CN105699646B - A kind of preparation method and application of the electrogenerated chemiluminescence nonyl phenol sensor based on titanium dioxide nanoplate composite - Google Patents
A kind of preparation method and application of the electrogenerated chemiluminescence nonyl phenol sensor based on titanium dioxide nanoplate composite Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/558—Immunoassay; Biospecific binding assay; Materials therefor using diffusion or migration of antigen or antibody
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
- G01N33/531—Production of immunochemical test materials
- G01N33/532—Production of labelled immunochemicals
Abstract
The invention discloses a kind of preparation method of the electrogenerated chemiluminescence nonyl phenol sensor based on titanium dioxide nanoplate composite.Belong to Nano-function thin films and biosensor technology field.The method comprises the steps of firstly, preparing a kind of magnetic Nano light-sensitive material FeCo N@TiO of New Two Dimensional sheet2, using the good biocompatibility of the material, big specific surface area and ferromagnetism, nonyl phenol antibody in load, then by the crosslinked action horseradish peroxidase of glutaraldehyde, when being detected, because horseradish peroxidase can produce oxygen so that catalyzing hydrogen peroxide is in situ, and and then be to be electrochemically reacted with bottom liquid, produce high and stabilization electrochemiluminescence signal, recycle antibody that the influence to electron transport ability is combined with the specific quantification of antigen, so that electrochemiluminescence signal is accordingly reduced, low cost finally has been obtained, sensitivity is high, specificity is good, detection is quick, prepare the electroluminescent chemiluminescence biosensor of simple detection nonyl phenol.
Description
Technical field
The present invention relates to a kind of preparation method of electrogenerated chemiluminescence nonyl phenol sensor.Belong to Nano-function thin films
With biosensor technology field.
Background technology
Environmental estrogens refer to synthesis, release with normal endocrine material in interfering bodies, fortune after a class enters body
It is defeated, with reference to, metabolism etc. process, activation or suppress internal system function so that destroy maintenance organism stability and regulation and control make
Compound, environmental estrogens species is various, including artificial-synthetic compound and natural plant estrogen, is distributed widely in certainly
In right boundary.Nonyl phenol is a species bisphenols synthetic estrogen.At present, the method for detection nonyl phenol mainly has chromatography, matter
Spectrometry etc..Such method instrument is valuable, complex operation, and laboratory personnel can just be detected after needing professional training.Therefore, research and develop
Low cost, detection is fast, sensitivity is high, high specificity nonyl phenol sensor is significant.
Electrochemiluminescsensor sensor the advantages of its sensitivity is high, specificity is good, easy to operate due to being widely used in
The fields such as clinical diagnosis, Pharmaceutical Analysis, environmental monitoring.The superior electrochemical luminescence sensor of processability, its most critical technology
It is exactly the raising of the performances such as effective fixed and reappearance of luminous intensity and stability and immune molecule.Titanium dioxide is using most
It is a kind of extensive photocatalyst material, because sheet-like titanium dioxide nanomaterial can expose more high miller index surfaces, tool
There is photocatalytic activity higher, titanium dioxide nanoplate has than nano-particle preferably application prospect, received for titanium dioxide
The research of rice piece also receives much concern.Meanwhile, titanium dioxide poorly conductive also limit and be built by single titanium dioxide nano material
Electrochemiluminescsensor sensor sensitivity it is universal not high, be unfavorable for practical application.But, repaiied on semiconductor nano material
Decorations or compound special nano material, can effectively improve the Resonance energy transfer of semiconductor surface, produce stronger luminous strong
Degree, and greatly improve detection sensitivity.Therefore, it is system to design, prepare the efficient, titanium dioxide nanoplate of stabilization and its trim
The key technology of standby Electrochemiluminescsensor sensor.
The content of the invention
Prepare that simple, sensitivity is high, detection is quick, high specificity electroluminescent chemistry it is an object of the invention to provide a kind of
The preparation method of luminous nonyl phenol sensor, prepared sensor can be used for quick, the Sensitive Detection of nonyl phenol.Based on this
Purpose, the method comprises the steps of firstly, preparing a kind of magnetic Nano material of two-dimensional sheet, i.e. the nitrogen of iron and cobalt dual-metal In-situ reaction is mixed
Miscellaneous titanium dioxide nanoplate FeCo-N@TiO2, using the good biocompatibility of the material, big specific surface area and ferromagnetic
Property, then nonyl phenol antibody in load fix horseradish peroxidase by the crosslinked action of glutaraldehyde, when being detected,
Because horseradish peroxidase can be with catalyzing hydrogen peroxide in-situ preparation O2, and with bottom liquid in K2S2O8It is electrochemically reacted,
Electrochemiluminescence signal is produced, recycles antibody that the influence to electron transport ability is combined with the specific quantification of antigen, made
Current strength reduction is obtained, so as to reduce luminous intensity, is finally realized and nonyl is detected using unmarked electrogenerated chemiluminescence method
The structure of the biology sensor of base phenol.
