CN108007992B - Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrode of hemoglobin - Google Patents
Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrode of hemoglobin Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of poly ion liquid@3D nanogold cluster modified electrode for detecting hemoglobin, successively carries out in accordance with the following steps: preparing glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode；Three-dimensional manometer gold cluster modified electrode is prepared using electrodeposition process；Prepare poly ion liquid@3D nanogold cluster modified electrode.Instrument and equipment needed for the present invention is easy, and operating procedure is simple.Due to the special nature of ionic liquid used and the specific structure of 3D nanogold cluster, make poly ion liquid@3D nanogold cluster modified electrode obtained that can identify hemoglobin well, it is applied to the electrochemical sensor of detection hemoglobin as sensing electrode, it being capable of quick and high sensitivity detection hemoglobin.
Description
Technical field
The present invention relates to a kind of preparation method of electrochemical sensor sensing electrode, especially one kind can quick, Gao Ling
Sensitivity detects the preparation method of the poly ion liquid@3D nanogold cluster modified electrode of hemoglobin.
Background technique
Hemoglobin is a kind of key protein for being responsible for delivery oxygen in higher organism body, it participates in CO in blood2Fortune
Defeated and pH value of blood adjusting, clinically, the detection of hemoglobin can be cardiovascular disease, pulmonary disease, certain tumour diseases
Disease etc. provides diagnosis basis, and therefore, content of hemoglobin is of great significance in sensitive, accurate detection serum.
The common detection method of hemoglobin has radio immunoassay, enzyme-linked immunosorbent assay and molecular engram at present
Technology etc., radio immunoassay and enzyme-linked immunosorbent assay need to prepare antibody, are occurred using hemoglobin and its antibody
Idiosyncrasy (being immunoreacted) is detected.The Antibody preparation period is long, and the price is very expensive for especially monoclonal antibody, together
When, radiommunoassay needs special experimental laboratory, and it is serious to operator's somatic damage, and ELISA time-consuming is more.
Molecular imprinting technology is a kind of new and effective isolation technics, and centrifugation derives from molecularly imprinted polymer (molecularly
Imprinted polymers, MIP) possessed by similar natural antibody or enzyme molecular recognition function.
The core of molecular imprinting technology is the preparation of MIP, and existing preparation method is by template molecule and function monomer
Interact (such as hydrogen bond, Van der Waals force, electrostatic interaction) formation compound, and function monomer is made under the action of initiator, is handed over
Connection agent polymerize to form the polymer with appropriate rigidity, finally removes template molecule under certain condition, is just formed in polymer
With the multiple complementary hole such as template molecule size, space structure, distribution of charges, to have identification selection to template molecule
Property." activity "/controllable free-radical polymerisation is research field very active in current polymer science, and atom transferred free radical is poly-
Closing (ATRP) is the effective means for realizing " activity "/controllable polymerization, it is using organohalogen compounds as initiator, lower valency transition metal
Complex (further including the complex of Fe, Co, Ti etc. in addition to common Cu) is halogen atom carrier (transition-metal catalyst), is led to
Oxidization-reduction reaction, establishes dynamic equilibrium between reactive species and suspend mode kind, can end group to polymer, composition, structure,
Molecular weight etc. control effectively；Meanwhile ATRP can be realized the initiation of the surface under water phase, room temperature, certain pH, in-situ polymerization
Deng.Have the relevant report that three-electrode system is introduced to ATRP at present, disclosed operating method is as follows: initiator is modified into electricity
Pole constitutes three-electrode system to electrode as working electrode, working electrode and reference electrode；This three-electrode system is put by function
Can in the ionic liquid that is configured to of monomer, crosslinking agent, template molecule and lower valency transient metal complex, working electrode with
Constant potential certain time between reference electrode, obtains polymer；Again with elution template molecule and Removal of catalyst, obtain
To imprinted polymer.
Although having the record for being applied to electrochemical sensor using molecularly imprinted polymer as sensing element at present, so far
Until the present, there are no the correlations of the electrochemical sensor sensing electrode of quick about preparation, highly sensitive detection hemoglobin
Report.
Summary of the invention
The present invention is to solve above-mentioned technical problem present in the prior art, and providing one kind can be quick, highly sensitive
Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrode of hemoglobin.
The technical solution of the invention is as follows: a kind of poly ion liquid@3D nanogold cluster modification electricity detecting hemoglobin
The preparation method of pole, it is characterised in that successively carry out in accordance with the following steps:
A. prepare glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode: using glass-carbon electrode as working electrode, platinum filament is pair
Electrode, saturated calomel electrode are reference electrode, are containing 1 × 10–5~1 × 10–4The acetate salt buffer of mol/L toluidine blue is molten
In liquid, with current potential for -0.8V~1.3V, sweeping speed is 50mV/s, and 50 circle of scanning carries out cyclic voltammetric electrochemical polymerization, obtains glass
Carbon/ploymerized toluidine blue modified electrode；Then again using glass carbon/ploymerized toluidine blue as working electrode, platinum filament is to be saturated sweet to electrode
Mercury electrode is reference electrode, is containing 0.002~0.05mol/L HPtCl6·6H2Timing is utilized in O acetate buffer solution
Current method electro-deposition Platinum Nanoparticles under the current potential of -0.7V obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode；
B. three-dimensional manometer gold cluster modified electrode is prepared using electrodeposition process: is containing 0.005~0.1 mol/L
CuSO4·5H2O and 0.2~1.5 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V
Constant potential electro-deposition 400s is carried out in naked gold surface, the electrode after electro-deposition is then placed in 0.5~10mol/L nitric acid solution
1 ~ 8h of middle immersion obtains three-dimensional manometer gold cluster modified electrode；
C. it poly ion liquid@3D nanogold cluster modified electrode: is modified first with the bromine-containing compound of sulfydryl sealing end three-dimensional
Nanogold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then it will contain 0.5~5 moL/L1- ethylene
Base -3- propyl sulfonic acid imidazole salts or 1- methyl -3-(4- vinyl benzyl) imidazoles chlorine ionic liquid, 0.5~10mg/mL it is blood red
Albumen and 0.2~5 moL/L N, N- methylene-bisacrylamide mixed solution are put into electrolytic cell, at room temperature, by bromine-containing compound
Modification three-dimensional manometer gold cluster electrode is inserted into the mixed solution, while with glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, under -0.51V, applies constant potential 2.5h；By table
Face has the bromine-containing compound modification three-dimensional manometer gold cluster electrode of polymer to take out, and being immersed in volumetric concentration after being cleaned with ultrapure water is
2h in the acetum of 10% lauryl sodium sulfate, then with naturally dry after ultrapure water, obtain poly ion liquid@3D
Nanogold cluster modified electrode.
Instrument and equipment needed for the present invention is easy, and operating procedure is simple.Due to the special nature and 3D of ionic liquid used
The specific structure of nanogold cluster makes poly ion liquid@3D nanogold cluster modified electrode obtained that can identify hemoglobin well,
It is applied to the electrochemical sensor of detection hemoglobin as sensing electrode, it being capable of quick and high sensitivity detection hemoglobin.
Detailed description of the invention
Fig. 1 is in the electrode production process of the embodiment of the present invention 1, different modifying electrode containing 5mM [Fe CN)6]3-/4-
7.0 PBS of+0.1 M KCl(PH) cyclic voltammetry curve figure in solution.
Fig. 2 is the poly ion liquid@3D nanogold cluster modified electrode surface scan electron microscope of the embodiment of the present invention 1.
Fig. 3 is the selective schematic diagram of the poly ion liquid@3D nanogold cluster modified electrode of the embodiment of the present invention 1.
Fig. 4 is the difference that the poly ion liquid@3D nanogold cluster modified electrode of the embodiment of the present invention 1 detects hemoglobin
Sectors rushes volt-ampere curve (A) and working curve (B) figure.
Specific embodiment
Embodiment 1:
A kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrode detecting hemoglobin, successively according to such as
Lower step carries out:
A. it prepares glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode: clean glass-carbon electrode is made
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, is containing 5 × 10–5Mol/L toluidine blue (TB)
Acetate buffer solution (ABS, pH 5.0) in, with current potential be -0.8V~1.3V, sweep speed be 50mV/s, scanning 50 enclose into
Row cyclic voltammetric (CV) electrochemical polymerization obtains glass carbon/ploymerized toluidine blue (GCE/PTB) modified electrode；Then again with glass carbon/poly-
Toluidine blue (GCE/PTB) is used as working electrode, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, is being contained
0.01mol/L HPtCl6·6H2Utilize chronoamperometry in the current potential of -0.7V in O acetate buffer solution (ABS, pH 5.0)
Lower electro-deposition Platinum Nanoparticles obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode；
B. three-dimensional (3D) nanogold cluster modified electrode is prepared using electrodeposition process: is containing 0.02 mol/L CuSO4·
5H2O and 0.8 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold
Surface carries out constant potential electro-deposition 400s, and then the electrode after electro-deposition is placed in 3mol/L nitric acid solution and impregnates 3h, to
Cu is removed, three-dimensional manometer gold cluster modified electrode is obtained；
C. it prepares poly ion liquid@3D nanogold cluster modified electrode: being modified first with the bromine-containing compound of sulfydryl sealing end
Three-dimensional manometer gold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then it will contain 1moL/L1- vinyl-
Ionic liquid, 2mg/mL hemoglobin and 1moL/L N, the N- methylene-bisacrylamide of 3- propyl sulfonic acid imidazole salts mix molten
Liquid is put into electrolytic cell, at room temperature, bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into the mixed solution, simultaneously
Using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electricity
Pole under -0.51V, applies constant potential 2.5h；There is the bromine-containing compound modification three-dimensional manometer gold cluster electrode of polymer to take on surface
Out, it is immersed in 2h in the acetum for the lauryl sodium sulfate that volumetric concentration is 10% after being cleaned with ultrapure water, then uses ultrapure water
Naturally dry after flushing obtains poly ion liquid@3D nanogold cluster modified electrode.
Different modifying electrode in the electrode production process of the embodiment of the present invention 1 containing 5mM [Fe CN)6]3-/4-+0.1
7.0 PBS of M KCl(PH) cyclic voltammetry curve in solution is as shown in Figure 1.
In Fig. 1, curve 1 is the CV curve of naked gold electrode in the solution, which occurs a pair of reversible near 0.2 V
[Fe(CN)6]3-/4-Probe ion redox peaks；Curve 2 is the CV curve of 3D nanogold cluster modified electrode, and peak current is higher than song
Line 1, after illustrating 3D nanogold cluster, electrode conductivuty is sharply increased；Curve 3 is poly ion liquid@when not removing hemoglobin
The CV curve of 3D nanogold cluster modified electrode, peak current are significantly lower than curve 2, the reason is that poly ion liquid film is as inertia electricity
Son and mass transfer barrier layer hinder probe ion and spread to electrode surface；Curve 4 is 1 gained polyion liquid of the embodiment of the present invention
The CV curve of body@3D nanogold cluster modified electrode, peak current are apparently higher than curve 3, after removing hemoglobin, electrode surface
There is imprinted cavity, is conducive to probe ion and reaches electrode surface, peak current is caused to increase.
The poly ion liquid@3D nanogold cluster modified electrode surface scan electron microscope of the embodiment of the present invention 1 is as shown in Figure 2.
As can be seen from Figure 2 the surface topography of poly ion liquid@3D nanogold cluster modified electrode obtained by the embodiment of the present invention 1,3D
Nanogold cluster is in dendroid, and electrode surface has many holes, this is after hemoglobin is removed, and the imprinted cavity left (is known
Other site).
In order to study poly ion liquid@3D nanogold cluster modified electrode to the selectivity of new hemoglobin (Hb), in experiment
With lysozyme (LYZ) (14.4 kDa of MW), human serum albumins (HSA) (69 kDa of MW), human immunoglobulin(HIg) (HIgG) (MW
155 kDa) it is used as chaff interferent.Trace electrode (3D nanometers of poly ion liquid@of present invention gained is utilized using differential pulse voltammetry
Golden cluster modified electrode) and non-trace electrode (preparation method is identical as trace electrode, and hemoglobin is not added when only preparing) measurement
Same concentrations (102mg·L -1) not homologous protein response signal difference, as a result as shown in Figure 3.It can from Fig. 3
Trace electrode out, detection hemoglobin response signal Δ I are 9.733 μ A, are the 4.79 of HIgG, Lyz and HSA, 5.84 Hes respectively
6.21 again.The result shows that the poly ion liquid@3D nanogold cluster modified electrode of the embodiment of the present invention 1 is blood red to target protein
Protein selectivity is more preferable.
The selectivity of electrode can also by imprinting factor (β) assessed.Accounting equation isβ=ΔI(trace)/Δ
I(non-trace), wherein Δ I(non-trace)It is response signal of the non-trace electrode to protein, and Δ I(trace)Be the embodiment of the present invention 1 gather from
Response signal of the sub- liquid@3D nanogold cluster modified electrode to protein.As shown in figure 3, by equation calculation HIgG, Lyz,
HSA's and HbβValue is respectively 1.05,1.09,1.38 and 8.85.The k value of Hb is maximum, shows poly ion liquid@3D nanogold cluster
The ability of modified electrode detection Hb is significantly larger than non-trace electrode.The above result shows that poly ion liquid@3D nanogold cluster is modified
Electrode only has good selectivity to target protein.
Fig. 4 is the difference that the poly ion liquid@3D nanogold cluster modified electrode of the embodiment of the present invention 1 detects hemoglobin
Sectors rushes volt-ampere curve (A) and working curve (B) figure.
In Fig. 4 (A), the corresponding hemoglobin concentration of curve 1~16 is respectively 0,10- 15,10- 14, 10- 13,10- 12,
10- 11,10- 10, 10- 9, 10- 8, 10-7,10- 6, 10- 5, 10- 4, 10- 3,10- 2, 10- 1mg/L.As can be seen that with
The increase differential pulse voltammetry curve peak current reduction of Hb concentration.This is because in conjunction with the poly ion liquid@3D after hemoglobin
Nanogold cluster modified electrode, imprinted cavity are occupied by Hb, hinder probe ion to reach electrode surface, to reduce the difference of electrode
Sectors rushes volt-ampere curve peak point current.Hb concentration is higher, and imprinted cavity is occupied more, and peak point current decline is more.Fig. 4
It (B) is relationship of the peak point current decaying (signal response, Δ I) with Hb log concentration.From Fig. 4 (B) it can be seen that the present invention is implemented
The concentration range of linearity of the poly ion liquid@3D nanogold cluster modified electrode detection hemoglobin of example 1 is 1.0 × 10- 15~1.0
×10- 1Mg/mL, equation of linear regression are ΔI (μA)=0.548log C (mg/mL)+12.676, related coefficient is
0.989.Find out from standard curve, detection is limited to (LOD, S/N=3) 3.13 × 10- 16 mg/mL。
Embodiment 2:
A kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrode detecting hemoglobin, successively according to such as
Lower step carries out:
A. it prepares glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode: clean glass-carbon electrode is made
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, is containing 2 × 10–5Mol/L toluidine blue (TB)
Acetate buffer solution (ABS, pH 5.0) in, with current potential be -0.8V~1.3V, sweep speed be 50mV/s, scanning 50 enclose into
Row cyclic voltammetric (CV) electrochemical polymerization obtains glass carbon/ploymerized toluidine blue (GCE/PTB) modified electrode；Then again with glass carbon/poly-
Toluidine blue (GCE/PTB) is used as working electrode, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, is being contained
0.004mol/L HPtCl6·6H2Utilize chronoamperometry in the electricity of -0.7V in O acetate buffer solution (ABS, pH 5.0)
The lower electro-deposition Platinum Nanoparticles in position, obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode；
B. three-dimensional (3D) nanogold cluster modified electrode is prepared using electrodeposition process: is containing 0.01 mol/L CuSO4·
5H2O and 0.4 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold
Surface carries out constant potential electro-deposition 400s, and then the electrode after electro-deposition is placed in 1mol/L nitric acid solution and impregnates 8h, to
Cu is removed, three-dimensional manometer gold cluster modified electrode is obtained；
C. it prepares poly ion liquid@3D nanogold cluster modified electrode: being modified first with the bromine-containing compound of sulfydryl sealing end
Three-dimensional manometer gold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then it will contain 0.6moL/L1- ethylene
Ionic liquid, 0.8mg/mL hemoglobin and 0.4moL/L N, the N- methylene-bisacrylamide of base -3- propyl sulfonic acid imidazole salts
Mixed solution is put into electrolytic cell, at room temperature, bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into the mixed solution
In, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to electrode, and saturated calomel electrode is
Reference electrode under -0.51V, applies constant potential 2.5h；There is the bromine-containing compound of polymer to modify three-dimensional manometer gold cluster on surface
Electrode takes out, and 2h in the acetum for the lauryl sodium sulfate that volumetric concentration is 10% is immersed in after being cleaned with ultrapure water, then use
Naturally dry after ultrapure water obtains poly ion liquid@3D nanogold cluster modified electrode.
Embodiment 3:
A kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrode detecting hemoglobin, successively according to such as
Lower step carries out:
A. it prepares glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode: clean glass-carbon electrode is made
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, is containing 4 × 10–5Mol/L toluidine blue (TB)
Acetate buffer solution (ABS, pH 5.0) in, with current potential be -0.8V~1.3V, sweep speed be 50mV/s, scanning 50 enclose into
Row cyclic voltammetric (CV) electrochemical polymerization obtains glass carbon/ploymerized toluidine blue (GCE/PTB) modified electrode；Then again with glass carbon/poly-
Toluidine blue (GCE/PTB) is used as working electrode, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, is being contained
0.008mol/L HPtCl6·6H2Utilize chronoamperometry in the electricity of -0.7V in O acetate buffer solution (ABS, pH 5.0)
The lower electro-deposition Platinum Nanoparticles in position, obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode；
B. three-dimensional (3D) nanogold cluster modified electrode is prepared using electrodeposition process: is containing 0.015 mol/L CuSO4·
5H2O and 0.6 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold
Surface carries out constant potential electro-deposition 400s, and then the electrode after electro-deposition is placed in 2mol/L nitric acid solution and impregnates 5h, to
Cu is removed, three-dimensional manometer gold cluster modified electrode is obtained；
C. it prepares poly ion liquid@3D nanogold cluster modified electrode: being modified first with the bromine-containing compound of sulfydryl sealing end
Three-dimensional manometer gold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then by 0.8 moL/L ionic liquid
1- methyl -3-(4- vinyl benzyl) imidazoles chlorine ionic liquid, 1.5mg/mL hemoglobin and 0.8moL/L N, N- methylene
Bisacrylamide mixed solution is put into electrolytic cell, at room temperature, bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into institute
It states in mixed solution, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to electrode, saturation
Calomel electrode is reference electrode, under -0.51V, applies constant potential 2.5h；Surface is had to the bromine-containing compound modification three of polymer
It ties up nanogold cluster electrode to take out, the acetic acid that the lauryl sodium sulfate that volumetric concentration is 10% is immersed in after being cleaned with ultrapure water is molten
2h in liquid, then with naturally dry after ultrapure water, obtain poly ion liquid@3D nanogold cluster modified electrode.
Embodiment 4:
A. it prepares glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode: clean glass-carbon electrode is made
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, is containing 6 × 10–5Mol/L toluidine blue (TB)
Acetate buffer solution (ABS, pH 5.0) in, with current potential be -0.8V~1.3V, sweep speed be 50mV/s, scanning 50 enclose into
Row cyclic voltammetric (CV) electrochemical polymerization obtains glass carbon/ploymerized toluidine blue (GCE/PTB) modified electrode；Then again with glass carbon/poly-
Toluidine blue (GCE/PTB) is used as working electrode, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, is being contained
0.02mol/L HPtCl6·6H2Utilize chronoamperometry in the current potential of -0.7V in O acetate buffer solution (ABS, pH 5.0)
Lower electro-deposition Platinum Nanoparticles obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode；
B. three-dimensional (3D) nanogold cluster modified electrode is prepared using electrodeposition process: is containing 0.05 mol/L CuSO4·
5H2O and 1mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked golden watch
Face carries out constant potential electro-deposition 400s, and then the electrode after electro-deposition is placed in 5mol/L nitric acid solution and impregnates 2h, to remove
Cu is removed, three-dimensional manometer gold cluster modified electrode is obtained；
C. it prepares poly ion liquid@3D nanogold cluster modified electrode: being modified first with the bromine-containing compound of sulfydryl sealing end
Three-dimensional manometer gold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then by 2 moL/L ionic liquid 1-
Methyl -3-(4- vinyl benzyl) imidazoles chlorine ionic liquid, 5mg/mL hemoglobin and 2moL/L N, N- methylene bisacrylamide
Amide mixed solution is put into electrolytic cell, at room temperature, bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into the mixing
In solution, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to be saturated calomel electricity to electrode
Extremely reference electrode under -0.51V, applies constant potential 2.5h；There is the bromine-containing compound of polymer to modify three-dimensional manometer on surface
Golden cluster electrode takes out, and 2h in the acetum for the lauryl sodium sulfate that volumetric concentration is 10% is immersed in after being cleaned with ultrapure water,
Again with naturally dry after ultrapure water, poly ion liquid@3D nanogold cluster modified electrode is obtained.
Embodiment 5:
A. it prepares glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode: clean glass-carbon electrode is made
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, is containing 8 × 10–5Mol/L toluidine blue (TB)
Acetate buffer solution (ABS, pH 5.0) in, with current potential be -0.8V~1.3V, sweep speed be 50mV/s, scanning 50 enclose into
Row cyclic voltammetric (CV) electrochemical polymerization obtains glass carbon/ploymerized toluidine blue (GCE/PTB) modified electrode；Then again with glass carbon/poly-
Toluidine blue (GCE/PTB) is used as working electrode, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, is being contained
0.04mol/L HPtCl6·6H2Utilize chronoamperometry in the current potential of -0.7V in O acetate buffer solution (ABS, pH 5.0)
Lower electro-deposition Platinum Nanoparticles obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles (GCE/PTB/nPt) modified electrode；
B. three-dimensional (3D) nanogold cluster modified electrode is prepared using electrodeposition process: is containing 0.08 mol/L CuSO4·
5H2O and 1.2mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold
Surface carries out constant potential electro-deposition 400s, and then the electrode after electro-deposition is placed in 9mol/L nitric acid solution and impregnates 1h, to
Cu is removed, three-dimensional manometer gold cluster modified electrode is obtained；
C. it prepares poly ion liquid@3D nanogold cluster modified electrode: being modified first with the bromine-containing compound of sulfydryl sealing end
Three-dimensional manometer gold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then by 4 moL/L ionic liquid 1-
Methyl -3-(4- vinyl benzyl) imidazoles chlorine ionic liquid, 8mg/mL hemoglobin and 4moL/L N, N- methylene bisacrylamide
Amide mixed solution is put into electrolytic cell, at room temperature, bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into the mixing
In solution, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to be saturated calomel electricity to electrode
Extremely reference electrode under -0.51V, applies constant potential 2.5h；There is the bromine-containing compound of polymer to modify three-dimensional manometer on surface
Golden cluster electrode takes out, and 2h in the acetum for the lauryl sodium sulfate that volumetric concentration is 10% is immersed in after being cleaned with ultrapure water,
Again with naturally dry after ultrapure water, poly ion liquid@3D nanogold cluster modified electrode is obtained.
Claims (1)
1. a kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrode for detecting hemoglobin, it is characterised in that according to
It is secondary to carry out in accordance with the following steps:
A. prepare glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode: using glass-carbon electrode as working electrode, platinum filament is to electricity
Pole, saturated calomel electrode are reference electrode, are containing 1 × 10–5~1 × 10–4The acetate buffer solution of mol/L toluidine blue
In, with current potential for -0.8V~1.3V, sweeping speed is 50mV/s, and 50 circle of scanning carries out cyclic voltammetric electrochemical polymerization, obtains glass
Carbon/ploymerized toluidine blue modified electrode；Then again using glass carbon/ploymerized toluidine blue as working electrode, platinum filament is to be saturated sweet to electrode
Mercury electrode is reference electrode, is containing 0.002~0.05mol/L HPtCl6·6H2Timing is utilized in O acetate buffer solution
Current method electro-deposition Platinum Nanoparticles under the current potential of -0.7V obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode；
B. three-dimensional manometer gold cluster modified electrode is prepared using electrodeposition process: is containing 0.005~0.1 mol/L CuSO4·5H2O
With 0.2~1.5 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in naked gold surface
Constant potential electro-deposition 400s is carried out, the electrode after electro-deposition is then placed in 1 ~ 8h of immersion in 0.5~10mol/L nitric acid solution,
Obtain three-dimensional manometer gold cluster modified electrode；
C. it prepares poly ion liquid@3D nanogold cluster modified electrode: being modified first with the bromine-containing compound of sulfydryl sealing end three-dimensional
Nanogold cluster modified electrode obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then it will contain 0.5~5 moL/L1- ethylene
Base -3- propyl sulfonic acid imidazole salts or 1- methyl -3-(4- vinyl benzyl) imidazoles chlorine ionic liquid, 0.5~10mg/mL it is blood red
Albumen and 0.2~5 moL/L N, N- methylene-bisacrylamide mixed solution are put into electrolytic cell, at room temperature, by bromine-containing compound
Modification three-dimensional manometer gold cluster electrode is inserted into the mixed solution, while with glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode
For working electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, under -0.51V, applies constant potential 2.5h；By table
Face has the bromine-containing compound modification three-dimensional manometer gold cluster electrode of polymer to take out, and being immersed in volumetric concentration after being cleaned with ultrapure water is
2h in the acetum of 10% lauryl sodium sulfate, then with naturally dry after ultrapure water, obtain poly ion liquid@3D
Nanogold cluster modified electrode.
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| CN108931564B (en) * | 2018-05-11 | 2020-10-30 | 辽宁师范大学 | 3D nickel-gold alloy nanocluster imprinting modified electrode for high-sensitivity detection of erythromycin |
| CN110231385A (en) * | 2019-05-23 | 2019-09-13 | 桂林理工大学 | A method of preparing coalescence crystalviolet-gold composite nano particle modified electrode |
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