CN106018514A - Preparation method of photoelectrochemical diethylstilbestrol sensor based on copper-doped nano photoelectric material - Google Patents
Preparation method of photoelectrochemical diethylstilbestrol sensor based on copper-doped nano photoelectric material Download PDFInfo
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Abstract
The invention discloses a preparation method of a photoelectrochemical diethylstilbestrol sensor and belongs to the technical field of novel nano functional materials and biosensors. Firstly, a novel two-dimensional nano photoelectric material, namely a copper-doped nano photoelectric material, specifically a two-dimensional nano composite Cu-TiO2/MoS2 obtained through in-situ compounding of molybdenum disulfide on a copper-doped titanium dioxide nano cube is prepared, and an diethylstilbestrol antibody is loaded and alkaline phosphatase is fixed to the material by the application of good biocompatibility and a large specific surface area of the material. During detection, due to the fact that alkaline phosphatase can catalyze L-ascorbic acid-2-trisodium phosphate AAP to generate L-ascorbic acid AA in situ and then provide an electron donor for photoelectric detection, by the application of the influences of specific quantitative combination of the antibody and an antigen on electron transmission capacity, the photoelectric current intensity is lowered accordingly, and finally the photoelectric sensor for detecting diethylstilbestrol through an unmarked photoelectrochemical method is constructed.
Description
Technical field
The present invention relates to the preparation method of a kind of Optical Electro-Chemistry diethylstilbestrol sensor.Belong to Nano-function thin films and biosensor technology field.
Background technology
After environmental estrogens refers to that a class enters body, have the synthesis of normal endocrine material in interfering bodies, discharge, transport, combine, the process such as metabolism, activate or the function of suppression hormonal system, thus destroy maintenance organism stability and the compound of regulating and controlling effect, environmental estrogens is of a great variety, including artificial-synthetic compound and natural plant estrogen, it is distributed widely in nature.Diethylstilbestrol is the non steroidal estrogen material of a kind of synthetic.At present, the method for detection diethylstilbestrol mainly has chromatography, mass spectrography etc..This type of method instrument is valuable, operation complexity, and laboratory personnel just can detect after needing professional training.Therefore, R&D costs are low, it is fast, highly sensitive to detect, the diethylstilbestrol sensor of high specificity is significant.
Optical Electro-Chemistry sensor, due to the feature such as highly sensitive, testing cost is low, was paid close attention to by increasing researcher in recent years.Optical Electro-Chemistry sensor is to cause electron-hole pair to separate based on additional light source activation Electrophotosensitivmaterial material, under potential condition the most partially, it is achieved the electronics quick transmission on electrode, quasiconductor and trim and analyte, and forms photoelectric current.In optimal conditions, the change of analyte concentration can directly affect the size of photoelectric current, and recycling biological immune combines, it is possible to realize the qualitative and quantitative analysis to analyte according to the change of photoelectric current.
Optical Electro-Chemistry sensor most critical technology is exactly the raising of the performances such as the size to photoelectric current and stability.Titanium dioxide is a kind of photocatalyst and light induced electron host material being most widely used, but, the actual application level of titanium dioxide to be given full play to, need one side to improve Optical Electro-Chemistry activity by regulating and controlling its material morphology to expose more high activity crystal faces, on the other hand regulate and control photosensitive wavelength by doping different metal or metal-oxide and improve the utilization rate of sunlight to visible-range extension.Due to two dimension titanium dioxide nano material, such as titanium dioxide nanoplate, nano titania square etc., more high activity crystal face can be exposed, there is higher Optical Electro-Chemistry activity, titanium dioxide nanoplate has ratio nanoparticle preferably application prospect, and the research for titanium dioxide nanoplate also receives much concern.And the photosensitive wavelength of single titanium dioxide nano material is typically in ultra-violet (UV) band, and interact due to bad dispersibility, easily stacking, thus reduce Optical Electro-Chemistry activity, be unfavorable for actual application.Therefore, R&D costs are low, photosensitive dose active of titanium dioxide has important scientific meaning and using value to prepare simple high Optical Electro-Chemistry.