The technical solution adopted by the present invention is as follows：
1. a kind of preparation side of the electrogenerated chemiluminescence nonyl phenol sensor based on titanium dioxide nanoplate composite
Method, described titanium dioxide nanoplate composite is iron and the nitrogen-doped titanium dioxide nanometer sheet of cobalt dual-metal In-situ reaction
FeCo-N@TiO2, described electrogenerated chemiluminescence nonyl phenol sensor is by working electrode, FeCo-N TiO2, nonyl phenol antibody, ox
Seralbumin, glutaraldehyde, horseradish peroxidase composition；
Characterized in that, described preparation method includes following preparation process：
a. FeCo-N@TiO2Preparation；
B. the preparation of electrogenerated chemiluminescence nonyl phenol sensor；
Wherein, step a prepares FeCo-N@TiO2Concretely comprise the following steps：
First, 0.8 mmol molysite, 0.8 ~ 1.2 mmol cobalt salts and 1 mmol ammonium salts are taken and is added to 5 mL butyl titanates
In, in whipping process, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, reacted in a kettle. at 160 ~ 200 DEG C 18 ~ 24 hours, it is cold
But to after room temperature, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be vacuum dried at 50 DEG C；Then, the powder that will be ground
It is put into Muffle furnace, programming rate is 1 ~ 3 DEG C/min, at 480 ~ 560 DEG C under nitrogen protection, calcines 10 ~ 60 min；Finally,
Powder after calcining is cooled to room temperature, that is, FeCo-N@TiO are obtained2；
Described molysite is selected from one of following：Ferric sulfate, iron chloride, ferric nitrate；
Described cobalt salt is selected from one of following：Cobaltous sulfate, cobalt chloride, cobalt nitrate；
Described ammonium salt is selected from one of following：Ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate；
Step b prepares concretely comprising the following steps for electrogenerated chemiluminescence nonyl phenol sensor：
（1）With ITO electro-conductive glass as working electrode, in the FeCo-N@TiO of the μ L of electrode surface drop coating 8 ~ 122Colloidal sol, room
Dried under temperature；
（2）By step（1）In the electrode cushioning liquid PBS that obtains, continue in the μ L of electrode surface drop coating 8 ~ 12
The nonyl phenol antibody-solutions of 10 μ g/mL, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In the electrode PBS that obtains, it is 100 to continue in the μ L concentration of electrode surface drop coating 8 ~ 12
The bovine serum albumin solution of μ g/mL, preserves in 4 DEG C of refrigerators and dries；
（4）By step（3）In the electrode PBS that obtains, continue molten in the glutaraldehyde of the μ L of electrode surface drop coating 2 ~ 4
Liquid, preserves in 4 DEG C of refrigerators and dries；
（5）By step（4）In the electrode PBS that obtains, it is 20 to continue in the μ L concentration of electrode surface drop coating 6 ~ 10
The horseradish peroxidase solution of μ g/mL, preserves in 4 DEG C of refrigerators and dries；
（6）By step（5）In the electrode PBS that obtains, preserved in 4 DEG C of refrigerators after drying, that is, be obtained electroluminescent
Chemiluminescence nonyl phenol sensor；
Described FeCo-N@TiO2Solution is by the FeCo-N@TiO of 50 mg2Powder is dissolved in 10 mL ultra-pure waters, and is surpassed
The obtained hydrosol after the min of sound 30；
Described PBS is the PBS of 10mmol/L, and the pH value of described PBS is 7.4；
Described glutaraldehyde solution is glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the electrogenerated chemiluminescence nonyl phenol sensor prepared by preparation method of the present invention, its feature
It is, including following applying step：
A. standard liquid is prepared：Prepare one group of nonyl phenol standard liquid including the various concentrations including blank standard specimen；
B. working electrode modification：By the electrogenerated chemiluminescence nonyl phenol prepared by preparation method as claimed in claim 1
Sensor is working electrode, and the nonyl phenol standard liquid of the various concentrations that will be prepared in step a distinguishes drop coating to working electrode table
Face, preserves in 4 DEG C of refrigerators；
C. working curve is drawn：Using Ag/AgCl electrodes as reference electrode, platinum electrode as to electrode, with step b
The working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell successively
