CN106198682B - A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent - Google Patents
A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent Download PDFInfo
- Publication number
- CN106198682B CN106198682B CN201610521792.6A CN201610521792A CN106198682B CN 106198682 B CN106198682 B CN 106198682B CN 201610521792 A CN201610521792 A CN 201610521792A CN 106198682 B CN106198682 B CN 106198682B
- Authority
- CN
- China
- Prior art keywords
- furazolidone
- manganese
- chemistry
- mos
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
-
- 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
- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/54366—Apparatus specially adapted for solid-phase testing
- G01N33/54386—Analytical elements
-
- 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
- G01N33/94—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving narcotics or drugs or pharmaceuticals, neurotransmitters or associated receptors
- G01N33/9446—Antibacterials
Abstract
The invention discloses a kind of preparation methods of optical electro-chemistry furazolidone sensor.Belong to Nano-function thin films and biosensor technology field.The method comprises the steps of firstly, preparing a kind of novel dual metal codope two-dimensional light sensitive agent, i.e. the two-dimensional nano composite material FeMn-TiO of iron, manganese codoped nano titania square and molybdenum disulfide In-situ reaction2/MoS2Good biocompatibility and big specific surface area using the material, furazolidone 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 furazolidone is finally realized.
Description
Technical field
The present invention relates to a kind of preparation methods of optical electro-chemistry furazolidone sensor.Belong to Nano-function thin films with
Biosensor technology field.
Background technique
Furazolidone (furazolidone) is a kind of Nitrofuran antibiotics, is broad spectrum antibiotic.As veterinary drug in use, furan
Oxazolone of muttering has good drug effect to certain protozoosises, saprolegniasis, bacterial gill rot disease, red skin disease, hemorrhage etc. is prevented and treated.In aquaculture
In, furazolidone can be used for treating animal and bird intestines infection, as piglet is yellow, dysentery characterized by white mucous stool.In aquatic products industry, furazolidone is to Salmonoidei sense
Dye Myxosoma cerebralis has certain curative effect.But furazolidone is classified as the drug being forbidden to use by the Ministry of Agriculture, China, must not be eaten in animality
It is detected in product.FDA also prohibited use of the itrofurans (including furazolidone) in animal food in 2002.
Currently, the method for detection furazolidone mainly has chromatography, mass spectrography etc..Such method instrument is valuable, operation is multiple
Miscellaneous, laboratory personnel just can be carried out detection after needing professional training.Therefore, research and development are at low cost, detection is fast, high sensitivity, specificity
Strong furazolidone 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 furazolidone sensor, prepared sensor can be used for quick, the Sensitive Detection of furazolidone.Based on this
Purpose, the method comprises the steps of firstly, preparing a kind of novel dual metal codope two-dimensional light sensitive agent, i.e. iron, manganese codoped nano titania
The two-dimensional nano composite material FeMn-TiO of square and molybdenum disulfide In-situ reaction2/MoS2, utilize the good biology of the material
Compatibility and big specific surface area, furazolidone antibody in load, alkaline phosphatase in fixation, when being detected, due to alkali
Acid phosphatase can be catalyzed L-AA -2- tricresyl phosphate sodium salt AAP and generate L-AA AA in situ, and examine in turn for photoelectricity
It surveys and electron donor is provided, recycle antibody in conjunction with the specific quantification of antigen to the influence of electron transport ability, so that photoelectricity
Intensity of flow accordingly reduces, and finally realizes the structure of the photoelectric sensor using unmarked PhotoelectrochemicalMethod Method detection furazolidone
It builds.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent,
It is characterized in that the bimetallic codope two-dimensional light sensitive agent is iron, manganese codoped nano titania square and molybdenum disulfide
The two-dimensional nano composite material FeMn-TiO of In-situ reaction2/MoS2, the optical electro-chemistry furazolidone sensor is by work electricity
Pole, FeMn-TiO2/MoS2, furazolidone antibody, alkaline phosphatase, bovine serum albumin(BSA) composition；
It is characterized in that, the preparation method includes following preparation step:
A. FeMn-TiO is prepared2/MoS2；
