CN106841351B - A kind of molybdenum disulfide nano sheet electrochemical sensor and the preparation method and application thereof - Google Patents
A kind of molybdenum disulfide nano sheet electrochemical sensor and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of molybdenum disulfide nano sheet electrochemical sensors and the preparation method and application thereof.The molybdenum disulfide nano sheet electrochemical sensor, including glass-carbon electrode substrate, contact conductor and insulating layer, the glass-carbon electrode substrate surface is coated with thiourea modified molybdenum disulfide nano sheet, and the thiourea modified molybdenum disulfide nano sheet is connect with GE11 polypeptide.The molybdenum disulfide nano sheet electrochemical sensor construction method is simple, immersion can be obtained, the detection to HepG2 liver cancer cells can be achieved, show good electro catalytic activity, and have the characteristics that the response time is fast, the range of linearity is wide, it is high to detect low limit, favorable reproducibility, stability, there is potentiality to be exploited and application prospect.
Description
Technical field
The invention belongs to electrochemical biosensor fields, and in particular to a kind of molybdenum disulfide nano sheet electrochemical sensor and
Preparation method and application.
Background technique
There are many ways to currently used for cell detection, such as immunocytochemical method, round pcr, electrochemical process and micro-
Flow control apparatus etc..Although these method sensitivity are higher, and are widely used in laboratory testing and hospital clinical diagnosis, most
Method needs the operating process of advanced instrument and equipment and complexity, takes time and effort, and is not suitable for quickly detecting.Therefore, simple, fast
The detection method of speed still needs to further study.In recent years, with the development of nanotechnology, nano material is ground biosensor
System aspect is used widely, and has started new situation for the research of cell sensor.The building and modification of sensing interface are systems
The core and committed step of standby cell sensor, directly influence response sensitivity, the range of linearity and the use of cell sensor
Service life etc..Using the skin effect, dimensional effect and quantum effect of nano material, such as by the nano material of different structure and form
Nano particle, nanotube, nano wire or nano material compound be introduced into the building at bio-sensing interface, can significantly improve
The detection performance of biosensor.Therefore, the nano material for introducing different structure constructs ideal cell sensing interface, in turn
The cell sensor for obtaining function admirable is the research hotspot of sensor field and one of the main target that researcher explores.Nearly ten
Nian Lai, the very big concern and knot as graphene that graphene obtains scientists in the application study of field of biosensors
Structure analog, MoS2With two-dimensional layered structure, unique properties, there are big surface area, good electron mobility and height electricity
The sub- density of states shows excellent electrochemical sensing performance.Current MoS2The biosensor of nanometer sheet preparation is mainly used for examining
Survey the biomolecule such as Paracetamol, glucose, dopamine, DNA.(Adv.Funct.Mater.2015,25,5086；
Chem.Soc.Rev.2015,44,4433；Chem.Soc.Rev.2013,42,5944；Anal.Chem.2015,87,230；
Small 2013,9,1160；Electroanal.2010,22,1027；Angew.Chem.Int.Ed.2010,49,2114；ACS
Sens.2016,1,5；Nat.Chem.2013,5,263；Nat.Nanotechnol.2012,7,699；Small 2014,10,
1101；Biosens.Bioelectron.2015,74,227；Biosens.Bioelectron.2014,55,195；
Nanoscale 2014,6,11971；Anal.Chem.2014,86,12064；Anal.Chem.2013,85,10289；
Sci.Rep.2016,6,34587；Sci.Rep.2014,4；J.Phys.Chem.C 2011,115,13303；
J.Am.Chem.Soc.2013,135,4584；Chem.Mater.2014,26,5892).But MoS2Direct detection for cell
Document report is still less, and simultaneously for the building of sensing interface, there are interface building complexity, poor biocompatibility, sensitivity are low
The problems such as.
Summary of the invention
The primary purpose of the present invention is that proposing a kind of molybdenum disulfide nano sheet electrochemical sensor.
Another object of the present invention is to provide the preparation methods of the molybdenum disulfide nano sheet electrochemical sensor.The party
Method is to be connect using thiourea modified molybdenum disulfide nano sheet with polypeptide, constructs sensing interface with simple and convenient modification mode,
Obtain electrochemical sensor；This method is simple and easy to control, economical rationality.
Another object of the present invention is to provide the application of the molybdenum disulfide nano sheet electrochemical sensor.
The object of the invention is achieved through the following technical solutions: a kind of molybdenum disulfide nano sheet electrochemical sensor, including glass
Carbon electrode substrate, contact conductor and insulating layer, the glass-carbon electrode substrate surface are coated with thiourea modified molybdenum disulfide and receive
Rice piece, the thiourea modified molybdenum disulfide nano sheet are connect with GE11 polypeptide.
The size of the thiourea modified molybdenum disulfide nano sheet is 200~300nm, is adsorbed with a large amount of thiocarbamide, deposits
In amino abundant.
The thiourea modified molybdenum disulfide nano sheet is preferably prepared via a method which to obtain: by molybdate and sulphur source
It is dissolved in the water, then solution is heated to 220 DEG C under the conditions of microwave radiation and reacted, washed, be centrifuged, dry, obtain
Thiourea modified molybdenum disulfide nano sheet.
The sulphur source and molybdate is that 12:1 is matched in molar ratio.
The molybdate is preferably Ammonium Molybdate Tetrahydrate ((NH4)6Mo7O24·4H2O)。
The sulphur source is preferably thiocarbamide.
The time of the reaction is preferably 10 minutes.
The water is preferably distilled water.
The washing is to be washed with distilled water 3 times or ethanol washing 3 times, preferably respectively washs 3 with distilled water and ethyl alcohol
It is secondary.
The condition of the centrifugation is preferably 10000r/min centrifugation 5min.
The temperature of the drying is preferably 50 DEG C, and the dry time is preferably for 24 hours.
The preparation method of the molybdenum disulfide nano sheet electrochemical sensor, includes the following steps:
(1) by thiourea modified molybdenum disulfide nano sheet ultrasonic disperse in mixed solution A, two thiourea modified sulphur are obtained
Change molybdenum dispersion liquid, wherein mixed solution A is molten by perfluorinated sulfonic acid (Nafion) solution, PVDF (Kynoar) solution and ethyl alcohol
Liquid composition；
(2) molybdenum disulfide dispersion liquid Tu thiourea modified obtained in step (1) is overlayed on glass-carbon electrode, it is dry, it obtains
To the glass-carbon electrode for being coated with thiourea modified molybdenum disulfide dispersion liquid；
(3) by obtained in step (2) be coated with thiourea modified molybdenum disulfide dispersion liquid glass-carbon electrode be immersed in by
PBS buffer solution, GE11 polypeptide and EDCHCl (1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride) are formed mixed
It closes in solution B, 4 DEG C of preservations obtain molybdenum disulfide nano sheet electrochemical sensor.
Thiourea modified molybdenum disulfide nano sheet additive amount is to match 4mg by every mL (milliliter) mixed solution A in step (1)
Thiourea modified molybdenum disulfide nano sheet calculates.
Perfluorinated sulfonic acid (Nafion) solution, PVDF (Kynoar) solution and second in mixed solution A described in step (1)
4:3:100 proportion calculates alcoholic solution by volume.
The time of ultrasound described in step (1) is preferably 30 minutes.
Perfluorinated sulfonic acid (Nafion) solution described in step (1) is preferably the Nafion of Sigma-Aldrich company molten
Liquid.
The concentration of the Nafion solution is mass percent 5%.
PVDF (Kynoar) solution described in step (1) is preferably prepared via a method which to obtain: PVDF is molten
For solution in N-Methyl pyrrolidone, stirring obtains PVDF solution.
The PVDF is preferably PVDF solid powder.
The additive amount of the N-Methyl pyrrolidone is based on every g (gram) PVDF proportion 12mL N-Methyl pyrrolidone
It calculates.
The time of the stirring is preferably 12 hours.
Ethanol solution described in step (1) is ethanol water, and preferably 1:4 matches to obtain second alcohol and water by volume
Ethanol solution.
Glass-carbon electrode described in step (2) is preferably the glass-carbon electrode that diameter is 3mm.
Coating described in step (2) is preferably realized by the following method: being taken thiourea modified molybdenum disulfide dispersion liquid, is adopted
With the coating method of drop Tu, it is uniformly coated on the surface of clean glass-carbon electrode.
The glass-carbon electrode of the cleaning is preferably prepared via a method which to obtain: glass-carbon electrode is successively used to 2000 molybdenum ores
Paper, aluminium powder polishing, then successively supersound washing is distinguished with ultrapure water, aqueous solution of nitric acid, ethanol water, naturally dry obtains clean
Net glass-carbon electrode.
The aqueous solution of nitric acid is that 1:1 matches to obtain by the volume ratio of nitric acid and water.
The ethanol water is that 1:1 matches to obtain by the volume ratio of second alcohol and water.
The time of the supersound washing is preferably 2 minutes.
Drying described in step (2) preferably spontaneously dries at room temperature.
The time of preservation described in step (3) is preferably 2.5 hours.
Application of the molybdenum disulfide nano sheet electrochemical sensor in field of biomedicine.
Application of the molybdenum disulfide nano sheet electrochemical sensor in cell detection.
The cell is preferably HepG2 liver cancer cells.
Compared with prior art, the present invention has the following advantages and beneficial effects:
1, the thiourea modified molybdenum disulfide nano sheet of the method for the present invention preparation has well-regulated two-dimensional sheet structure and big
Specific surface, there are amino abundant to be conducive in conjunction with biomolecule, therefore this thiourea modified molybdenum disulfide nano sheet exists
It is applied in field of biosensors.
2, the method for the present invention preparation condition is simple and easy to control, and process conditions are at low cost, and preparation efficiency is high, product quality and at
Product rate is high, there is good application and industrialization prospect.To this method systematic research, novel electrochemical student can be not only provided
Object sensor material, and synthesis methodology to material and clinical application have wide significance.
3, thiourea modified molybdenum disulfide nano sheet specific surface produced by the present invention is high, and active site is more, and keeps good
Nanometer sheet pattern, need to carry out that surface is modified and assembling conducive to for actual, there is potentiality to be exploited and application prospect.
4, the electrochemical sensor of the thiourea modified molybdenum disulfide nano sheet building of polypeptide-produced by the present invention, modification side
Method is simple, will not damage to detected target molecule.
5, polypeptide-produced by the present invention it is thiourea modified molybdenum disulfide nano sheet building electrochemical sensor, it can be achieved that
Detection to HepG2 liver cancer cells, and have the advantages that the response time is fast, the range of linearity is wide, favorable reproducibility, stability are high, it is right
The detection range of linearity of HepG2 liver cancer cells is 50~1.0 × 106cells mL-1, detect and be limited to 50cells mL-1。
6, the thiourea modified molybdenum disulfide nano sheet of microwave method synthesis is coated in glassy carbon electrode surface by the present invention, then is soaked
Bubble connects GE11 polypeptide in GE11 polypeptide solution, sensor needed for both obtaining.The thiourea modified molybdenum disulfide of the polypeptide-is received
The electrochemical sensor of rice piece building can realize the detection to HepG2 liver cancer cells, and (GE11 polypeptide can be with HepG2 cell-specific
Property identification), show good electro catalytic activity, and have the response time is fast, the range of linearity is wide, detection limit is low, favorable reproducibility,
The features such as stability is high.
7, the present invention be directed to the prior art defects of biosensor to improve, and main feature is shown: (1) sensing
The synthesis of material has thiourea modified molybdenum disulfide nano sheet as sensing material, with microwave method one-step synthesis, just in the present invention
Method high-efficient simple, and the appearance structure of material itself is not destroyed in material modification, while improving biocompatibility, compared with
The prior art is easier；(2) building of sensor, the present invention are to pass with the thiourea modified molybdenum disulfide nano sheet of GE11 polypeptide-
Sensor, construction method only needs to impregnate (there are amino abundant to be connected with polypeptide for thiocarbamide), more convenient compared with the prior art；(3)
Detection method, for the electrochemical method that the present invention uses compared to the more efficient simplicity of conventional method, sensitivity is higher.
Detailed description of the invention
Fig. 1 is molybdenum disulfide nano sheet electrochemical sensor structural schematic diagram, wherein 1 is thiourea modified molybdenum disulfide
Nanometer sheet, 2 be glass-carbon electrode substrate, and 3 be insulating layer, and 4 be contact conductor.
The schematic diagram that Fig. 2 constructs for the synthetic route and electrochemical sensor of thiourea modified molybdenum disulfide nano sheet,
In, figure a is synthetic route chart, and figure b is the schematic diagram of electrochemical sensor building.
Fig. 3 is scanning electron microscope (SEM) figure of molybdenum disulfide (product A) thiourea modified made from embodiment 1.
Fig. 4 is transmission electron microscope (TEM) figure of product A made from embodiment 1.
Fig. 5 is high-resolution-ration transmission electric-lens (HRTEM) figure of product A made from embodiment 1.
Fig. 6 is X-ray powder diffraction (XRD) figure of product A made from embodiment 1.
Fig. 7 is infrared spectroscopy (IR) figure of product A made from embodiment 1.
Fig. 8 is thermogravimetric analysis (TGA) figure of product A made from embodiment 1.
Fig. 9 is the thiourea modified molybdenum disulfide electrochemical sensor of the polypeptide-in embodiment 2 for detecting HepG2 liver cancer
Ac impedance spectroscopy (EIS) figure of cell.
Figure 10 is the thiourea modified molybdenum disulfide electrochemical sensor of the polypeptide-in embodiment 2 for detecting HepG2 liver cancer
AC impedance (Δ R obtained by cellct) with the logarithm (logC of HepG2 cell concentrationcell) linear relationship chart.
Figure 11 is scanning electron microscope (SEM) figure of product B made from embodiment 1.
Figure 12 is high-resolution-ration transmission electric-lens (HRTEM) figure of product B made from embodiment 1.
Figure 13 is X-ray powder diffraction (XRD) figure of product B made from embodiment 1.
Figure 14 is the exchange that polypeptide-molybdenum disulfide electrochemical sensor in embodiment 2 is used to detect HepG2 liver cancer cells
Impedance spectrum (EIS) figure.
Figure 15 is that polypeptide-molybdenum disulfide electrochemical sensor in embodiment 2 is handed over obtained by HepG2 liver cancer cells for detecting
Logarithm (logCcell) linear relationship chart of flow impedance value (Δ Rct) and HepG2 cell concentration.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Reagent used in the embodiment of the present invention is commercially available.
Equipment used in the embodiment of the present invention: Shanghai stands erect Yao's microwave dissolver (WX-8000), CHI650E electrochemistry work
It stands, ZEISS ULTRA55 type field emission scanning electron microscope, JEOL JEM 2100F type transmission electron microscope, Bruker D8 type X-ray
Diffractometer.
Embodiment 1
1, thiourea modified molybdenum disulfide nano sheet is prepared according to the following steps:
(1) by 0.35g (NH4)6Mo7O24·4H2O and 1.83g thiocarbamide is dissolved in 15mL distilled water, then turns solution
It moves in microwave reaction kettle, 220 DEG C is heated under the conditions of microwave radiation, react 10 minutes, obtain black solid, be product A
(thiourea modified molybdenum disulfide nano sheet)；Obtained product A distilled water, ethyl alcohol are respectively washed 3 times, 10000r/min centrifugation
5min, 50 DEG C of dryings are for 24 hours.
(2) the product A of step (1) after dry is added to the H of 15mL 0.05mol/L2SO4, add under the conditions of microwave radiation
Heat is reacted 2 hours to 150 DEG C, and obtained product B (molybdenum disulfide nano sheet of removal thiocarbamide) is washed with distilled water for several times, 50
It is DEG C dry for 24 hours, for thering is thiourea modified molybdenum disulfide nano sheet to do comparative experiments with prepared by step (1).
2, the preparation method of the thiourea modified molybdenum disulfide nano sheet electro-chemical cells sensor of polypeptide-:
(1) the thiourea modified molybdenum disulfide nano sheet (product A) obtained the 4mg above method ultrasonic (the ultrasonic time
It is 30 minutes or more) it is dispersed in 40 μ L Nafion (perfluorinated sulfonic acid) solution, 30 μ L PVDF (Kynoar) solution and 1mL second
In alcohol solution (volume ratio of second alcohol and water is 1:4) mixed solution, the thiourea modified molybdenum disulfide of uniform black is obtained
Dispersion liquid；The thiourea modified molybdenum disulfide dispersion liquid of 5 μ L is uniformly coated on cleaning using the coating method of drop Tu
The surface glass-carbon electrode (diameter 3mm).It spontaneously dries at room temperature；Wherein, clean glass-carbon electrode the preparation method comprises the following steps: by glass
Carbon electrode successively uses 2000 molybdenum ore paper, aluminium powder polishing, then successively with ultrapure water, aqueous solution of nitric acid (volume ratio 1:1), ethanol water
Solution (volume ratio 1:1) supersound washing 2 minutes respectively, naturally dry；In mixed solution:
Nafion solution: be purchased from Sigma-Aldrich company (be dispersed in for 5wt% in the mixed solution of fatty alcohol and water,
Wherein, water: 15%~20% (v/v))；
PVDF solution: 6mL is dissolved in 0.5g PVDF (molecular weight 530000, be purchased from Sigma-Aldrich) solid powder
In N-Methyl pyrrolidone, 12 hours gained are stirred, it is ready-to-use.
(2) above-mentioned glass-carbon electrode is immersed in 0.5mL PBS buffer solution (concentration 0.01M, pH 7.4) and 1.0mg
GE11 polypeptide (being purchased from GL Biochem Ltd. (Shanghai)) and 0.1mM EDCHCl (1- ethyl-(3- dimethylamino
Propyl) carbodiimide hydrochloride, be purchased from Sigma-Aldrich) mixed solution in, save 2.5 hours under the conditions of 4 DEG C, i.e.,
Sensor (thiourea modified molybdenum disulfide nano sheet electro-chemical cells sensor) needed for obtaining.
Embodiment 2
1, the stereoscan photograph (SEM) of the product (product A and product B) of embodiment 1 is in ZEISS ULTRA55 instrument
Upper intake, lens photo (TEM) absorb on JEOL JEM 2100F instrument.
Fig. 3 and Figure 11 is respectively the thiourea modified molybdenum disulfide nano sheet (product A) and acid being prepared in embodiment 1
The stereoscan photograph of the molybdenum disulfide nano sheet (product B) of thiocarbamide is removed after processing, it can be seen that product A, B be in 200~
The thin nano-sheet of 300nm illustrates that the absorption of thiocarbamide can't change the pattern of material itself.Lens photo (Fig. 4), which is observed, to be received
Loose state is presented in rice piece after having adsorbed excessive thiocarbamide, while high-resolution-ration transmission electric-lens photo (Fig. 5 and Figure 12) is observed
After adsorbing excessive thiocarbamide, interplanar distance is big after the sourer processing of (002) crystal face removes thiocarbamide, but activity crystal face (010) and
(100) interplanar distance does not change, and (002) crystal face is big compared with the molybdenum disulfide interplanar distance of hexagonal crystal system, it was demonstrated that excessive
Thiocarbamide absorption obtains amino abundant without the active crystal face of destruction and after adsorbing thiocarbamide.With XRD (in Bruker D8 type X-ray
Carried out on diffractometer) products therefrom A and product B are characterized, as a result see that Fig. 6 and Figure 13, Fig. 6 and Figure 13 demonstrate product and be
The MoS of hexagonal crystal system2(JCPDS:37-1492), (002) crystallographic plane diffraction peak is moved to 9.64 ° simultaneously, it was demonstrated that successfully adsorbs sulphur
Urea, so that interlamellar spacing increases.
Fig. 7 and Fig. 8 is respectively the infrared spectrogram and thermogravimetric analysis figure of product A.By 7 as it can be seen that the thiocarbamide that embodiment 1 synthesizes
The molybdenum disulfide nano sheet (product A) of modification has compared with acid handles the molybdenum disulfide nano sheet (product B) for removing excessive thiocarbamide
Apparent vN-H(3140cm-1), vC=S(1400cm-1), vC-N(1108cm-1) and δN-H(619cm-1) absorption peak, illustrate embodiment 1
The product A of preparation adsorbs a large amount of thiocarbamides, and there are amino abundant.Thermogravimetric analysis figure (Fig. 8) is it is found that there is thiourea modified curing
Molybdenum nanometer sheet (product A) has apparent weightlessness in 280~350 DEG C of temperature ranges, the weightless temperature range with bright sulfur urea
(175~245 DEG C) compared to there is apparent lag, illustrate the interaction for having strong between thiocarbamide and molybdenum disulfide.
2, to be used to detect HepG2 liver cancer for thiourea modified molybdenum disulfide electrochemical sensor obtained in embodiment 1 thin
Born of the same parents.Wherein, human hepatocellular HepG2 cell origin used in the present invention is in Chinese Shanghai cell resource center life science institute.
Cell culture processes: cell is placed in 24 hole glass culture dish and cultivates, and includes 10% (v/v) fetal calf serum, 100 μ g in culture medium
mL-1Penicillin and 100 μ g mL-1Streptomysin, and culture medium is placed in 37 DEG C, 5%CO2It is saved in insulating box.Determination condition: it surveys
Determining medium is 0.01M phosphate buffer solution (pH 7.4), 10mM [Fe (CN)6]3-/4-With the mixed solution of 0.5M KCl；Using
AC impedence method (EIS), location parameter are as follows: operating voltage is open-circuit voltage, frequency range: 10-1~105Hz, amplitude: 5mV.
Fig. 9 is to be used to detect HepG2 liver cancer cells for the thiourea modified molybdenum disulfide electrochemical sensor of polypeptide-of the present invention
AC impedance spectroscopy, wherein the cell concentration of HepG2 liver cancer cells be respectively 50cells/ml, 100cells/ml,
200cells/ml、103cells/ml、104cells/ml、105Cells/ml and 106cells/ml.As seen from Figure 9, with
The increase of HepG2 cell concentration, impedance value increase therewith, illustrate the thiourea modified molybdenum disulfide of polypeptide-constructed by the present invention
Electrochemical sensor can successfully capture HepG2 liver cancer cells, and electrochemically detect to it.
Figure 10 is that the thiourea modified molybdenum disulfide electrochemical sensor of polypeptide-is handed over obtained by HepG2 liver cancer cells for detecting
Flow impedance value (Δ Rct) with the logarithm (logC of HepG2 cell concentrationcell) linear relationship chart, as can be known from Fig. 10, in HepG2
Cell concentration range is 50~106cells mL-1Middle Δ RctWith logCcellIn good linear relationship, coefficient (R is determined2) be
0.991, detection limit reaches 50cells mL-1。
Figure 14 is that acid handles the sensor (construction method of sensor constructed by the molybdenum disulfide nano sheet after removing thiocarbamide
The preparation method of the thiourea modified molybdenum disulfide nano sheet electro-chemical cells sensor of polypeptide-in reference implementation example 1), for examining
Survey AC impedance figure obtained by HepG2 liver cancer cells.As seen from the figure, with the increase of HepG2 cell concentration, impedance value does not press one
Set pattern rule changes therewith, and the interior illustration in Figure 15 also indicates that AC impedance (Δ Rct) with the logarithm of HepG2 cell concentration
(logCcell) not in a linear relationship, after illustrating that acid processing removes thiocarbamide, molybdenum disulfide nano sheet lacks amino groups, causes
It can not be connect with GE11 polypeptide, so that HepG2 cell can not be captured.
Since such molybdenum disulfide nano sheet makes excessive thiocarbamide more in the synthesis process under the auxiliary of microwave radiation
It is easily adsorbed in active sites, makes to adsorb thiocarbamide on molybdenum disulfide, obtain amino groups abundant, then the side for passing through simply immersing
Method is connect with GE11 polypeptide, finally obtains polypeptide-thiocarbamide absorption molybdenum disulfide electrochemica biological sensor, and be used for HepG2
The detection of liver cancer cells.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of molybdenum disulfide nano sheet electrochemical sensor, including glass-carbon electrode substrate, contact conductor and insulating layer, feature
Be: the glass-carbon electrode substrate surface is coated with thiourea modified molybdenum disulfide nano sheet, thiourea modified two
Molybdenum sulfide nanometer sheet is connect with GE11 polypeptide；
The molybdenum disulfide nano sheet electrochemical sensor is prepared via a method which to obtain:
(1) thiourea modified molybdenum disulfide nano sheet ultrasonic disperse is obtained into thiourea modified molybdenum disulfide in mixed solution A
Dispersion liquid, wherein mixed solution A is made of perfluorinated sulfonic acid solution, PVDF solution and ethanol solution；
(2) molybdenum disulfide dispersion liquid Tu thiourea modified obtained in step (1) is overlayed on glass-carbon electrode, it is dry, it is applied
It is covered with the glass-carbon electrode of thiourea modified molybdenum disulfide dispersion liquid；
(3) glass-carbon electrode for being coated with thiourea modified molybdenum disulfide dispersion liquid obtained in step (2) is immersed in and is delayed by PBS
In the mixed solution B of fliud flushing, GE11 polypeptide and EDCHCl composition, 4 DEG C of preservations obtain molybdenum disulfide nano sheet electrochemical sensing
Device；
Thiourea modified molybdenum disulfide nano sheet additive amount is thiourea modified by every mL mixed solution A proportion 4mg in step (1)
Molybdenum disulfide nano sheet calculates；
4:3:100 matches by volume for perfluorinated sulfonic acid solution, PVDF solution and ethanol solution in mixed solution A described in step (1)
Than calculating.
2. molybdenum disulfide nano sheet electrochemical sensor according to claim 1, it is characterised in that: described is thiourea modified
Molybdenum disulfide nano sheet be prepared via a method which to obtain: molybdate and sulphur source are dissolved in the water, then by solution micro-
It is heated to 220 DEG C under the conditions of wave radiation to be reacted, washs, be centrifuged, dry, obtains thiourea modified molybdenum disulfide nano sheet.
3. molybdenum disulfide nano sheet electrochemical sensor according to claim 1 or 2, it is characterised in that: the thiocarbamide
The size of the molybdenum disulfide nano sheet of modification is 200~300nm.
4. molybdenum disulfide nano sheet electrochemical sensor according to claim 2, it is characterised in that: the sulphur source and molybdenum
Hydrochlorate is that 12:1 is matched in molar ratio；The molybdate is Ammonium Molybdate Tetrahydrate；The sulphur source is thiocarbamide；Described
The time of reaction is 10 minutes.
5. the preparation method of the described in any item molybdenum disulfide nano sheet electrochemical sensors of Claims 1 to 4, it is characterised in that
Include the following steps:
(1) thiourea modified molybdenum disulfide nano sheet ultrasonic disperse is obtained into thiourea modified molybdenum disulfide in mixed solution A
Dispersion liquid, wherein mixed solution A is made of perfluorinated sulfonic acid solution, PVDF solution and ethanol solution；
(2) molybdenum disulfide dispersion liquid Tu thiourea modified obtained in step (1) is overlayed on glass-carbon electrode, it is dry, it is applied
It is covered with the glass-carbon electrode of thiourea modified molybdenum disulfide dispersion liquid；
(3) glass-carbon electrode for being coated with thiourea modified molybdenum disulfide dispersion liquid obtained in step (2) is immersed in and is delayed by PBS
In the mixed solution B of fliud flushing, GE11 polypeptide and EDCHCl composition, 4 DEG C of preservations obtain molybdenum disulfide nano sheet electrochemical sensing
Device；
Thiourea modified molybdenum disulfide nano sheet additive amount is thiourea modified by every mL mixed solution A proportion 4mg in step (1)
Molybdenum disulfide nano sheet calculates；
4:3:100 matches by volume for perfluorinated sulfonic acid solution, PVDF solution and ethanol solution in mixed solution A described in step (1)
Than calculating.
6. the preparation method of molybdenum disulfide nano sheet electrochemical sensor according to claim 5, it is characterised in that:
PVDF solution described in step (1) is prepared via a method which to obtain: PVDF is dissolved in N-Methyl pyrrolidone,
Stirring, obtains PVDF solution；
The additive amount of the N-Methyl pyrrolidone is to match 12mL N-Methyl pyrrolidone by every g PVDF to calculate；
Coating described in step (2) is realized by the following method: thiourea modified molybdenum disulfide dispersion liquid is taken, using drop Tu
Coating method is uniformly coated on the surface of clean glass-carbon electrode.
7. the preparation method of molybdenum disulfide nano sheet electrochemical sensor according to claim 5, it is characterised in that:
The time of ultrasound described in step (1) is 30 minutes；
Drying described in step (2) is to spontaneously dry at room temperature；
The time of preservation described in step (3) is 2.5 hours.
8. described in any item molybdenum disulfide nano sheet electrochemical sensor the answering in field of biomedicine of Claims 1 to 4
With.
9. application of the described in any item molybdenum disulfide nano sheet electrochemical sensors of Claims 1 to 4 in cell detection.
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