CN107436316B - 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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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.By 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 play the role of fixing glucose oxidase in conjunction with the amino on glucose oxidase and improve electrode stability.Glucose oxidase graphene modified electrode is supported as working electrode using above-mentioned, and calomel electrode is reference electrode, and platinum plate electrode is the sensor that constitutes to electrode, it can be achieved that the fast electrochemical of glucose measures.Graphene composite material prepared by the present invention had not only been conducive to the fixation of enzyme but also had been able to achieve its direct electron transfer with electrode, biosensor high sensitivity, stability is good, and the range of linearity is wide, anti-interference ability with higher can be widely used for the monitoring of the blood glucose and glucose in urine of diabetes patient.
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 technique
Diabetes are a kind of common disease, frequently-occurring disease, all very high in China and whole world disease incidence.With diabetic
The extension of sick time, the intracorporal metabolic disorder of body cannot such as control well, can lead to eye, kidney, nerve, blood vessel and heart
The chronic complicating diseases of equal tissues, 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 50,000,000 or more, become after cardiovascular and tumour
Third position " Health Killer ".Therefore, danger of the early detection and diagnosis of diabetes to glycemic control and mitigation diabetic complication
Evil is of great significance for diabetic.
Currently, variation of the diabetic through common blood glucose meter monitoring blood glucose, blood glucose meter need to be acquired with needle point Trace Blood come
It realizes measurement, larger pain can be caused to user in this way.In particular, having suffered from the Healthy People that diabetes are not diagnosed but
Group, will not generally test the blood glucose of oneself using such blood glucose meter.If there is one as survey blood glucose meter easily urinate
Sugared instrument monitors the glucose in urine of diabetes group of people at high risk, it should be easy people is allowed to receive.
However, the general concentration of concentration of glucose in urine is lower, it is higher to it requires that the sensor of measurement 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 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 conducive to improve the loading of enzyme, thus improves the performances such as the sensitivity of sensor；The excellent electric property of graphene makes
Its Direct electron transfer that glucose oxidase electric activity center and electrode can be effectively facilitated in electrochemical process improves
The response time is shortened in the sensitivity and response signal of biosensor；Graphene also has good biocompatibility, energy simultaneously
Enough bioactivity for keeping load enzyme are conducive to the stability for improving biosensor.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 modification can effectively improve conduction on the electrode
Property.The graphene surface of chemical oxidization method preparation has oxygen-containing functional group abundant, can be with the amino shape on glucose oxidase
It at chemical bond, and is fixed on glucose oxidase on graphene, can thus significantly improve the stability of sensor.And
And both graphene basic structures are identical, therefore the two is firmly combined, and are improved the stability of electrode.And it is 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:
Chinese invention patent application (patent publication No. is respectively as follows: CN102507693A and CN104833714A), metal nanoparticle exists
It is combined loosely on graphene, the stability of electrode can be made to reduce.Meanwhile preparation cost can be also improved, increase the complexity of preparation,
It is unfavorable for functionization.
Summary of the invention
Chemical vapour deposition technique (CVD) graphene is based on the purpose of the present invention is to provide a ` kind and graphene oxide is multiple
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 not only can guarantee that glucose oxidase realized the Direct electron transfer with electrode, but also electrode can be improved
Stability, this sensor have 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 as follows:
(1) preparation of graphene modified electrode
Filmy graphite alkene prepared by chemical vapour deposition technique is transferred to clean glassy carbon electrode surface；Alternatively, will change
The foamy graphite alkene for learning vapour deposition process preparation is transferred to clean glassy carbon electrode surface；
It disperses graphene oxide prepared by chemical oxidization method in chitosan acetic acid solution and forms stable dispersion liquid, it 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
It is impregnated in liquid, obtains being made to remove the glucose oxidase not being firmly combined with graphene oxide after taking-up room temperature is dried
Standby modified electrode；
(2) on modified electrode graphene oxide reduction
0.05~0.5mol/L phosphate buffer solution is put into using modified electrode made from step (1) as working electrode
In, and three-electrode system is constituted 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 made to be reduced into graphene, further increases the electric conductivity of modified electrode,
Glucase is promoted to react with the Direct Electrochemistry of modified electrode；
(3) detection of the graphene modified electrode sensor to glucose concentration
The modified electrode of step (2) preparation and saturated calomel electrode and platinum plate electrode are constituted into three-electrode system as sensing
Device is added glucose in 0.05~0.5mol/L phosphate buffer solution and constitutes electrolyte, 0.6 on electrochemical workstation
Cyclic voltammetry scan is done in~-0.6V voltage range, the redox peak current on CV curve is with the concentration of glucose in rule
Property variation, to realize the test of concentration of glucose.