(chemical formula is MoS to molybdenum bisuphide2) nano material, there is two-dimensional layered structure, be one of most widely used kollag.Lamellar two-dimension nano materials after its stripping, is the semiconductor nano material of excellent performance, except having big specific surface area, can improve load capacity as catalyst and the carrier of biological antibody, also have excellent electron transmission performance simultaneously as promoter.
At present, most synthesizing mean be all be separately synthesized after, then catalyst is combined with carrier, process is loaded down with trivial details, and productivity is the highest.Therefore, for In-situ reaction preparation, there is the photosensitizer of excellent photoelectrochemical behaviour to be with a wide range of applications and important scientific meaning.
In addition, the photo-generate electron-hole of single titanium dioxide nano material is to the most compound, thus cause weakening of photosignal, and titanium dioxide poorly conductive to also limit the sensitivity of the Optical Electro-Chemistry sensor built by single titanium dioxide nano material generally the highest, be unfavorable for actual application.Therefore, design, prepare efficient, stable doping titanium dioxide nano sheet and trim is the key technology preparing Optical Electro-Chemistry sensor.
Summary of the invention
It is an object of the invention to provide a kind of prepare simple, highly sensitive, detection quickly, the preparation method of the Optical Electro-Chemistry diethylstilbestrol sensor of high specificity, prepared sensor, can be used for quick, the Sensitive Detection of diethylstilbestrol.Based on this purpose, a kind of New Two Dimensional nanometer photoelectronic material Copper-cladding Aluminum Bar nanometer photoelectronic material, i.e. the two-dimensional nano composite Cu-TiO of copper-doped titanium dioxide nano square In-situ reaction molybdenum bisuphide are the method comprises the steps of firstly, preparing2/MoS2Utilize the good biocompatibility of this material and big specific surface area, diethylstilbestrol antibody, fixing upper alkali phosphatase in load, when detecting, L-AA AA is produced in situ owing to alkali phosphatase can be catalyzed L-AA-2-tricresyl phosphate sodium salt AAP, and and then for Photoelectric Detection provide electron donor, recycling antibody is combined the impact on electron transport ability with the specific quantification of antigen, photo-current intensity is reduced accordingly, finally achieves the structure of the photoelectric sensor using unmarked PhotoelectrochemicalMethod Method detection diethylstilbestrol.
The technical solution used in the present invention is as follows:
1. the preparation method of an Optical Electro-Chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material, it is characterised in that described Copper-cladding Aluminum Bar nanometer photoelectronic material is the two-dimensional nano composite Cu-TiO of copper-doped titanium dioxide nano square In-situ reaction molybdenum bisuphide2/MoS2, described Optical Electro-Chemistry diethylstilbestrol sensor is by working electrode, Cu-TiO2/MoS2, diethylstilbestrol antibody, alkali phosphatase, bovine serum albumin composition；
It is characterized in that, described preparation method includes following preparation process:
A. Cu-TiO is prepared2/MoS2；
B. Optical Electro-Chemistry diethylstilbestrol sensor is prepared；
Wherein, step a prepares Cu-TiO2/MoS2Concretely comprise the following steps:
(1) take 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol mantoquita joins 3 ~ 10 jointly
In mL n-butyllithium solution, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, obtain reacted solution；
