CN105136888A - Graphene derivative based glucose oxidase electrode and preparation method thereof - Google Patents
Graphene derivative based glucose oxidase electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene derivative based glucose oxidase electrode and a preparation method thereof. The electrode is sequentially composed of a conductive electrode substrate, a graphene derivative/dopamine composite layer, a polydopamine layer, a nanogold array, a 4-mercaptophenylboronic acid layer, and a glucose oxidase layer. According to the invention, dopamine is employed to reduce graphene oxide partially into reduced graphene oxide to form a graphene derivative/dopamine composite layer gathering on the surface of the conductive electrode substrate, also electropolymerization of a layer of polydopamine is carried out on the surface of the graphene derivative/dopamine composite layer, self-assembly of nanogold particles is performed on the platform, and then 4-mercaptophenylboronic acid is loaded to the nanogold array so as to fix glucose oxidase. The glucose oxidase electrode has the advantages of simple preparation method, low detection limit, high sensitivity and high enzyme bonding strength, and can realize sensitive detection of glucose.
Description
Technical field
The invention belongs to electrochemical analysis detection technique field, be specifically related to a kind of glucose oxidase electrode based on Graphene derivative and preparation method thereof.
Background technology
Diabetes are a kind of take hyperglycaemia as the metabolic disease of feature caused by insulin deficit, is one of reason causing dead and disability.Diagnosis and control the glucose level that diabetes need in monitoring of blood at any time, therefore thousands of diabetic needs detect blood sugar every day.How to carry out reliably, nearly glycemic control be still one be worth research problem.Wherein, in blood sugar monitoring, glucose electrochemica biological sensor plays an important role, and the current enzyme electrode on electrode based on fixing glucose oxidase is widely used in the research of glucose electrochemica biological sensor.
In recent years glucose detection from the stage of artificial visual inspection chemical reaction progressively develop into automation equipment monitoring, use electrochemical reaction measure blood sugar, rapid sensitive, has become a megatrend of investigation and application.Glucose oxidase detects glucose and has high specificity, and glucose oxidase is fixed on electrode surface, uses electrochemical method that biochemical reaction signal is converted into electric signal, can improve sensitivity and the accuracy of detection.Existing glucose oxidase electrode fixing, reuse and having much room for improvement in detection sensitivity at enzyme.The people such as JuanTian directly utilize graphene oxide to build electrode to carry out signal amplification, but graphene oxide solubleness in water is higher, in aqueous systems detects, the recycling degree of electrode is low, in addition poor (the TianJ of the electric conductivity of graphene oxide, YuanPX, ShanD, etal.Biosensingplatformbasedongrapheneoxideviaself-assem blyinducedbysynergicinteractions [J] .Analyticalbiochemistry, 2014,460:16-21.).
Summary of the invention
The object of the present invention is to provide glucose oxidase electrode based on Graphene derivative that a kind of preparation method is easy, detectability is low, highly sensitive, enzyme bond strength is high and preparation method thereof.
In order to achieve the above object, the invention provides a kind of glucose oxidase electrode based on Graphene derivative, this electrode is made up of conductive electrode substrate, Graphene derivative/dopamine composite bed, poly-DOPA amine layer, nm of gold array, 4-mercaptophenyl boronic acid (MPBA) layer and glucose oxidase layer successively, described Graphene derivative/dopamine composite bed is after dopamine mixes with graphene oxide, the potpourri after dopamine and partial oxidation Graphene generation redox reaction.
Described conductive electrode substrate is selected from carbon-based electrode substrate, conductive metal electrode substrate or semi-conducting electrode substrate.
Glucose oxidase electrode of the present invention uses nano material amplifying signal layer by layer, reduces detectability, improves detection sensitivity; The basis of graphene oxide is introduced reduced form graphene oxide, improves hydrophobicity and enhance the electric conductivity of electrode; Utilize the sulfydryl of MPBA one end to be combined with nm of gold, the hydroxyl of the other end catches glucose oxidase simultaneously, significantly improves bond strength when not affecting sensitivity.
The present invention also provides the preparation method of above-mentioned glucose oxidase electrode, concrete steps are as follows: first by etc. the Dopamine hydrochloride of quality and graphene oxide to be dissolved in pH value be in the Tris-HCl damping fluid of 8.5, react after being uniformly dispersed, then eccentric cleaning, be drying to obtain Graphene derivative/dopamine compound, again compound is dissolved and be prepared into Graphene derivative/dopamine complex solution, and adopt Graphene derivative/dopamine complex solution modified conducting electrode basement, adopt electrochemical process at electrode surface electropolymerization dopamine afterwards, adopt nano-Au solution and 4-mercaptophenyl boronic acid solution modified electrode successively again, finally use glucose oxidase solution modified electrode, obtain described glucose oxidase electrode.
Described electrochemical process is for working electrode with the conductive electrode substrate of Graphene derivative/dopamine complex solution modified, Ag/AgCl is contrast electrode, platinum electrode is to electrode, the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilize the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine.
The concentration of described Graphene derivative/dopamine complex solution is the concentration of 0.5 ~ 3mg/mL, 4-mercaptophenyl boronic acid is 1 ~ 10mM, and the concentration of glucose oxidase is 10 ~ 12mg/mL.
Further, the concentration of described Graphene derivative/dopamine complex solution is preferably 1 ~ 2mg/mL.
Further, the concentration of 4-mercaptophenyl boronic acid is preferably 5 ~ 8mM.
Compared with prior art, its remarkable advantage is in the present invention: (1) electrode production process is simple and quick; (2) this system multi-layer nano material amplifies layer by layer to signal, and the glucose oxidase electrode obtained has high detection sensitivity and wide linear detection range to glucose, and detection speed is fast; (3) utilize reduced form graphene oxide, improve hydrophobicity and enhance the electric conductivity of electrode, being beneficial to the recycling of electrode; (4) MPBA is firmly combined with nm of gold and glucose oxidase respectively, significantly improves bond strength when not affecting sensitivity, has good stability.
Accompanying drawing explanation
Fig. 1 is the building process schematic diagram of the glucose oxidase electrode based on Graphene derivative of the present invention.
Fig. 2 is the ultraviolet spectrum phenogram of the nm of gold that embodiment 1 prepares.
Fig. 3 is the time m-response current curve that in embodiment 5, glucose oxidase electrode detects glucose, and interior illustration is the time m-response current enlarged drawing of 900-1300 second.
Fig. 4 is concentration-response current curve that in embodiment 5, glucose oxidase electrode detects glucose, and interior illustration is concentration of glucose-current correction curve.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Based on the preparation method of the glucose oxidase electrode of Graphene derivative, concrete steps are as follows:
Dry up after step 1, basal electrode polishing, cleaning;
Step 2, by etc. the Dopamine hydrochloride of quality and graphene oxide be dissolved in the Tris-HCl damping fluid of pH8.5, stirring reaction then eccentric cleaning after being uniformly dispersed, be drying to obtain Graphene derivative/dopamine compound, compound dissolved Graphene derivative/dopamine complex solution that preparation concentration is 0.5 ~ 3mg/mL afterwards;
Step 3, Graphene derivative/dopamine complex solution step 2 obtained drip the conductive electrode substrate being coated in and processing;
Step 4, the electrode that obtains with step 3 are for working electrode, Ag/AgCl is contrast electrode, and platinum electrode is to electrode, and the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilize the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine;
Step 5, according to Frens legal system for nm of gold, be that to join massfraction be that in 1% tetra chlorauric acid solution, heating is boiled to 1% sodium citrate solution by massfraction, until solution is claret, cools and obtain nano-Au solution;
Step 6, nm of gold step 5 obtained drip the electrode being coated in step 4 and obtaining, self assembly 40min, and nm of gold is combined in order with dopamine;
Step 7, the MPBA solution of 1 ~ 10mM is dripped the electrode being coated in step 6 and obtaining, room temperature 2h, rinse dry;
Step 8, the glucose oxidase solution of 5 ~ 15mg/mL is dripped the electrode being coated in step 7 and obtaining, obtain glucose oxidase electrode.
Embodiment 1
Step 1, be the Al of 0.3 μm and 0.05 μm respectively with particle diameter by platinum electrode
2o
3suspension is polished to minute surface at chamois leather, then uses absolute ethyl alcohol and each ultrasonic 2min of ultrapure water successively, is placed in exsiccator inner drying for subsequent use;
Step 2,30mg Dopamine hydrochloride is dissolved in PH=8.5Tris-HCl solution, the graphene oxide of quality such as then to add, ultrasonic disperse is even, after stirring reaction 4h, in 14000rpm, 4 DEG C of centrifugal 30min, remove supernatant, redistilled water eccentric cleaning three times, precipitation dried afterwards, redistilled water dissolves compound, ultrasonic Graphene derivative/dopamine complex solution to dispersed preparation 0.5mg/mL;
Step 3, drip Graphene derivative/dopamine complex solution that 10 μ L steps 2 obtain on the platinum electrode processed;
Step 4, the electrode that obtains with step 3 are for working electrode, Ag/AgCl is contrast electrode, platinum electrode is to electrode, the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilize the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine, scanning voltage is-0.6 ~ 0.6V, sweep velocity is 50mV/s, and scanning hop count is 20;
The preparation method of step 5, nm of gold improves according to Frens method, conical flask is after chloroazotic acid process, add the redistilled water of 100mL boiling, add 1mL1% tetra chlorauric acid solution subsequently, vigorous stirring, adds 2.5mL1% sodium citrate solution along whirlpool direction immediately, and solution becomes after blueness becomes claret from colourless, constantly boiling 10min, then stops adding thermal agitation and is cooled to room temperature and namely obtains nano-Au solution;
On the electrode that the nano-Au solution that step 6, the step 5 dripping 10 μ L obtain obtains in step 4, self assembly 40min, nm of gold is combined in order with dopamine;
On the electrode that step 7, the MPBA solution dripping the 1mM of 10 μ L obtain in step 6, it is dry that room temperature leaves standstill 2h post-flush;
On the electrode that step 8, the glucose oxidase solution dripping the 5mg/mL of 10 μ L obtain in step 7, room temperature leaves standstill 6h, obtains glucose oxidase electrode.
Detect with ultraviolet-visible spectrometer after step 2 dilutes 10 times with the fresh nm of gold colloid redistilled water that Frens method prepares, result as shown in Figure 2.As we know from the figure, 523nm place is maximum absorption band, and the nanogold particle diameter that can be calculated preparation by colloid gold particle particle diameter and the peak-to-peak regression curve equation Y=0.786X+505.53 of absorption maximum is approximately 22nm.The nm of gold color prepared is claret, and even size distribution, agglomeration does not occur.
Embodiment 2
Step 1, be the Al of 0.3 μm and 0.05 μm respectively with particle diameter by platinum electrode
2o
3suspension is polished to minute surface at chamois leather, then uses absolute ethyl alcohol and each ultrasonic 2min of ultrapure water successively, is placed in exsiccator inner drying for subsequent use;
Step 2,30mg Dopamine hydrochloride is dissolved in PH=8.5Tris-HCl solution, the graphene oxide of quality such as then to add, ultrasonic disperse is even, after stirring reaction 4h, in 14000rpm, 4 DEG C of centrifugal 30min, remove supernatant, redistilled water eccentric cleaning three times, precipitation dried afterwards, redistilled water dissolves compound, ultrasonic Graphene derivative/dopamine complex solution to dispersed preparation 1mg/mL;
Step 3, drip Graphene derivative/dopamine complex solution that 10 μ L steps 2 obtain on the platinum electrode processed;
Step 4, the electrode that obtains with step 3 are for working electrode, Ag/AgCl is contrast electrode, platinum electrode is to electrode, the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilize the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine, scanning voltage is-0.6 ~ 0.6V, sweep velocity is 50mV/s, and scanning hop count is 20;
The preparation method of step 5, nm of gold improves according to Frens method, conical flask is after chloroazotic acid process, add the redistilled water of 100mL boiling, add 1mL1% tetra chlorauric acid solution subsequently, vigorous stirring, adds 2.5mL1% sodium citrate solution along whirlpool direction immediately, and solution becomes after blueness becomes claret from colourless, constantly boiling 10min, then stops adding thermal agitation and is cooled to room temperature and namely obtains nano-Au solution;
On the electrode that the nano-Au solution that step 6, the step 5 dripping 10 μ L obtain obtains in step 4, self assembly 40min, nm of gold is combined in order with dopamine;
On the electrode that step 7, the MPBA solution dripping the 5mM of 10 μ L obtain in step 6, it is dry that room temperature leaves standstill 2h post-flush;
On the electrode that step 8, the glucose oxidase solution dripping the 10mg/mL of 10 μ L obtain in step 7, room temperature leaves standstill 6h, obtains glucose oxidase electrode.
Embodiment 3
Step 1, be the Al of 0.3 μm and 0.05 μm respectively with particle diameter by platinum electrode
2o
3suspension is polished to minute surface at chamois leather, then uses absolute ethyl alcohol and each ultrasonic 2min of ultrapure water successively, is placed in exsiccator inner drying for subsequent use;
Step 2,30mg Dopamine hydrochloride is dissolved in PH=8.5Tris-HCl solution, the graphene oxide of quality such as then to add, ultrasonic disperse is even, after stirring reaction 4h, in 14000rpm, 4 DEG C of centrifugal 30min, remove supernatant, redistilled water eccentric cleaning three times, precipitation dried afterwards, redistilled water dissolves compound, ultrasonic Graphene derivative/dopamine complex solution to dispersed preparation 2mg/mL;
Step 3, drip Graphene derivative/dopamine complex solution that 10 μ L steps 2 obtain on the platinum electrode processed;
Step 4, the electrode that obtains with step 3 are for working electrode, Ag/AgCl is contrast electrode, platinum electrode is to electrode, the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilize the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine, scanning voltage is-0.6 ~ 0.6V, sweep velocity is 50mV/s, and scanning hop count is 20;
The preparation method of step 5, nm of gold improves according to Frens method, conical flask is after chloroazotic acid process, add the redistilled water of 100mL boiling, add 1mL1% tetra chlorauric acid solution subsequently, vigorous stirring, adds 2.5mL1% sodium citrate solution along whirlpool direction immediately, and solution becomes after blueness becomes claret from colourless, constantly boiling 10min, then stops adding thermal agitation and is cooled to room temperature and namely obtains nano-Au solution;
On the electrode that the nano-Au solution that step 6, the step 5 dripping 10 μ L obtain obtains in step 4, self assembly 40min, nm of gold is combined in order with dopamine;
On the electrode that step 7, the MPBA solution dripping the 8mM of 10 μ L obtain in step 6, it is dry that room temperature leaves standstill 2h post-flush;
On the electrode that step 8, the glucose oxidase solution dripping the 12mg/mL of 10 μ L obtain in step 7, room temperature leaves standstill 6h, obtains glucose oxidase electrode.
Embodiment 4
Step 1, be the Al of 0.3 μm and 0.05 μm respectively with particle diameter by platinum electrode
2o
3suspension is polished to minute surface at chamois leather, then uses absolute ethyl alcohol and each ultrasonic 2min of ultrapure water successively, is placed in exsiccator inner drying for subsequent use;
Step 2,30mg Dopamine hydrochloride is dissolved in PH=8.5Tris-HCl solution, the graphene oxide of quality such as then to add, ultrasonic disperse is even, after stirring reaction 4h, in 14000rpm, 4 DEG C of centrifugal 30min, remove supernatant, redistilled water eccentric cleaning three times, precipitation dried afterwards, redistilled water dissolves compound, ultrasonic Graphene derivative/dopamine complex solution to dispersed preparation 3mg/mL;
Step 3, drip Graphene derivative/dopamine complex solution that 10 μ L steps 2 obtain on the platinum electrode processed;
Step 4, the electrode that obtains with step 3 are for working electrode, Ag/AgCl is contrast electrode, platinum electrode is to electrode, the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilize the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine, scanning voltage is-0.6 ~ 0.6V, sweep velocity is 50mV/s, and scanning hop count is 20;
The preparation method of step 5, nm of gold improves according to Frens method, conical flask is after chloroazotic acid process, add the redistilled water of 100mL boiling, add 1mL1% tetra chlorauric acid solution subsequently, vigorous stirring, adds 2.5mL1% sodium citrate solution along whirlpool direction immediately, and solution becomes after blueness becomes claret from colourless, constantly boiling 10min, then stops adding thermal agitation and is cooled to room temperature and namely obtains nano-Au solution;
On the electrode that the nano-Au solution that step 6, the step 5 dripping 10 μ L obtain obtains in step 4, self assembly 40min, nm of gold is combined in order with dopamine;
On the electrode that step 7, the MPBA solution dripping the 8mM of 10 μ L obtain in step 6, it is dry that room temperature leaves standstill 2h post-flush;
On the electrode that step 8, the glucose oxidase solution dripping the 15mg/mL of 10 μ L obtain in step 7, room temperature leaves standstill 6h, obtains glucose oxidase electrode.
Embodiment 5
Glucose detection
First glucose is dissolved in the glucose phosphate buffer solution being made into 1M in the phosphate buffer solution of pH=7.0, by concentration dilution when taking.Then electrochemical workstation is utilized, observe the time current curve of the glucose oxidase electrode that embodiment 2 prepares, arranging voltage is 0.6V, the pH=7.0 phosphate buffer solution of 10mL, the PH=7.0 glucose phosphate buffer solution of 1mM, 10mM, 100mM, 1M is dripped successively after within 500 seconds, response current is stablized, each concentration drips according to 10 μ L, 10 μ L, 20 μ L, 20 μ L, 40 μ L, 40 μ L, 80 μ L, 80 μ L orders, and result as shown in Figure 3, Figure 4.Wherein, Fig. 3 is the time current curve that glucose oxidase electrode detects glucose, and Fig. 4 is concentration-response current curve that glucose oxidase electrode detects glucose.As can be seen from Figure 3, along with the increase of concentration of glucose, the stepped increase of response current, when concentration is increased to 3.0 × 10
-2during M, response current increase is slowed down.Interior illustration is the time m-response current enlarged drawing of 900-1300 second.In Fig. 4, response current represents enzyme ' s reaction speeding, and when as can be seen from the figure concentration of glucose is lower, response current and concentration of glucose be I (μ A)=0.8378 [glucose]/mM+0.0774 linearly, and related coefficient is 0.9935.Linear response glucose concentration range is 6.00 × 10
-6-3.97 × 10
-3m is first order reaction.Along with the continuous increase of concentration of glucose, the increase of response current is slowed down, until response current does not increase with concentration and increases, be zero-order reaction, now the enzyme of electrode surface is all saturated by substrate glucose oxidase, and reaction reaches maximum reaction rate.Interior illustration is concentration of glucose-current correction curve.
Claims (7)
1. the glucose oxidase electrode based on Graphene derivative, it is characterized in that, described electrode is made up of conductive electrode substrate, Graphene derivative/dopamine composite bed, poly-DOPA amine layer, nm of gold array, 4-mercaptophenyl boronic acid layer and glucose oxidase layer successively, described Graphene derivative/dopamine composite bed is after dopamine mixes with graphene oxide, the potpourri after dopamine and partial oxidation Graphene generation redox reaction.
2., as claimed in claim 1 based on the glucose oxidase electrode of Graphene derivative, it is characterized in that, described conductive electrode substrate is selected from carbon-based electrode substrate, conductive metal electrode substrate or semi-conducting electrode substrate.
3. the preparation method based on the glucose oxidase electrode of Graphene derivative, it is characterized in that, concrete steps are as follows: first by etc. the Dopamine hydrochloride of quality and graphene oxide to be dissolved in pH value be in the Tris-HCl damping fluid of 8.5, react after being uniformly dispersed, then eccentric cleaning, be drying to obtain Graphene derivative/dopamine compound, again compound is dissolved and be prepared into Graphene derivative/dopamine complex solution, and adopt Graphene derivative/dopamine complex solution modified conducting electrode basement, adopt electrochemical process at electrode surface electropolymerization dopamine afterwards, adopt nano-Au solution and 4-mercaptophenyl boronic acid solution modified electrode successively again, finally use glucose oxidase solution modified electrode, obtain described glucose oxidase electrode.
4. as claimed in claim 3 based on the preparation method of the glucose oxidase electrode of Graphene derivative, it is characterized in that, described electrochemical process is for working electrode with the conductive electrode substrate of Graphene derivative/dopamine complex solution modified, Ag/AgCl is contrast electrode, platinum electrode is to electrode, the dopamine phosphate buffer solution that concentration is 4mM, pH value is 7.5 is electrolytic solution, utilizes the cyclic voltammetry scan of electrochemical workstation, at working electrode surface electropolymerization dopamine.
5. as claimed in claim 3 based on the preparation method of the glucose oxidase electrode of Graphene derivative, it is characterized in that, the concentration of described Graphene derivative/dopamine complex solution is 0.5 ~ 3mg/mL, the concentration of 4-mercaptophenyl boronic acid is 1 ~ 10mM, and the concentration of glucose oxidase is 10 ~ 12mg/mL.
6., as claimed in claim 3 based on the preparation method of the glucose oxidase electrode of Graphene derivative, it is characterized in that, the concentration of described Graphene derivative/dopamine complex solution is 1 ~ 2mg/mL.
7., as claimed in claim 3 based on the preparation method of the glucose oxidase electrode of Graphene derivative, it is characterized in that, the concentration of described 4-mercaptophenyl boronic acid is 5 ~ 8mM.
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