The preparation of the glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Chemical vapour deposition technique filmy graphite alkene to the transfer method of glass-carbon electrode use Bubbling method or etching method, graphene film
Transfer number be 1~5 time.
The preparation of the 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 range 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 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 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 glucose sensor based on graphene and graphene oxide composite material, step (1) are described
Soaking 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 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 glucose sensor based on graphene and graphene oxide composite material, this method preparation
Glucose sensor detects the glucose in the glucose or detection urine in blood for detecting glucose.
Design philosophy of the invention is:
The present invention is by graphene and the compound decorative layer as electrode of graphene oxide, the excellent electric conductivity of graphene
The direct electron transfer of glucose oxidase and electrode is helped to realize, carboxyl energy and glucose oxidase on graphene oxide
On amino combine play the role 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 constituted to electrode, can
Realize the fast electrochemical measurement of glucose.
Compared with existing blood glucose sensor, the invention has the following advantages and beneficial effects:
(1) novel modified electrode of the present invention has used CVD method graphene, and the graphene-structured is complete, has excellent
Good electric conductivity, therefore greatly improve the sensitivity when modified electrode detects blood glucose and glucose in urine.
(2) on novel modified electrode of the present invention due to the graphene oxide for using surface to contain carboxyl functional group,
It can guarantee that graphene oxide and glucose oxidase form effective chemical bonding, glucose oxidase is made to firmly fix electricity
On extremely.Glucose oxidase stability also can be improved in the good biocompatibility of graphene, that is, improves the stabilization of sensor electrode
Property.Chitosan is used when 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 building and the stability and standard of glucose in urine sensor
True property.
(3) in novel modified electrode of the present invention, CVD method graphene and redox graphene be only used, both
Not using nano metal nanoparticle such as gold or platinum, also without using electron mediator, therefore preparation process is simplified, dropped
Low preparation cost, while also improving the stability of electrode.
In short, the preparation method of modified electrode provided by the invention is simple, graphene has excellent electric conductivity and good
Good biocompatibility, simultaneous oxidation graphene are conducive 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, it can be used 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 had not only had important learning value but also had had practical value.
Detailed description of the invention
Fig. 1 is cyclic voltammetry electric current-potential curve of CVD method graphene and the common modified electrode of redox graphene
(CV curve, 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 is that CVD method graphene and the common modified electrode difference of redox graphene sweep the CV curve under speed.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 method graphene and the common modified electrode of redox graphene and redox graphene modified electrode
CV cyclic curve comparison (sweep speed be 100mv/s).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 method graphene and redox graphene are total
Same modified electrode, GCE-RGO-GOD-CS are redox graphene modified electrode.
Fig. 4 is the CV cyclic curve of CVD method graphene modified electrode (sweeping speed is 50mv/s).In figure, abscissa E/V is represented
Current potential, unit are volts；Ordinate I/mA represents electric current, and unit is milliampere.
Specific embodiment
In the specific implementation process, the present invention is based on the third generation glucose of graphene and graphene oxide composite material biographies
The preparation method of sensor, be first by chemical vapour deposition technique (CVD) preparation 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 repaired
It adorns on electrode, for fixing glucose oxidase and keeps its bioactivity, and then improve the stability of sensor.Finally exist
The phosphate buffer solution (PBS) that 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.
Specific step is as follows for the preparation method:
(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 mirror surface on chamois leather, finally clean with dehydrated alcohol and secondary distilled water ultrasonic cleaning respectively,
It is spare；
(2) preparation of modified glassy carbon electrode:
A) the filmy graphite alkene by CVD method preparation is transferred to the polished glass carbon handled well using Bubbling method or etching method
The surface of electrode can significantly improve the electric conductivity of electrode, and the matrix for growing graphene can be copper, be also possible to nickel or platinum
Equal sheet metals.In order to reach ideal electric conductivity, the transfer number of graphene film be can be 1~5 time, and the most commonly used is 2 times.
Alternatively, foam-like graphene prepared by CVD method to be transferred to the surface of the polished glass-carbon electrode handled well, foam
Graphene had not only had excellent electric conductivity, but also had duct abundant, these ducts are conducive to support graphene oxide, and then support
More glucose oxidases improve the sensitivity of glucose test.The thickness of CVD method foamy graphite alkene can be according to working electrode
Examination of glucose concentration range 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 by the sensitivity of working electrode test glucose, the thickness and sedimentation time of matrix nickel foam
It determines, 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) it disperses graphene oxide prepared by chemical oxidization method in chitosan acetic acid solution and forms stable dispersion liquid,
Compound concentration is that (wherein, shell is poly- for the chitosan acetic acid solution of 0.5mg/ml~5mg/ml (being commonly used for 1mg/ml) graphene oxide
The concentration of sugared acetic acid solution is 5mg/ml~30mg/ml, and the concentration of acetic acid solution is 0.5~5wt%), 1~20 is taken 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, it dries at room temperature.Wherein, the mass ratio of chemical vapour deposition technique graphene and graphene oxide is 1:(0.5~2), it commonly uses
Mass ratio be 1:1.
C) compound concentration is that (wherein, phosphate is slow for the phosphate buffer solution of 5mg/ml~30mg/ml glucose oxidase
Rush solution concentration be 0.01~0.5mol/L, pH=4.5~5.5), with pipettor take 1~20 μ l of volume (usual amounts be 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 impregnates 0.5~5 hour in phosphate buffer solution
(usually impregnating 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 to be easier to understand the contents of the present invention, combined with specific embodiments below to technical solutions according to the invention
It is described further, but the present invention is not limited only to these.
Embodiment 1
The single-layer graphene on copper foil will be grown in using Bubbling method (see Chinese invention patent, publication number using CVD method
CN102719877A it) shifts, and is fixed on the glass-carbon electrode handled through clean surface 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 is slow for 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 of CVD graphene modifies above-mentioned surface modification, 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 the glucose of 10 μ l is added dropwise
The phosphate buffer solution of oxidizing ferment.After pole drying, which is inserted into 0.1mol/L phosphate buffer solution (pH=
5.1) it is impregnated 2 hours in, to remove the unstable glucose oxidase in conjunction with graphene oxide, graphene modified is finally made
Electrode.Use 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 constituted, using the phosphate buffer solution of 0.lmol/L as electrolyte, electrification is carried out using cyclic voltammetry
Learn test.It can be seen that apparent redox peaks (Fig. 1) from obtained cyclic voltammetry curve；It is analyzed according to Fig. 1 it is found that modifying
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 bonding of black alkene and glucose oxidase contributes positively to realize the direct electricity at glucose oxidase activity center and electrode
Son transmitting, it can realize the detection of concentration of glucose.
Embodiment 2
The single-layer graphene of the CVD method being grown on copper foil preparation is shifted from matrix copper foil using Bubbling method,
And it is fixed in diameter and isOn glass-carbon electrode.Better conductive effect, aforesaid operations are repeated once in order to obtain, i.e.,
Bilayer graphene is modified in glassy carbon electrode surface.Other processing methods and electrochemistry experiment are the same as embodiment 1.The experimental results showed that obtaining
Cyclic voltammetry curve on redox peaks peak position and redox peak current it is essentially the same with embodiment 1.It proves in work
Ideal conductive reinforcing effect can be obtained by making one layer of graphene of modification on electrode.
Embodiment 3
Difference from Example 1 is, uniformly coats one layer of macromolecule in the graphene surface containing nickel foam substrate
Polymer is dissolved with etching liquid appropriate and removes nickel foam, is protected the polymer of covering on the surface of graphene with organic solvent
Layer dissolution removal, 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 the graphene oxide of 2mg/ml, concentration is that the glucose oxidase phosphate-buffered of 15mg/ml 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 the graphite oxide of 15 μ l 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 are obtained 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 conducive 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 can be improved the sensitivity of sensor, this is that the sensitivity for improving sensor has to the glucose of detection lower concentration
It is of practical meaning.
Embodiment 4
The method of modifying and electrochemical test method of working sensor electrode are with embodiment 1, and only cyclic voltammetry is adopted
With different scanning speeds, the increase redox peaks electricity with scanning speed can be seen that from obtained cyclic voltammetry curve
Stream linearly increases, and experimental result is as shown in Fig. 2, illustrate that the reaction of glucose oxidase on the electrode is granule surface contral electrochemistry
Process.
Embodiment 5
Electrode modification method is only done in the 0.1mol/L phosphate buffer solution of cyclic voltammetry and is contained with embodiment 1
There is the glucose of 5mmol/L.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 reduce, illustrate that the sensor can detecte the variation of concentration of glucose, that is, realize to Portugal
The detection of grape sugar concentration.
Comparative example 1
The chitosan acetic acid for the graphene oxide in embodiment 1 that 10 μ l are added dropwise on the electrode through cleaning processing first is molten
Liquid.After electrode drying at room temperature, then the phosphate buffer solution of the glucose oxidase of 10 μ l is added dropwise.It, will after pole drying
The electrode, which is inserted into 0.1mol/L phosphate buffer solution (pH=5.1), to be impregnated 2 hours, to remove in conjunction with graphene oxide not
Graphene modified electrode is finally made in firm glucose oxidase.Use above-mentioned modified electrode as working electrode, and with it is full
Three-electrode system is constituted with calomel electrode (reference electrode) and platinum plate electrode (to electrode), it is molten with the phosphate-buffered of 0.lmol/L
Liquid carries out electro-chemical test as electrolyte, using cyclic voltammetry, from obtained cyclic voltammetry curve it can be seen that weaker
Redox peaks (Fig. 3)；It is analyzed according to Fig. 3 it is found that lacking one layer of CVD method graphene on modified electrode, the electric conductivity of electrode is aobvious
Writing reduces, and redox peak current is substantially reduced, this result may will limit the test scope of concentration of glucose.
Comparative example 2
Will using CVD method be grown in the filmy graphite alkene on copper foil using Bubbling method (see patent CN102719877A) from
It shifts, and is fixed on the glass-carbon electrode handled through clean surface on matrix copper foil, is then added dropwise on the electrode
The phosphate buffer solution of the glucose oxidase of 10 μ l.After pole drying, electrode insertion 0.1mol/L phosphate is delayed
It rushes in solution (pH=5.1) and impregnates 2 hours, to remove the unstable glucose oxidase in conjunction with graphene, 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 method graphene modified, non-oxidation reduction on cyclic voltammetry curve
Peak illustrates that oxygen-containing functional group is few on CVD method graphene, and effective chemical bonding, therefore nothing cannot be formed with glucose oxidase
Oxygen-containing functional group graphene cannot promote glucose oxidase that Direct Electrochemistry reaction occurs on the electrode.
Embodiment and comparative example the result shows that, graphene composite material prepared by the present invention had not only been conducive to the fixation of enzyme but also can be real
The direct electron transfer of existing itself and electrode, and preparation method is simple, is suitble to industrial-scale production.The biology that the present invention makes passes
Sensor high sensitivity, stability is good, and the range of linearity is wide, and anti-interference ability with higher can be widely used for the blood of diabetes patient
The monitoring of sugar and glucose in urine.
Claims (8)
1. a kind of preparation method of glucose sensor, which is characterized in that this method step are as follows:
(1) preparation of modified electrode
Filmy graphite alkene prepared by chemical vapour deposition technique is transferred to clean glassy carbon electrode surface；Alternatively, by chemical gas
The foamy graphite alkene of phase sedimentation preparation is transferred to clean glassy carbon electrode surface；
It disperses graphene oxide prepared by chemical oxidization method in chitosan acetic acid solution and forms stable dispersion liquid, 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 is soaked
Bubble obtains to be prepared repair to remove the glucose oxidase not being firmly combined with graphene oxide after taking-up room temperature is dried
Adorn electrode；
(2) on modified electrode graphene oxide reduction
It is put into 0.05~0.5mol/L phosphate buffer solution using modified electrode made from step (1) as working electrode, and
Three-electrode system is constituted to electrode with saturated calomel reference electrode and platinized platinum, in 0~-1.5V voltage model on electrochemical workstation
Cyclic voltammetry scan is done in enclosing, graphene oxide is made to be reduced into graphene, further increases the electric conductivity of modified electrode, promotes Portugal
Grape carbohydrate oxidase is reacted with the Direct Electrochemistry of modified electrode；
(3) detection of the glucose sensor to glucose concentration
The modified electrode of step (2) preparation and saturated calomel electrode and platinum plate electrode are constituted three-electrode system as glucose to pass
Sensor, in 0.05~0.5mol/L phosphate buffer solution be added glucose constitute electrolyte, on electrochemical workstation
Cyclic voltammetry scan, the redox peak current on cyclic voltammetry electric current-potential curve are done in 0.6~-0.6V voltage range
With the concentration of glucose in regularity variation, to realize the test of concentration of glucose.
2. the preparation method of glucose sensor according to claim 1, which is characterized in that chemistry described in step (1)
Vapour deposition process filmy graphite alkene uses Bubbling method or etching method, the transfer of graphene film to the transfer method of glass-carbon electrode
Number is 1~5 time.
3. the preparation method of glucose sensor according to claim 1, which is characterized in that chemistry described in step (1)
The thickness of vapour deposition process foamy graphite alkene is according to the examination of glucose concentration range and sensitivity requirement of working electrode 0.05
~1mm variation, the thickness of foamy graphite alkene are determined by the thickness and sedimentation time of matrix nickel foam.
4. the preparation method of glucose sensor according to claim 1, which is characterized in that oxidation described in step (1)
Concentration of the graphene in chitosan acetic acid solution is 0.5mg/mL~5mg/mL, graphene oxide chitosan used in modified electrode
The amount of acetic acid solution is 1~20 μ L.
5. the preparation method of glucose sensor according to claim 1, which is characterized in that grape described in step (1)
Concentration of the carbohydrate oxidase in phosphate buffer solution is 5mg/mL~30mg/mL, glucose oxidase used in modified electrode
The amount of phosphate buffer solution is 1~20 μ L.
6. the preparation method of glucose sensor according to claim 1, which is characterized in that modification described in step (1)
Having soaking time of the electrode of glucose oxidase in phosphate buffer solution is 0.5~5 hour, removing and graphene oxide
In conjunction with unstable glucose oxidase.
7. the preparation method of glucose sensor according to claim 1, which is characterized in that chemistry described in step (1)
The mass ratio of vapour deposition process graphene and graphene oxide is 1:(0.5~2).
8. the preparation method of glucose sensor according to claim 1, which is characterized in that the glucose of this method preparation
Sensor detects the glucose in the glucose or detection urine in blood for detecting 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 |
| CN111936854A (en) * | 2018-03-29 | 2020-11-13 | 塞洛蒂克斯公司 | Improved electrode for electrochemical devices |
| CN108918614B (en) * | 2018-06-29 | 2020-08-18 | 同济大学 | 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 |
| US20220099673A1 (en) * | 2020-09-28 | 2022-03-31 | Academia Sinica | Biosensor, bio-sensing system comprising the same and method for preparing the same |
| 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 |
| 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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