(2) reacted solution in non-polar solven washing step (1) is utilized, then at 30 ~ 60 DEG C, water bath sonicator process is carried out, the solution after having processed, after recycling non-polar solven carrying out washing treatment, vacuum drying, obtains the molybdenum disulfide nano material of copper intercalation；
(3) 10 are taken ~
The molybdenum disulfide nano material of copper intercalation that 500 mg steps (2) prepare joins in 5 mL butyl titanates, after stirring 1 hour, is slowly added to 0.5 ~ 0.8 mL Fluohydric acid. while stirring, then reacts 18 ~ 24 hours in a kettle. at 160 ~ 200 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C, i.e. prepares Cu-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described mantoquita is selected from one of following: copper sulfate, copper chloride, copper nitrate, copper acetate, organocopper compound；
Described non-polar solven is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
Described water bath sonicator processes, and the process time is 1 hour；
Step b prepares concretely comprising the following steps of Optical Electro-Chemistry diethylstilbestrol sensor:
(1) with ITO electro-conductive glass as working electrode, at the Cu-TiO of electrode surface drop coating 8 ~ 12 L2/MoS2Colloidal sol, dries under room temperature；
(2) the electrode buffer solution PBS that will obtain in step (1), continues the diethylstilbestrol antibody solution at electrode surface drop coating 8 ~ 12 L 10 g/mL, preserves and dry in 4 DEG C of refrigerators；
(3) the electrode PBS that will obtain in step (2), continues at the alkaline phosphatase enzymatic solution that electrode surface drop coating 6 ~ 10 L concentration is 20 g/mL, preserves and dry in 4 DEG C of refrigerators；
(4) the electrode PBS that will obtain in step (3), continues at the bovine serum albumin solution that electrode surface drop coating 8 ~ 12 L concentration is 100 g/mL, preserves and dry in 4 DEG C of refrigerators；
(5) the electrode PBS that will obtain in step (4), preserves in 4 DEG C of refrigerators after drying, i.e. prepares Optical Electro-Chemistry diethylstilbestrol sensor；
Described Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultra-pure waters, and the hydrosol prepared after ultrasonic 30 min；
Described PBS is 10
The phosphate buffered solution of mmol/L, the pH value of described phosphate buffered solution is 7.4.
The application of the Optical Electro-Chemistry diethylstilbestrol sensor prepared by preparation method the most of the present invention, it is characterised in that include following applying step:
A. standard solution preparation: prepare the diethylstilbestrol standard solution of one group of variable concentrations including blank standard specimen；
B. working electrode is modified: be working electrode by the Optical Electro-Chemistry diethylstilbestrol sensor prepared by preparation method as claimed in claim 1, by the drop coating respectively of the diethylstilbestrol standard solution of the variable concentrations of preparation in step b to working electrode surface, 4 DEG C of refrigerators preserve；
C. working curve is drawn: saturated calomel electrode, be connected on Optical Electro-Chemistry detection equipment as reference electrode, platinum electrode as auxiliary electrode, the working electrode composition three-electrode system modified with step b；Successively add Tris HCl buffer solution and the L-AA-2-tricresyl phosphate sodium salt AAP solution of 5 mL 10 mmol/L of 15mL pH=9.6 in a cell；Use i-t means of testing, according to the relation between photocurrent values and the diethylstilbestrol concentration of standard solution of gained, drawing curve；
D. the detection of diethylstilbestrol: replace the diethylstilbestrol standard solution in step a with testing sample, detect according to the method in step b and c, according to intensity level and the working curve of response signal, obtains the content of diethylstilbestrol in testing sample.
