CN106248754A - A kind of chemical modification GCE electrode based on functionalization rGO and its preparation method and application - Google Patents
A kind of chemical modification GCE electrode based on functionalization rGO and its preparation method and application Download PDFInfo
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- CN106248754A CN106248754A CN201610647538.0A CN201610647538A CN106248754A CN 106248754 A CN106248754 A CN 106248754A CN 201610647538 A CN201610647538 A CN 201610647538A CN 106248754 A CN106248754 A CN 106248754A
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a kind of chemical modification GCE electrode based on functionalization rGO and its preparation method and application, the present invention is applied by rGO COOLa complex or drop coating is on GCE electrode, and preferably ctab surface activating agent is coated on rGO COOLa complex modification GCE electrode, obtain a kind of new modified electrode.The sensitivity of this modified electrode, selectivity measure at the same time in the system of DA, UA and are significantly improved.
Description
Technical field
The present invention relates to GCE electrode of a kind of chemical modification based on functionalization rGO and its preparation method and application, this electricity
Pole measures while can be used for two kinds of biomolecule of DA, UA, belongs to electro chemical analysis field.
Background technology
Dopamine (DA), uric acid (UA) are very important biomolecule in the metabolism of organism.Dopamine
(DA) very important effect is all played at nervus centralis, kidney, cardiovascular system and hormonal system, it addition, DOPAMINE CONTENT IN RABBIT
Exception can cause numerous disease, such as Alzheimer, parkinson disease, alzheimer disease, schizophrenia and HIV (human immunodeficiency virus)
Infect.Therefore, invent efficient detection means to the dopamine that measures in organism it is critical that.Uric acid (Uric
Acid, UA) it is the end product in purine nucleotides catabolic process in human body, in body fluid, the change of uric acid amount can reflect
The situation of the function such as human metabolism, immunity.In organism, DA and UA coexists, and selects to measure in dopamine coexists system
The research tool of uric acid is of great significance.Yet with DA Yu UA oxidation peak closely, almost overlap, use
It is extremely difficult that common bare electrode is wanted to distinguish DA Yu UA.In the simultaneous system of DA Yu UA, it is possible to
Time detection both materials, obtain the oxidation peak of both materials, and can substantially distinguish, in biomolecule Electrochemical Detection
In significant.
In order to overcome these problems, various modified electrodes be produced and be applied to DA, UA selectivity or
Measure simultaneously.Wherein, polymer modified electrode due to have stronger selectivity, preferable stability, higher repeatability, with
And the advantage such as can control at the thickness of electrode surface and occupy irreplaceable one seat in electro chemical analysis field all the time.
Summary of the invention
It is an object of the invention to provide a kind of chemical modification based on functionalization rGO glass-carbon electrode (i.e. GCE electrode) and
Its preparation method, and this electrode is for measuring the application of DA, UA simultaneously.
Technical scheme is as follows:
The present invention provides a kind of chemical modification GCE electrode based on functionalization rGO, and the end face of described electrode has rGO-
COOLa composite layer.
Preferably, outside described rGO-COOLa composite layer, also there is surfactant layer.
Preferably, described surfactant is CTAB.
The present invention also provides for the preparation method of a kind of chemical modification GCE electrode based on functionalization rGO, including walking as follows
Rapid:
First, prepare rGO-COOLa complex, in turn include the following steps: prepare graphene oxide suspension, preparation also
Former graphene oxide rGO, preparation rGO-COOH, preparation rGO-COOLa complex；
Second, prepared rGO-COOLa composite coated or drop coating in GCE electrode end surface and are dried.
Preferably, described preparation method farther includes:
3rd, surfactant solution is coated on the electrode surface of rGO-COOLa modification and is dried.
Preferably, described surfactant is CTAB.
The present invention also provides for described modification GCE electrode for measuring the application of DA, UA simultaneously.
