CN106018514B - A kind of preparation method of the optical electro-chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material - Google Patents
A kind of preparation method of the optical electro-chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of optical electro-chemistry diethylstilbestrol sensor.Belong to Nano-function thin films and biosensor technology field.The method comprises the steps of firstly, preparing a kind of New Two Dimensional nanometer photoelectronic materials --- Copper-cladding Aluminum Bar nanometer photoelectronic material, i.e. the two-dimensional nano composite material Cu-TiO of copper-doped titanium dioxide nano square In-situ reaction molybdenum disulfide2/MoS2Good biocompatibility and big specific surface area using the material, diethylstilbestrol antibody in load, alkaline phosphatase in fixation, when being detected, L-AA AA is generated in situ since alkaline phosphatase can be catalyzed L-AA -2- tricresyl phosphate sodium salt AAP, and electron donor is provided for Photoelectric Detection in turn, recycle antibody in conjunction with the specific quantification of antigen to the influence of electron transport ability, so that photo-current intensity accordingly reduces, the building of the photoelectric sensor using unmarked PhotoelectrochemicalMethod Method detection diethylstilbestrol is finally realized.
Description
Technical field
The present invention relates to a kind of preparation methods of optical electro-chemistry diethylstilbestrol sensor.Belong to Nano-function thin films with
Biosensor technology field.
Background technique
After environmental estrogens refer to that one kind enters body, synthesis, release, fortune with normal endocrine substance in interfering bodies
The processes such as defeated, combination, metabolism, activate or inhibit the function of endocrine system, maintain organism stability and regulation to make to destroy
Compound, environmental estrogens are many kinds of, including artificial-synthetic compound and natural plant estrogen, are distributed widely in certainly
In right boundary.Diethylstilbestrol is a kind of artificial synthesized non steroidal estrogen substance.Currently, the method for detection diethylstilbestrol is main
There are chromatography, mass spectrography etc..Such method instrument is valuable, complicated for operation, and laboratory personnel just can be carried out inspection after needing professional training
It surveys.Therefore, research and development are at low cost, detection is fast, high sensitivity, high specificity diethylstilbestrol sensor is of great significance.
Optical electro-chemistry sensor due to high sensitivity, testing cost is low the features such as, in recent years by more and more researchers
It is of interest.Optical electro-chemistry sensor is to cause electron-hole pair to be separated based on additional light source activation Electrophotosensitivmaterial material,
Under suitable potential condition partially, quick transmitting of the electronics on electrode, semiconductor and modifier and analyte is realized, and form light
Electric current.In optimal conditions, the variation of analyte concentration will have a direct impact on the size of photoelectric current, and biological immune is recycled to combine,
The qualitative and quantitative analysis to analyte can be realized according to the variation of photoelectric current.
Optical electro-chemistry sensor most critical technology is exactly the raising to performances such as the size of photoelectric current and stability.Titanium dioxide
Titanium is a kind of photochemical catalyst and light induced electron host material being most widely used, however, to give full play to the reality of titanium dioxide
Border application level needs on the one hand living to improve optical electro-chemistry with the more high activity crystal faces of exposure by regulating and controlling its material morphology
Property, photosensitive wavelength is on the other hand regulated and controled by doping different metal or metal oxide and improves the sun to visible-range extension
The utilization rate of light.It, can due to two-dimentional titanium dioxide nano material, such as titanium dioxide nanoplate, nano titania square
The more high activity crystal faces of exposure have higher optical electro-chemistry activity, and titanium dioxide nanoplate has more preferable than nanoparticle
Ground application prospect is also concerned the research of titanium dioxide nanoplate.And single titanium dioxide nano material is photosensitive
Wavelength generally in ultra-violet (UV) band, and due to bad dispersibility, easily stack and interact, thus reduce optical electro-chemistry activity, it is unfavorable
In practical application.Therefore, at low cost, preparing simple bloom electro-chemical activity photosensitive dose of titanium dioxide is researched and developed with important
Scientific meaning and application value.
Molybdenum disulfide (chemical formula MoS2) nano material, there is two-dimensional layered structure, be most widely used solid profit
One of lubrication prescription.Its sheet two-dimension nano materials after removing, is the semiconductor nano material haveing excellent performance, in addition to big ratio
Surface area, can be used as the carrier of catalyst and biological antibody, improve load capacity, while also have as co-catalyst excellent
Electron transmission performance.
Currently, most of synthesizing mean is all after being separately synthesized, then catalyst and carrier progress is compound, process is numerous
Trivial, yield is not high.Therefore, before being had a wide range of applications for In-situ reaction preparation with the photosensitizer of excellent photoelectrochemical behaviour
Scape and important scientific meaning.
In addition, the photo-generate electron-hole of single titanium dioxide nano material to easily it is compound, so as to cause photosignal
Weaken, and titanium dioxide poorly conductive also limits the optical electro-chemistry sensor constructed by single titanium dioxide nano material
Sensitivity is not generally high, is unfavorable for practical application.Therefore, design, prepare efficient, stable doping titanium dioxide nano piece and its
Modifier is the key technology for preparing optical electro-chemistry sensor.
Summary of the invention
The purpose of the present invention is to provide it is a kind of prepare simple, high sensitivity, detection quickly, the optical electro-chemistry of high specificity
The preparation method of diethylstilbestrol sensor, prepared sensor can be used for quick, the Sensitive Detection of diethylstilbestrol.Based on this
Purpose, the method comprises the steps of firstly, preparing a kind of New Two Dimensional nanometer photoelectronic materials --- Copper-cladding Aluminum Bar nanometer photoelectronic material, i.e. Copper-cladding Aluminum Bar
The two-dimensional nano composite material Cu-TiO of nano titania square In-situ reaction molybdenum disulfide2/MoS2, utilize the good of the material
Good biocompatibility and big specific surface area, diethylstilbestrol antibody in load, alkaline phosphatase in fixation, are being detected
When, L-AA AA is generated in situ since alkaline phosphatase can be catalyzed L-AA -2- tricresyl phosphate sodium salt AAP, is gone forward side by side
And electron donor is provided for Photoelectric Detection, recycle antibody in conjunction with the specific quantification of antigen to the shadow of electron transport ability
It rings, so that photo-current intensity accordingly reduces, finally realizes the light using unmarked PhotoelectrochemicalMethod Method detection diethylstilbestrol
The building of electric transducer.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of the optical electro-chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material, special
Sign is that the Copper-cladding Aluminum Bar nanometer photoelectronic material is the two dimension of copper-doped titanium dioxide nano square In-situ reaction molybdenum disulfide
Nanocomposite Cu-TiO2/MoS2, the optical electro-chemistry diethylstilbestrol sensor is by working electrode, Cu-TiO2/MoS2、
Diethylstilbestrol antibody, alkaline phosphatase, bovine serum albumin(BSA) composition；
It is characterized in that, the preparation method includes following preparation step:
A. Cu-TiO is prepared2/MoS2；
B. optical electro-chemistry diethylstilbestrol sensor is prepared；
Wherein, step a prepares Cu-TiO2/MoS2Specific steps are as follows:
(1) 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol mantoquita is taken to be added to 3 ~ 10 mL n-BuLis jointly molten
In liquid, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water-bath is then carried out at 30 ~ 60 DEG C
Ultrasonic treatment, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain two sulphur of copper intercalation
Change molybdenum nano material；
(3) the molybdenum disulfide nano material of copper intercalation made from 10 ~ 500 mg steps (2) is taken to be added to 5 mL metatitanic acids four
In butyl ester, after stirring 1 hour, it is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, is then reacting at 160 ~ 180 DEG C
It is reacted 18 ~ 20 hours in kettle；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C
Sky is dry, obtains Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is selected from one of following: copper sulphate, copper chloride, copper nitrate, organocopper compound；
The nonpolar solvent is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
The water bath sonicator processing, processing time are 1 hour；
The specific steps of step b preparation optical electro-chemistry diethylstilbestrol sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the Cu-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, room
It is dried under temperature；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 ~ 12 μ L of electrode surface drop coating
The diethylstilbestrol antibody solution of 10 μ g/mL is saved in 4 DEG C of refrigerators and is dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 6 ~ 10 μ L concentration of electrode surface drop coating to be 20
The alkaline phosphatase enzyme solutions of μ g/mL are saved in 4 DEG C of refrigerators and are dried；
(4) electrode obtained in step (3) is cleaned with PBS, continues in 8 ~ 12 μ L concentration of electrode surface drop coating to be 100
The bovine serum albumin solution of μ g/mL is saved in 4 DEG C of refrigerators and is dried；
(5) electrode obtained in step (4) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains photoelectricity
Chemical diethylstilbestrol sensor；
The Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and
The hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
2. the application of optical electro-chemistry diethylstilbestrol sensor, feature prepared by preparation method of the present invention exist
In, including following applying step:
A. standard solution is prepared: preparing the diethylstilbestrol standard solution of one group of various concentration including blank standard specimen；
B. working electrode is modified: optical electro-chemistry diethylstilbestrol prepared by preparation method as described in claim 1 is passed
Sensor is working electrode, and the diethylstilbestrol standard solution for the various concentration prepared in step b is distinguished drop coating to working electrode table
Face saves in 4 DEG C of refrigerators；
C. working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step
The working electrode composition three-electrode system that rapid b has been modified, is connected on optical electro-chemistry detection device；Successively add in a cell
L-AA -2- tricresyl phosphate sodium salt the AAP for entering 10 mmol/L of Tris-HCl buffer solution and 5 mL of pH=9.6 15mL is molten
Liquid；Work is drawn according to the relationship between resulting photocurrent values and diethylstilbestrol concentration of standard solution using i-t means of testing
Make curve；
D. the detection of diethylstilbestrol: replacing the diethylstilbestrol standard solution in step a with sample to be tested, according to step b and
Method in c is detected, according to response the intensity value and working curve of signal, obtains containing for diethylstilbestrol in sample to be tested
Amount.
Beneficial achievement of the invention
(1) optical electro-chemistry diethylstilbestrol sensor preparation of the present invention is simple, easy to operate, realizes to sample
Quickly, sensitive, highly selective detection, and it is at low cost, it can be applied to portable inspectiont, there is market development prospect；
(2) present invention is prepared for novel photocatalyst Cu-TiO using the method for In-situ reaction for the first time2/MoS2, this method master
Will be there are three advantage: first is that, due to growth in situ of the copper on nano titania square sufficiently with nano titania side
Block contact is acted on using the metal surface plasma body of copper, effectively prevents the compound of photo-generate electron-hole pair, greatly mention
High photocatalytic activity, due to the effect of metal ion, range, realizes in visible region light and urges with having widened photosensitive wavelength
Change acts on, with greatly improving sunlight utilization efficiency, although solving two-dimentional titanium dioxide nano material photocatalysis effect
It is good, but under sunlight irradiation photocatalysis effect difference technical problem；Second is that due to molybdenum disulfide sheet two-dimension nano materials
Load characteristic and nano titania square on it fully dispersed, greatly increase the light of nano titania square
It catalytic activity and solves two-dimentional titanium dioxide nano material and is unfavorable for dispersing and the technical issues of reduce photocatalytic activity；Three
It is, since copper ion is in this process not only as intercalation material but also as reaction dopant material, finally to use the side of In-situ reaction
Method realizes one pot of preparation of the composite material, not only saves time, material loss, and make the two of the Copper-cladding Aluminum Bar prepared
TiOx nano square can preferably be evenly spread to above molybdenum disulfide sheet two-dimension nano materials.Therefore, the material
Effectively preparation has important scientific meaning and application value；
(3) present invention is for the first time by Cu-TiO2/MoS2Applied in the preparation of Photoelectrochemistrbiosensor biosensor, significantly improve
The effective concentration of photo-generated carrier substantially increases the detection sensitivity of optical electro-chemistry sensor, so that optical electro-chemistry biology passes
Sensor realizes application in actual operation；The application of the material is also associated biomolecule sensor, as electrogenerated chemiluminescence passes
Sensor, electrochemical sensor etc. provide Technical Reference, have extensive potential use value.
Specific embodiment
1 Cu-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder and 0.2 mmol mantoquita is taken to be added in 3mL n-butyllithium solution jointly, in nitrogen
At gas shielded and 60 DEG C, stir 12 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water bath sonicator is then carried out at 60 DEG C
Processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain the molybdenum disulfide of copper intercalation
Nano material；
(3) the molybdenum disulfide nano material of copper intercalation made from 500 mg steps (2) is taken to be added to 5 mL butyl titanates
In, after stirring 1 hour, it is slowly added to 0.5 mL hydrofluoric acid while stirring, then reacts in a kettle 18 hours at 160 DEG C；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C
Sky is dry, obtains Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is copper sulphate；
The nonpolar solvent is hexane；
The water bath sonicator processing, processing time are 1 hour.
2 Cu-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder and 1.0 mmol mantoquitas is taken to be added in 5 mL n-butyllithium solutions jointly, in nitrogen
At gas shielded and 30 DEG C, stir 24 hours, the solution after being reacted；
(2) using the solution after reaction in nonpolar solvent washing step (1), water bath sonicator is then carried out at 30 DEG C
Processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain the molybdenum disulfide of copper intercalation
Nano material；
(3) the molybdenum disulfide nano material of copper intercalation made from 200 mg steps (2) is taken to be added to 5 mL butyl titanates
In, after stirring 1 hour, it is slowly added to 0.6 mL hydrofluoric acid while stirring, then reacts in a kettle 20 hours at 180 DEG C；
(4) by step (3) resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, it is true at 50 DEG C
Sky is dry, obtains Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is copper chloride；
The nonpolar solvent is carbon tetrachloride；
The water bath sonicator processing, processing time are 1 hour.
The preparation method of 3 optical electro-chemistry diethylstilbestrol sensor of embodiment
(1) using the ITO electro-conductive glass that width is 1 cm, a length of 4 cm as working electrode, 8 μ L's of electrode surface drop coating
Cu-TiO2/MoS2Colloidal sol dries at room temperature；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 μ L of electrode surface drop coating, 10 μ
The diethylstilbestrol antibody solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 8 μ L concentration of electrode surface drop coating to be 100 μ
The bovine serum albumin solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(4) electrode obtained in step (3) is cleaned with PBS, continues in 6 μ L concentration of electrode surface drop coating to be 20 μ g/
The alkaline phosphatase enzyme solutions of mL are saved in 4 DEG C of refrigerators and are dried；
(5) electrode obtained in step (4) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains photoelectricity
Chemical diethylstilbestrol sensor；
The Cu-TiO2/MoS2Colloidal sol is Cu-TiO prepared by the embodiment 1 by 50 mg2/MoS2Powder is dissolved in
In 10 mL ultrapure waters, and the hydrosol obtained after 30 min of ultrasound；
The PBS is the phosphate buffer solution of 10mmol/L, and the pH value of the phosphate buffer solution is 7.4.
The preparation method of 4 optical electro-chemistry diethylstilbestrol sensor of embodiment
All preparation steps are the same as embodiment 4, only Cu-TiO used in step2/MoS2For Cu- prepared by embodiment 2
TiO2/MoS2。
The optical electro-chemistry diethylstilbestrol sensor of 5 embodiment 1 and 3 of embodiment preparation, applied to the detection of diethylstilbestrol,
Steps are as follows:
(1) standard solution is prepared: preparing the diethylstilbestrol standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: optical electro-chemistry diethylstilbestrol prepared by preparation method as described in claim 1 is passed
Sensor is working electrode, and the diethylstilbestrol standard solution for the various concentration prepared in step (1) is distinguished drop coating to working electrode
Surface saves in 4 DEG C of refrigerators；
(3) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step
Suddenly the working electrode that (2) have been modified forms three-electrode system, is connected on optical electro-chemistry detection device；In a cell successively
L-AA -2- tricresyl phosphate sodium salt the AAP of 10 mmol/L of Tris-HCl buffer solution and 5 mL of pH=9.6 15mL is added
Solution；It is drawn using i-t means of testing according to the relationship between resulting photocurrent values and diethylstilbestrol concentration of standard solution
Working curve；The linear detection range of diethylstilbestrol are as follows: 0.002 ~ 200 ng/mL, detection limit are as follows: 0.8 pg/mL；
(4) actual sample detects: the diethylstilbestrol standard solution in step (1) is replaced with sample to be tested, according to step (2)
(3) method in is detected, and the intensity value and working curve of signal, obtain diethylstilbestrol in sample to be tested according to response
Content.
The optical electro-chemistry diethylstilbestrol sensor of 6 embodiment 2 and 4 of embodiment preparation, applied to the detection of diethylstilbestrol,
Steps are as follows:
(1) standard solution is prepared: preparing the diethylstilbestrol standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: optical electro-chemistry diethylstilbestrol prepared by preparation method as described in claim 1 is passed
Sensor is working electrode, and the diethylstilbestrol standard solution for the various concentration prepared in step (1) is distinguished drop coating to working electrode
Surface saves in 4 DEG C of refrigerators；
(3) working curve is drawn: using saturated calomel electrode as reference electrode, platinum electrode is as auxiliary electrode, with step
Suddenly the working electrode that (2) have been modified forms three-electrode system, is connected on optical electro-chemistry detection device；In a cell successively
L-AA -2- tricresyl phosphate sodium salt the AAP of 10 mmol/L of Tris-HCl buffer solution and 5 mL of pH=9.6 15mL is added
Solution；It is drawn using i-t means of testing according to the relationship between resulting photocurrent values and diethylstilbestrol concentration of standard solution
Working curve；The linear detection range of diethylstilbestrol are as follows: 0.002 ~ 200 ng/mL, detection limit are as follows: 0.8 pg/mL；
(4) actual sample detects: the diethylstilbestrol standard solution in step (1) is replaced with sample to be tested, according to step (2)
(3) method in is detected, and the intensity value and working curve of signal, obtain diethylstilbestrol in sample to be tested according to response
Content.
Claims (1)
1. a kind of preparation method of the optical electro-chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material, it is characterised in that
The Copper-cladding Aluminum Bar nanometer photoelectronic material is that the two-dimensional nano of copper-doped titanium dioxide nano square In-situ reaction molybdenum disulfide is multiple
Condensation material Cu-TiO2/MoS2, the optical electro-chemistry diethylstilbestrol sensor is by working electrode, Cu-TiO2/MoS2, hexene it is female
Phenol antibody, alkaline phosphatase, bovine serum albumin(BSA) composition；
The Cu-TiO2/MoS2Preparation step are as follows: take 0.6 g molybdenum disulfide powder and 0.2 ~ 2.0 mmol mantoquita common
It is added in 3 ~ 10 mL n-butyllithium solutions, at nitrogen protection and 30 ~ 60 DEG C, stirs 12 ~ 48 hours, reacted
Solution afterwards；Using the solution after nonpolar solvent washing reaction, water bath sonicator processing, place are then carried out at 30 ~ 60 DEG C
After having managed, recycle nonpolar solvent carrying out washing treatment after solution, vacuum drying, obtain the molybdenum disulfide nano material of copper intercalation
Material, takes the molybdenum disulfide nano material of copper intercalation made from 10 ~ 500 mg to be added in 5 mL butyl titanates, and stirring 1 is small
Shi Hou is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, then reacts 18 ~ 20 in a kettle at 160 ~ 180 DEG C
Hour, by resulting reaction product, with ultrapure water and dehydrated alcohol centrifuge washing three times after, be dried in vacuo, obtain at 50 DEG C
Cu-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The mantoquita is selected from one of following: copper sulphate, copper chloride, copper nitrate, organocopper compound；
The nonpolar solvent is selected from one of following: hexane, hexamethylene, carbon tetrachloride, benzene, toluene；
The water bath sonicator processing, processing time are 1 hour；
The preparation step of the optical electro-chemistry diethylstilbestrol sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the Cu-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, at room temperature
It dries；
(2) electrode obtained in step (1) is cleaned with buffer solution PBS, is continued in 8 ~ 12 μ L of electrode surface drop coating, 10 μ
The diethylstilbestrol antibody solution of g/mL is saved in 4 DEG C of refrigerators and is dried；
(3) electrode obtained in step (2) is cleaned with PBS, continues in 6 ~ 10 μ L concentration of electrode surface drop coating to be 20 μ g/
The alkaline phosphatase enzyme solutions of mL are saved in 4 DEG C of refrigerators and are dried；
(4) electrode obtained in step (3) is cleaned with PBS, continues in 8 ~ 12 μ L concentration of electrode surface drop coating to be 100 μ g/
The bovine serum albumin solution of mL is saved in 4 DEG C of refrigerators and is dried；
(5) electrode obtained in step (4) is cleaned with PBS, is saved in 4 DEG C of refrigerators after drying, obtains optical electro-chemistry
Diethylstilbestrol sensor；
The Cu-TiO2/MoS2Colloidal sol is by the Cu-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters, and ultrasound
The hydrosol obtained after 30 min；
The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is 7.4.
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| CN104297464B (en) * | 2014-09-06 | 2016-04-20 | 济南大学 | A kind of in-situ preparation CdS mycotoxin Optical Electro-Chemistry transducer production method and application |
| CN104569435B (en) * | 2015-01-25 | 2015-10-21 | 济南大学 | A kind of preparation method of unmarked Optical Electro-Chemistry alpha-fetoprotein immunosensor |
| CN104849331B (en) * | 2015-05-17 | 2016-04-20 | 济南大学 | A kind of based on Ag 2the preparation method of the Optical Electro-Chemistry sensor of the sandwich type serum cardiac troponin T of SeCdSe mark and application |
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2016
- 2016-07-05 CN CN201610526870.1A patent/CN106018514B/en not_active Expired - Fee Related
Non-Patent Citations (4)
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| Chemically exfoliated metallic MoS<sub>2</sub> nanosheets: A promising supporting co-catalyst for enhancing the photocatalytic performance of TiO<sub>2</sub> nanocrystals;Song Bai et al.;《Nano Research》;20141106;第8卷;176-177 |
| Hierarchical MoS<sub>2</sub> Nanosheet@TiO<sub>2</sub> Nanotube Array Composites with Enhanced Photocatalytic and Photocurrent Performances;Lingxia Zheng et al.;《small》;20160122;第12卷(第11期);1527–1536 |
| Photoelectrochemical Immunosensor for Detection of Carcinoembryonic Antigen Based on 2D TiO<sub>2</sub> Nanosheets and Carboxylated Graphitic Carbon Nitride;Huan Wang, et al.;《Scientific Reports》;20160606;第6卷;27385 |
| Synthesis and Characterization of Cobalt-Doped WS<sub>2</sub> Nanorods for Lithium Battery Applications;Shiquan Wang et al.;《Nanoscale Res Lett》;20100523;第5卷;1302 |
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