CN104297495A - Making method and application of CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor - Google Patents
Making method and application of CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor Download PDFInfo
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- CN104297495A CN104297495A CN201410451337.4A CN201410451337A CN104297495A CN 104297495 A CN104297495 A CN 104297495A CN 201410451337 A CN201410451337 A CN 201410451337A CN 104297495 A CN104297495 A CN 104297495A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/74—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving hormones or other non-cytokine intercellular protein regulatory factors such as growth factors, including receptors to hormones and growth factors
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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
Abstract
The invention relates to a making method and an application of a CdS sensitized TiO2 environmental estrogen photoelectrochemical sensor. The method uses TiO2 as an antigen capture substrate material, a CdS photoelectric active material is in situ generated on the surface of a Cd2<+> functional TiP nanomaterial maker modified electrode through a direct Na2S dropping technology, and CdS is irritated by an LED lamp of visible light wavelength to be converted to a photoelectric current signal. The substrate material TiO2 can be well matched with CdS energy band, so the photocurrent conversion signal of CdS is further improved, thereby the competitive photoelectrochemical immunosensor for ultra sensitive detection of estradiol, estriol, diethylstilbestrol, bisphenol A, nonylphenol, oestrone and other environmental pollutants is made.
Description
Technical field
The present invention relates to a kind of CdS sensitization TiO
2environmental estrogens Optical Electro-Chemistry transducer production method and application, be specifically related to a kind of in-situ preparation CdS sensitization TiO
2the preparation method of competitive type environmental estrogens Photoelectrochemistrbiosensor biosensor and application, belong to new function material and environmental contaminants bio-sensing detection technique field.
Background technology
Along with the fast development of modern industrial or agricultural, a large amount of environmentally hazardous substance enters human habitat along with the activity in production of the mankind, produces high risks to the health of the mankind.Environmental estrogens refers to and is present in environment, has the chemical substance of similar biosome inner estrogen activity, can produce the environmental toxin with simulation estrogen action after entering human body.Trace estrogen in environment enters human body by food chain, false hormone being formed, by affecting the endocrinal glands that the body weight for humans such as human adrenal, thyroid gland is wanted, making its abnormal secretion, thus cause nerve system of human body and immune dysfunction, have a strong impact on human physical and mental health.
Monitoring is the important step ensureing food security, sets up a kind of method that is quick, easy, Sensitive Detection environmental estrogens very important.The domestic and international method to environmental estrogens detection mainly contains high performance liquid chromatography, immunological method, electrochemical method, bioanalysis etc. at present, but majority needs expensive instrument, and its complicated operation, detects limit for height, can not well be applied.Therefore, in order to solve the weak point of said method, the invention provides a kind of simple, fast, sensitivity and the high Optical Electro-Chemistry immune analysis method of selectivity.
Optical Electro-Chemistry sensor is the class pick-up unit determining testing concentration based on the light transfer characteristic of material.Optical Electro-Chemistry detection method have highly sensitive, equipment simple, be easy to microminiaturized feature, become a kind of analytical approach having application potential, had broad application prospects in food, environment, medicine and other fields.
The present invention adopts the rhodamine B-sensitized TiO with good efficiency of light absorption
2semiconductor composite catches substrate as haptens, utilizes Cd
2+the porous TiP nanoparticle label antibody of functionalization, by directly dripping Na at electrode surface
2s, the narrow band gap CdS of in-situ preparation high optoelectronic conversion ratio.Due to base material TiO
2matching degree can be with good with CdS, the photocurrent switching signal of CdS can be improved further.A kind of CdS sensitization TiO prepared by the present invention
2environmental estrogens Optical Electro-Chemistry sensor, there is low cost, highly sensitive, specificity good, the advantage such as quick detection, and preparation process is simple, achieves quick, the Sensitive Detection to multiple environmental estrogens, effectively overcome the deficiency of current environmental estrogens detection method in visible region.
Summary of the invention
An object of the present invention is based on in-situ preparation narrow band gap CdS, constructs a kind of simple, quick, sensitive competitive type Optical Electro-Chemistry immunosensor.
Two of object of the present invention is by generated in-situ narrow band gap CdS and substrate broad-band gap TiO
2can mate by band, achieve quick, the Sensitive Detection object of visible region to multiple environmental estrogens.
technical scheme of the present invention is as follows:
1. a CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method, is characterized in that, comprise the following steps:
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 2 ~ 4mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 400 ~ 500 DEG C of calcining 30 ~ 60min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.1 ~ 1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 1 ~ 3% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiP@Cd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1 pg/mL ~ 20 ng/mL.
2. rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.01 ~ 0.03 mol butyl titanate is dissolved in 30mL ethanol, add 10mL water, stir 30 ~ 120min, mixed solution is transferred in autoclave, 5 ~ 10h is reacted at 200 DEG C, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 70 ~ 90 DEG C of conditions, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10 mg TiO
2powder joins in 2.5 mL, 0.1 ~ 0.2 mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/L NaOH, and vibration 4 ~ 24 h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2 mg/mL with water
2solution.
3. TiP@Cd
2+the preparation of-Ab antibody hatching solution
(1) preparation of TiP
The lauryl sodium sulfate of 0.3 g adds 20 mL EtOH Sonicate, adds 2 ~ 4 mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4 h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5 mL butyl titanates and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:4 ~ 8, stirs 20 min, 80 DEG C of backflow 6 h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiP@Cd
2+the preparation of solution
By the Cd (NO of 1 mL, 40 mg/mLTiP aqueous solution and 17 mL, 6 ~ 14 mmol/L
3)
24H
2o aqueous solution is blended, stirs 4 ~ 24 h at 50 DEG C, centrifugal, water washing 3 times, the TiP@Cd obtained
2+with the TiP@Cd that aqueous dispersion is 20 mg/mL
2+solution;
(3) TiP@Cd
2+the preparation of-Ab antibody hatching solution
To the TiP@Cd of 2mL, 20 mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5 mL, 1 ~ 3 mg/mL is added, ultrasonic 20 ~ 60 min, centrifuge washing in solution; Being dispersed in 2 mL, massfraction is in the glutaraldehyde water solution of 1.0 ~ 3.5%, shake 2 h and centrifugal, is 2 mL with the PBS dilution that pH is 7.4; Add 10 ~ 100 μ L, 1 mg/mL environmental estrogens antibody A b solution, vibrate 20 h, is the PBS centrifuge washing of 7.4 with pH, and being finally dispersed in 5 mL, pH is in the PBS of 7.4, obtained TiP@Cd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
4. the detecting step of environmental estrogens
(1) at prepared Optical Electro-Chemistry sensor electrode surface, the Na of 4 μ L, 0.7 mol/L is dripped
2s solution, places 30 ~ 80 min;
(2) electrochemical workstation is used to test with three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is auxiliary electrode, prepared Optical Electro-Chemistry sensor electrical very working electrode, tested in containing in the PBS buffer solution of 0.1mol/L ascorbic acid of 10 mL, pH 7.0 ~ 7.5;
(3) used time m-current method to environmental stimulus element standard solution detect, arranging voltage is 0.1 V, working time 100 s, irradiation LED lamp wavelength is 400 ~ 450 nm;
(4) after background current tends towards stability, to turn on light prolonged exposure 10 s every 20 s, recording light electric current, drawing curve;
(5) environmental estrogens standard solution is replaced to detect environmental estrogens sample solution to be measured.
5. environmental estrogens of the present invention is selected from one of following: estradiol, estriol, diethylstilbestrol, bisphenol-A, nonylphenol, oestrone.
useful achievement of the present invention
(1) with simple TiO
2compare, adopt rhodamine B functionalization TiO
2, effectively can improve photoelectric transformation efficiency.
(2) Cd is utilized
2+the TiP nano particle of functionalization is labeled thing as antibody, adopts and directly drips Na at electrode surface
2the CdS semiconductor nano material of S in-situ preparation narrow band gap, raw material is cheap, method is simple.
(3) the generated in-situ CdS of electrode surface with as the TiO catching base material
2have and good can be with coupling, effectively raise the photoelectric transformation efficiency of CdS, obtained sensor achieves the super sensitivity detection to environmental estrogens.
(5) the present invention utilizes the immune response of haptens, antibody, improves the specificity of detection method.
(6) the competitive type Optical Electro-Chemistry immunosensor prepared of the present invention, for the detection of multiple environmental estrogens, the response time is short, and detectability is low, and the range of linearity is wide, can realize simple, quick, highly sensitive and specific detection.
Embodiment
embodiment 1a kind of CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method and application
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 2mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 400 DEG C of calcining 30 min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 1% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiP@Cd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1 pg/mL ~ 20 ng/mL.
embodiment 2a kind of CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method and application
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 3mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 450 DEG C of calcining 45 min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.5 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 2% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiP@Cd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1 pg/mL ~ 20 ng/mL.
embodiment 3a kind of CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method and application
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 4 mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 500 DEG C of calcining 60 min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 3% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiP@Cd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1 pg/mL ~ 20 ng/mL.
embodiment 4rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.01mol butyl titanate is dissolved in 30 mL ethanol, adds 10 mL water, stirs 30 min, mixed solution is transferred in autoclave, at 200 DEG C, react 5 h, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, under 70 DEG C of conditions, vacuum drying 12 h, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10 mg TiO
2powder joins in 2.5 mL, 0.1 mg/mL rhodamine B aqueous solution, and regulate pH to 7 with 0.1mol/L NaOH, vibrate 4 h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2 mg/mL with water
2solution.
Embodiment 5 rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.02 mol butyl titanate is dissolved in 30 mL ethanol, adds 10 mL water, stirs 60 min, mixed solution is transferred in autoclave, at 200 DEG C, react 8 h, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, under 80 DEG C of conditions, vacuum drying 12 h, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10 mg TiO
2powder joins in 2.5 mL, 0.15 mg/mL rhodamine B aqueous solution, and regulate pH to 7 with 0.1mol/L NaOH, vibrate 10 h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2 mg/mL with water
2solution.
embodiment 6rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.03 mol butyl titanate is dissolved in 30 mL ethanol, adds 10 mL water, stirs 120 min, mixed solution is transferred in autoclave, at 200 DEG C, react 10 h, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, under 90 DEG C of conditions, vacuum drying 12 h, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10 mg TiO
2powder joins in 2.5 mL, 0.2 mg/mL rhodamine B aqueous solution, and regulate pH to 7 with 0.1mol/LNaOH, vibrate 24 h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2 mg/mL with water
2solution.
embodiment 7tiP@Cd
2+the preparation of-Ab antibody hatching solution
(1) preparation of TiP
The lauryl sodium sulfate of 0.3 g adds 20 mL EtOH Sonicate, adds 2 mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4 h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5 mL butyl titanates and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:4, stirs 20 min, 80 DEG C of backflow 6 h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiP@Cd
2+the preparation of solution
By the Cd (NO of 1 mL, 40 mg/mLTiP aqueous solution and 17 mL, 6 ~ 14 mol/L
3)
24H
2o aqueous solution is blended, stirs 4 h at 50 DEG C, centrifugal, water washing 3 times, the TiP@Cd obtained
2+with the TiP@Cd that aqueous dispersion is 20 mg/mL
2+solution;
(3) TiP@Cd
2+the preparation of-Ab antibody hatching solution
To the TiP@Cd of 2mL, 20 mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5 mL, 1 mg/mL is added, ultrasonic 20min, centrifuge washing in solution; Being dispersed in 2 mL, massfraction is in the glutaraldehyde water solution of 1.0%, shake 2 h and centrifugal, is 2 mL with the PBS dilution that pH is 7.4; Add 10 μ L, 1 mg/mL environmental estrogens antibody A b solution, vibrate 20 h, is the PBS centrifuge washing of 7.4 with pH, and being finally dispersed in 5 mL, pH is in the PBS of 7.4, obtained TiP@Cd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
embodiment 8tiP@Cd
2+the preparation of-Ab antibody hatching solution
(1) preparation of TiP
The lauryl sodium sulfate of 0.3 g adds 20 mL EtOH Sonicate, adds 3 mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4 h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5 mL butyl titanates and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:6, stirs 20 min, 80 DEG C of backflow 6 h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiP@Cd
2+the preparation of solution
By the Cd (NO of 1 mL, 40 mg/mLTiP aqueous solution and 17 mL, 10 mmol/L
3)
24H
2o aqueous solution is blended, stirs 20 h at 50 DEG C, centrifugal, water washing 3 times, the TiP@Cd obtained
2+with the TiP@Cd that aqueous dispersion is 20 mg/mL
2+solution;
(3) TiP@Cd
2+the preparation of-Ab antibody hatching solution
To the TiP@Cd of 2mL, 20 mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5 mL, 2 mg/mL is added, ultrasonic 45 min, centrifuge washing in solution; Being dispersed in 2 mL, massfraction is in the glutaraldehyde water solution of 2.0%, shake 2 h and centrifugal, is 2 mL with the PBS dilution that pH is 7.4; Add 50 μ L, 1 mg/mL environmental estrogens antibody A b solution, vibrate 20 h, is the PBS centrifuge washing of 7.4 with pH, and being finally dispersed in 5 mL, pH is in the PBS of 7.4, obtained TiP@Cd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
embodiment 9tiP@Cd
2+the preparation of-Ab antibody hatching solution, step is as follows:
(1) preparation of TiP
The lauryl sodium sulfate of 0.3 g adds 20 mL EtOH Sonicate, adds 4 mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4 h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5 mL butyl titanates and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:8, stirs 20 min, 80 DEG C of backflow 6 h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiP@Cd
2+the preparation of solution
By the Cd (NO of 1 mL, 40 mg/mLTiP aqueous solution and 17 mL, 14 mmol/L
3)
24H
2o aqueous solution is blended, stirs 24 h at 50 DEG C, centrifugal, water washing 3 times, the TiP@Cd obtained
2+with the TiP@Cd that aqueous dispersion is 20 mg/mL
2+solution;
(3) TiP@Cd
2+the preparation of-Ab antibody hatching solution
To the TiP@Cd of 2mL, 20 mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5 mL, 3 mg/mL is added, ultrasonic 60 min, centrifuge washing in solution; Being dispersed in 2 mL, massfraction is in the glutaraldehyde water solution of 3.5%, shake 2 h and centrifugal, is 2 mL with the PBS dilution that pH is 7.4; Add 100 μ L, 1 mg/mL environmental estrogens antibody A b solution, vibrate 20 h, is the PBS centrifuge washing of 7.4 with pH, and being finally dispersed in 5 mL, pH is in the PBS of 7.4, obtained TiP@Cd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
embodiment 10the detection of estradiol
(1) at prepared Optical Electro-Chemistry sensor electrode surface, the Na of 4 μ L, 0.7 mol/L is dripped
2s solution, places 30 ~ 80 min;
(2) electrochemical workstation is used to test with three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is auxiliary electrode, prepared Optical Electro-Chemistry sensor electrical very working electrode, tested in containing in the PBS buffer solution of 0.1 mol/L ascorbic acid of 10 mL, pH 7.0 ~ 7.5;
(3) used time m-current method detects analysis thing standard solution, and arranging voltage is 0.1 V, working time 100 s, irradiation LED lamp wavelength is 400 ~ 450 nm;
(4) after background current tends towards stability, to turn on light prolonged exposure 10 s every 20 s, recording light electric current, drawing curve;
(5) carry out estradiol sample analysis according to the method for drawing curve, recording the range of linearity is 5 pg/mL ~ 10 ng/mL, detects and is limited to 2pg/mL.
embodiment 11the detection of estriol
Drawing curve step, with embodiment 10, carries out estriol sample analysis according to the method for drawing curve, and recording the range of linearity is 1.5 pg/mL ~ 10 ng/mL, detects and is limited to 0.85pg/mL.
embodiment 12the detection of diethylstilbestrol
Drawing curve step, with embodiment 10, carries out diethylstilbestrol sample analysis according to the method for drawing curve, and recording the range of linearity is 7.5 pg/mL ~ 13 ng/mL, detects and is limited to 2.3pg/mL.
embodiment 13the detection of bisphenol-A
Drawing curve step, with embodiment 10, carries out bisphenol-A sample analysis according to the method for drawing curve, and recording the range of linearity is 5 pg/mL ~ 8 ng/mL, detects and is limited to 1.5pg/mL.
embodiment 14the detection of nonylphenol
Drawing curve step, with embodiment 10, carries out nonylphenol sample analysis according to the method for drawing curve, and recording the range of linearity is 10 pg/mL ~ 20 ng/mL, detects and is limited to 2.8pg/mL.
embodiment 14the detection of oestrone
Drawing curve step, with embodiment 10, carries out oestrone sample analysis according to the method for drawing curve, and recording the range of linearity is 8 pg/mL ~ 18 ng/mL, detects and is limited to 1.8pg/mL.
Claims (5)
1. a CdS sensitization TiO
2environmental estrogens Optical Electro-Chemistry transducer production method, is characterized in that, comprise the following steps:
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 2 ~ 4mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 400 ~ 500 DEG C of calcining 30 ~ 60min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.1 ~ 1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 1 ~ 3% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor;
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiP@Cd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained;
The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1 pg/mL ~ 20 ng/mL.
2. a kind of CdS sensitization TiO as claimed in claim 1
2environmental estrogens Optical Electro-Chemistry transducer production method, described rhodamine B functionalization TiO
2solution, is characterized in that, preparation process is as follows:
(1) TiO
2the preparation of powder
0.01 ~ 0.03 mol butyl titanate is dissolved in 30mL ethanol, add 10mL water, stir 30 ~ 120min, mixed solution is transferred in autoclave, 5 ~ 10h is reacted at 200 DEG C, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 70 ~ 90 DEG C of conditions, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10 mg TiO
2powder joins in 2.5 mL, 0.1 ~ 0.2 mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/L NaOH, and vibration 4 ~ 24 h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2 mg/mL with water
2solution.
3. a kind of CdS sensitization TiO as claimed in claim 1
2environmental estrogens Optical Electro-Chemistry transducer production method, described TiP@Cd
2+-Ab antibody hatching solution, it is characterized in that, preparation process is as follows:
(1) preparation of TiP
The lauryl sodium sulfate of 0.3 g adds 20 mL EtOH Sonicate, adds 2 ~ 4 mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4 h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5 mL butyl titanates and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:4 ~ 8, stirs 20 min, 80 DEG C of backflow 6 h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiP@Cd
2+the preparation of solution
By the Cd (NO of 1 mL, 40 mg/mLTiP aqueous solution and 17 mL, 6 ~ 14 mmol/L
3)
24H
2o aqueous solution is blended, stirs 4 ~ 24 h at 50 DEG C, centrifugal, water washing 3 times, the TiP@Cd obtained
2+with the TiP@Cd that aqueous dispersion is 20 mg/mL
2+solution;
(3) TiP@Cd
2+the preparation of-Ab antibody hatching solution
To the TiP@Cd of 2mL, 20 mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5 mL, 1 ~ 3 mg/mL is added, ultrasonic 20 ~ 60 min, centrifuge washing in solution; Being dispersed in 2 mL, massfraction is in the glutaraldehyde water solution of 1.0 ~ 3.5%, shake 2 h and centrifugal, is 2 mL with the PBS dilution that pH is 7.4; Add 10 ~ 100 μ L, 1 mg/mL environmental estrogens antibody A b solution, vibrate 20 h, is the PBS centrifuge washing of 7.4 with pH, and being finally dispersed in 5 mL, pH is in the PBS of 7.4, obtained TiP@Cd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
4. a kind of CdS sensitization TiO of obtaining of preparation method as claimed in claim 1
2environmental estrogens Optical Electro-Chemistry transducer production method, is characterized in that, for the detection of environmental estrogens, detecting step is as follows:
(1) at prepared Optical Electro-Chemistry sensor electrode surface, the Na of 4 μ L, 0.7 mol/L is dripped
2s solution, places 30 ~ 80 min;
(2) electrochemical workstation is used to test with three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is auxiliary electrode, prepared Optical Electro-Chemistry sensor electrical very working electrode, tested in containing in the PBS buffer solution of 0.1mol/L ascorbic acid of 10 mL, pH 7.0 ~ 7.5;
(3) m-current method detects environmental estrogens standard solution the used time, and arranging voltage is 0.1 V, working time 100 s, irradiation LED lamp wavelength is 400 ~ 450 nm;
(4) after background current tends towards stability, to turn on light prolonged exposure 10 s, then recording light electric current every 20 s, drawing curve;
(5) environmental estrogens standard solution is replaced to detect environmental estrogens sample solution to be measured.
5. a kind of CdS sensitization TiO as claimed in claim 1
2environmental estrogens Optical Electro-Chemistry transducer production method, is characterized in that, described ambient environment estrogen is selected from one of following: estradiol, estriol, diethylstilbestrol, bisphenol-A, nonylphenol, oestrone.
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