B. optical electro-chemistry furazolidone sensor is prepared；
Wherein, step a prepares FeMn-TiO2/MoS2Specific steps are as follows:
(1) 0.6 g molybdenum disulfide powder, 0.2 ~ 2.0 mmol molysite and 0.2 ~ 2.0 mmol manganese salt is taken to be added jointly
Into 3 ~ 10 mL n-butyllithium solutions, at nitrogen protection and 30 ~ 60 DEG C, stir 12 ~ 48 hours, after being reacted
Solution；
(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 iron, manganese is total to intercalation
Molybdenum disulfide nano material；
(3) the molybdenum disulfide nano material for taking iron made from 10 ~ 500 mg steps (2), manganese to be total to intercalation is added to 5 mL
In butyl titanate, after stirring 1 hour, it is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, then at 160 ~ 180 DEG C
It reacts 18 ~ 20 hours in a 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 FeMn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The molysite is selected from one of following: ferric sulfate, iron chloride, ferric nitrate, organoiron compound；
The manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate, organo-manganese 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 furazolidone sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the FeMn-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol,
It dries at room 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 furazolidone antibody-solutions of 10 μ g/mL are saved in 4 DEG C of refrigerators and are 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 furazolidone sensor；
The FeMn-TiO2/MoS2Colloidal sol is by the FeMn-TiO of 50 mg2/MoS2Powder is dissolved in 10 mL ultrapure waters
In, 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 furazolidone sensor, feature prepared by preparation method of the present invention exist
In, including following applying step:
A. standard solution is prepared: preparing the furazolidone standard solution of one group of various concentration including blank standard specimen；
B. working electrode is modified: optical electro-chemistry furazolidone prepared by preparation method as described in claim 1 is passed
Sensor is working electrode, and the furazolidone 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 furazolidone concentration of standard solution using i-t means of testing
Make curve；
D. the detection of furazolidone: replacing the furazolidone 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 furazolidone in sample to be tested
Amount.
Beneficial achievement of the invention
(1) optical electro-chemistry furazolidone 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 FeMn-TiO using the method for In-situ reaction for the first time2/MoS2, this method
It is main that there are three advantages: first is that, due to iron, manganese jointly the growth in situ on nano titania square and sufficiently and titanium dioxide
The contact of titanium nano square effectively prevents light using the metal surface plasma body effect of iron, manganese and the synergistic effect of the two
The compound of electron-hole pair is given birth to, photocatalytic activity is greatly improved, due to the effect of metal ion, has widened photosensitive wavelength
Ground range realizes in visible region photocatalysis, with greatly improving sunlight utilization efficiency, solves two dimension two
Although titanium dioxide nano material photocatalysis effect is good, the technical problem of photocatalysis effect difference under sunlight irradiation；Second is that
Due to load characteristic and nano titania square on it fully dispersed of molybdenum disulfide sheet two-dimension nano materials, greatly
Ground increase nano titania square photocatalytic activity and solve two-dimentional titanium dioxide nano material be unfavorable for dispersion and
The technical issues of reducing photocatalytic activity；Third is that since iron ion, manganese ion are not only used as intercalation material but also conduct in this process
React dopant material, one pot of composite material preparation finally realized using the method for In-situ reaction, not only save the time,
Material loss, and the iron of preparation, the nano titania square of additive Mn is enabled preferably to evenly spread to curing
Above molybdenum sheet shape two-dimension nano materials.Therefore, effective preparation of the material has important scientific meaning and application value；
(3) present invention is for the first time by FeMn-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 is biological
Sensor realizes application in actual operation；The application of the material is also associated biomolecule sensor, such as electrogenerated chemiluminescence
Sensor, electrochemical sensor etc. provide Technical Reference, have extensive potential use value.
