CN109490389A - The preparation method of the imprinted polymer modified electrode of high sensitivity detection myoglobins - Google Patents
The preparation method of the imprinted polymer modified electrode of high sensitivity detection myoglobins Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins, prepares Au/3DG/Cs/nAu electrode first, prepares GCE/GR/CTAB/Cs electrode later;Au/3DG/Cs/nAu electrode is modified with the bromine-containing compound that sulfydryl blocks, obtain bromide modified electrode, then it will contain α-methacrylic acid, myoglobins and N, the PBS solution of N- methylene-bisacrylamide is put into electrolytic cell, gained bromide modified electrode is placed in the solution in electrolytic cell at room temperature, it is reference electrode that use GCE/GR/CTAB/Cs electrode, which be to electrode, saturated calomel electrode as working electrode, platinum filament, at 0.185V, apply constant potential 50min, the bromide modified electrode of polymer must be deposited;The bromide modified electrode for depositing upper polymer is taken out, the myoglobins template in polymer is removed.
Description
Technical field
The present invention discloses a kind of preparation method of imprinted polymer modified electrode, especially a kind of to prepare simple, saving energy
Source, clean and environmental protection highly sensitive detection myoglobins imprinted polymer modified electrode preparation method.
Background technique
Myoglobins (Myoglobin, Mb) is the protein of storage and distribution oxygen, is primarily present in the sarcoplasm of musculature
In, content is about 0.2% ~ 2%, isoelectric point 6.78, is a kind of plyability chromoprotein matter.Currently, the method for detecting Mb
Many, including gold nano grain colorimetric analysis, the local surface plasma resonance of gold nanorods, microfluid fluorescence of fluorescence chip, fluorescence
Immunochromatography and the electrochemical analysis methods such as nanocrystalline, self-assembled monolayer modified based on graphene, ZnS.But it is above-mentioned
Method there is sensitivity it is low, specificity is poor, expensive and higher to instrument requirements the disadvantages of.
Molecular imprinting technology is the subject technology that developed recently gets up, it using molecularly imprinted polymer analogue enztme with
Interaction between substrate carries out single-minded identification to template molecule.The core of molecular imprinting technology is molecularly imprinted polymer,
Its preparation generally comprises three processes: (1) suitable function monomer, function monomer and template molecule being selected to pass through the two functional group
Between interaction (including covalent, hydrogen bond and some other weak effect) form certain reversible compound;(2) crosslinking is added
Agent causes monomer under the action of initiator and is polymerize, and the reversible compound that template molecule and function monomer are formed " is frozen
Knot " gets up, and is embedded in template molecule and is formed by rigid macromolecule material;(3) using method physically or chemically by template
Molecule is eluted out from high molecular material, leaves three-dimensional cavity at the spatial position and structure occupied by template molecule, should
Hole matches in size, shape and configuration aspects and template molecule.Since function monomer is with mutual with template molecule functional group
The functional functional group of benefit, therefore synthesized molecularly imprinted polymer is capable of being identified and being tied with template molecule for specificity
It closes.
Electrochemical sensor is by working electrode, reference electrode and to the three-electrode system that electrode is constituted, and is a kind of utilization
Electrochemical signals change the device detected to sample, and with high sensitivity, preparation is easy, at low cost, is easy to miniature
Change, be suitble to the features such as on-site test, is one of biosensor technique the most mature so far.But so far not
About the imprinted polymer modified electrode system for preparing simple, energy saving, clean and environmental protection highly sensitive detection myoglobins
The relevant report of Preparation Method.
Summary of the invention
The present invention be directed to the above-mentioned technical problem present in the prior art, provide it is a kind of prepare it is simple, energy saving, clear
The preparation method of the imprinted polymer modified electrode of the highly sensitive detection myoglobins of clean environmental protection.
The technical solution of the invention is as follows: a kind of imprinted polymer modified electrode of highly sensitive detection myoglobins
Preparation method successively carries out in accordance with the following steps:
A. 5mg chitosan is dissolved in 2ml 0.2mol/L acetic acid solution, obtains the acetic acid solution of chitosan;Take 1 ~ 2mg foam
For graphene dispersion in the acetic acid solution of chitosan, adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;First is mixed
Solution drop coating is closed to clean naked gold electrode surface, is statically placed in shady place 12h, Au/3DG/Cs electrode is made;By Au/3DG/Cs
It is used as to electrode, saturated calomel electrode as working electrode, platinum filament as reference electrode, at room temperature, is containing 0.1mol/L
HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, obtains Au/3DG/
Cs/nAu electrode;
B. 1mg graphene is dissolved in the cetyl trimethylammonium bromide (CTAB) that 1ml pH is 7.0, mass fraction is 0.1%
PBS solution in, add the acetic acid solution of chitosan after forming black suspension shape, obtain the second mixed solution;By the second mixing
Solution drop coating stands 12h to glassy carbon electrode surface in the cool, obtains GCE/GR/CTAB/Cs electrode;
C. Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, obtains bromide modified electrode, then will contains
0.0125 ~ 0.2mol/L α-methacrylic acid, 0.05~0.8mg/mL myoglobins and 0.0025~0.04mol/L N, N- are sub-
The PBS solution of bisacrylamide is put into electrolytic cell, and gained bromide modified electrode is placed in electrolytic cell at room temperature
In solution, it is reference electrode that use GCE/GR/CTAB/Cs electrode, which be to electrode, saturated calomel electrode as working electrode, platinum filament,
At 0.185V, applies constant potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid solution of 0.5mol/L
Middle immersion 0.5h, then with ultrapure water to get the polymer modified electrode Au/3DG/ of highly sensitive detection myoglobins
PIPs。
The present invention has many advantages, such as to prepare simple, energy saving, clean and environmental protection, prepared imprinted polymer modified electrode
It, being capable of quick, highly sensitive detection myoglobins applied to electrochemistry trace sensor.The experimental results showed that myoglobins mark
The range of linearity of quasi- solution detection is 1.0 × 10-10~1.0×10-1Mg/L, detection are limited to 1.10076 × 10-11Mg/L(LOD,
S/N=3).
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1 in electrode production process, and the modified electrode of different phase is containing 5mmol/L [Fe
(CN)6]3-/4-7.0 PBS of+0.1mol/L KCl(PH) cyclic voltammogram in solution.
Fig. 2 is the selective schematic diagram of the polymer modified electrode of the embodiment of the present invention 1.
Fig. 3 be the differential pulse voltammetry curve A that the polymer modified electrode of the embodiment of the present invention 1 detects myoglobins and
Working curve B.
Specific embodiment
Embodiment 1:
The preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins of the invention, successively according to following step
It is rapid to carry out:
A. 5mg chitosan (Cs) is dissolved in 2ml 0.2mol/L acetic acid solution, obtains the acetic acid solution of chitosan;2mg is taken to steep
Foam graphene (3DG) is dispersed in the acetic acid solution of chitosan, and adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;
By the first mixed solution drop coating to clean naked gold electrode surface, it is statically placed in 12h at shady and cool dark, Au/3DG/Cs electrode is made;
Using Au/3DG/Cs as working electrode, platinum filament as, as reference electrode, at room temperature, containing to electrode, saturated calomel electrode
0.1mol/L HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, is obtained
To Au/3DG/Cs/nAu electrode;
B. 1mg graphene (GR) is dissolved in the cetyl trimethylammonium bromide that 1ml pH is 7.0, mass fraction is 0.1%
(CTAB) in PBS solution, the acetic acid solution of chitosan is added after formation black suspension shape, obtains the second mixed solution;By
Two mixed solution drop coatings stand 12h at shady and cool dark, obtain GCE/GR/CTAB/Cs electrode to glassy carbon electrode surface;
C. Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, obtains bromide modified electrode, then will contains
The PBS of 0.05mol/L α-methacrylic acid, 0.2 mg/mL myoglobins and 0.01mol/L N, N- methylene-bisacrylamide
Solution is put into electrolytic cell, and gained bromide modified electrode is placed in the solution in electrolytic cell at room temperature, uses GCE/GR/
It is reference electrode that CTAB/Cs electrode, which is to electrode, saturated calomel electrode as working electrode, platinum filament, at 0.185V, is applied permanent
Determine current potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid (OX) of 0.5mol/L
0.5h is impregnated in solution, to remove the myoglobins template in polymer, then with ultrapure water to get high sensitivity detection flesh
The polymer modified electrode Au/3DG/PIPs of Lactoferrin.
For the embodiment of the present invention 1 in electrode production process, the modified electrode of different phase is containing 5mmol/L [Fe
(CN)6]3-/4-7.0 PBS of+0 .1ml/L KCl(PH) cyclic voltammogram in solution is as shown in Figure 1.
Fig. 1 is the CV curve of modified electrode, and a pair of reversible redox occurs near 0.2V in naked gold electrode in curve 1
Peak be on naked gold electrode surface [FeCN)6]3-/4-The redox peaks of probe ion.Curve 2 is deposition decorated by nano-gold electrode CV
Curve, peak current are higher than curve 1, illustrate after depositing nanogold, the electric conductivity of modified electrode sharply increases.Curve 3 is initiator
The CV curve of modified gold electrode, peak current are lower than curve 1, are because self assembly initiator hinders probe ion to reach electrode table
Face.As shown in curve 4, the peak point current of polymer modified electrode is obviously dropped CV curve when polymerizeing with α-methacrylic acid
It is low, show after polymerizeing with α-methacrylic acid, form thick-layer on electrode surface polymer film, probe ion is hindered to reach electricity
Pole surface causes peak current to reduce.After myoglobins is eluted from polymer modified electrode, redox peak current increases curve 5
Add, this is attributed to the elution of myoglobins and forms trace gap after increasing conductivity.
In order to investigate the selectivity of Au/3DG/PIPs modified electrode obtained by the embodiment of the present invention, with lysozyme (Lyz) (MW
14.4kDa), hemoglobin (Hb) (MW 64kDa), bovine serum albumin(BSA) (BSA) (MW 66.44kDa), mouse antibodies (IgG)
(MW 150kDa) is compared as the chaff interferent of experiment.It is 10 by measurement concentration using differential pulse voltammetry-3mg/L
When not homologous protein to trace electrode (polymer modified electrode) and non-trace electrode (preparation method is identical as trace electrode,
Myoglobins is not added during only) difference of response signal studies the selectivity of the electrode obtained of the present invention, as a result such as Fig. 2 institute
Show.Fig. 2 can be seen that Au/3DG/PIPs modified electrode detection hemoglobin response signal Δ of the inventionIFor 21.70 μ A, divide
It is not 6.36,10.64,10.83 and 12.35 times of Lyz, Hb, BSA and IgG.The result shows that Au/3DG/PIPs modified electrode pair
Target protein (Mb) selectivity is more preferable.The selectivity of electrode is assessed by imprinting factor (K), and accounting equation is K=ΔI
(PIPs/Au)/ΔI(NIPs/Au), wherein ΔIIt (NIPs) is response signal of the Au/3DG/NIPs modified electrode to protein,
And ΔIIt (PIPs) is response signal of the Au/3DG/PIPs modified electrode to protein.By calculating Lyz, Hb, BSA, IgG and Mb
K value be respectively 2.21,1.40,1.43,1.46 and 8.23.The K value of Mb is maximum, shows that Au/3DG/PIPs modified electrode detects
The ability of Mb is significantly larger than Au/3DG/NIPs modified electrode.
Fig. 3 be the differential pulse voltammetry curve A that the polymer modified electrode of the embodiment of the present invention 1 detects myoglobins and
Working curve B.
In Fig. 3 A, the corresponding myoglobin concentration of curve 1~11 is respectively 0,10-10, 10-9, 10-8, 10-7, 10-6, 10-5,
10-4, 10-3, 10-2, 10-1mg/L.As seen from Figure 3, as Mb concentration increases, DPV peak current reduces instead.According to DPV
Peak current difference (response signal, ΔI) map with Mb log concentration, obtain the working curve (figure of modified electrode detection Mb
Shown in 3B).The result shows that Au/3DG/PIPs modified electrode is 1.0 × 10 for the concentration linear response range of Mb-10~1.0×
10-1Mg/L, equation of linear regression are ΔI(μA)=3.07972logC(mg/L)+32.45557, related coefficient 0.99972.
Detection is limited to 1.10076 × 10-11Mg/L(LOD, S/N=3).
Embodiment 2:
The preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins of the invention, successively according to following step
It is rapid to carry out:
A. 5mg chitosan (Cs) is dissolved in 2ml 0.2mol/L acetic acid solution, obtains the acetic acid solution of chitosan;1mg is taken to steep
Foam graphene (3DG) is dispersed in the acetic acid solution of chitosan, and adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;
By the first mixed solution drop coating to clean naked gold electrode surface, it is statically placed in 12h at shady and cool dark, Au/3DG/Cs electrode is made;
Using Au/3DG/Cs as working electrode, platinum filament as, as reference electrode, at room temperature, containing to electrode, saturated calomel electrode
0.1mol/L HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, is obtained
To Au/3DG/Cs/nAu electrode;
B. 1mg graphene (GR) is dissolved in the cetyl trimethylammonium bromide that 1ml pH is 7.0, mass fraction is 0.1%
(CTAB) in PBS solution, the acetic acid solution of chitosan is added after formation black suspension shape, obtains the second mixed solution;By
Two mixed solution drop coatings stand 12h at shady and cool dark, obtain GCE/GR/CTAB/Cs electrode to glassy carbon electrode surface;
C. Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, obtains bromide modified electrode, then will contains
The PBS of 0.1mol/L α-methacrylic acid, 0.4 mg/mL myoglobins and 0.02mol/L N, N- methylene-bisacrylamide
Solution is put into electrolytic cell, and gained bromide modified electrode is placed in the solution in electrolytic cell at room temperature, uses GCE/GR/
It is reference electrode that CTAB/Cs electrode, which is to electrode, saturated calomel electrode as working electrode, platinum filament, at 0.185V, is applied permanent
Determine current potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid (OX) of 0.5mol/L
0.5h is impregnated in solution, to remove the myoglobins template in polymer, then with ultrapure water to get high sensitivity detection flesh
The polymer modified electrode Au/3DG/PIPs of Lactoferrin.
Embodiment 3:
The preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins of the invention, successively according to following step
It is rapid to carry out:
A. 5mg chitosan (Cs) is dissolved in 2ml 0.2mol/L acetic acid solution, obtains the acetic acid solution of chitosan;2mg is taken to steep
Foam graphene (3DG) is dispersed in the acetic acid solution of chitosan, and adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;
By the first mixed solution drop coating to clean naked gold electrode surface, it is statically placed in 12h at shady and cool dark, Au/3DG/Cs electrode is made;
Using Au/3DG/Cs as working electrode, platinum filament as, as reference electrode, at room temperature, containing to electrode, saturated calomel electrode
0.1mol/L HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, is obtained
To Au/3DG/Cs/nAu electrode;
B. 1mg graphene (GR) is dissolved in the cetyl trimethylammonium bromide that 1ml pH is 7.0, mass fraction is 0.1%
(CTAB) in PBS solution, the acetic acid solution of chitosan is added after formation black suspension shape, obtains the second mixed solution;By
Two mixed solution drop coatings stand 12h at shady and cool dark, obtain GCE/GR/CTAB/Cs electrode to glassy carbon electrode surface;
C. Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, obtains bromide modified electrode, then will contains
The PBS of 0.2mol/L α-methacrylic acid, 0.8 mg/mL myoglobins and 0.04mol/L N, N- methylene-bisacrylamide
Solution is put into electrolytic cell, and gained bromide modified electrode is placed in the solution in electrolytic cell at room temperature, uses GCE/GR/
It is reference electrode that CTAB/Cs electrode, which is to electrode, saturated calomel electrode as working electrode, platinum filament, at 0.185V, is applied permanent
Determine current potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid (OX) of 0.5mol/L
0.5h is impregnated in solution, to remove the myoglobins template in polymer, then with ultrapure water to get high sensitivity detection flesh
The polymer modified electrode Au/3DG/PIPs of Lactoferrin.
Embodiment 4:
The preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins of the invention, successively according to following step
It is rapid to carry out:
A. 5mg chitosan (Cs) is dissolved in 2ml 0.2mol/L acetic acid solution, obtains the acetic acid solution of chitosan;2mg is taken to steep
Foam graphene (3DG) is dispersed in the acetic acid solution of chitosan, and adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;
By the first mixed solution drop coating to clean naked gold electrode surface, it is statically placed in 12h at shady and cool dark, Au/3DG/Cs electrode is made;
Using Au/3DG/Cs as working electrode, platinum filament as, as reference electrode, at room temperature, containing to electrode, saturated calomel electrode
0.1mol/L HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, is obtained
To Au/3DG/Cs/nAu electrode;
B. 1mg graphene (GR) is dissolved in the cetyl trimethylammonium bromide that 1ml pH is 7.0, mass fraction is 0.1%
(CTAB) in PBS solution, the acetic acid solution of chitosan is added after formation black suspension shape, obtains the second mixed solution;By
Two mixed solution drop coatings stand 12h at shady and cool dark, obtain GCE/GR/CTAB/Cs electrode to glassy carbon electrode surface;
C. Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, obtains bromide modified electrode, then will contains
0.025mol/L α-methacrylic acid, 0.1 mg/mL myoglobins and 0.005mol/L N, N- methylene-bisacrylamide
PBS solution is put into electrolytic cell, and gained bromide modified electrode is placed in the solution in electrolytic cell at room temperature, uses GCE/GR/
It is reference electrode that CTAB/Cs electrode, which is to electrode, saturated calomel electrode as working electrode, platinum filament, at 0.185V, is applied permanent
Determine current potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid (OX) of 0.5mol/L
0.5h is impregnated in solution, to remove the myoglobins template in polymer, then with ultrapure water to get high sensitivity detection flesh
The polymer modified electrode Au/3DG/PIPs of Lactoferrin.
Embodiment 5:
The preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins of the invention, successively according to following step
It is rapid to carry out:
A. 5mg chitosan (Cs) is dissolved in 2ml 0.2mol/L acetic acid solution, obtains the acetic acid solution of chitosan;1mg is taken to steep
Foam graphene (3DG) is dispersed in the acetic acid solution of chitosan, and adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;
By the first mixed solution drop coating to clean naked gold electrode surface, it is statically placed in 12h at shady and cool dark, Au/3DG/Cs electrode is made;
Using Au/3DG/Cs as working electrode, platinum filament as, as reference electrode, at room temperature, containing to electrode, saturated calomel electrode
0.1mol/L HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, is obtained
To Au/3DG/Cs/nAu electrode;
B. 1mg graphene (GR) is dissolved in the cetyl trimethylammonium bromide that 1ml pH is 7.0, mass fraction is 0.1%
(CTAB) in PBS solution, the acetic acid solution of chitosan is added after formation black suspension shape, obtains the second mixed solution;By
Two mixed solution drop coatings stand 12h at shady and cool dark, obtain GCE/GR/CTAB/Cs electrode to glassy carbon electrode surface;
C. Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, obtains bromide modified electrode, then will contains
0.0125mol/L α-methacrylic acid, 0.05 mg/mL myoglobins and 0.0025mol/L N, N- methylene-bisacrylamide
PBS solution be put into electrolytic cell, gained bromide modified electrode is placed in the solution in electrolytic cell at room temperature, uses GCE/
It is reference electrode that GR/CTAB/Cs electrode, which is to electrode, saturated calomel electrode as working electrode, platinum filament, at 0.185V, is applied
Add constant potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid (OX) of 0.5mol/L
0.5h is impregnated in solution, to remove the myoglobins template in polymer, then with ultrapure water to get high sensitivity detection flesh
The polymer modified electrode Au/3DG/PIPs of Lactoferrin.
Claims (1)
1. a kind of preparation method of the imprinted polymer modified electrode of highly sensitive detection myoglobins, successively in accordance with the following steps
It carries out:
5mg chitosan is dissolved in 2ml 0.2mol/L acetic acid solution, the acetic acid solution of chitosan is obtained;Take 1 ~ 2mg foam stone
Black alkene is dispersed in the acetic acid solution of chitosan, and adjusting pH with NaOH or HCl is 6.0, obtains the first mixed solution;By the first mixing
Solution drop coating is statically placed in shady place 12h to clean naked gold electrode surface, and Au/3DG/Cs electrode is made;Au/3DG/Cs is made
It is used as to electrode, saturated calomel electrode for working electrode, platinum filament as reference electrode, at room temperature, is containing 0.1mol/L
HAuCl6·6H2In the solution of O, the electro-deposition of 400s is carried out under the current potential of -0.9V using chronoamperometry, obtains Au/3DG/
Cs/nAu electrode;
The PBS that 1mg graphene is dissolved in the cetyl trimethylammonium bromide that 1ml pH is 7.0, mass fraction is 0.1% is molten
In liquid, the acetic acid solution of chitosan is added after formation black suspension shape, obtains the second mixed solution;By the second mixed solution drop coating
To glassy carbon electrode surface, 12h is stood in the cool, obtains GCE/GR/CTAB/Cs electrode;
Au/3DG/Cs/nAu electrode first is modified with the bromine-containing compound that sulfydryl blocks, bromide modified electrode is obtained, then will contain
0.0125 ~ 0.2mol/L α-methacrylic acid, 0.05~0.8mg/mL myoglobins and 0.0025~0.04mol/L N, N- are sub-
The PBS solution of bisacrylamide is put into electrolytic cell, and gained bromide modified electrode is placed in electrolytic cell at room temperature
In solution, it is reference electrode that use GCE/GR/CTAB/Cs electrode, which be to electrode, saturated calomel electrode as working electrode, platinum filament,
At 0.185V, applies constant potential 50min, the bromide modified electrode of polymer must be deposited;
D. the bromide modified electrode for depositing upper polymer is taken out, is cleaned with ultrapure water, is placed in the oxalic acid solution of 0.5mol/L
Middle immersion 0.5h, then with ultrapure water to get the polymer modified electrode Au/3DG/ of highly sensitive detection myoglobins
PIPs。
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