrode.It dries at room temperature, so
30 min are calcined in 450 °C of Muffle furnaces afterwards, cooled to room temperature after taking-up obtains ITO/Ce:TiO2Electrode；
(c) electrode surface successively modifies the indium sulfide aqueous solution and vulcanization cadmium solution that 6 μ L concentration are 5 mg/mL, and in room temperature
Lower naturally dry, obtains ITO/Ce:TiO2/In2S3/ CdS electrode；
(d) in ITO/Ce:TiO2/In2S34 μ L thioacetic acid of/CdS electrode face finish, naturally dry and with ultrapure water,
10 mg/mL 1- ethyls-(3- dimethylamino third class) carbodiimide hydrochloride that volume ratio is 1:1 is added dropwise on modified electrode surface
The 6 μ L of mixed liquor of salt and 5 mg/mL n-hydroxysuccinimides is for assisting condensation reaction；Ultrapure water electrode surface,
It is dried in the air naturally at room temperature to wetting film state；
(e) electrode surface further modify 6 μ L concentration be 2 μM 17 beta estradiol aptamer of amination and be incubated for 4 under 4 °C
H makes the amino on aptamer that electrode surface is reacted and be fixed to the carboxyl in thioacetic acid, is removed with milli-Q water unbonded
17 beta estradiol aptamers, dry at room temperature；
(f) 3 μ L6- sulfydryl of electrode face finish-hex- 1- alcohol reacts 1 h to close nonspecific binding site at room temperature, uses
Milli-Q water dries at room temperature；
(g) 17 beta estradiol solution of 6 μ L various concentrations are added dropwise in electrode surface, are incubated for 1 h at room temperature, by object and fit
The immune response of body specific recognition is fixed in electrode surface, then 17 extra beta estradiols are cleaned with ultrapure water, 4 °C of ice
It is dried in case, obtains 17 beta estradiol aptamer sensor of optical electro-chemistry.
The detection of 9 17 beta estradiol of case study on implementation
A. standard solution is prepared: preparing 17 beta estradiol standard solution of one group of various concentration including blank standard specimen；
B. working electrode is modified: using prepared 17 beta estradiol aptamer sensor of optical electro-chemistry as working electrode, by step
In the 17 beta estradiol standard solution difference drop coating to working electrode for the various concentration prepared in a；
C. working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, is modified with step b
Good working electrode forms three-electrode system, is tested in PBS buffer solution；Using i-t means of testing to analyte into
Row detection, setting voltage are 0 V, and 120 s of runing time, optical source wavelength is 400 nm；Detect 17 β-female two to various concentration
The photo-current intensity that alcohol standard solution generates draws working curve；The light of the 17 beta estradiol standard solution containing various concentration
Current strength is denoted asI i,I iWith 17 beta estradiol concentration of standard solutioncLogarithm between it is linear, drawI i - logcWork
Make curve；
The PBS buffer solution is the phosphate buffer solution containing 0.1 mol/L ascorbic acid that 10 mL, pH are 7.4.
The detection of 10 17 beta estradiol of case study on implementation
A. standard solution is prepared: preparing 17 beta estradiol standard solution of one group of various concentration including blank standard specimen；
B. working electrode is modified: using prepared 17 beta estradiol aptamer sensor of optical electro-chemistry as working electrode, by step
In the 17 beta estradiol standard solution difference drop coating to working electrode for the various concentration prepared in a；
C. working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, is modified with step b
Good working electrode forms three-electrode system, is tested in PBS buffer solution；Using i-t means of testing to analyte into
Row detection, setting voltage are 0 V, and 120 s of runing time, optical source wavelength is 450 nm；Detect 17 β-female two to various concentration
The photo-current intensity that alcohol standard solution generates draws working curve；The light of the 17 beta estradiol standard solution containing various concentration
Current strength is denoted asI i,I iWith 17 beta estradiol concentration of standard solutioncLogarithm between it is linear, drawI i - logcWork
Make curve；
The PBS buffer solution is the phosphate buffer solution containing 0.1 mol/L ascorbic acid that 10 mL, pH are 7.4.