The useful achievement of the present invention
(1) Optical Electro-Chemistry diethylstilbestrol sensor of the present invention preparation is simple, easy to operate, it is achieved that the selective enumeration method quick, sensitive, high to sample, and low cost, can be applicable to portable inspectiont, has market development prospect；
(2) present invention uses the method for In-situ reaction to be prepared for novel photocatalyst Cu-TiO first2/MoS2, the method mainly has three advantages: one is, fully contact with nano titania square due to copper growth in situ on nano titania square, utilize the metal surface plasma body effect of copper, effectively prevent photo-generate electron-hole to being combined, drastically increase photocatalytic activity, effect due to metal ion, widen photosensitive wavelength ground scope, achieve in visible region ground photocatalysis, drastically increase sunlight ground utilization ratio, although it is good to solve two dimension titanium dioxide nano material photocatalysis effect, but the technical problem of photocatalysis effect difference under sunlight；Two are, due to the load characteristic of molybdenum bisuphide lamellar two-dimension nano materials and nano titania square thereon fully dispersed, greatly increase the photocatalytic activity of nano titania square and solve two dimension titanium dioxide nano material and be unfavorable for that dispersion reduces the technical problem of photocatalytic activity；Three are, due to copper ion the most not only as intercalation material but also as reaction dopant material, the method finally using In-situ reaction achieves one pot of preparation of this composite, not only save time, spillage of material, and the nano titania square of the Copper-cladding Aluminum Bar of preparation can preferably be evenly spread to above molybdenum bisuphide lamellar two-dimension nano materials.Therefore, effective preparation of this material, there is important scientific meaning and using value；
(3) present invention is first by Cu-TiO2/MoS2It is applied in the preparation of Photoelectrochemistrbiosensor biosensor, significantly improves the valid density of photo-generated carrier, substantially increase the detection sensitivity of Optical Electro-Chemistry sensor so that Photoelectrochemistrbiosensor biosensor achieves the application in real work；The application of this material, is also associated biomolecule sensor, as Electrochemiluminescsensor sensor, electrochemical sensor etc. provide Technical Reference, has the most potential use value.
Detailed description of the invention
Embodiment 1 Cu-TiO2/MoS2Preparation
(1) take 0.6 g molybdenum disulfide powder and 0.2 mmol mantoquita joins in 3mL n-butyllithium solution jointly, at nitrogen protection and 60 DEG C, stir 12 hours, obtain reacted solution；
(2) utilize reacted solution in non-polar solven washing step (1), at 60 DEG C, then carry out water bath sonicator process, after having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain the molybdenum disulfide nano material of copper intercalation；
(3) 500 are taken
The molybdenum disulfide nano material of copper intercalation that mg step (2) prepares joins in 5 mL butyl titanates, after stirring 1 hour, is slowly added to 0.5 mL Fluohydric acid. while stirring, then reacts 18 hours in a kettle. at 160 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C, i.e. prepares Cu-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described mantoquita is copper sulfate；
Described non-polar solven is hexane；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 2 Cu-TiO2/MoS2Preparation
(1) take 0.6 g molybdenum disulfide powder and 1.0 mmol mantoquitas join in 5 mL n-butyllithium solutions jointly, at nitrogen protection and 30 DEG C, stir 24 hours, obtain reacted solution；
(2) utilize reacted solution in non-polar solven washing step (1), at 30 DEG C, then carry out water bath sonicator process, after having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain the molybdenum disulfide nano material of copper intercalation；
(3) 200 are taken
The molybdenum disulfide nano material of copper intercalation that mg step (2) prepares joins in 5 mL butyl titanates, after stirring 1 hour, is slowly added to 0.6 mL Fluohydric acid. while stirring, then reacts 20 hours in a kettle. at 180 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C, i.e. prepares Cu-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described mantoquita is copper chloride；
Described non-polar solven is carbon tetrachloride；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 3 Cu-TiO2/MoS2Preparation
(1) take 0.6 g molybdenum disulfide powder and 2.0 mmol mantoquitas join in 10 mL n-butyllithium solutions jointly, at nitrogen protection and 50 DEG C, stir 48 hours, obtain reacted solution；
(2) utilize reacted solution in non-polar solven washing step (1), at 50 DEG C, then carry out water bath sonicator process, after having processed, the solution after recycling non-polar solven carrying out washing treatment, vacuum drying, obtain the molybdenum disulfide nano material of copper intercalation；
(3) take the molybdenum disulfide nano material of copper intercalation that 10 mg steps (2) prepare and join in 5 mL butyl titanates, after stirring 1 hour, be slowly added to 0.8 mL Fluohydric acid. while stirring, then react 24 hours in a kettle. at 200 DEG C；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C, i.e. prepares Cu-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described mantoquita is copper acetate；
Described non-polar solven is benzene；
Described water bath sonicator processes, and the process time is 1 hour.