Compared with prior art, beneficial effects of the present invention is as follows:
First, a kind of based on functionalization rGO the chemical modification GCE electrode of the present invention, due to directly multiple by rGO-COOLa
Surfactant CTAB, at electrode surface, is coated in its surface by condensation material coating or drop coating the most again, surfactant with
RGO-COOLa creates collaborative effect so that this electrode has more preferable selectivity and sensitive to the mensuration of DA, UA mixture
Degree；
Second, a kind of based on functionalization rGO the chemical modification GCE electrode of the present invention, its preparation process is simple, the time
Short；
3rd, the chemical modification GCE electrode based on functionalization rGO that the present invention prepares has that repeatability is strong, stability is high,
Selectivity is good, simple to operate and has the advantages such as longer life-span, can be applicable to the qualitative and quantitative analysis of DA, UA.
Certainly, the arbitrary product implementing the present invention it is not absolutely required to reach all the above advantage simultaneously.
Accompanying drawing explanation
Fig. 1 (a) and Fig. 1 (b) is that the electrode solution respective to DA, UA of various embodiments of the present invention and each reference examples is surveyed
Fixed result figure；
Fig. 2 is the result figure that the mixed solution of DA, UA is measured by the electrode of various embodiments of the present invention and each reference examples.
Detailed description of the invention
The present invention provides a kind of chemical modification GCE electrode based on functionalization rGO, can be used for surveying DA, UA simultaneously
Fixed.
New material graphene oxide (GO) is that we probe into the suitable material of modified electrode and provide thinking.At present, stone
Ink alkene molecule is applied widely in terms of electrochemical sensor, has a lot of features and excellent performance.Especially when
After it is oxidized, on it, oxygen-containing functional group increases and makes character relatively Graphene more active, can be via various and oxygen-containing functional group
Reaction and improve nature.Redox graphene (rGO) is the grapheme material of a kind of chemical modification.Meanwhile, various
The existence of functional group also gives the chemism that rGO is excellent, and makes its surface electronegative, it is possible in water, (or in aqueous alkali) is formed
Nanoscale disperses, thus the Application of composite or nano ordered assembling for rGO lays a good foundation.Graphene oxide can be considered one
Plant the flexible material of non-traditional kenel, there is polymer, colloid, property of thin film, boundary can be generally present in such as interfacial agent
Face, and reduce the energy between interface.Therefore, selectivity inspection can be carried out with it according to the performance of graphene oxide under proper condition
Survey DA, UA.
Recently, RE composite causes a lot of concern.Owing to coming from the optics of 4f electronics, electronics and chemical characteristic,
Rare earth is used widely in every field, such as optics, diagnostics, biological classification, and other functional materials.Lanthanum is rare earth
In an important element, lanthanum ion has the highest chemical principle power to oxygen-containing functional group.Additionally, lanthanum ion has relatively low
Toxicity and outstanding catalytic property, it is used to constructing environment friendly biosensor.
Based on rGO and the advantage of rare earth metal, the complex of rare-earth elements of lanthanum can be used as decorative material, drip to throw
The mode being coated with modifies GCE, and for selective enumeration method DA, UA, to prepare, good stability, repeatability be strong, highly sensitive, selectivity
Good efficient sensor.
Surfactant have moistening or anti-stick, emulsifying or breakdown of emulsion, foaming or froth breaking and solubilising, disperse, wash, anti-
The series of physical chemical actions such as corruption, antistatic and corresponding actual application.So, no matter produce or Technological research in life
In, surfactant all plays important role.Surfactant, can be in solution surface due to its hydrophilic and lipophile
Align.In terms of electro chemical analysis, adding surfactant can affect diffusion and the electrochemical reaction of measured matter.
The present inventor uses some cationic surfactants to be modified electrode, such as Dodecyl trimethyl ammonium chloride
(DTAB), Tetradecyl Trimethyl Ammonium Bromide (TTAB), cetyl trimethylammonium bromide (CTAB), bromohexadecane base pyrroles
(CPB) four kinds of cationic surfactants.Understanding through multiple test analysis, CTAB is optimal to the intercalation effect of rGO.Meanwhile,
Result shows, CTAB is more preferable for the performance of modified electrode.
A kind of based on functionalization rGO the chemical modification GCE electrode that the present invention provides, the end face of described electrode has rGO-
COOLa composite layer.
Preferably, outside described rGO-COOLa composite layer, also there is CTAB layer.
The preparation method of the modification GCE electrode of the present invention, specifically can comprise the steps:
(1) graphene oxide suspension is prepared.
Instantiation is as follows: according to improving Hummers method, is used for synthesizing graphene oxide as raw material using graphite powder.
Under the conditions of ice bath 30min, 1.0g graphite powder is joined in 23mL concentrated sulphuric acid, continuously stirred, then add 0.5g sodium nitrate and 3g
Potassium permanganate, the cloudy mixture obtained is cooled to constant temperature；Remove ionized water to be added in said mixture, after 15 minutes, then add
Enter 25 DEG C of warm water to be diluted, be subsequently adding the hydrogen peroxide of 0.1mol/L, yellow solution is become glassy yellow, obtain graphite oxide
Alkene suspension.
(2) the graphene oxide rGO of preparation reduction.
Instantiation is as follows: take the graphene oxide suspension 500mL of preparation in step (1), and the thiourea adding 500mg enters
Row backflow, reflux course temperature maintains 40-60 DEG C, return time 24 hours, in this reduction process, scattered oxidation stone
Ink alkene mixture is become dark solution by brown.After reaction terminates, the mixture distilled water of backflow and ethanol rinse are clean.
The mixture cleaned, in the drying of 60 DEG C of vacuum drying oven, prepares rGO.
(3) rGO-COOH is prepared.
Instantiation is as follows: 0.5g sodium hydroxide and 0.5g sodium chloroacetate are joined the 1mg/mL rGO's after being formulated
In suspension, by suspension water-bath sonication 2 hours.
Neutralize, with the hydrochloric acid solution of dilution, the rGO-COONa obtained, be then purified process, prepare rGO-COOH
Suspension, is finally dried uniform rGO-COOH suspension at 80 DEG C.
(4) rGO-COOLa complex is prepared.
Instantiation is as follows: the rGO-COOH obtained in step (3) is configured to the carboxylated oxidation that concentration is 1mg/mL
Graphene (rGO-COOH) suspension, then measures 10mL, and and the LaCl of 5mL, 0.4mol/mL3Solution mixing ultrasonic place
Manage 3 hours.The suspension obtained is neutralized dialysis 5 days, to eliminate residual chlorine ion and lanthanum ion；The complex obtained is at 60 DEG C
Lower vacuum drying, prepares the complex of rGO-COOLa.
(5) rGO-COOLa/GCE electrode is prepared.
Instantiation is as follows: the other end of contact conductor is polished to minute surface on Corium Cervi or pan paper, then by 10 μ L
The complex of step (4) gained be configured to the solution that concentration is 1mg/mL, coating or drop coating are in GCE electrode end surface, and are dried,
Prepare rGO-COOLa/GCE electrode.
Wherein, before by rGO-COOLa composite coated to electrode, also include the pre-treatment step of electrode, particularly as follows:
Using particle diameter on Corium Cervi successively is 1 μm, 0.3 μm, the alumina powder of 0.05 μm polishing electrode, after through volume fraction be
The ethanol solution of 95%, deionized water carries out ultrasonic cleaning, and the washing of each step all uses deionized water to clean, and is processed
After naked glass-carbon electrode.
In the preferred version of the present invention, also include: (6) coating surface active agent layer: surfactant is preferably
The concentration of CTAB is chosen to be 0.2-1g/L, and surfactant solution is coated on rGO-COOLa/GCE electrode surface, dry under room temperature
Dry.
In the present invention, " numerical value is to another numerical value " scope represented, is that one avoids a string in the description
Lift the summary representation of all numerical value in this scope.Therefore, the record of a certain special value scope, contain this numerical value model
Enclose interior any number and the relatively fractional value scope defined by any number in this numerical range, as in the description
Write out this any number in plain text the same compared with fractional value scope with this.
Below in conjunction with specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright, rather than limit protection scope of the present invention.Those skilled in the art are according to changing that the present invention makes in actual applications
Enter and adjust, still falling within protection scope of the present invention.
Reagent used in following example and the following Tables 1 and 2 of instrument.
Table 1 reagent type table
| Reagent name | Molecular formula | Rank | Manufacturer |
| Sodium hydroxide | NaOH | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Potassium dihydrogen phosphate | KH2PO4 | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Ascorbic acid | C6H8O6 | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Uric acid | C5H4N4O3 | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Dopamine | C8H11O2N | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
| Sodium nitrite | NaNO2 | Analytical pure | Chemical Reagent Co., Ltd., Sinopharm Group |
Table 2 instrument type table
| Device name | Model | Manufacturer |
| Vacuum drying oven | NKV400 | Shanghai Fuma Experiment Equipment Co., Ltd. |
| Electronic analytical balance | AL104 | Prunus mume (sieb.) sieb.et zucc. Teller-torr benefit Instrument Ltd. |
| Electrochemical workstation | CHI760e | Shanghai Chen Hua instrument company |
Deionized water, volumetric flask, beaker, magnetic stirring apparatus, oil bath pan, aluminium oxide is also included used in following example
Polishing powder 1,0.3,0.05 μm, Pt electrode, saturated calomel electrode, liquid-transfering gun, chamois leather.
Embodiment 1
A kind of preparation method of the rGO-COOLa/GCE electrode of the present embodiment, including following step:
(1) according to improving Hummers method, it is used for synthesizing graphene oxide as raw material using graphite powder.At ice bath 30min
Under the conditions of, 1.0g graphite powder is joined in 23mL concentrated sulphuric acid, continuously stirred, then add 0.5g sodium nitrate and 3g potassium permanganate,
To cloudy mixture be cooled to constant temperature；Removing ionized water to be added in said mixture, after 15 minutes, adding 25 DEG C of warm water will
Its dilution, the hydrogen peroxide being subsequently adding 0.1mol/L reacts, and yellow solution is become glassy yellow, obtains graphene oxide and hangs
Turbid liquid.
(2) the graphene oxide suspension 500mL of preparation in step (1), the thiourea adding 500mg refluxes, backflow
Process temperature maintains 40-60 DEG C, return time 24 hours, in this reduction process, and scattered graphene oxide mixture
Dark solution is become by brown.After reaction terminates, the mixture distilled water of backflow and ethanol rinse are clean.That is cleaned is mixed
Compound, in the drying of 60 DEG C of vacuum drying oven, prepares rGO.
(3) rGO of above-mentioned preparation is configured to the suspension that concentration is 1mg/mL rGO, is subsequently adding 0.5g sodium hydroxide
With 0.5g sodium chloroacetate, water bath sonicator processes 2 hours.The rGO-COONa prepared is neutralized with dilute hydrochloric acid solution.Then carry out
Purification process, prepares rGO-COOH suspension, is finally dried at 80 DEG C by uniform rGO-COOH suspension；
(4) preparation of rGO-COOLa complex: the rGO-COOH obtained in step (3) is configured to concentration is 1mg/mL
Carboxylated graphene oxide (rGO-COOH) suspension, then measure 10mL, and and the LaCl of 5mL, 0.4mol/mL3Solution
Mixing also sonication three hours, the suspension obtained is neutralized dialysis 5 days, and at 60 DEG C, vacuum drying obtains rGO-COOLa again
Compound.
(5) electrode surface coating: one end of contact conductor is first polished to minute surface, then by step (4) institute on pan paper
The rGO-COOLa complex obtained, is configured to the dispersion liquid that concentration is 1mg/L, and drop coating is being polished to this electrode cable of minute surface
One end, then under room temperature be dried, obtain the modified electrode of rGO-COOLa.
Embodiment 2
A kind of preparation method of the table of the present embodiment-rGO-COOLa/GCE electrode alive, including following step:
(1) according to improving Hummers method, it is used for synthesizing graphene oxide as raw material using graphite powder.At ice bath 30min
Under the conditions of, 1.0g graphite powder is joined in 23mL concentrated sulphuric acid, continuously stirred, then add 0.5g sodium nitrate and 3g potassium permanganate,
To cloudy mixture be cooled to constant temperature；Removing ionized water to be added in said mixture, after 15 minutes, adding 25 DEG C of warm water will
Its dilution, the hydrogen peroxide being subsequently adding 0.1mol/L reacts, and yellow solution is become glassy yellow, obtains graphene oxide and hangs
Turbid liquid.
(2) the graphene oxide suspension 500mL of preparation in step (1), the thiourea adding 500mg refluxes, backflow
Process temperature maintains 40-60 DEG C, return time 24 hours, in this reduction process, and scattered graphene oxide mixture
Dark solution is become by brown.After reaction terminates, the mixture distilled water of backflow and ethanol rinse are clean.That is cleaned is mixed
Compound, in the drying of 60 DEG C of vacuum drying oven, prepares rGO.
(3) rGO of above-mentioned preparation is configured to the suspension that concentration is 1mg/mL rGO, is subsequently adding 0.5g sodium hydroxide
With 0.5g sodium chloroacetate, water bath sonicator processes 2 hours.The rGO-COONa prepared is neutralized with dilute hydrochloric acid solution.Then carry out
Purification process, prepares rGO-COOH suspension, is finally dried at 80 DEG C by uniform rGO-COOH suspension；
(4) preparation of rGO-COOLa complex: the rGO-COOH obtained in step (3) is configured to concentration is 1mg/mL
Carboxylated graphene oxide (rGO-COOH) suspension, then measure 10mL, and and the LaCl of 5mL, 0.4mol/mL3Solution
Mixing also sonication three hours, the suspension obtained is neutralized dialysis 5 days, and at 60 DEG C, vacuum drying obtains rGO-COOLa again
Compound.
(5) concentration of selection table CTAB alive is 0.2g/L.
One end of contact conductor is first polished to minute surface on pan paper, then by step (4) that 10 μ L concentration are 1mol/L
The dispersion of the complex of the rGO-COOLa of gained in the one end at this electrode cable being polished to minute surface, then room
Temperature is lower to be dried, then is coated on rGO-COOLa modified electrode by the CTAB solution of step (5) gained, obtains CTAB/rGO-
COOLa modified electrode.
Comparative example 1
This comparative example provides the preparation method of a kind of rGO-COOH/GCE electrode, including following step:
(1) according to improving Hummers method, it is used for synthesizing graphene oxide as raw material using graphite powder.At ice bath 30min
Under the conditions of, 1.0g graphite powder is joined in 23mL concentrated sulphuric acid, continuously stirred, then add 0.5g sodium nitrate and 3g potassium permanganate,
To cloudy mixture be cooled to constant temperature；Removing ionized water to be added in said mixture, after 15 minutes, adding 25 DEG C of warm water will
Its dilution, is subsequently adding the certain density hydrogen peroxide of 0.1mol/L, yellow solution is become glassy yellow, obtains graphene oxide and hangs
Turbid liquid, and then obtain graphene oxide.
(2) graphene oxide that 500mg step (1) prepares and the distilled water of the 300mg 2h that degrades under sound wave is utilized to make
The dispersion of standby graphene oxide.The thiourea of 500mg joins in the dispersion liquid of graphene oxide and refluxes.Reflux course
Temperature maintains 40-60 DEG C and persistently 24 hours, and in this reduction process, scattered graphene oxide mixture is become by brown
Become dark solution.Finally, the mixture distilled water of backflow and ethanol rinse are clean, the end product reduction obtained
Graphene oxide, the graphene oxide of the reduction cleaned, in the drying of 60 DEG C of vacuum drying oven, obtains rGO.
(3) rGO of above-mentioned preparation is configured to the suspension that concentration is 1mg/mL rGO, is subsequently adding 0.5g sodium hydroxide
With 0.5g sodium chloroacetate, suspension water bath sonicator is processed 2 hours.The rGO-prepared is neutralized with the hydrochloric acid solution of dilution
COONa.The necessary purification of the product obtained, dialyses 3 days with deionized water.Adding hydrochloric acid makes it neutralize, and finally, suspension is at 80 DEG C
Under be dried to obtain uniform rGO-COOH.
Electrode surface coats: one end of contact conductor is first polished to minute surface, then by 10 μ L step (3) institutes on pan paper
The complex of rGO-COOH be configured to the dispersant liquid drop that concentration is 1mg/L and be coated in this electrode cable being polished to minute surface
One end, is then dried under room temperature, obtains the modified electrode of rGO-COOH.
Comparative example 2
This comparative example provides a naked glass-carbon electrode.
Application Example 1
By the modified electrode of rGO-COOLa of above-described embodiment 1 gained, the CTAB/rGO-COOLa of embodiment 2 gained
Modified electrode, the modified electrode of rGO-COOH of comparative example 1 gained and the naked glass-carbon electrode of comparative example 2 are directly used in containing
The phosphate buffered solution of DA, UA detects, and specifically comprises the following steps that
Repair with the modified electrode of rGO-COOLa, the CTAB/rGO-COOLa of embodiment 2 gained of embodiment 1 gained respectively
Decorations electrode, the modified electrode of rGO-COOH of comparative example 1 gained and the naked glass-carbon electrode of comparative example 2 are as working electrode, with full
Separately constitute three-electrode system with calomel electrode, platinum electrode respectively as reference electrode with to electrode, use electrochemical workstation
(Shanghai Chen Hua Instrument Ltd., model is CHI760D) is respectively by the modified electrode of rGO-COOLa of embodiment 1 gained, reality
Execute modified electrode and the comparative example 2 of the rGO-COOH of the modified electrode of CTAB/rGO-COOLa of example 2 gained, comparative example 1 gained
The naked glass-carbon electrode of gained measures the phosphate buffered solution of DA and UA.Survey timing voltage and be chosen to be-0.2～0.8v, scanning speed
Rate is 100mv/s, and concentration is DA and UA of 1mmol/L.Solvent used by phosphate buffered solution preparation is 0.1mol/L, pH
It it is the PBS solution (phosphate buffered saline(PBS)) of 7.0.
Shown in measurement result such as Fig. 1 (a) and Fig. 1 (b), when Fig. 1 (a) is individualism DA in solution, embodiment 1, enforcement
Example 2 and comparative example 1, the comparison diagram of comparative example 2.When Fig. 1 (b) is individualism UA in solution, embodiment 1, embodiment 2 and contrast
Example 1, the comparison diagram of comparative example 2.The modification electricity of the CTAB/rGO-COOLa of embodiment 2 is can be seen that from Fig. 1 (a) and Fig. 1 (b)
Extremely UA and DA to individualism is respectively provided with the peak current of maximum, illustrates that the CTAB/rGO-COOLa of embodiment 2 has the highest
Sensitivity；It can also be seen that the modified electrode of the rGO-COOLa of embodiment 1 has certain sensitivity to DA and UA, but it is imitated
Fruit is inferior to embodiment 2.
Therefore, the most visible, the modified electrode of the rGO-COOLa of embodiment 1 and the CTAB/rGO-of embodiment 2
Two kinds of biomolecule of UA and AA individually can be analyzed detection, detect sensitive by COOLa modified electrode.
Application Example 2
The modified electrode utilizing the table-rGO-COOLa alive of embodiment 1, embodiment 2 and comparative example 1, comparative example 2 gained is straight
Connecing the Electrochemical Detection for DA, UA, step is as follows:
Detection method is referred to the method for existing determination of electrode DA, UA, with embodiment 1, embodiment 2 and comparative example 1, right
The modified electrode of the CTAB/rGO-COOLa of ratio 2 gained, as working electrode, is made respectively with saturated calomel electrode, platinum electrode
Three-electrode system is separately constituted, by electrochemical workstation (Shanghai Chen Hua Instrument Ltd., type for reference electrode and auxiliary electrode
Number it is CHI760D) measure the modified electrode of rGO-COOLa of embodiment 1 gained, the CTAB/rGO-COOLa of embodiment 2 gained
Modified electrode, the modified electrode of rGO-COOH of comparative example 1 gained and the naked glass-carbon electrode of the comparative example 2 mixing phosphorus to DA, UA
The electro-catalysis of hydrochlorate buffer solution (wherein DA concentration be 1.0mmol/L, UA concentration be the phosphate buffered solution of 0.1mmol/L)
Performance.
Solvent used by the preparation of above-mentioned each solution is the PBS solution that 0.1mol/L, pH are 7.0, and (phosphate-buffered salt is molten
Liquid).
The measurement result of above-mentioned experiment as in figure 2 it is shown, from Fig. 2, curve can be seen that UA and DA respectively at 420mV and
About 580mV occurs in that an oxidation peak, and the oxidation peak between DA with UA is separated the most, illustrates to utilize embodiment 2
The modified electrode of CTAB/rGO-COOLa measures while likely realizing two kinds of materials.Further, comparison diagram 1 (a), Fig. 1 (b)
With the curve of Fig. 2 it can be seen that when, after two kinds of materials mixing of DA, UA, respective oxidation peak current, spike potential are individually surveyed with them
The almost no change of the peak current of timing, spike potential, illustrates on the modified electrode of CTAB/rGO-COOLa, UA and DA without interference with
The mutual detection to DA and UA of the modified electrode of this CTAB/rGO-COOLa, and then show the modification electricity of this CTAB/rGO-COOLa
Extremely DA, UA both materials can be detected simultaneously.It can further be seen from figure 2 that the rGO-COOLa of embodiment 1 gained
Modified electrode also is able to measure DA, UA both materials in mixed solution.
Repeated experiment: utilize embodiment 2 gained CTAB/rGO-COOLa modified electrode this to DA concentration be
Cyclic voltammetry curve continuous detecting in the phosphate buffered solution of 1.0mmol/L 5 times, finds that peak current does not almost have change
Change, calculate its relative standard deviation (RSD) and be less than 2%, show that the modified electrode of this table-rGO-COOLa alive has well
Repeatability.
The contrast of embodiment 1 and embodiment 2 also illustrates, CTAB has the most collaborative for rGO-COOLa modified electrode
Effect, and detect at the same time and have good sensitivity and high efficiency in tri-kinds of biomolecule of DA, UA.
Above said content is only the basic explanation under present inventive concept, and scope should be not limited to example and be taken off
The content shown, any equivalent transformation made according to technical scheme, protection scope of the present invention all should be belonged to.At this
Under the teaching of invention and above-described embodiment, those skilled in the art be easy to it is envisioned that the present invention cited or enumerate each former
Material or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention, and each raw material and processing method
Parameter bound value, interval value can realize the present invention, embodiment numerous to list herein.
Claims (8)
1. a chemical modification GCE electrode based on functionalization rGO, it is characterised in that the end face of described electrode has rGO-
COOLa composite layer.
2. chemical modification GCE electrode based on functionalization rGO as claimed in claim 1, it is characterised in that described rGO-
Also there is outside COOLa composite layer surfactant layer.
3. chemical modification GCE electrode based on functionalization rGO as claimed in claim 2, it is characterised in that described surface activity
Agent is CTAB.
4. the preparation method of a chemical modification GCE electrode based on functionalization rGO, it is characterised in that comprise the steps:
First, prepare rGO-COOLa complex, in turn include the following steps: prepare graphene oxide suspension, preparation is reduced
Graphene oxide rGO, preparation rGO-COOH, preparation rGO-COOLa complex；
Second, prepared rGO-COOLa composite coated or drop coating in GCE electrode end surface and are dried.
5. the preparation method of chemical modification GCE electrode based on functionalization rGO as claimed in claim 4, it is characterised in that institute
State preparation method to farther include:
3rd, surfactant solution is coated on the electrode surface of rGO-COOLa modification and is dried.
6. the preparation method of chemical modification GCE electrode based on functionalization rGO as claimed in claim 5, it is characterised in that institute
Stating surfactant is CTAB.
7. the preparation method of chemical modification GCE electrode based on functionalization rGO as claimed in claim 6, it is characterised in that institute
The concentration stating CTAB is 0.2-1g/L.
8. the chemical modification GCE electrode based on functionalization rGO described in a claim 1 or 2 or 3 for measure simultaneously DA,
The application of UA.
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