Add the K of 15 mL2S2O8The H of solution and 100 μ L2O2Solution；Circulation electricity is applied to the working electrode for assembling with cyclic voltammetry
Pressure；Relation between the light signal strength and nonyl phenol antigen concentration of standard solution of the electrogenerated chemiluminescence according to gained, draws
Working curve；The light signal strength of blank standard specimen is designated asD 0, the light signal strength of the nonyl phenol standard liquid containing various concentrations
It is designated asD i, the difference of response light signal strength reduction is ΔD=D 0-D i, ΔDWith the mass concentration of nonyl phenol standard liquidCBetween
It is linear, draw ΔD-CWorking curve；
D. the detection of nonyl phenol：Replace the nonyl phenol standard liquid in step a with testing sample, according in step b and c
Method detected, according to response light signal strength reduction difference DELTADAnd working curve, obtain nonyl phenol in testing sample
Content；
Described K2S2O8Solution is by 1 mol K2S2O8It is dissolved in the pH=6.5 cushioning liquid of 10 L with 1 mol KCl and is made
Standby to obtain, described pH=6.5 cushioning liquid is PBS that pH value is 6.5；
Described H2O2Solution is aqueous hydrogen peroxide solution, and the concentration of described aqueous hydrogen peroxide solution is 10%.
Useful achievement of the invention
（1）Electrogenerated chemiluminescence nonyl phenol sensor of the present invention is prepared simply, easy to operate, is realized to sample
The detection of quick, sensitive, high selectivity, and low cost can be applied to portable inspectiont, with market development prospect；
（2）The present invention is prepared for New Two Dimensional sheet light-sensitive material FeCo-N TiO first2, because iron, cobalt are in titanium dioxide
Growth in situ in titanium nanometer sheet and fully contacted with titanium dioxide nanoplate, the metal surface plasma body using iron, cobalt is made
With and the mutual promoting action of the two, effectively increase semiconductor substrate Resonance energy transfer ability, solve titanium dioxide
Although nanometer sheet specific surface area is applied to electrogenerated chemiluminescence host material, electrogenerated chemiluminescence than larger and mesoporous characteristic
The technical problem of jitter；Simultaneously because the doping of nitrogen and cause titanium dioxide nanoplate preferably increase layer gap spacing and
It is fully dispersed, the exposure of the high energy crystal face of titanium dioxide nanoplate, electron transmission and fully dispersed are greatly increased, greatly
Electrogenerated chemiluminescence intensity is increased, titanium dioxide nanoplate poorly conductive is solved and electrogenerated chemiluminescence intensity is weak and unfavorable
In the technical problem for preparing Electrochemiluminescsensor sensor, therefore, effective preparation of the material, with important scientific meaning and
Application value；
（3）The present invention is first by FeCo-N@TiO2It is applied in the preparation of electroluminescent chemiluminescence biosensor, significantly carries
The strength and stability of electrogenerated chemiluminescence high, substantially increases the detection sensitivity of Electrochemiluminescsensor sensor so that
Electroluminescent chemiluminescence biosensor realizes the application in real work；The application of the material, also for associated biomolecule is sensed
Device, such as Optical Electro-Chemistry sensor, electrochemical sensor provide Technical Reference, with extensive potential use value.
Specific embodiment
The FeCo-N@TiO of embodiment 12Preparation
First, 0.8 mmol molysite and 0.8 mmol cobalt salts are taken and 1 mmol ammonium salts are added in 5 mL butyl titanates,
In whipping process, 0.5 mL hydrofluoric acid is slowly added to, is reacted in a kettle. at 160 DEG C 24 hours, after being cooled to room temperature, used
After ultra-pure water and absolute ethyl alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Then, the powder of grinding is put into Muffle furnace,
Programming rate is 1 DEG C/min, and 60 min are calcined at 480 DEG C；Finally, the powder after calcining is cooled to room temperature, that is, is obtained
FeCo-N@TiO2；
Described molysite is ferric sulfate；
Described cobalt salt is cobaltous sulfate；
Described ammonium salt is ammonium sulfate.
The FeCo-N@TiO of embodiment 22Preparation
First, 0.8 mmol molysite and 1.0 mmol cobalt salts are taken and 1 mmol ammonium salts are added in 5 mL butyl titanates,
In whipping process, 0.65 mL hydrofluoric acid is slowly added to, is reacted in a kettle. at 180 DEG C 21 hours, after being cooled to room temperature, used
After ultra-pure water and absolute ethyl alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Then, the powder of grinding is put into Muffle furnace,
Programming rate is 2 DEG C/min, and 30 min are calcined at 520 DEG C；Finally, the powder after calcining is cooled to room temperature, that is, is obtained
FeCo-N@TiO2；
Described molysite is iron chloride；
Described cobalt salt is cobalt chloride；
Described ammonium salt is ammonium chloride.
The FeCo-N@TiO of embodiment 32Preparation
First, 0.8 mmol molysite and 1.2 mmol cobalt salts are taken and 1 mmol ammonium salts are added in 5 mL butyl titanates,
In whipping process, 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle. at 200 DEG C 18 hours, after being cooled to room temperature, used
After ultra-pure water and absolute ethyl alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C；Then, the powder of grinding is put into Muffle furnace,
Programming rate is 3 DEG C/min, and 10 min are calcined at 560 DEG C；Finally, the powder after calcining is cooled to room temperature, that is, is obtained
FeCo-N@TiO2；
Described molysite is ferric nitrate；
Described cobalt salt is cobalt nitrate；
Described ammonium salt is ammonium nitrate.
The preparation method of the electrogenerated chemiluminescence nonyl phenol sensor of embodiment 4
（1）Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 8
FeCo-N@TiO2Colloidal sol, dries at room temperature；
（2）By step（1）In the electrode cushioning liquid PBS that obtains, continue in the μ of 8 μ L of electrode surface drop coating 10
The nonyl phenol antibody-solutions of g/mL, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In the electrode PBS that obtains, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 8
The bovine serum albumin solution of g/mL, preserves in 4 DEG C of refrigerators and dries；
（4）By step（3）In the electrode PBS that obtains, continue molten in the glutaraldehyde of the μ L of electrode surface drop coating 2
Liquid, preserves in 4 DEG C of refrigerators and dries；
（5）By step（4）In the electrode PBS that obtains, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 6
The horseradish peroxidase solution of mL, preserves in 4 DEG C of refrigerators and dries；
（6）By step（5）In the electrode PBS that obtains, preserved in 4 DEG C of refrigerators after drying, that is, be obtained electroluminescent
Chemiluminescence nonyl phenol sensor；
Described FeCo-N@TiO2Colloidal sol is by the FeCo-N@TiO of 50 mg2Powder is dissolved in 10 mL ultra-pure waters, and is surpassed
The obtained hydrosol after the min of sound 30；
Described PBS is the PBS of 10mmol/L, and the pH value of described PBS is 7.4；
Described glutaraldehyde solution is glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the electrogenerated chemiluminescence nonyl phenol sensor of embodiment 5
（1）Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 10
FeCo-N@TiO2Colloidal sol, dries at room temperature；
（2）By step（1）In the electrode cushioning liquid PBS that obtains, continue in the μ L 10 of electrode surface drop coating 10
The nonyl phenol antibody-solutions of μ g/mL, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In the electrode PBS that obtains, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 10
The bovine serum albumin solution of g/mL, preserves in 4 DEG C of refrigerators and dries；
（4）By step（3）In the electrode PBS that obtains, continue molten in the glutaraldehyde of the μ L of electrode surface drop coating 3
Liquid, preserves in 4 DEG C of refrigerators and dries；
（5）By step（4）In the electrode PBS that obtains, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 8
The horseradish peroxidase solution of mL, preserves in 4 DEG C of refrigerators and dries；
（6）By step（5）In the electrode PBS that obtains, preserved in 4 DEG C of refrigerators after drying, that is, be obtained electroluminescent
Chemiluminescence nonyl phenol sensor；
Described FeCo-N@TiO2Colloidal sol is by the FeCo-N@TiO of 50 mg2Powder is dissolved in 10 mL ultra-pure waters, and is surpassed
The obtained hydrosol after the min of sound 30；
Described PBS is the PBS of 10 mmol/L, and the pH value of described PBS is 7.4；
Described glutaraldehyde solution is glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the electrogenerated chemiluminescence nonyl phenol sensor of embodiment 6
（1）Using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, the μ L's of electrode surface drop coating 12
FeCo-N@TiO2Colloidal sol, dries at room temperature；
（2）By step（1）In the electrode cushioning liquid PBS that obtains, continue in the μ L 10 of electrode surface drop coating 12
The nonyl phenol antibody-solutions of μ g/mL, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In the electrode PBS that obtains, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 12
The bovine serum albumin solution of g/mL, preserves in 4 DEG C of refrigerators and dries；
（4）By step（3）In the electrode PBS that obtains, continue molten in the glutaraldehyde of the μ L of electrode surface drop coating 4
Liquid, preserves in 4 DEG C of refrigerators and dries；
（5）By step（4）In the electrode PBS that obtains, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 10
The horseradish peroxidase solution of mL, preserves in 4 DEG C of refrigerators and dries；
（6）By step（5）In the electrode PBS that obtains, preserved in 4 DEG C of refrigerators after drying, that is, be obtained electroluminescent
Chemiluminescence nonyl phenol sensor；
Described FeCo-N@TiO2Colloidal sol is by the FeCo-N@TiO of 50 mg2Powder is dissolved in 10 mL ultra-pure waters, and is surpassed
The obtained hydrosol after the min of sound 30；
Described PBS is the PBS of 10 mmol/L, and the pH value of described PBS is 7.4；
Described glutaraldehyde solution is glutaraldehyde water solution that volume ratio is 2.5%.