Embodiment 4 The preparation method of Optical Electro-Chemistry diethylstilbestrol sensor
(1) using a width of 1 cm, a length of 4 cm ITO electro-conductive glass as working electrode, at the Cu-TiO of electrode surface drop coating 8 L2/MoS2Colloidal sol, dries under room temperature；
(2) the electrode buffer solution PBS that will obtain in step (1), continues the diethylstilbestrol antibody solution at electrode surface drop coating 8 L 10 g/mL, preserves and dry in 4 DEG C of refrigerators；
(3) the electrode PBS that will obtain in step (2), continues at the bovine serum albumin solution that electrode surface drop coating 8 L concentration is 100 g/mL, preserves and dry in 4 DEG C of refrigerators；
(4) the electrode PBS that will obtain in step (3), continues at the alkaline phosphatase enzymatic solution that electrode surface drop coating 6 L concentration is 20 g/mL, preserves and dry in 4 DEG C of refrigerators；
(5) the electrode PBS that will obtain in step (4), preserves in 4 DEG C of refrigerators after drying, i.e. prepares Optical Electro-Chemistry diethylstilbestrol sensor；
Described Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO prepared by the embodiment 1 of 50 mg2/MoS2Powder is dissolved in 10 mL ultra-pure waters, and the hydrosol prepared after ultrasonic 30 min；
Described PBS is the phosphate buffered solution of 10mmol/L, and the pH value of described phosphate buffered solution is 7.4.
Embodiment 5 The preparation method of Optical Electro-Chemistry diethylstilbestrol sensor
All preparation processes are with embodiment 4, the Cu-TiO of a middle use2/MoS2For the Cu-TiO prepared by embodiment 22/MoS2。
Embodiment 6 The preparation method of Optical Electro-Chemistry diethylstilbestrol sensor
All preparation processes are with embodiment 4, the Cu-TiO of a middle use2/MoS2For the Cu-TiO prepared by embodiment 32/MoS2。
Embodiment 7 The Optical Electro-Chemistry diethylstilbestrol sensor of embodiment 1 and 3 preparation, is applied to the detection of diethylstilbestrol, and step is as follows:
(1) standard solution preparation: prepare the diethylstilbestrol standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: be working electrode by the Optical Electro-Chemistry diethylstilbestrol sensor prepared by preparation method as claimed in claim 1, by the drop coating respectively of the diethylstilbestrol standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C of refrigerators preserve；
(3) working curve is drawn: saturated calomel electrode, be connected on Optical Electro-Chemistry detection equipment as reference electrode, platinum electrode as auxiliary electrode, the working electrode composition three-electrode system modified with step (2)；Successively add Tris HCl buffer solution and the L-AA-2-tricresyl phosphate sodium salt AAP solution of 5 mL 10 mmol/L of 15mL pH=9.6 in a cell；Use i-t means of testing, according to the relation between photocurrent values and the diethylstilbestrol concentration of standard solution of gained, drawing curve；The linear detection range of diethylstilbestrol is: 0.002 ~ 200
Ng/mL, detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the diethylstilbestrol standard solution in step (1) with testing sample, detect according to the method in step (2) and (3), according to intensity level and the working curve of response signal, obtains the content of diethylstilbestrol in testing sample.
Embodiment 8 The Optical Electro-Chemistry diethylstilbestrol sensor of embodiment 2 and 4 preparation, is applied to the detection of diethylstilbestrol, and step is as follows:
(1) standard solution preparation: prepare the diethylstilbestrol standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: be working electrode by the Optical Electro-Chemistry diethylstilbestrol sensor prepared by preparation method as claimed in claim 1, by the drop coating respectively of the diethylstilbestrol standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C of refrigerators preserve；
(3) working curve is drawn: saturated calomel electrode, be connected on Optical Electro-Chemistry detection equipment as reference electrode, platinum electrode as auxiliary electrode, the working electrode composition three-electrode system modified with step (2)；Successively add Tris HCl buffer solution and the L-AA-2-tricresyl phosphate sodium salt AAP solution of 5 mL 10 mmol/L of 15mL pH=9.6 in a cell；Use i-t means of testing, according to the relation between photocurrent values and the diethylstilbestrol concentration of standard solution of gained, drawing curve；The linear detection range of diethylstilbestrol is: 0.002 ~ 200
Ng/mL, detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the diethylstilbestrol standard solution in step (1) with testing sample, detect according to the method in step (2) and (3), according to intensity level and the working curve of response signal, obtains the content of diethylstilbestrol in testing sample.