Specific embodiment
1 FeMn-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder, 0.2 mmol molysite and 0.2 mmol manganese salt is taken to be added to 3mL normal-butyl jointly
In lithium solution, at nitrogen protection 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 iron, manganese is total to two sulphur of intercalation
Change molybdenum nano material；
(3) the molybdenum disulfide nano material for taking iron made from 500 mg steps (2), manganese to be total to intercalation is added to 5 mL metatitanic acids four
In butyl ester, after stirring 1 hour, it is slowly added to 0.5 mL hydrofluoric acid while stirring, then reacts 18 in a kettle at 160 DEG C
Hour；
(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 FeMn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The molysite is ferric sulfate；
The manganese salt is manganese sulfate；
The nonpolar solvent is hexane；
The water bath sonicator processing, processing time are 1 hour.
2 FeMn-TiO of embodiment2/MoS2Preparation
(1) 0.6 g molybdenum disulfide powder, 1.0 mmol molysite and 1.0 mmol manganese salts is taken to be added to 5 mL normal-butyls jointly
In lithium solution, at nitrogen protection 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 iron, manganese is total to two sulphur of intercalation
Change molybdenum nano material；
(3) the molybdenum disulfide nano material for taking iron made from 200 mg steps (2), manganese to be total to intercalation is added to 5 mL metatitanic acids four
In butyl ester, after stirring 1 hour, it is slowly added to 0.6 mL hydrofluoric acid while stirring, then reacts 20 in a kettle at 180 DEG C
Hour；
(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 FeMn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The molysite is iron chloride；
The manganese salt is manganese 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 furazolidone 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
FeMn-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 furazolidone antibody-solutions of g/mL are saved in 4 DEG C of refrigerators and are 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 furazolidone sensor；
The FeMn-TiO2/MoS2Colloidal sol is FeMn-TiO prepared by the embodiment 1 by 50 mg2/MoS2Powder
It is dissolved 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 furazolidone sensor of embodiment
All preparation steps are the same as embodiment 3, only FeMn-TiO used in step2/MoS2For prepared by embodiment 2
FeMn-TiO2/MoS2。
The optical electro-chemistry furazolidone sensor of 5 embodiment 1 and 3 of embodiment preparation, applied to the detection of furazolidone,
Steps are as follows:
(1) standard solution is prepared: preparing the furazolidone standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: optical electro-chemistry furazolidone prepared by preparation method as described in claim 1 is passed
Sensor is working electrode, and the furazolidone 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 furazolidone concentration of standard solution
Working curve；The linear detection range of furazolidone are as follows: 0.002 ~ 200 ng/mL, detection limit are as follows: 0.8 pg/mL；
(4) actual sample detects: the furazolidone 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 furazolidone in sample to be tested according to response
Content.
The optical electro-chemistry furazolidone sensor of 6 embodiment 2 and 4 of embodiment preparation, applied to the detection of furazolidone,
Steps are as follows:
(1) standard solution is prepared: preparing the furazolidone standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: optical electro-chemistry furazolidone prepared by preparation method as described in claim 1 is passed
Sensor is working electrode, and the furazolidone 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 furazolidone concentration of standard solution
Working curve；The linear detection range of furazolidone are as follows: 0.002 ~ 200 ng/mL, detection limit are as follows: 0.8 pg/mL；
(4) actual sample detects: the furazolidone 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 furazolidone in sample to be tested according to response
Content.
Claims (1)
1. a kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent, feature
It is that the bimetallic codope two-dimensional light sensitive agent is that iron, manganese codoped nano titania square and molybdenum disulfide are multiple in situ
The two-dimensional nano composite material FeMn-TiO of conjunction2/MoS2, the optical electro-chemistry furazolidone sensor by working electrode,
FeMn-TiO2/MoS2, furazolidone antibody, alkaline phosphatase, bovine serum albumin(BSA) composition；
The FeMn-TiO2/MoS2Specific preparation step are as follows: take 0.6 g molybdenum disulfide powder, 0.2 ~ 2.0 mmol iron
Salt and 0.2 ~ 2.0 mmol manganese salt are added to jointly in 3 ~ 10 mL n-butyllithium solutions, in nitrogen protection and 30 ~ 60 DEG C
Under, it stirs 12 ~ 48 hours, the solution after being reacted；Using the solution after nonpolar solvent washing reaction, then 30 ~
At 60 DEG C carry out water bath sonicator processing, after handle, recycle nonpolar solvent carrying out washing treatment after solution, be dried in vacuo, obtain
The molybdenum disulfide nano material of intercalation is total to iron, manganese；Iron made from 10 ~ 500 mg, manganese is taken to be total to the molybdenum disulfide nano of intercalation
Material is added in 5 mL butyl titanates, after stirring 1 hour, is slowly added to 0.5 ~ 0.8 mL hydrofluoric acid while stirring, so
It reacts in a kettle 18 ~ 20 hours at 160 ~ 180 DEG C afterwards；Resulting reaction product is centrifuged with ultrapure water and dehydrated alcohol
After washing three times, it is dried in vacuo at 50 DEG C, obtains FeMn-TiO2/MoS2；
The n-butyllithium solution is the hexane solution of n-BuLi, and concentration is 1.6 mol/L；
The molysite is selected from one of following: ferric sulfate, iron chloride, ferric nitrate, organoiron compound；
The manganese salt is selected from one of following: manganese sulfate, manganese chloride, manganese nitrate, organo-manganese 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 preparation step of the optical electro-chemistry furazolidone sensor are as follows:
(1) using ITO electro-conductive glass as working electrode, in the FeMn-TiO of 8 ~ 12 μ L of electrode surface drop coating2/MoS2Colloidal sol, room temperature
Under dry；
(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 furazolidone antibody-solutions of g/mL are saved in 4 DEG C of refrigerators and are 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
Furazolidone sensor；
The FeMn-TiO2/MoS2Colloidal sol is by the FeMn-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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610521792.6A CN106198682B (en) | 2016-07-05 | 2016-07-05 | A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610521792.6A CN106198682B (en) | 2016-07-05 | 2016-07-05 | A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106198682A CN106198682A (en) | 2016-12-07 |
| CN106198682B true CN106198682B (en) | 2019-03-12 |
Family
ID=57464843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610521792.6A Expired - Fee Related CN106198682B (en) | 2016-07-05 | 2016-07-05 | A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106198682B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111812170A (en) * | 2020-07-10 | 2020-10-23 | 苏州科技大学 | Three-dimensional paper-based electrochemical sensing device and preparation method and application thereof |
| CN114235931B (en) * | 2021-12-17 | 2024-01-19 | 湘潭大学 | Method for improving performance of flexible photoelectric detector |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103913565A (en) * | 2014-04-26 | 2014-07-09 | 济南大学 | Preparation method and application of immunosensor constructed by difunctional marker |
| CN105572193A (en) * | 2016-02-25 | 2016-05-11 | 王亚莉 | Preparation method and application of electrochemical chlordimeform sensor based on composite cerium-doped porous nanocomposite |
| CN105675689A (en) * | 2016-03-16 | 2016-06-15 | 济南大学 | Preparation method for hydrogen peroxide non-enzymatic sensor established based on molybdenum sulfide composite and application |
| CN105699368A (en) * | 2016-03-16 | 2016-06-22 | 济南大学 | Preparation method and application of difunctional hydrogen peroxide non-enzymatic sensor built based on two-dimensional composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060239907A1 (en) * | 2003-06-03 | 2006-10-26 | The Trustees Of The University Of Pennsylvania | Stealthy nano agents |
| CN105572197B (en) * | 2016-02-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of the optical electro-chemistry estradiol sensor based on magnetic Nano light-sensitive material |
-
2016
- 2016-07-05 CN CN201610521792.6A patent/CN106198682B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103913565A (en) * | 2014-04-26 | 2014-07-09 | 济南大学 | Preparation method and application of immunosensor constructed by difunctional marker |
