CN108007992A - Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrodes of hemoglobin - Google Patents
Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrodes of hemoglobin Download PDFInfo
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- CN108007992A CN108007992A CN201711261292.4A CN201711261292A CN108007992A CN 108007992 A CN108007992 A CN 108007992A CN 201711261292 A CN201711261292 A CN 201711261292A CN 108007992 A CN108007992 A CN 108007992A
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Abstract
The present invention discloses a kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrodes for detecting hemoglobin, carries out in accordance with the following steps successively：Prepare 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 electrodes.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 clusters, obtained poly ion liquid@3D nanogold cluster modified electrodes are made to identify hemoglobin well, as sensing electrode be applied to detection hemoglobin electrochemical sensor, can quickly and high sensitivity detect hemoglobin.
Description
Technical field
The present invention relates to a kind of preparation method of electrochemical sensor sensing electrode, especially one kind can quickly, Gao Ling
The preparation method of the poly ion liquid@3D nanogold cluster modified electrodes of sensitivity detection hemoglobin.
Background technology
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 angiocardiopathy, pulmonary disease, some 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（That is immune response）It is detected.The Antibody preparation cycle is grown, and especially the price is very expensive for monoclonal antibody, together
When, radiommunoassay needs special experimental laboratory, serious to operating personnel's somatic damage, and ELISA take it is more.
Molecular imprinting technology is a kind of new and effective isolation technics, its centrifugation derives from molecularly imprinted polymer（molecularly
Imprinted polymers, MIP）Possessed similar natural antibody or the molecular recognition function of enzyme.
The core of molecular imprinting technology is the preparation of MIP, and existing preparation method is by template molecule and function monomer
Interaction（Such as hydrogen bond, Van der Waals force, electrostatic interaction）Compound is formed, function monomer is made under the action of initiator, is handed over
Connection agent polymerize to be formed with appropriate rigid polymer, 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, so as 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 gathers
Close（ATRP）It is the effective means for realizing " activity "/controllable polymerization, it is using organohalogen compounds as initiator, lower valency transition metal
Complex（In addition to common Cu, the complex of Fe, Co, Ti etc. are further included）For halogen atom carrier（Transition-metal catalyst）, lead to
Oxidization-reduction react, establish dynamic equilibrium between reactive species and dormancy kind, can to the end group of polymer, composition, structure,
Molecular weight etc. control effectively；Meanwhile ATRP can realize surface under water phase, room temperature, certain pH trigger, in-situ polymerization
Deng.Three-electrode system is introduced to the relevant report of ATRP at present, disclosed operating method is as follows：Initiator is modified into electricity
As working electrode, working electrode forms three-electrode system with reference electrode, to electrode for pole；This three-electrode system is put into by work(
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, obtain polymer；Again with elution template molecule and Removal of catalyst, obtain
To imprinted polymer.
Although it is applied to the record of electrochemical sensor using molecularly imprinted polymer as sensing element at present, so far
Untill the present, also not on preparing the correlation of quick, high sensitivity detection hemoglobin electrochemical sensor sensing electrode
Report.
The content of the invention
The present invention is to solve the above-mentioned technical problem present in the prior art, there is provided one kind can quickly, high sensitivity
Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrodes of hemoglobin.
The present invention technical solution be：A kind of poly ion liquid@3D nanogold cluster modification electricity for detecting hemoglobin
The preparation method of pole, it is characterised in that carry out in accordance with the following steps successively：
A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode is prepared：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 blues
In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 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 sweet to electrode, saturation
Mercury electrode is reference electrode, is containing 0.002~0.05mol/L HPtCl6·6H2Timing is utilized in O acetate buffer solutions
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：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 in naked gold
Surface carries out constant potential electro-deposition 400s, and then the electrode after electro-deposition is placed in 0.5~10mol/L salpeter solutions and soaks 1
~ 8h, obtains three-dimensional manometer gold cluster modified electrode；
C. poly ion liquid@3D nanogold cluster modified electrode：Three-dimensional manometer is modified first with the bromine-containing compound of sulfydryl end-blocking
Golden cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then 0.5~5 moL/L1- vinyl -3- will be contained
Propyl sulfonic acid imidazole salts or 1- methyl -3-（4- vinyl benzyls）Ionic liquid, the 0.5~10mg/mL hemoglobins of imidazoles chlorine
Electrolytic cell is put into 0.2~5 moL/L N, N- methylene-bisacrylamide mixed solutions, at room temperature, bromine-containing compound is modified
Three-dimensional manometer gold cluster electrode is inserted into the mixed solution, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as work
Make electrode, platinum filament is to electrode, and saturated calomel electrode is reference electrode, under -0.51V, applies constant potential 2.5h；Surface is had
The bromine-containing compound modification three-dimensional manometer gold cluster electrode of polymer takes out, and volumetric concentration is immersed in after being cleaned with ultra-pure water as 10%
Lauryl sodium sulfate acetum in 2h, then with naturally dry after ultrapure water, obtain 3D nanometers of poly ion liquid@
Golden 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 obtained poly ion liquid@3D nanogold cluster modified electrodes to identify hemoglobin well,
As sensing electrode be applied to detection hemoglobin electrochemical sensor, can quickly and high sensitivity detect hemoglobin.
Brief description of the drawings
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-
+0.1 M KCl（PH 7.0 PBS）Cyclic voltammetry curve figure in solution.
Fig. 2 is the poly ion liquid@3D nanogold cluster modified electrode surface scan electron microscopes of the embodiment of the present invention 1.
Fig. 3 is the selective schematic diagram of the poly ion liquid@3D nanogold cluster modified electrodes of the embodiment of the present invention 1.
Fig. 4 is the difference that the poly ion liquid@3D nanogold cluster modified electrodes of the embodiment of the present invention 1 detect hemoglobin
Sectors rushes volt-ampere curve（A）And working curve（B）Figure.
Embodiment
Embodiment 1：
A kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrodes for detecting hemoglobin, successively according to following step
It is rapid to carry out：
A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles are prepared（GCE/PTB/nPt）Modified electrode：Using clean glass-carbon electrode as work
Make electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 5 × 10 to electrode–5Mol/L toluidine blues（TB）Vinegar
Hydrochlorate buffer solution（ABS, pH 5.0）In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 is followed
Ring volt-ampere（CV）Electrochemical polymerization, obtains glass carbon/ploymerized toluidine blue（GCE/PTB）Modified electrode；Then again with glass carbon/polymethyl benzene
Amine is blue（GCE/PTB）As working electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 0.01mol/L to electrode
HPtCl6·6H2O acetate buffer solutions（ABS, pH 5.0）It is middle that using chronoamperometry, electro-deposition is received under the current potential of -0.7V
Miboplatin, obtains glass carbon/ploymerized toluidine blue/Platinum Nanoparticles（GCE/PTB/nPt）Modified electrode；
B. prepared using electrodeposition process three-dimensional（3D）Nanogold cluster modified electrode：Containing 0.02 mol/L CuSO4·5H2O
With 0.8 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold surface
Constant potential electro-deposition 400s is carried out, then the electrode after electro-deposition is placed in 3mol/L salpeter solutions and soaks 3h, to remove
Cu, obtains three-dimensional manometer gold cluster modified electrode；
C. poly ion liquid@3D nanogold cluster modified electrodes are prepared：Modified first with the bromine-containing compound of sulfydryl end-blocking three-dimensional
Nanogold cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then 1moL/L1- vinyl -3- sulphurs will be contained
Ionic liquid, 2mg/mL hemoglobins and 1moL/L N, N- the methylene-bisacrylamide mixed solutions of sour propyl imidazole salt are put
Enter electrolytic cell, at room temperature, 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 is working electrode, and platinum filament is that saturated calomel electrode is reference electrode to electrode ,-
Under 0.51V, apply constant potential 2.5h；The bromine-containing compound modification three-dimensional manometer gold cluster electrode that there is polymer on surface is taken out,
2h in the acetum for the lauryl sodium sulfate that volumetric concentration is 10% is immersed in after being cleaned with ultra-pure water, then is rushed with ultra-pure water
Rear naturally dry is washed, obtains poly ion liquid@3D nanogold cluster modified electrodes.
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
M KCl（PH 7.0 PBS）Cyclic voltammetry curve in solution is as shown in Figure 1.
In Fig. 1, curve 1 is the CV curves 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 curves of 3D nanogold cluster modified electrodes, and peak current is higher than song
Line 1, after illustrating 3D nanogold clusters, electrode conductivuty sharply increases；Curve 3 is poly ion liquid@when not removing hemoglobin
The CV curves of 3D nanogold cluster modified electrodes, 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 are spread to electrode surface；Curve 4 is 1 gained polyion liquid of the embodiment of the present invention
The CV curves of body@3D nanogold cluster modified electrodes, peak current is apparently higher than curve 3, after removing hemoglobin, electrode surface
There is imprinted cavity, be conducive to probe ion and reach electrode surface, cause peak current to increase.
The poly ion liquid@3D nanogold cluster modified electrode surface scan electron microscopes of the embodiment of the present invention 1 are as shown in Figure 2.
As can be seen from Figure 2 the surface topography of poly ion liquid@3D nanogold cluster modified electrodes 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, the imprinted cavity left（Know
Other site）.
In order to study poly ion liquid@3D nanogold cluster modified electrodes to new hemoglobin（Hb）Selectivity, in experiment
With lysozyme（LYZ）（MW 14.4 kDa）, human serum albumins（HSA）（MW 69 kDa）, human immunoglobulin(HIg)（HIgG）（MW
155 kDa）As chaff interferent.Trace electrode is utilized using differential pulse voltammetry（3D nanometers of poly ion liquid@of gained of the invention
Golden cluster modified electrode）With non-trace electrode（Preparation method is identical with trace electrode, and hemoglobin is not added with when simply preparing）Measure
Same concentrations（102mg·L -1）Not homologous protein response signal difference, the results are shown in Figure 3.Can from Fig. 3
Go out trace electrode, detection hemoglobin response signal Δ I is 9.733 μ A, is 4.79,5.84 Hes of HIgG, Lyz and HSA respectively
6.21 again.The result shows that the poly ion liquid@3D nanogold cluster modified electrodes of the embodiment of the present invention 1 are 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 the response signal of non-trace electrode pair 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 electrodes 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 values of Hb are maximum, show poly ion liquid@3D nanogold clusters
The ability of modified electrode detection Hb is significantly larger than non-trace electrode.Result above 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 electrodes of the embodiment of the present invention 1 detect hemoglobin
Sectors rushes volt-ampere curve（A）And working curve（B）Figure.
Fig. 4（A）In, 1~16 corresponding hemoglobin concentration of curve 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 with reference to the poly ion liquid@3D after hemoglobin
Nanogold cluster modified electrode, its imprinted cavity are occupied by Hb, hinder probe ion to reach electrode surface, so as 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 declines more.Fig. 4
（B）It is peak point current decay（Signal responds, Δ I）With the relation of Hb log concentrations.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 clusters 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 electrodes for detecting hemoglobin, successively according to following step
It is rapid to carry out：
A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles are prepared（GCE/PTB/nPt）Modified electrode：Using clean glass-carbon electrode as work
Make electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 2 × 10 to electrode–5Mol/L toluidine blues（TB）Vinegar
Hydrochlorate buffer solution（ABS, pH 5.0）In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 is followed
Ring volt-ampere（CV）Electrochemical polymerization, obtains glass carbon/ploymerized toluidine blue（GCE/PTB）Modified electrode；Then again with glass carbon/polymethyl benzene
Amine is blue（GCE/PTB）As working electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 0.004mol/ to electrode
L HPtCl6·6H2O acetate buffer solutions（ABS, pH 5.0）It is middle to utilize chronoamperometry electro-deposition under the current potential of -0.7V
Platinum Nanoparticles, obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles（GCE/PTB/nPt）Modified electrode；
B. prepared using electrodeposition process three-dimensional（3D）Nanogold cluster modified electrode：Containing 0.01 mol/L CuSO4·5H2O
With 0.4 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold surface
Constant potential electro-deposition 400s is carried out, then the electrode after electro-deposition is placed in 1mol/L salpeter solutions and soaks 8h, to remove
Cu, obtains three-dimensional manometer gold cluster modified electrode；
C. poly ion liquid@3D nanogold cluster modified electrodes are prepared：Modified first with the bromine-containing compound of sulfydryl end-blocking three-dimensional
Nanogold cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then 0.6moL/L1- vinyl -3- will be contained
Ionic liquid, 0.8mg/mL hemoglobins and the mixing of 0.4moL/L N, N- methylene-bisacrylamide of propyl sulfonic acid imidazole salts
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, together
When using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament be to electrode, saturated calomel electrode is reference
Electrode, under -0.51V, applies constant potential 2.5h；The bromine-containing compound that there is polymer on surface is modified into three-dimensional manometer gold cluster electrode
Take out, 2h in the acetum for the lauryl sodium sulfate that volumetric concentration is 10% is immersed in after being cleaned with ultra-pure water, then with ultrapure
Naturally dry after water rinses, obtains poly ion liquid@3D nanogold cluster modified electrodes.
Embodiment 3：
A kind of preparation method for the poly ion liquid@3D nanogold cluster modified electrodes for detecting hemoglobin, successively according to following step
It is rapid to carry out：
A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles are prepared（GCE/PTB/nPt）Modified electrode：Using clean glass-carbon electrode as work
Make electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 4 × 10 to electrode–5Mol/L toluidine blues（TB）Vinegar
Hydrochlorate buffer solution（ABS, pH 5.0）In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 is followed
Ring volt-ampere（CV）Electrochemical polymerization, obtains glass carbon/ploymerized toluidine blue（GCE/PTB）Modified electrode；Then again with glass carbon/polymethyl benzene
Amine is blue（GCE/PTB）As working electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 0.008mol/ to electrode
L HPtCl6·6H2O acetate buffer solutions（ABS, pH 5.0）It is middle to utilize chronoamperometry electro-deposition under the current potential of -0.7V
Platinum Nanoparticles, obtain glass carbon/ploymerized toluidine blue/Platinum Nanoparticles（GCE/PTB/nPt）Modified electrode；
B. prepared using electrodeposition process three-dimensional（3D）Nanogold cluster modified electrode：Containing 0.015 mol/L CuSO4·5H2O
With 0.6 mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold surface
Constant potential electro-deposition 400s is carried out, then the electrode after electro-deposition is placed in 2mol/L salpeter solutions and soaks 5h, to remove
Cu, obtains three-dimensional manometer gold cluster modified electrode；
C. poly ion liquid@3D nanogold cluster modified electrodes are prepared：Modified first with the bromine-containing compound of sulfydryl end-blocking three-dimensional
Nanogold cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then by 0.8 moL/L ionic liquid 1- first
Base -3-（4- vinyl benzyls）Ionic liquid, 1.5mg/mL hemoglobins and 0.8moL/L N, the N- di-2-ethylhexylphosphine oxide third of imidazoles chlorine
Acrylamide mixed solution is put into electrolytic cell, at room temperature, bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into described mixed
Close in 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；The bromine-containing compound that there is polymer on surface is modified into three wieners
The golden cluster electrode of rice takes out, and is immersed in after being cleaned with ultra-pure water in the acetum for the lauryl sodium sulfate that volumetric concentration is 10%
2h, then with naturally dry after ultrapure water, obtain poly ion liquid@3D nanogold cluster modified electrodes.
Embodiment 4：
A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles are prepared（GCE/PTB/nPt）Modified electrode：Using clean glass-carbon electrode as work
Make electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 6 × 10 to electrode–5Mol/L toluidine blues（TB）Vinegar
Hydrochlorate buffer solution（ABS, pH 5.0）In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 is followed
Ring volt-ampere（CV）Electrochemical polymerization, obtains glass carbon/ploymerized toluidine blue（GCE/PTB）Modified electrode；Then again with glass carbon/polymethyl benzene
Amine is blue（GCE/PTB）As working electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 0.02mol/L to electrode
HPtCl6·6H2O acetate buffer solutions（ABS, pH 5.0）It is middle that using chronoamperometry, electro-deposition is received under the current potential of -0.7V
Miboplatin, obtains glass carbon/ploymerized toluidine blue/Platinum Nanoparticles（GCE/PTB/nPt）Modified electrode；
B. prepared using electrodeposition process three-dimensional（3D）Nanogold cluster modified electrode：Containing 0.05 mol/L CuSO4·5H2O
With 1mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V clean naked gold surface into
Electrode after electro-deposition, is then placed in 5mol/L salpeter solutions and soaks 2h by row constant potential electro-deposition 400s, to remove Cu,
Obtain three-dimensional manometer gold cluster modified electrode；
C. poly ion liquid@3D nanogold cluster modified electrodes are prepared：Modified first with the bromine-containing compound of sulfydryl end-blocking three-dimensional
Nanogold cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then by 2 moL/L ionic liquid 1- first
Base -3-（4- vinyl benzyls）Ionic liquid, 5mg/mL hemoglobins and 2moL/L N, N- the methylene bisacrylamide acyls of imidazoles chlorine
Amine mixed solution is put into electrolytic cell, at room temperature, it is molten that bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into the mixing
In liquid, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to electrode, saturated calomel electrode
For reference electrode, under -0.51V, apply constant potential 2.5h；Surface is had to the bromine-containing compound modification three-dimensional manometer gold of polymer
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 ultra-pure water, then
With naturally dry after ultrapure water, poly ion liquid@3D nanogold cluster modified electrodes are obtained.
Embodiment 5：
A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles are prepared（GCE/PTB/nPt）Modified electrode：Using clean glass-carbon electrode as work
Make electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 8 × 10 to electrode–5Mol/L toluidine blues（TB）Vinegar
Hydrochlorate buffer solution（ABS, pH 5.0）In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 is followed
Ring volt-ampere（CV）Electrochemical polymerization, obtains glass carbon/ploymerized toluidine blue（GCE/PTB）Modified electrode；Then again with glass carbon/polymethyl benzene
Amine is blue（GCE/PTB）As working electrode, platinum filament is that saturated calomel electrode is reference electrode, is containing 0.04mol/L to electrode
HPtCl6·6H2O acetate buffer solutions（ABS, pH 5.0）It is middle that using chronoamperometry, electro-deposition is received under the current potential of -0.7V
Miboplatin, obtains glass carbon/ploymerized toluidine blue/Platinum Nanoparticles（GCE/PTB/nPt）Modified electrode；
B. prepared using electrodeposition process three-dimensional（3D）Nanogold cluster modified electrode：Containing 0.08 mol/L CuSO4·5H2O
With 1.2mol/L HAuCl4·4H2In the acetate buffer solution of O, with the chronoamperometry of -0.9V in clean naked gold surface
Constant potential electro-deposition 400s is carried out, then the electrode after electro-deposition is placed in 9mol/L salpeter solutions and soaks 1h, to remove
Cu, obtains three-dimensional manometer gold cluster modified electrode；
C. poly ion liquid@3D nanogold cluster modified electrodes are prepared：Modified first with the bromine-containing compound of sulfydryl end-blocking three-dimensional
Nanogold cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then by 4 moL/L ionic liquid 1- first
Base -3-（4- vinyl benzyls）Ionic liquid, 8mg/mL hemoglobins and 4moL/L N, N- the methylene bisacrylamide acyls of imidazoles chlorine
Amine mixed solution is put into electrolytic cell, at room temperature, it is molten that bromine-containing compound modification three-dimensional manometer gold cluster electrode is inserted into the mixing
In liquid, while using glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode as working electrode, platinum filament is to electrode, saturated calomel electrode
For reference electrode, under -0.51V, apply constant potential 2.5h；Surface is had to the bromine-containing compound modification three-dimensional manometer gold of polymer
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 ultra-pure water, then
With naturally dry after ultrapure water, poly ion liquid@3D nanogold cluster modified electrodes are obtained.
Claims (1)
- A kind of 1. preparation method for the poly ion liquid@3D nanogold cluster modified electrodes for detecting hemoglobin, it is characterised in that according to It is secondary to carry out in accordance with the following steps：A. glass carbon/ploymerized toluidine blue/Platinum Nanoparticles modified electrode is prepared：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 blues In, using current potential as -0.8V~1.3V, it is 50mV/s to sweep speed, and the circle of scanning 50 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 sweet to electrode, saturation Mercury electrode is reference electrode, is containing 0.002~0.05mol/L HPtCl6·6H2Timing is utilized in O acetate buffer solutions 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：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 salpeter solutions, Obtain three-dimensional manometer gold cluster modified electrode；C. poly ion liquid@3D nanogold cluster modified electrodes are prepared：Modified first with the bromine-containing compound of sulfydryl end-blocking three-dimensional Nanogold cluster modified electrode, obtains bromine-containing compound modification three-dimensional manometer gold cluster electrode；Then 0.5~5 moL/L1- ethene will be contained Base -3- propyl sulfonic acids imidazole salts or 1- methyl -3-（4- vinyl benzyls）Ionic liquid, the 0.5~10mg/mL of imidazoles chlorine are blood red Albumen and 0.2~5 moL/L N, N- methylene-bisacrylamide mixed solutions 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 The bromine-containing compound modification three-dimensional manometer gold cluster electrode that there is polymer in face takes out, and being immersed in volumetric concentration after being cleaned with ultra-pure 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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