Electrogenerated chemiluminescence nonyl phenol sensor prepared by 7 embodiment of embodiment 1 ~ 6, is applied to the detection of nonyl phenol, walks
It is rapid as follows：
（1）Standard liquid is prepared：Prepare one group of nonyl phenol standard liquid including the various concentrations including blank standard specimen；
（2）Working electrode is modified：By the electrogenerated chemiluminescence nonyl phenol prepared by preparation method as claimed in claim 1
Sensor is working electrode, by step（1）The nonyl phenol standard liquid of the various concentrations of middle preparation distinguishes drop coating to working electrode
Surface, preserves in 4 DEG C of refrigerators；
（3）Working curve is drawn：Using saturated calomel electrode as reference electrode, platinum electrode as auxiliary electrode, with step
Suddenly（2）The working electrode composition three-electrode system modified, is connected in electrochemiluminescdetection detection equipment；In a cell
Successively add the K of 15 mL2S2O8The H of solution and 100 μ L2O2Solution；The working electrode for assembling is applied to follow with cyclic voltammetry
Loop voltag；Relation between the light signal strength and nonyl phenol antigen concentration of standard solution of the electrogenerated chemiluminescence according to gained,
Drawing curve；The light signal strength of blank standard specimen is designated asD 0, the optical signal of the nonyl phenol standard liquid containing various concentrations
Intensity is designated asD i, the difference of response light signal strength reduction is ΔD= D 0-D i, ΔDWith the mass concentration of nonyl phenol standard liquidC
Between it is linear, draw ΔD-CWorking curve；The linear detection range of nonyl phenol is：0.001 ~ 100 ng/mL, detection
It is limited to：0.3 pg/mL；
（4）The detection of nonyl phenol：Replace the nonyl phenol standard liquid in step a with testing sample, according in step b and c
Method detected, according to response light signal strength reduction difference DELTADAnd working curve, obtain nonyl phenol in testing sample
Content；
Described K2S2O8Solution is by 1 mol K2S2O8It is dissolved in the pH=6.5 cushioning liquid of 10 L with 1 mol KCl and is made
Standby to obtain, described pH=6.5 cushioning liquid is PBS that pH value is 6.5；
Described H2O2Solution is aqueous hydrogen peroxide solution, and the concentration of described aqueous hydrogen peroxide solution is 10%.