| CN105572193A (en) * | 2016-02-25 | 2016-05-11 | 王亚莉 | Preparation method and application of electrochemical chlordimeform sensor based on composite cerium-doped porous nanocomposite |
| CN105675689A (en) * | 2016-03-16 | 2016-06-15 | 济南大学 | Preparation method for hydrogen peroxide non-enzymatic sensor established based on molybdenum sulfide composite and application |
| CN105699368A (en) * | 2016-03-16 | 2016-06-22 | 济南大学 | Preparation method and application of difunctional hydrogen peroxide non-enzymatic sensor built based on two-dimensional composite material |
Non-Patent Citations (1)
| Title |
|---|
| Amperometric immunobiosensor for α-fetoprotein using Au nanoparticles/chitosan/ TiO2–graphene composite based platform;Ke-Jing Huang等;《Bioelectrochemistry》;20121107;第90卷;第18-23页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106198682A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106018514B (en) | A kind of preparation method of the optical electro-chemistry diethylstilbestrol sensor based on Copper-cladding Aluminum Bar nanometer photoelectronic material | |
| CN105628758B (en) | A kind of preparation method and application of the optical electro-chemistry parathion sensor based on two-dimensional nano light-sensitive material | |
| CN105717180B (en) | A kind of preparation method and application of the optical electro-chemistry aflatoxin biology sensor based on two-dimensional nano composite | |
| CN105572197B (en) | A kind of preparation method and application of the optical electro-chemistry estradiol sensor based on magnetic Nano light-sensitive material | |
| CN106198501B (en) | A kind of preparation method for the Electrochemiluminescsensor sensor detecting aflatoxin | |
| CN105572193A (en) | Preparation method and application of electrochemical chlordimeform sensor based on composite cerium-doped porous nanocomposite | |
| CN105699645B (en) | A kind of preparation method and application of electrochemistry salbutamol sensor | |
| CN105572108B (en) | A kind of preparation method and application of electrogenerated chemiluminescence demeton sensor | |
| CN106198682B (en) | A kind of preparation method of the optical electro-chemistry furazolidone sensor based on bimetallic codope two-dimensional light sensitive agent | |
| CN106124588B (en) | A kind of preparation method of the electrochemistry nonyl phenol sensor based on titania-doped/molybdenum disulfide composite material | |
| CN106198683B (en) | A kind of preparation method of the optical electro-chemistry chloramphenicol biosensor based on two-dimensional nano photoelectric material | |
| CN105738353B (en) | A kind of preparation method and application of optical electro-chemistry decis sensor | |
| CN106053566B (en) | A kind of preparation method of the optical electro-chemistry salbutamol sensor based on two-dimensional magnetic nanometer photoelectronic material | |
| CN106248753B (en) | A kind of preparation method of the optical electro-chemistry Spanon sensor based on load type double-metal codope photosensitizer | |
| CN106198668B (en) | A kind of preparation method of the optical electro-chemistry demeton sensor based on cobalt doped two-dimensional nano photoelectric material | |
| CN106053572B (en) | A kind of preparation method of electrochemistry bisphenol-A sensor | |
| CN106124591B (en) | A kind of preparation method based on titanium dioxide/molybdenum disulfide composite material estradiol sensor | |
| CN105717099B (en) | A kind of preparation method and application of electrogenerated chemiluminescence furazolidone biology sensor | |
| CN106124589B (en) | A kind of preparation method of the electrochemica biological sensor based on the building of Fe2O3 doping two-dimension nano materials | |
| CN106053573B (en) | A kind of preparation method of the electrochemical sensor based on load type double-metal co-doped nano composite material | |
| CN106053442B (en) | A kind of preparation method of the electrogenerated chemiluminescence decis sensor based on iron cobalt codope two-dimension nano materials | |
| CN105738352B (en) | A kind of preparation method and application of the optical electro-chemistry Ractopamine sensor based on bimetallic codope two-dimension nano materials | |
| CN106198672B (en) | A kind of preparation method for the electrochemical sensor detecting carbamate | |
| CN106198500B (en) | A kind of preparation method for the electroluminescent chemiluminescence biosensor detecting organo-chlorine pesticide | |
| CN105717179B (en) | A kind of preparation method and application of optical electro-chemistry organo-chlorine pesticide biology sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190312 Termination date: 20210705 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |