CN107436316A - The preparation of glucose sensor based on graphene and graphene oxide composite material - Google Patents
The preparation of glucose sensor based on graphene and graphene oxide composite material Download PDFInfo
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- 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
- G01N27/28—Electrolytic cell components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention belongs to field of biosensors, and in particular to a kind of preparation method of the glucose biological sensor based on graphene and graphene oxide composite material.Using graphene and the compound decorative layer as electrode of graphene oxide, the excellent electric conductivity of graphene helps to realize the direct electron transfer of glucose oxidase and electrode, and the carboxyl on graphene oxide can be combined with the amino on glucose oxidase to be played a part of fixing glucose oxidase and improve electrode stability.Glucose oxidase graphene modified electrode is supported as working electrode using above-mentioned, calomel electrode is reference electrode, and platinum plate electrode is the sensor formed to electrode, and the fast electrochemical measure of glucose can be achieved.Graphene composite material prepared by the present invention both realized its direct electron transfer with electrode beneficial to the fixation and can of enzyme, biology sensor high sensitivity, stability is good, and the range of linearity is wide, with higher antijamming capability, the monitoring of the blood glucose and glucose in urine of diabetes patient can be widely used for.
Description
Technical field
The invention belongs to field of biosensors, and in particular to a kind of based on graphene and graphene oxide composite material
The preparation method of glucose biological sensor.
Background technology
Diabetes are a kind of common disease, frequently-occurring disease, all very high in China and the whole world incidence of disease.With diabetic
The extension of sick time, the metabolic disorder in body cannot such as control well, can cause eye, kidney, nerve, blood vessel and heart
Deng tissue, the chronic complicating diseases of organ, so that blindness, lower limb gangrene, uremia, headstroke or myocardial infarction finally occurs, very
To threat to life.Up to the present, national diabetic's number oneself more than 50,000,000, turn into after cardiovascular and tumour
3rd " Health Killer ".Therefore, diabetes early detection and diagnosis to glycemic control and mitigate diabetic complication danger
Evil is significant for diabetic.
At present, diabetic monitors the change of blood glucose through conventional blood glucose meter, blood glucose meter need to be gathered with needle point Trace Blood come
Measurement is realized, larger pain can be so caused to user.Particularly, the Healthy People not being diagnosed but with diabetes
Group, typically the blood glucose of oneself will not be tested using such blood glucose meter.Easily urinated as surveying blood glucose meter if one
Sugared instrument monitors the glucose in urine of diabetes group of people at high risk, it should is easily allow people to receive.
However, the general concentration of concentration of glucose in urine is relatively low, it is higher to it requires that the sensor for measuring glucose in urine will have
Sensitivity.The theoretical specific surface area of graphene is up to 2600m2/ g, the pi bond electronic structure of long-range order, makes stone in its structure
Black alkene has excellent electric conductivity and electron mobility 1.5 × 10 high at room temperature4cm2/(V·s).The high ratio table of graphene
Area is advantageous to improve the loading of enzyme, thus improves the performances such as the sensitivity of sensor；The excellent electric property of graphene makes
It can be effectively facilitated the Direct electron transfer of glucose oxidase electric activity center and electrode in electrochemical process, improve
The sensitivity of biology sensor and response signal, shorten the response time；Graphene also has good biocompatibility, energy simultaneously
Enough bioactivity for keeping load enzyme, be advantageous to improve the stability of biology sensor.Therefore, graphene is applied to sensor
Electrode is expected to obtain the glucose sensor of rapid sensitive, realizes that diabetic early has found early treatment, improves diabetic
Life quality.
Chemical vapor deposition graphene has perfect two dimensional crystal structure, and conduction can be effectively improved on electrode by modifying
Property.Graphenic surface prepared by chemical oxidization method has abundant oxygen-containing functional group, can be with the amino shape on glucose oxidase
Into chemical bond, and glucose oxidase is fixed on graphene, can thus significantly improve the stability of sensor.And
And both graphene basic structures are identical, therefore the two is firmly combined with, and is improved the stability of electrode.It is and public
Opening oxygenated graphene sensor, which is typically employed on graphene, deposits gold or nano platinum particle to improve the electric conductivity of electrode, such as：
(patent publication No. is respectively Chinese invention patent application：CN102507693A and CN104833714A), metal nanoparticle exists
Combined loosely on graphene, the stability of electrode can be made reduce.Meanwhile preparation cost can be also improved, increase the complexity of preparation,
It is unfavorable for practical.
The content of the invention
Chemical vapour deposition technique (CVD) graphene is based on it is an object of the invention to provide a ` kinds and graphene oxide is answered
The preparation method of the third generation glucose sensor of condensation material.By chemical vapour deposition technique graphene with graphene oxide is compound makes
For modifying sensor electrode, it both can guarantee that glucose oxidase realized the Direct electron transfer with electrode, and can improves electrode
Stability, this sensor has practical value.
The technical scheme is that：
A kind of preparation of the glucose sensor based on graphene and graphene oxide composite material, this method step are：
(1) preparation of graphene modified electrode
Filmy graphite alkene prepared by chemical vapour deposition technique is transferred to the glassy carbon electrode surface of cleaning；Or it will change
Learn the glassy carbon electrode surface that foamy graphite alkene prepared by vapour deposition process is transferred to cleaning；
Graphene oxide prepared by chemical oxidization method is scattered in stable dispersion liquid is formed in chitosan acetic acid solution, will
The dispersant liquid drop is added on the glass-carbon electrode of afore mentioned chemical vapour deposition process graphene modified, and glass-carbon electrode is dried at room temperature for
Afterwards, then it is added dropwise glucose oxidase phosphate buffer solution；It is molten that glass-carbon electrode after drying at room temperature is immersed into phosphate-buffered
Soaked in liquid, to remove the glucose oxidase not being firmly combined with graphene oxide, after taking-up room temperature is dried, obtain being made
Standby modified electrode；
(2) on modified electrode graphene oxide reduction
Modified electrode made from step (1) is put into 0.05~0.5mol/L phosphate buffer solutions as working electrode
In, and three-electrode system is formed to electrode with saturated calomel reference electrode and platinized platinum, in 0~-1.5V on electrochemical workstation
Cyclic voltammetry scan is done in voltage range, graphene oxide is reduced into graphene, further improves the electric conductivity of modified electrode,
The Direct Electrochemistry of glucase and modified electrode is promoted to react；
(3) detection of the graphene modified electrode sensor to glucose concentration
Modified electrode prepared by step (2) and saturated calomel electrode and platinum plate electrode are formed into three-electrode system as sensing
Device, glucose composition electrolyte is added in 0.05~0.5mol/L phosphate buffer solutions, 0.6 on electrochemical workstation
Do cyclic voltammetry scan in~-0.6V voltage ranges, the redox peak current on CV curves is in rule with the concentration of glucose
Property change, so as to realize the test of concentration of glucose.
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Chemical vapour deposition technique filmy graphite alkene use Bubbling method or etching method, graphene film to the transfer method of glass-carbon electrode
Transfer number be 1~5 time.
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Chemical vapour deposition technique foamy graphite alkene thickness according to the examination of glucose concentration scope and sensitivity requirement of working electrode
Change in 0.05~1mm, the thickness of foamy graphite alkene is determined by the thickness and sedimentation time of matrix nickel foam.
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Concentration of the graphene oxide in chitosan acetic acid solution be 0.5mg/ml~5mg/ml, graphene oxide used in modified electrode
The amount of chitosan acetic acid solution is 1~20 μ l.
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Concentration of the glucose oxidase in phosphate buffer solution be 5mg/ml~30mg/ml, grape glycosyloxy used in modified electrode
The amount for changing the phosphate buffer solution of enzyme is 1~20 μ l.
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Soak time of the electrode for being modified with glucose oxidase in phosphate buffer solution be 0.5~5 hour, remove and oxidation
Graphene combines unstable glucose oxidase.
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Chemical vapour deposition technique graphene and graphene oxide mass ratio be 1：(0.5~2).
The preparation of the described glucose sensor based on graphene and graphene oxide composite material, prepared by this method
Glucose sensor is used to detect glucose, detects the glucose in the glucose or detection urine in blood.
The present invention design philosophy be：
The present invention is using graphene and the compound decorative layer as electrode of graphene oxide, the excellent electric conductivity of graphene
Help to realize the direct electron transfer of glucose oxidase and electrode, carboxyl energy and glucose oxidase on graphene oxide
On amino combine play a part of fixing glucose oxidase and improve electrode stability.To support grape glycoxidative with above-mentioned
Enzyme graphene modified electrode is working electrode, and calomel electrode is reference electrode, and platinum plate electrode is the sensor formed to electrode, can
Realize the fast electrochemical measure of glucose.
Compared with existing blood glucose sensor, the invention has the advantages that and beneficial effect：
(1) new modified electrode of the present invention has used CVD graphene, and the graphene-structured is complete, has excellent
Good electric conductivity, therefore drastically increase the sensitivity when modified electrode detects blood glucose and glucose in urine.
(2) due to containing the graphene oxide of carboxyl functional group using surface on new modified electrode of the present invention,
It can ensure that graphene oxide forms effective chemical bond with glucose oxidase, glucose oxidase is firmly fixed electricity
On extremely.The good biocompatibility of graphene can also improve glucose oxidase stability, that is, improve the stabilization of sensor electrode
Property.Chitosan is used during modified electrode simultaneously, the excellent biocompatibility of chitosan also has protection to glucose oxidase
Effect, therefore the modified electrode has extremely strong stability, ensure that the blood glucose of structure and the stability and standard of glucose in urine sensor
True property.
(3) in new modified electrode of the present invention, CVD graphene and redox graphene are only used, both
It is also no to use electron mediator not using nano metal nano-particle such as gold or platinum, therefore preparation technology is simplified, drop
Low preparation cost, while also improve the stability of electrode.
In a word, the preparation method of modified electrode provided by the invention is simple, and graphene has excellent electric conductivity and good
Good biocompatibility, simultaneous oxidation graphene are beneficial to the fixation of glucose oxidase.The graphene and graphene oxide are compound
Material and glucose oxidase composite modified electrode have good glucose detection performance, show high sensitivity, wide
The features such as detection range, good anti-interference property, available for preparing novel glucose sensor.Preparation method of the present invention is simple
It is easy, it is easy to accomplish large-scale production.Therefore, the present invention is not only with important learning value but also with practical value.
Brief description of the drawings
Fig. 1 is cyclic voltammetry electric current-potential curve of CVD graphene and the common modified electrode of redox graphene
(CV curves, Cyclic Voltammetry).In figure, abscissa E/V represents current potential, and unit is volt；Ordinate I/mA is represented
Electric current, unit are milliamperes.
Fig. 2 sweeps the CV curves under speed for CVD graphene with the common modified electrode difference of redox graphene.In figure,
Abscissa E/V represents current potential, and unit is volt；Ordinate I/mA represents electric current, and unit is milliampere.
Fig. 3 is CVD graphene and the common modified electrode of redox graphene and redox graphene modified electrode
CV cyclic curves contrast (it is 100mv/s to sweep speed).In figure, abscissa E/V represents current potential, and unit is volt；Ordinate I/mA
Electric current is represented, unit is milliampere.Wherein, GCE-CVDGNS-RGO-GOD-CS is that CVD graphene and redox graphene are total to
Same modified electrode, GCE-RGO-GOD-CS are redox graphene modified electrode.
Fig. 4 is the CV cyclic curves of CVD graphene modified electrode (it is 50mv/s to sweep speed).In figure, abscissa E/V is represented
Current potential, unit are volts；Ordinate I/mA represents electric current, and unit is milliampere.
Embodiment
In specific implementation process, the present invention is passed based on the third generation glucose of graphene and graphene oxide composite material
The preparation method of sensor, be first by chemical vapour deposition technique (CVD) prepare graphene be transferred to it is cleaned after sensor
On electrode, for realizing the Direct electron transfer of glucose oxidase.Then the chitosan acetic acid solution of graphene oxide is repaiied
Adorn on electrode, for fixing glucose oxidase and keep its bioactivity, and then improve the stability of sensor.Finally exist
The phosphate buffer solution (PBS) of glucose oxidase is modified on the electrode, through drying at room temperature i.e. obtain being modified with graphene and
The glucose sensor electrode of graphene oxide composite material.
The preparation method comprises the following steps that：
(1) pretreatment of glass-carbon electrode：First by glass-carbon electrodeSuccessively with 1.0 μm, 0.3 μm and 0.05 μm grains
The A1 of degree2O3Suspension is polished to minute surface on chamois leather, is finally cleaned by ultrasonic totally with absolute ethyl alcohol and redistilled water respectively,
It is standby；
(2) preparation of modified glassy carbon electrode：
A) filmy graphite alkene prepared by CVD is transferred to the polished glass carbon handled well using Bubbling method or etching method
The surface of electrode, the electric conductivity of electrode can be significantly improved, the matrix for growing graphene can be copper or nickel or platinum
Deng sheet metal.In order to reach preferable electric conductivity, the transfer number of graphene film can be 1~5 time, and conventional is 2 times.
Or the foam-like graphene for preparing CVD is transferred to the surface of the polished glass-carbon electrode handled well, foam
Graphene both has excellent electric conductivity, has abundant duct again, these ducts are beneficial to support graphene oxide, and then support
More glucose oxidases, improve the sensitivity of glucose test.The thickness of CVD foamy graphite alkene can be according to working electrode
Examination of glucose concentration scope and sensitivity requirement 0.05~1mm change, the preferable thickness of effect be 50 μm, 100 μm or
0.5mm.The thickness of foamy graphite alkene is tested the sensitivity of glucose, the thickness and sedimentation time of matrix nickel foam by working electrode
Determine, the amount of the contained glucose oxidase of electrode is directly proportional to the thickness of foamy graphite alkene, and the sensitivity of electrode is by its institute
What the glucose oxidase amount of load was determined.
B) graphene oxide prepared by chemical oxidization method is scattered in and stable dispersion liquid is formed in chitosan acetic acid solution,
For the chitosan acetic acid solution of 0.5mg/ml~5mg/ml (being commonly used for 1mg/ml) graphene oxide, (wherein, shell gathers compound concentration
The concentration of sugared acetic acid solution is 5mg/ml~30mg/ml, and the concentration of acetic acid solution is 0.5~5wt%), take 1~20 with pipettor
The chitosan acetic acid solution of μ l (usual amounts are 5~10 μ l) above-mentioned graphene oxide is added drop-wise to the glass-carbon electrode modified through step a)
On, dry at room temperature.Wherein, the mass ratio of chemical vapour deposition technique graphene and graphene oxide is 1：(0.5~2), commonly use
Mass ratio be 1：1.
C) for the phosphate buffer solutions of 5mg/ml~30mg/ml glucose oxidases, (wherein, phosphate delays compound concentration
The concentration for rushing solution is 0.01~0.5mol/L, pH=4.5~5.5), with pipettor take the μ l of volume 1~20 (usual amounts are 5~
10 μ l) glucose oxidase phosphate buffer solution be added drop-wise to through step b) modification glass-carbon electrode on, dry at room temperature.
D) the above-mentioned glass-carbon electrode for being modified with glucose oxidase soaks 0.5~5 hour in phosphate buffer solution
(generally immersion 2 hours), removes the glucose oxidase not being firmly combined with graphene oxide.Then it is dried at room temperature for, i.e.,
The glucose sensor electrode of graphene and graphene oxide composite material is obtained, is finally sensed on electrochemical workstation
The performance test of device.
In order that present disclosure is easier to understand, with reference to specific embodiment to technical solutions according to the invention
It is described further, but the present invention is not limited only to these.
Embodiment 1
By the single-layer graphene being grown in using CVD on copper foil using Bubbling method (see Chinese invention patent, publication number
CN102719877A) shift, and be fixed on the glass-carbon electrode handled through clean surfaceization from matrix copper foil.It is first
First distinguish the chitosan acetic acid solution (concentration of acetic acid solution is 2wt%) that compound concentration is 10mg/ml, concentration is 1mg/ml's
The chitosan acetic acid solution of graphene oxide, (phosphate delays the glucose oxidase phosphate buffer solution that concentration is 10mg/ml
The concentration for rushing solution is 0.1mol/L).Then the glass-carbon electrode for having CVD graphenes to above-mentioned surface modification is modified, in electricity
The chitosan acetic acid solution of the extremely upper graphene oxide that 10 μ l are added dropwise.After electrode drying at room temperature, then 10 μ l glucose is added dropwise
The phosphate buffer solution of oxidizing ferment.After pole drying, the electrode is inserted into 0.1mol/L phosphate buffer solutions (pH=
5.1) immersion 2 hours in, unstable glucose oxidase is combined with graphene oxide to remove, graphene modified is finally made
Electrode.By the use of above-mentioned modified electrode as working electrode, and with saturated calomel electrode (reference electrode) and platinum plate electrode (to electricity
Pole) three-electrode system is formed, using 0.lmol/L phosphate buffer solution as electrolyte, electrification is carried out using cyclic voltammetry
Learn test.It can be seen that obvious redox peaks (Fig. 1) from obtained cyclic voltammetry curve；Understood according to Fig. 1 analyses, modification
Glucose oxidase realizes the Direct electron transfer with electrode on electrode, it was demonstrated that the excellent electric conductivity of graphene and oxidation stone
The chemical bond of black alkene and glucose oxidase contributes positively to realize the direct electricity of glucose oxidase activity center and electrode
Son transmits, you can to realize the detection of concentration of glucose.
Embodiment 2
Single-layer graphene prepared by the CVD being grown on copper foil is shifted using Bubbling method from matrix copper foil,
And it is fixed in a diameter ofOn glass-carbon electrode.In order to obtain more preferable conductive effect, aforesaid operations are repeated once, i.e.,
Bilayer graphene is modified in glassy carbon electrode surface.Other processing methods and electrochemistry experiment are the same as embodiment 1.Test result indicates that obtain
Cyclic voltammetry curve on redox peaks peak position and redox peak current it is essentially the same with embodiment 1.Prove in work
Preferable conductive enhancing effect can be obtained by making to modify a layer graphene on electrode.
Embodiment 3
Difference from Example 1 is, a floor height molecule is uniformly coated in the graphenic surface containing nickel foam substrate
Polymer, nickel foam is removed with appropriate etching liquid dissolving, is protected the polymer for being covered in graphenic surface with organic solvent
Layer dissolving removes, and obtains foamy graphite alkene (see Chinese invention patent, publication number CN102674321).
The chitosan acetic acid solution (concentration of acetic acid solution is 2wt%) that compound concentration is 5mg/ml, concentration are distinguished first
For the chitosan acetic acid solution of 2mg/ml graphene oxide, concentration is that 15mg/ml glucose oxidase phosphate-buffered is molten
Liquid (concentration of phosphate buffer solution is 0.2mol/L).
Then by foamy graphite alkene be transferred to it is cleaned after glassy carbon electrode surface, then 15 μ l graphite oxide is added dropwise respectively
The phosphate buffer solution of the chitosan acetic acid solution of alkene and 15 μ l glucose oxidases.Other experimental methods obtain with embodiment 1
The cyclic voltammetry curve arrived is close with embodiment 1.Illustrate that foamy graphite alkene as single-layer graphene, can also significantly improve work
The electric conductivity of electrode, while the micro-nano hole inside foamy graphite alkene is also beneficial to improve graphene oxide modification amount.Aoxidize stone
Black alkene modification amount improves, and makes it possible the raising of glucose oxidase loading, and the raising of glucose oxidase loading,
Then mean to improve the sensitivity of sensor, this is that the sensitivity for improving sensor has to the glucose for detecting lower concentration
It is of practical meaning.
Embodiment 4
The method of modifying and electrochemical test method of working sensor electrode are adopted with embodiment 1, simply cyclic voltammetry
It is from obtained cyclic voltammetry curve it can be seen that electric with the increase redox peaks of sweep speed with different sweep speeds
Stream linearly increases, and experimental result is as shown in Fig. 2 reaction of the explanation glucose oxidase on electrode is granule surface contral electrochemistry
Process.
Embodiment 5
Electrode modification method is simply done in the 0.1mol/L phosphate buffer solutions of cyclic voltammetry and contained with embodiment 1
There is 5mmol/L glucose.Contain 5mmol/L it can be seen that working as in phosphate buffer solution from obtained cyclic voltammetry curve
Glucose when, reduction peak current significantly reduces, and illustrates that the sensor can detect the change of concentration of glucose, that is, realizes to Portugal
The detection of grape sugar concentration.
Comparative example 1
The chitosan acetic acid that the graphene oxide in 10 μ l embodiment 1 is added dropwise on the electrode through cleaning processing first is molten
Liquid.After electrode drying at room temperature, then the phosphate buffer solution of 10 μ l glucose oxidase is added dropwise., will after pole drying
Immersion 2 hours in electrode insertion 0.1mol/L phosphate buffer solutions (pH=5.1), are combined not with removing with graphene oxide
Firm glucose oxidase, graphene modified electrode is finally made.By the use of above-mentioned modified electrode as working electrode, and with satisfying
Three-electrode system is formed with calomel electrode (reference electrode) and platinum plate electrode (to electrode), it is molten with 0.lmol/L phosphate-buffered
Liquid carries out electro-chemical test using cyclic voltammetry, can be seen from obtained cyclic voltammetry curve weaker as electrolyte
Redox peaks (Fig. 3)；Understood according to Fig. 3 analyses, one layer of CVD graphene is lacked on modified electrode, the electric conductivity of electrode shows
Writing reduces, and redox peak current substantially reduces, and this result may limit the test scope of concentration of glucose.
Comparative example 2
To be grown in using CVD filmy graphite alkene on copper foil using Bubbling method (see patent CN102719877A) from
Shift, and be fixed on the glass-carbon electrode handled through clean surfaceization on matrix copper foil, is then added dropwise on electrode
The phosphate buffer solution of 10 μ l glucose oxidase.After pole drying, electrode insertion 0.1mol/L phosphate is delayed
Immersion 2 hours in solution (pH=5.1) are rushed, unstable glucose oxidase is combined with graphene to remove, stone is finally made
Black alkene modified electrode.Three-electrode system is constituted by working electrode of the electrode, and has done cyclic voltammetry, test result is shown in
Fig. 4, as can be seen from the figure individually with the glass-carbon electrode of CVD graphene modified, non-oxidation reduction on its cyclic voltammetry curve
Peak, illustrates that oxygen-containing functional group is few on CVD graphene, it is impossible to forms effective chemical bond, therefore nothing with glucose oxidase
Oxygen-containing functional group graphene can not promote glucose oxidase that Direct Electrochemistry reaction occurs on electrode.
Embodiment and comparative example result show that graphene composite material prepared by the present invention was both real beneficial to the fixation and can of enzyme
Its existing direct electron transfer with electrode, and preparation method is simple, is adapted to industrial-scale production.The biology biography that the present invention makes
Sensor high sensitivity, stability is good, and the range of linearity is wide, has higher antijamming capability, can be widely used for the blood of diabetes patient
The monitoring of sugar and glucose in urine.
Claims (8)
- A kind of 1. preparation of the glucose sensor based on graphene and graphene oxide composite material, it is characterised in that the party Method step is：(1) preparation of graphene modified electrodeFilmy graphite alkene prepared by chemical vapour deposition technique is transferred to the glassy carbon electrode surface of cleaning；Or by chemical gas Foamy graphite alkene prepared by phase sedimentation is transferred to the glassy carbon electrode surface of cleaning；Graphene oxide prepared by chemical oxidization method is scattered in stable dispersion liquid is formed in chitosan acetic acid solution, by this point Dispersion liquid is added drop-wise on the glass-carbon electrode of afore mentioned chemical vapour deposition process graphene modified, after glass-carbon electrode is dried at room temperature for, then Glucose oxidase phosphate buffer solution is added dropwise；Glass-carbon electrode after drying at room temperature is immersed in phosphate buffer solution and soaked Bubble, to remove the glucose oxidase not being firmly combined with graphene oxide, after taking-up room temperature is dried, obtain to be prepared repair Adorn electrode；(2) on modified electrode graphene oxide reductionModified electrode made from step (1) is put into 0.05~0.5mol/L phosphate buffer solutions as working electrode, and Three-electrode system is formed to electrode with saturated calomel reference electrode and platinized platinum, in 0~-1.5V voltage models on electrochemical workstation Cyclic voltammetry scan is done in enclosing, graphene oxide is reduced into graphene, further improves the electric conductivity of modified electrode, promotes Portugal The Direct Electrochemistry of grape carbohydrase and modified electrode is reacted；(3) detection of the graphene modified electrode sensor to glucose concentrationModified electrode and saturated calomel electrode and platinum plate electrode prepared by step (2) forms three-electrode system as sensor, Glucose is added in 0.05~0.5mol/L phosphate buffer solutions and forms electrolyte, on electrochemical workstation 0.6~- Do cyclic voltammetry scan in 0.6V voltage ranges, the redox peak current on CV curves becomes with the concentration of glucose in regular Change, so as to realize the test of concentration of glucose.
- 2. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, the chemical vapour deposition technique filmy graphite alkene described in step (1) uses drum to the transfer method of glass-carbon electrode Bubble method or etching method, the transfer number of graphene film is 1~5 time.
- 3. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, the thickness of the chemical vapour deposition technique foamy graphite alkene described in step (1) is dense according to the glucose of working electrode Spend detection range and sensitivity requirement in 0.05~1mm to change, the thickness of foamy graphite alkene is by the thickness of matrix nickel foam and heavy The product time determines.
- 4. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, concentration of the graphene oxide described in step (1) in chitosan acetic acid solution is 0.5mg/ml~5mg/ml, The amount of graphene oxide chitosan acetic acid solution used in modified electrode is 1~20 μ l.
- 5. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, concentration of the glucose oxidase described in step (1) in phosphate buffer solution is 5mg/ml~30mg/ Ml, the amount of the phosphate buffer solution of glucose oxidase used in modified electrode are 1~20 μ l.
- 6. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, soak time of the electrode for being modified with glucose oxidase described in step (1) in phosphate buffer solution For 0.5~5 hour, removing was combined unstable glucose oxidase with graphene oxide.
- 7. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, the mass ratio of the chemical vapour deposition technique graphene and graphene oxide described in step (1) is 1：(0.5~2).
- 8. the preparation of the glucose sensor according to claim 1 based on graphene and graphene oxide composite material, Characterized in that, glucose sensor prepared by this method is used to detect glucose, glucose or detection urine in blood are detected In glucose.
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| CN108490055A (en) * | 2018-03-22 | 2018-09-04 | 浙江工贸职业技术学院 | A kind of high-biocompatibility glucose biological sensor and preparation method thereof based on graphene oxide |
| CN108918614A (en) * | 2018-06-29 | 2018-11-30 | 同济大学 | A kind of glucose sensor and preparation method thereof |
| CN111665284A (en) * | 2019-03-08 | 2020-09-15 | 天津大学 | Application of doped graphene as sensing material |
| CN111936854A (en) * | 2018-03-29 | 2020-11-13 | 塞洛蒂克斯公司 | Improved electrode for electrochemical devices |
| CN112485312A (en) * | 2020-10-21 | 2021-03-12 | 华南农业大学 | Nafion/glucose oxidase/graphene oxide/nano porous platinum electrode and preparation method and application thereof |
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| CN115389596A (en) * | 2022-10-26 | 2022-11-25 | 可孚医疗科技股份有限公司 | Enzyme-free glucose electrochemical detection test paper and preparation method thereof |
| CN115389596B (en) * | 2022-10-26 | 2023-03-14 | 可孚医疗科技股份有限公司 | Enzyme-free glucose electrochemical detection test paper and preparation method thereof |
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