Embodiment 9 The Optical Electro-Chemistry diethylstilbestrol sensor of embodiment 3 and 6 preparation, is applied to the detection of diethylstilbestrol, and step is as follows:
(1) standard solution preparation: prepare the diethylstilbestrol standard solution of one group of variable concentrations including blank standard specimen；
(2) working electrode is modified: be working electrode by the Optical Electro-Chemistry diethylstilbestrol sensor prepared by preparation method as claimed in claim 1, by the drop coating respectively of the diethylstilbestrol standard solution of the variable concentrations of preparation in step (1) to working electrode surface, 4 DEG C of refrigerators preserve；
(3) working curve is drawn: saturated calomel electrode, be connected on Optical Electro-Chemistry detection equipment as reference electrode, platinum electrode as auxiliary electrode, the working electrode composition three-electrode system modified with step (2)；Successively add Tris HCl buffer solution and the L-AA-2-tricresyl phosphate sodium salt AAP solution of 5 mL 10 mmol/L of 15mL pH=9.6 in a cell；Use i-t means of testing, according to the relation between photocurrent values and the diethylstilbestrol concentration of standard solution of gained, drawing curve；The linear detection range of diethylstilbestrol is: 0.002 ~ 200
Ng/mL, detection is limited to: 0.8 pg/mL；
(4) actual sample detection: replace the diethylstilbestrol standard solution in step (1) with testing sample, detect according to the method in step (2) and (3), according to intensity level and the working curve of response signal, obtains the content of diethylstilbestrol in testing sample.
Claims (4)
1. the preparation method of an Optical Electro-Chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material, it is characterised in that described Copper-cladding Aluminum Bar nanometer photoelectronic material is the two-dimensional nano composite Cu-TiO of copper-doped titanium dioxide nano square In-situ reaction molybdenum bisuphide2/MoS2, described Optical Electro-Chemistry diethylstilbestrol sensor is by working electrode, Cu-TiO2/MoS2, diethylstilbestrol antibody, alkali phosphatase, bovine serum albumin composition.
2. the preparation method of Optical Electro-Chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material as claimed in claim 1, it is characterised in that described preparation method includes following two preparation process:
A. Cu-TiO is prepared2/MoS2；
B. Optical Electro-Chemistry diethylstilbestrol sensor is prepared.
3. the preparation method of the Optical Electro-Chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material as described in claim 1 and 2, it is characterised in that described Cu-TiO2/MoS2Concrete preparation process be:
(1) take 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol mantoquita joins in 3 ~ 10 mL n-butyllithium solutions jointly, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, obtain reacted solution；
(2) reacted solution in non-polar solven washing step (1) is utilized, then at 30 ~ 60 DEG C, water bath sonicator process is carried out, the solution after having processed, after recycling non-polar solven carrying out washing treatment, vacuum drying, obtains the molybdenum disulfide nano material of copper intercalation；
(3) the molybdenum disulfide nano material taking the copper intercalation that 10 ~ 500 mg steps (2) prepare joins in 5 mL butyl titanates, after stirring 1 hour, is slowly added to 0.5 while stirring
~ 0.8 mL Fluohydric acid., then reacts 18 ~ 24 hours at 160 ~ 200 DEG C in a kettle.；
(4) by the product of step (3) gained, after ultra-pure water and dehydrated alcohol centrifuge washing three times, it is vacuum dried at 50 DEG C, i.e. prepares Cu-TiO2/MoS2；
Described n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
Described mantoquita is selected from one of following: copper sulfate, copper chloride, copper nitrate, copper acetate, organocopper compound；
Described non-polar solven is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
Described water bath sonicator processes, and the process time is 1 hour.