Claims (2)
1. 17 beta estradiol aptamer sensor of the optical electro-chemistry preparation that a kind of indium sulfide cadmium sulfide is sensitized cerium doped titanium dioxide altogether
Method, which is characterized in that preparation step is as follows:
(a) preparation of cerium doped titanium dioxide:
1 ~ 2 mL tetrabutyl titanate of measurement, which is dissolved in 40 ~ 80 mL ethyl alcohol, obtains solution A；Weigh 1.6 ~ 9.3 mg nitric acid
Cerium hydrate is soluble in water to obtain solution B；Solution A is instilled into solution B dropwise at room temperature, is turned after being vigorously stirred 30 min
Move in reaction kettle, under 160 ~ 180 °C react 12 ~ 24 h be down to room temperature naturally after reaction, with ethyl alcohol and go from
Sub- water cleaning repeatedly, dries under 50 ~ 80 °C, obtains the titania nanoparticles of cerium dopping；
(b) preparation of indium sulfide
It weighs 0.1 ~ 0.2 g inidum chloride and 0.3 ~ 0.4 g Sodium Sulphate Nine Hydroxide ultrasound is dissolved in 50 mL deionized waters simultaneously
And 30 min of magnetic agitation obtains milky white solution and is transferred in 100 mL reaction kettles, under 160 ~ 200 °C react 16 ~
24 h after a large amount of ethanol washings of the yellow solid obtained after being cooled to room temperature, are placed in a vacuum drying oven at 50 ~ 80 °C
Under be dried overnight；
(c) preparation of cadmium sulfide
It takes 0.2 ~ 0.4 g Sodium Sulphate Nine Hydroxide to be dissolved in 10 ~ 30 mL ultrapure waters, 0.2 ~ 0.5 g cadmium acetate is taken to dissolve
In 10 ~ 40 mL ultrapure waters；After mixing by two solution, it is transferred in reaction kettle, hydro-thermal under the conditions of 160 ~ 200 °C
React 20 ~ 24 h；After being cooled to room temperature, products therefrom dehydrated alcohol and ultrapure water are respectively washed 3 times；Under 50 ~ 80 °C
12 ~ 24 h are dried in vacuo, cadmiumsulfide quantum dot is made；
(d) tin indium oxide ITO electrode is cut to the cm size of 2.5 cm × 0.8, it is successively super with acetone, ethyl alcohol and ultrapure water
Sound cleans 30 ~ 40 min, with being dried with nitrogen；
(e) the cerium doped titanium dioxide Ce:TiO for being 5 mg/mL by 8 ~ 10 μ L concentration2In solution modification to ITO electrode, room temperature
Under dry, then in 400 ~ 450 °C of Muffle furnaces calcine 30 ~ 60 min, cooled to room temperature after taking-up；
(f) the indium sulfide In that 6 ~ 8 μ L concentration are 5 ~ 8 mg/mL is successively modified in electrode surface2S3Solution and 6 ~ 8 μ L
Concentration is 5 ~ 8 mg/mL cadmium sulfide CdS solution, and naturally dry at room temperature；
(g) in ITO/Ce:TiO2/In2S34 ~ 6 μ L thioacetic acid of/CdS electrode face finish, naturally dry simultaneously use ultrapure water
It rinses, it is sub- that 10 mg/mL 1- ethyls-(3- dimethylamino third class) carbon two that volume ratio is 1:1 is added dropwise on modified electrode surface
4 ~ 6 μ L of mixed liquor of amine hydrochlorate and 5 mg/mL n-hydroxysuccinimides is for assisting condensation reaction；Ultrapure water
Electrode surface dries in the air naturally at room temperature to wetting film state；
(h) it further modifies the 17 beta estradiol aptamer of amination that 4 ~ 6 μ L concentration are 1 ~ 2 μM and is incubated for 4 under 4 °C
~ 6 h make the amino on aptamer that electrode surface is reacted and be fixed to the carboxyl in thioacetic acid, not with milli-Q water removal
In conjunction with 17 beta estradiol aptamers, dry at room temperature；
(i) modification 3 ~ 5 μ L 6- sulfydryls-hex- 1- alcohol reacts 1 ~ 2 h to close nonspecific binding site at room temperature, uses
Milli-Q water dries at room temperature；
(j) 17 beta estradiol solution of 6 ~ 8 μ L various concentrations are added dropwise, are incubated for 1 ~ 2 h at room temperature, by object and fit
The immune response of body specific recognition is fixed in electrode surface, then 17 extra beta estradiols are cleaned with ultrapure water, 4 °C of ice
It is dried in case, obtains 17 beta estradiol aptamer sensor of optical electro-chemistry.