Claims (2)
1. a kind of preparation method of the electrogenerated chemiluminescence nonyl phenol sensor based on titanium dioxide nanoplate composite, described
Titanium dioxide nanoplate composite be the nitrogen-doped titanium dioxide nanometer sheet FeCo-N@of iron and cobalt dual-metal In-situ reaction
TiO2, described electrogenerated chemiluminescence nonyl phenol sensor is by working electrode, FeCo-N TiO2, nonyl phenol antibody, ox blood it is pure
Albumen, glutaraldehyde, horseradish peroxidase composition；
Characterized in that, described preparation method includes following preparation process：
a. FeCo-N@TiO2Preparation；
B. the preparation of electrogenerated chemiluminescence nonyl phenol sensor；
Wherein, step a prepares FeCo-N@TiO2Concretely comprise the following steps：
First, 0.8 mmol molysite, 0.8 ~ 1.2 mmol cobalt salts and 1 mmol ammonium salts are taken to be added in 5 mL butyl titanates, is stirred
During mixing, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle. at 160 ~ 200 DEG C 18 ~ 24 hours, be cooled to
After room temperature, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be vacuum dried at 50 DEG C；Then, the powder of grinding is put into
In Muffle furnace, programming rate is 1 ~ 3 DEG C/min, at 480 ~ 560 DEG C under nitrogen protection, calcines 10 ~ 60 min；Finally, will forge
Powder after burning is cooled to room temperature, that is, FeCo-N@TiO are obtained2；
Described molysite is selected from one of following：Ferric sulfate, iron chloride, ferric nitrate；
Described cobalt salt is selected from one of following：Cobaltous sulfate, cobalt chloride, cobalt nitrate；
Described ammonium salt is selected from one of following：Ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate；
Step b prepares concretely comprising the following steps for electrogenerated chemiluminescence nonyl phenol sensor：
（1）With ITO electro-conductive glass as working electrode, in the FeCo-N@TiO of the μ L of electrode surface drop coating 8 ~ 122Colloidal sol, dries in the air at room temperature
It is dry；
（2）By step（1）In the electrode cushioning liquid PBS that obtains, continue in the μ of 8 ~ 12 μ L of electrode surface drop coating 10
The nonyl phenol antibody-solutions of g/mL, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In the electrode PBS that obtains, it is 100 μ g/ to continue in the μ L concentration of electrode surface drop coating 8 ~ 12
The bovine serum albumin solution of mL, preserves in 4 DEG C of refrigerators and dries；
（4）By step（3）In the electrode PBS that obtains, continue the glutaraldehyde solution in the μ L of electrode surface drop coating 2 ~ 4,4
Preserved in DEG C refrigerator and dried；
（5）By step（4）In the electrode PBS that obtains, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 6 ~ 10
The horseradish peroxidase solution of mL, preserves in 4 DEG C of refrigerators and dries；
（6）By step（5）In the electrode PBS that obtains, preserved in 4 DEG C of refrigerators after drying, that is, electroluminescent chemistry is obtained
Luminous nonyl phenol sensor；
Described FeCo-N@TiO2Colloidal sol is by the FeCo-N@TiO of 50 mg2Powder is dissolved in 10 mL ultra-pure waters, and ultrasound 30
The obtained hydrosol after min；
Described PBS is the PBS of 10mmol/L, and the pH value of described PBS is 7.4；
Described glutaraldehyde solution is glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the electrogenerated chemiluminescence nonyl phenol sensor prepared by preparation method as claimed in claim 1, its feature
It is, including following applying step：
A. standard liquid is prepared：Prepare one group of nonyl phenol standard liquid including the various concentrations including blank standard specimen；
B. working electrode modification：By the electrogenerated chemiluminescence nonyl phenol sensing prepared by preparation method as claimed in claim 1
Used as working electrode, the nonyl phenol standard liquid of the various concentrations that will be prepared in step a distinguishes drop coating to working electrode surface to device,
Preserved in 4 DEG C of refrigerators；
C. working curve is drawn：Ag/AgCl electrodes as reference electrode, platinum electrode are repaiied as to electrode with step b
The working electrode composition three-electrode system adornd, is connected in electrochemiluminescdetection detection equipment；Successively add in a cell
The K of 15 mL2S2O8The H of solution and 100 μ L2O2Solution；Cyclical voltage is applied to the working electrode for assembling with cyclic voltammetry；
Relation between the light signal strength and nonyl phenol antigen concentration of standard solution of the electrogenerated chemiluminescence according to gained, drawing
Curve；The light signal strength of blank standard specimen is designated asD 0, the light signal strength of the nonyl phenol standard liquid containing various concentrations is designated asD i, the difference of response light signal strength reduction is ΔD=D 0-D i, ΔDWith the mass concentration of nonyl phenol standard liquidCBetween into line
Sexual intercourse, draws ΔD-CWorking curve；
D. the detection of nonyl phenol：Replace the nonyl phenol standard liquid in step a with testing sample, according to the side in step b and c
Method is detected, according to the difference DELTA of response light signal strength reductionDAnd working curve, obtain containing for nonyl phenol in testing sample
Amount；
Described K2S2O8Solution is by 1 mol K2S2O8It is dissolved in the pH=6.5 cushioning liquid of 10 L with 1 mol KCl and is prepared into
Arrive, described pH=6.5 cushioning liquid is PBS that pH value is 6.5；
Described H2O2Solution is aqueous hydrogen peroxide solution, and the concentration of described aqueous hydrogen peroxide solution is 10%.
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