4. the preparation method of the Optical Electro-Chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material as described in claim 1 and 2, it is characterised in that the concrete preparation process of described Optical Electro-Chemistry diethylstilbestrol sensor is:
(1) with ITO electro-conductive glass as working electrode, at the Cu-TiO of electrode surface drop coating 8 ~ 12 L2/MoS2Colloidal sol, dries under room temperature；
(2) the electrode buffer solution PBS that will obtain in step (1), continues in electrode surface drop coating 8 ~ 12
The diethylstilbestrol antibody solution of L 10 g/mL, preserves in 4 DEG C of refrigerators and dries；
(3) the electrode PBS that will obtain in step (2), continues in electrode surface drop coating 6 ~ 10
L concentration is the alkaline phosphatase enzymatic solution of 20 g/mL, preserves and dry in 4 DEG C of refrigerators；
(4) the electrode PBS that will obtain in step (3), continues in electrode surface drop coating 8 ~ 12
L concentration is the bovine serum albumin solution of 100 g/mL, preserves and dry in 4 DEG C of refrigerators；
(5) the electrode PBS that will obtain in step (4), preserves in 4 DEG C of refrigerators after drying, i.e. prepares Optical Electro-Chemistry diethylstilbestrol sensor；
Described Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultra-pure waters, and the hydrosol prepared after ultrasonic 30 min；
Described PBS is the phosphate buffered solution of 10 mmol/L, and the pH value of described phosphate buffered solution is 7.4.
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| CN106770587A (en) * | 2016-11-25 | 2017-05-31 | 深圳大学 | A kind of Photoelectrochemistrbiosensor biosensor and preparation method thereof |
| CN106770566A (en) * | 2016-11-25 | 2017-05-31 | 深圳大学 | The detection method of Salmonella sensor, preparation method and salmonella concentration |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770587A (en) * | 2016-11-25 | 2017-05-31 | 深圳大学 | A kind of Photoelectrochemistrbiosensor biosensor and preparation method thereof |
| CN106770566A (en) * | 2016-11-25 | 2017-05-31 | 深圳大学 | The detection method of Salmonella sensor, preparation method and salmonella concentration |
| CN107255658A (en) * | 2017-07-10 | 2017-10-17 | 山东利源康赛环境咨询有限责任公司 | A kind of optical electro-chemistry diethylstilbestrol biology sensor built based on boron doping multi-element metal oxide and its preparation and application |
| CN108031477A (en) * | 2017-10-16 | 2018-05-15 | 浙江工商大学 | A kind of photocatalysis film of electrochemical treatments phosphorus-molybdenum sulfide codope iron oxide and its preparation method and application |
| CN108031477B (en) * | 2017-10-16 | 2019-08-27 | 浙江工商大学 | A kind of photocatalysis film and its preparation method and application of electrochemical treatments phosphorus-molybdenum sulfide codope iron oxide |
| CN108414482A (en) * | 2018-02-28 | 2018-08-17 | 复旦大学 | Utilize the method for molybdenum disulfide quantum dot inner filtering effect fluoroscopic examination alkaline phosphatase activities |
| CN110687176A (en) * | 2019-11-22 | 2020-01-14 | 济南大学 | Preparation method of photoelectrochemical diethylstilbestrol sensor based on zinc and molybdenum co-doped bismuth vanadate array |
| CN110911469A (en) * | 2019-12-19 | 2020-03-24 | 南京邮电大学 | Controllable preparation MoS2-Cu2WS4Microwave water-phase synthesis method of two-dimensional heterojunction material |
| CN114113265A (en) * | 2021-12-14 | 2022-03-01 | 郑州轻工业大学 | Aptamer sensor and preparation method thereof |
| CN114113265B (en) * | 2021-12-14 | 2023-08-08 | 郑州轻工业大学 | Aptamer sensor and preparation method thereof |
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