2. the 17 beta estradiol aptamer sensor of optical electro-chemistry of preparation method preparation as described in claim 1, female for 17 β-
The detection of glycol, which is characterized in that steps are as follows:
(a) standard solution is prepared: preparing 17 beta estradiol standard solution of one group of various concentration including blank standard specimen；
(b) working electrode is modified: using prepared 17 beta estradiol aptamer sensor of optical electro-chemistry as working electrode, by step
In the 17 beta estradiol standard solution difference drop coating to working electrode for the various concentration prepared in a；
(c) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, is modified with step b
Good working electrode forms three-electrode system, is tested in PBS buffer solution；Using i-t means of testing to analyte into
Row detection, setting voltage are 0 V, and 120 s of runing time, optical source wavelength is 400 ~ 450 nm；Detection is to the 17 of various concentration
The photo-current intensity that beta estradiol standard solution generates draws working curve；The 17 beta estradiol standards containing various concentration are molten
The photo-current intensity of liquid is denoted asI i,I iWith 17 beta estradiol concentration of standard solutioncLogarithm between it is linear, drawI i -
logcWorking curve；
(d) detection of 17 beta estradiols: replace 17 β-in step b female with the tap water of laboratory tap to be measured and lake water
Glycol standard solution is detected, according to response photo-current intensity according to the method in step b and cIAnd working curve, it obtains
The content of 17 beta estradiols in sample to be tested；
The PBS buffer solution is that the phosphate-buffered containing 0.1 mol/L ascorbic acid that 10 mL, pH are 5.0 ~ 8.0 is molten
Liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910776014.5A CN110441361B (en) | 2019-08-22 | 2019-08-22 | Preparation method of photoelectric chemical 17 beta-estradiol aptamer sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910776014.5A CN110441361B (en) | 2019-08-22 | 2019-08-22 | Preparation method of photoelectric chemical 17 beta-estradiol aptamer sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110441361A true CN110441361A (en) | 2019-11-12 |
| CN110441361B CN110441361B (en) | 2021-09-24 |
Family
ID=68437040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910776014.5A Active CN110441361B (en) | 2019-08-22 | 2019-08-22 | Preparation method of photoelectric chemical 17 beta-estradiol aptamer sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110441361B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110907511A (en) * | 2019-12-12 | 2020-03-24 | 济南大学 | Gold-curcumin nanoparticle quenched CdS hybrid TiO2Electrochemical luminescence sensor for detecting insulin by nanobelt |
| CN112326754A (en) * | 2020-11-13 | 2021-02-05 | 济南大学 | Detect Cu2+Of (2) a novel composite nanosystem |
| CN114002281A (en) * | 2021-10-22 | 2022-02-01 | 济南大学 | Preparation method of photoelectrochemical sensor for estriol detection |
| CN114280123A (en) * | 2021-12-20 | 2022-04-05 | 济南大学 | Preparation method of photoelectrochemical sensor for tetracycline detection |
| CN117645416A (en) * | 2024-01-29 | 2024-03-05 | 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 |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626642A (en) * | 2012-03-20 | 2012-08-08 | 浙江理工大学 | Preparation method of cadmium sulfide-titanium oxide nanosheet composite photocatalyst |
| CN103151175A (en) * | 2013-02-06 | 2013-06-12 | 天津大学 | Cadmium sulfide (CdS) quantum dot sensitized branching titanium dioxide (TiO2) nanorod array electrode and preparation method and usage thereof |
| CN103940867A (en) * | 2014-04-11 | 2014-07-23 | 同济大学 | Method for preparing photoelectric adapter sensor for detecting 17beta-estradiol |
| CN104297305A (en) * | 2014-09-06 | 2015-01-21 | 济南大学 | Making method and application of CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor |
| CN104297495A (en) * | 2014-09-06 | 2015-01-21 | 济南大学 | Making method and application of CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor |
| CN104934230A (en) * | 2015-06-23 | 2015-09-23 | 西南交通大学 | Preparation method of composite light anode of titanium dioxide nanotube array with wide light intensity application scope |
| CN105572197A (en) * | 2016-02-25 | 2016-05-11 | 济南大学 | Preparation method and application of photoelectrochemical estradiol sensor based on magnetic photosensitive nanomaterial |
| CN106449121A (en) * | 2016-11-29 | 2017-02-22 | 吉林大学 | CdS/TiO2 composite nanofilm, as well as preparation method and application thereof |
| CN106830071A (en) * | 2017-03-09 | 2017-06-13 | 吉林大学 | A kind of preparation method of the spherical nano titanium oxide doped with rare earth |
| US20170227486A1 (en) * | 2016-02-09 | 2017-08-10 | The Florida International University Board Of Trustees | Sensors for the detection of analytes |
| CN107202828A (en) * | 2017-07-10 | 2017-09-26 | 山东利源康赛环境咨询有限责任公司 | A kind of estradiol optical electro-chemistry sensor and its preparation and application based on boron doping iron cobalt/cobalt oxide two-dimensional nano composite |
| CN110124740A (en) * | 2019-06-12 | 2019-08-16 | 常州大学 | Cerium dopping NH2The preparation method of-UiO-66/ indium sulfide zinc composite visible light catalyst |
-
2019
- 2019-08-22 CN CN201910776014.5A patent/CN110441361B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626642A (en) * | 2012-03-20 | 2012-08-08 | 浙江理工大学 | Preparation method of cadmium sulfide-titanium oxide nanosheet composite photocatalyst |
| CN103151175A (en) * | 2013-02-06 | 2013-06-12 | 天津大学 | Cadmium sulfide (CdS) quantum dot sensitized branching titanium dioxide (TiO2) nanorod array electrode and preparation method and usage thereof |
| CN103940867A (en) * | 2014-04-11 | 2014-07-23 | 同济大学 | Method for preparing photoelectric adapter sensor for detecting 17beta-estradiol |
| CN104297305A (en) * | 2014-09-06 | 2015-01-21 | 济南大学 | Making method and application of CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor |
| CN104297495A (en) * | 2014-09-06 | 2015-01-21 | 济南大学 | Making method and application of CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor |
| CN104934230A (en) * | 2015-06-23 | 2015-09-23 | 西南交通大学 | Preparation method of composite light anode of titanium dioxide nanotube array with wide light intensity application scope |
| US20170227486A1 (en) * | 2016-02-09 | 2017-08-10 | The Florida International University Board Of Trustees | Sensors for the detection of analytes |
| CN105572197A (en) * | 2016-02-25 | 2016-05-11 | 济南大学 | Preparation method and application of photoelectrochemical estradiol sensor based on magnetic photosensitive nanomaterial |
| CN106449121A (en) * | 2016-11-29 | 2017-02-22 | 吉林大学 | CdS/TiO2 composite nanofilm, as well as preparation method and application thereof |
| CN106830071A (en) * | 2017-03-09 | 2017-06-13 | 吉林大学 | A kind of preparation method of the spherical nano titanium oxide doped with rare earth |
| CN107202828A (en) * | 2017-07-10 | 2017-09-26 | 山东利源康赛环境咨询有限责任公司 | A kind of estradiol optical electro-chemistry sensor and its preparation and application based on boron doping iron cobalt/cobalt oxide two-dimensional nano composite |
| CN110124740A (en) * | 2019-06-12 | 2019-08-16 | 常州大学 | Cerium dopping NH2The preparation method of-UiO-66/ indium sulfide zinc composite visible light catalyst |
Non-Patent Citations (4)
| Title |
|---|
| MORTEZA ALINEZHAD NAMEGHI 等: "An ultrasensitive electrochemical sensor for 17b-estradiol using split aptamers", 《ANALYTICA CHIMICA ACTA》 * |
| YONG ZUO 等: "Facile synthesis of TiO2/In2S3/CdS ternary porous heterostructure arrays with enhanced photoelectrochemical and visible-light photocatalytic properties", 《J. MATER. CHEM. C》 * |
| YUEWEN LI 等: "A photoelectrochemical aptasensor for the detection of 17b-estradiol based on In2S3 and CdS co-sensitized cerium doped TiO2", 《NEW J. CHEM.》 * |
| 李月雯: "铟基硫化物光电化学传感材料制备及检测雌二醇性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110907511A (en) * | 2019-12-12 | 2020-03-24 | 济南大学 | Gold-curcumin nanoparticle quenched CdS hybrid TiO2Electrochemical luminescence sensor for detecting insulin by nanobelt |
| CN112326754A (en) * | 2020-11-13 | 2021-02-05 | 济南大学 | Detect Cu2+Of (2) a novel composite nanosystem |
| CN114002281A (en) * | 2021-10-22 | 2022-02-01 | 济南大学 | Preparation method of photoelectrochemical sensor for estriol detection |
| CN114002281B (en) * | 2021-10-22 | 2023-06-20 | 济南大学 | Preparation method of photoelectrochemical sensor for detecting estriol |
| CN114280123A (en) * | 2021-12-20 | 2022-04-05 | 济南大学 | Preparation method of photoelectrochemical sensor for tetracycline detection |
| CN114280123B (en) * | 2021-12-20 | 2023-06-30 | 济南大学 | Preparation method of photoelectrochemical sensor for tetracycline detection |
| CN117645416A (en) * | 2024-01-29 | 2024-03-05 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110441361B (en) | 2021-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110441361A (en) | A kind of indium sulfide cadmium sulfide is sensitized the 17 beta estradiol aptamer sensor preparation method of optical electro-chemistry of cerium doped titanium dioxide altogether | |
| CN108318477B (en) | Based on TiO2Electrochemiluminescence probe prepared by metal organic framework and competitive immunosensing method of electrochemiluminescence probe for vomitoxin | |
| CN104927867B (en) | A kind of ratio fluorescent probe of bivalent cupric ion and its preparation method and application | |
| CN109060898B (en) | Based on CeO2Preparation method of-CdS-weakened brain natriuretic peptide antigen photoelectrochemical sensor | |
| CN110590753B (en) | Near-infrared SO of target mitochondria2Derivative ratiometric fluorescent probes and uses thereof | |
| CN103076316A (en) | Method for detecting trace amount of oxytetracycline by utilizing CdTe quantum dot fluorescent probe | |
| CN106596481A (en) | Method for detecting Pb<2+> by use of boron-nitrogen-doped fluorescent carbon point probe | |
| CN106290514A (en) | A kind of TiO based on silicon phthalocyanine functionalization2it is situated between and sees the aflatoxin Optical Electro-Chemistry detection method of crystal | |
| CN108587607B (en) | Luminescent metal organic framework material for detecting thiocyanate ions in water and preparation method and application thereof | |
| CN107118763A (en) | A kind of pair of emission ratios type fluorescence probe and its preparation and application | |
| CN109781818A (en) | A kind of Photoelectrochemistrbiosensor biosensor and preparation method thereof | |
| CN110308286A (en) | One kind being based on the enhanced thyroglobulin electrochemiluminescimmunosensor immunosensor of photo-thermal release signal | |
| CN110554027A (en) | preparation method and application of immunosensor for promoting gold nanocluster electroluminescent response based on iron oxide array coreaction | |
| CN112251216A (en) | Preparation method and application of bisphenol A carbon dot molecular imprinting fluorescent composite probe based on magnetic covalent organic framework | |
| CN102796737B (en) | A fluorescent molecular modified nano-silver probe, a kit thereof, and application of the kit in the detection of streptavidin | |
| Wang et al. | A “signal-off” type photoelectrochemical immunosensor for detecting carcinoembryonic antigen based on TiO2 NRs/BiOI heterojunction and SiO2/PDA-Au inhibitor | |
| CN102565020A (en) | Method for quantitatively detecting protein through quantum dot resonant scattering | |
| CN104076072A (en) | High-sensitivity photoelectrochemical sensor made from iridium oxide-ferriporphyrin-titanium oxide and preparation method for sensor | |
| CN104865300A (en) | Preparation method and application of photoelectrochemical sensor based on Au@TiO2/Bi2S3 modified electrode | |
| CN112526135A (en) | Preparation method and application of photoelectrochemical biosensor for detecting prostate specific antigen | |
| CN109852383B (en) | Fullerene-based fluorescent probe capable of rapidly and efficiently responding to glutathione and preparation method and application thereof | |
| CN113861962B (en) | Ratiometric fluorescent probe, preparation method thereof and application thereof in detecting hydrogen peroxide | |
| CN103555334B (en) | CdTe/ZnS core-shell quantum dots, preparation method and application of CdTe/ZnS core-shell quantum dots | |
| CN103529197B (en) | Aptamers modify Nano-Au probe and test kit thereof and detecting the application in PDGF-BB | |
| CN111812183B (en) | Preparation method and application of intramolecular photo-electrochemical sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |