CN103913499B - A kind of preparation method of the molecular imprinting electrochemical sensor for bovine hemoglobin detection - Google Patents
A kind of preparation method of the molecular imprinting electrochemical sensor for bovine hemoglobin detection Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the molecular imprinting electrochemical sensor for bovine hemoglobin detection, first surface treatment is carried out to glass-carbon electrode, then get scattered Graphene (GR) water-soluble drop and be coated in glassy carbon electrode surface, drip again and be coated with ionic liquid (IL) aqueous solution, then immerse in the phosphate buffer of the deoxygenation containing bovine hemoglobin (BHb) and pyrrole monomer, electropolymerization is carried out by cyclic voltammetry scan, immerse eluted template molecule BHb in eluent again, obtain MIPs/IL/GR/GCE; Using MIPs/IL/GR/GCE as working electrode, and contrast electrode, to Electrode connection on electrochemical workstation with ingredient trace electrochemical sensor.The present invention is based on IL can fix more template molecule BHb at electrode surface thus produce more trace hole to improve its sensitivity, and the time of Binding equilibrium can be shortened again, the Electrochemical Detection of BHb can be successfully used to, there is excellent sensitivity, high selectivity and fast equilibrium response, for the immunoassay of BHb and clinical detection provide possibility.
Description
Technical field
The present invention relates to a kind of preparation method of molecular imprinting electrochemical sensor, specifically relate to a kind of preparation method of the molecular imprinting electrochemical sensor for bovine hemoglobin detection.
Background technology
The identification that molecular imprinting (molecularimprintingtechnology, MIT) is biomolecule in sensory field due to specific recognition capability that its good chemical stability and thermal stability, reappearance, preparation are cheap and high to template molecule provides huge potential.In recent years, as the synthetic material of the biomolecule recognition system of the natural Ag-Ab of an analoglike, molecularly imprinted polymer (molecularimprintingpolymers, MIPs) is widely used in electrochemical sensing field.Molecularly imprinted polymer can not only assemble template molecule to improve the sensitivity of sensor at electrode surface, and can isolate template molecule to improve the selectivity of sensor from similar analysis thing.So far, molecular imprinting electrochemical sensor (molecularimprintingelectrochemicalsensors, MIECSs) has been employed successfully in trace biological micromolecule.Meanwhile, trace biomacromolecule especially trace protein molecule be applied to Electrochemical Detection and cause researchers and more and more pay close attention to.Although can improve its selectivity by molecularly imprinted polymer being modified electrode surface for the molecular imprinting electrochemical sensor identifying biological micromolecule, the trace electrochemical sensor of protein molecule or the sensitivity of biology sensor are faced with stern challenge due to the large molecular dimension of protein, bonding efficiency again that structure is changeable and lower always.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the molecular imprinting electrochemical sensor for bovine hemoglobin detection.
The technology used in the present invention solution is:
For a preparation method for the molecular imprinting electrochemical sensor that bovine hemoglobin detects, comprise the following steps:
(1) preparation of GR/GCE
Choose glass-carbon electrode, surface treatment is carried out to it, then get scattered graphene aqueous solution and drip and be coated in glassy carbon electrode surface, dry under being placed in infrared lamp, obtained GR/GCE;
(2) preparation of IL/GR/GCE
Drip in the GR/GCE surface that step (1) obtains and be coated with ionic liquid aqueous solution, after drying, obtain IL/GR/GCE;
(3) preparation of BHbMIPs/IL/GR/GCE
IL/GR/GCE step (2) obtained immerses in the phosphate buffer (pH=7.0) of the deoxygenation containing bovine hemoglobin and pyrrole monomer, and the concentration of bovine hemoglobin is 1g/L, and pyrrole concentrations is 1.0 × 10
-3mol/L-2.0 × 10
-2mol/L, in-0.2V ~ 1.2V potential range, dries with rear taking-up of fast cyclic voltammetry scan 4 ~ 7 circle of sweeping of 80 ~ 120mV/s, obtains BHbMIPs/IL/GR/GCE;
(4) preparation of MIPs/IL/GR/GCE
BHbMIPs/IL/GR/GCE step (3) obtained immerses eluted template molecule bovine hemoglobin in eluent, obtains MIPs/IL/GR/GCE;
(5) preparation of molecular imprinting electrochemical sensor
The MIPs/IL/GR/GCE that step (4) is obtained as working electrode, and contrast electrode, to electrode exact connect ion on electrochemical workstation with ingredient trace electrochemical sensor.
Preferably, in step (1), the surface treatment process of described glass-carbon electrode is as follows: first polished on abrasive paper for metallograph by glass-carbon electrode, on chamois leather, then use 0.3 μm and 0.05 μm of Al successively
2o
3powder is polished to minute surface, then rinses glassy carbon electrode surface with redistilled water, and is placed in redistilled water and ethanol supersound washing 20s respectively, dries for subsequent use under room temperature.
Preferably, in step (1): described Graphene is Graphene body or the Graphene through functionalization, and the concentration of described graphene aqueous solution is 1mg/mL, get 5.0 μ L and drip and be coated in glassy carbon electrode surface.
Preferably, in step (2): described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate, and the concentration of its aqueous solution is 1.0 × 10
-4g/L, gets 5.0 μ L and drips and be coated in glassy carbon electrode surface.Ionic liquid also for glyoxaline ion liquid or can form the ionic liquid of specific interaction with protein molecule.
Preferably, in step (3): described pyrrole concentrations is 5.0 × 10
-3mol/L, sweep speed for 100mV/s, the scanning number of turns is 5 circles.
Preferably, in step (4): described eluent is sulfuric acid solution, its concentration is 1mol/L.
Preferably, in step (5): described contrast electrode is saturated potassium chloride mercurous chloride electrode, is platinum electrode to electrode.
Advantageous Effects of the present invention is:
Molecular imprinting electrochemical sensor prepared by the present invention, based on ionic liquid BmimBF
4can more template molecule BHb be fixed on modified electrode surface thus produce more trace hole to improve its sensitivity, and the time of Binding equilibrium can be shortened again, can bonding more fast to bovine hemoglobin template molecule, the Sensitive Detection of BHb can be successfully used to, there is excellent sensitivity, high selectivity and fast equilibrium response, for the immunoassay of BHb and clinical detection provide possibility.
Accompanying drawing explanation
Fig. 1 is that Different electrodes is at [the Fe (CN) containing 0.1mmol/L
6]
3-/4-pH=7.0 phosphate buffer in EIS figure, frequency is 0.01-10
5hz, a are BHbMIPs/IL/GR/GCE, b be MIPs/IL/GR/GCE, c be BHbMIPs/GR/GCE and d is MIPs/GR/GCE.
Fig. 2 is that different trace electrode is at [the Fe (CN) containing 0.1mmol/L
6]
3-/4-pH=7.0 phosphate buffer in differential pulse voltammetry figure, sweep speed for 100mV/s, a be MIPs/IL/GR/GCE, b is MIPs/IL/GCE, and c is MIPs/GR/GCE and d is MIPs/GCE.
Fig. 3 be 1.0g/LBHb in aqueous, 1.0g/LBHb ionic liquid mutually in and the ultraviolet-visible light spectrogram of pure ionic liquid, wherein: Fig. 3 A illustrates 300-750nm, Fig. 3 B illustrates 450-750nm; In Fig. 3 A, 3B, a is BHb molecule ultraviolet-visible light spectrogram in aqueous, b be BHb molecule ionic liquid mutually in ultraviolet-visible light spectrogram;
Fig. 4 illustrates the optimization of MIPs/IL/GR/GCE preparation condition, wherein: Fig. 4 A illustrates the impact of pyrrole monomer concentration; Fig. 4 B illustrates the impact of the scanning number of turns; Fig. 4 C illustrates the impact of sweeping speed;
Fig. 5 illustrates [Fe (CN)
6]
3-/4-peak current on MIPs/IL/GR/GCE (a) and MIPs/GR/GCE (b) is along with the situation of change of bonding time again;
Fig. 6 illustrates that MIPs/IL/GR/GCE is to 1.0 × 10
-3the selectivity of g/LBHb, BSA and HSA;
Fig. 7 illustrates [Fe (CN)
6]
3-/4-response current changing value on MIPs/IL/GR/GCE and the relation of BHb concentration.
Embodiment
For a preparation method for the molecular imprinting electrochemical sensor that bovine hemoglobin detects, comprise the following steps:
(1) preparation of GR/GCE
Choose glass-carbon electrode, first it is polished on abrasive paper for metallograph, on chamois leather, then use 0.3 μm and 0.05 μm of Al successively
2o
3powder is polished to minute surface, then rinses glassy carbon electrode surface with redistilled water, and is placed in redistilled water and ethanol supersound washing 20s respectively, dries for subsequent use under room temperature.By Graphene ultrasonic disperse in water, compound concentration is the graphene aqueous solution of 1mg/mL, get the scattered graphene aqueous solution of 5.0 μ L and drip painting glassy carbon electrode surface after treatment, dry under being then placed in infrared lamp, the glass-carbon electrode (GR/GCE) of obtained graphene modified.
(2) preparation of IL/GR/GCE
Dripping painting 5.0 μ L concentration in the GR/GCE surface that step (1) obtains is 1.0 × 10
-41-butyl-3-methyl imidazolium tetrafluoroborate (the BmimBF of g/L
4) aqueous solution, obtain the glass-carbon electrode (IL/GR/GCE) of ionic liquid and graphene modified after drying.
(3) preparation of BHbMIPs/IL/GR/GCE
IL/GR/GCE step (2) obtained immerses in the phosphate buffer of the deoxygenation containing bovine hemoglobin and pyrrole monomer (pH=7.0), and in solution, the concentration of bovine hemoglobin (BHb) is 1g/L, and pyrrole concentrations is 5.0 × 10
-3mol/L, in-0.2V ~ 1.2V potential range, encloses rear taking-up dry with the fast cyclic voltammetry scan 5 of sweeping of 100mV/s, obtain polymer modified electrode IL/GR/GCE(BHbMIPs/IL/GR/GCE).
(4) preparation of MIPs/IL/GR/GCE
BHbMIPs/IL/GR/GCE step (3) obtained immerses eluted template molecule bovine hemoglobin (BHb) in the sulfuric acid solution of 1mol/L, obtains trace electrode MIPs/IL/GR/GCE.
(5) preparation of molecular imprinting electrochemical sensor
The MIPs/IL/GR/GCE that step (4) is obtained as working electrode, and contrast electrode, to electrode exact connect ion on electrochemical workstation with ingredient trace electrochemical sensor.Described contrast electrode is saturated calomel electrode, is platinum electrode to electrode.
Characterize below by the electrical property of corresponding experiment to molecular imprinting electrochemical sensor prepared by the present invention, as a comparison, the different modified electrode of said method is adopted to prepare corresponding polymer modified electrode BHbMIPs/GR/GCE respectively, BHbMIPs/IL/GCE and BHbMIPs/GCE, then wash-out obtains corresponding trace electrode MIPs/GR/GCE, MIPs/IL/GCE and MIPs/GCE.
As everyone knows, EIS is a kind of effective means analyzing modified electrode interfacial property, can be used in the building process characterizing sensor.Fig. 1 is that EIS investigates different modifying electrode at the [Fe (CN) containing 0.1mmol/L
6]
3-/4-pH=7.0 phosphate buffered solution in AC impedance curve.As curve a and c, occurred larger Nyquist circular arc, the molecular imprinted polymer membrane obtained after electropolymerization is described produces large charge transfer resistance to redox probe.But the Nyquist arc radius in curve b and d sharply reduces, should be owing to creating trace hole after template molecule elution, be [Fe (CN)
6]
3-/4-probe reaches electrode surface by imprinted polymer film to carry out redox reaction and provides infiltration lane.Relatively the changing value of two trace electrodes (MIPs/IL/GR/GCE and MIPs/GR/GCE) Nyquist circular arc of (a → b, c → d) before and after template protein molecule wash-out, can find that MIPs/IL/GR/GCE has larger changing value than MIPs/GR/GCE.This is because ionic liquid in conjunction with more template molecule, thus can obtain more trace hole, and then produces more passage, makes more electrochemical probe arrive IL/GR/GCE electrode surface through polymer film and produces redox electric signal.
In order to study the performance of molecular engram film modified electrode, test DPV figure (MIPs/GCE, MIPs/GR/GCE, MIPs/IL/GCE and MIPs/IL/GR/GCE) of different trace electrode further.As shown in Figure 2, MIPs/GR/GCE(curve c) with MIPs/GCE(curve d) compared with, there is larger [Fe (CN)
6]
3-/4-peak current, this is because the large specific surface area of Graphene and excellent electron transmission ability create larger redox conversion.After IL modifies glassy carbon electrode surface, with MIPs/GCE(curve d) compared with, MIPs/IL/GCE(curve b) there is larger peak current, this should be the high ionic conductivity due to IL, and the electric conductivity of the glass-carbon electrode that IL modifies significantly improves.When IL is modified after on GR/GCE, MIPs/IL/GR/GCE(curve peak current a) is maximum, and this may be because the Large ratio surface sum IL of GR can fix the synergy of more BHb at electrode surface.
In order to further illustrate ionic liquid BmimBF
4with the effect of bovine hemoglobin molecule BHb, investigated 1.0g/LBHb in aqueous, 1.0g/LBHb ionic liquid mutually in and the ultraviolet-visible spectrum of pure ionic liquid.As Fig. 3 A, (curve a) BHb molecule has a sharp-pointed Soret absorption peak at 416nm place, have a Q to be with absorption peak, have two characteristic absorption peaks in 575 and 630nm at 539nm place in aqueous; When BHb is when ionic liquid is middle mutually (curve b), Soret absorption peak is with absorption peak from 539nm red shift to the characteristic absorption peak red shift at 550nm, 575nm place to 646nm from 416nm blue shift to 406nm, Q, and the characteristic absorption peak at 630nm place disappears.Iron atom four-coordination in aqueous in protoheme, the 5th coordination site and water molecules; When BHb is in ionic liquid, imidazoles ring nitrogen coordination in the 5th coordination site of iron atom and ionic liquid, causes the significant change of BHb absorption peak.Therefore, BmimBF
4more BHb can be fixed thus the sensitivity of raising MIPs/IL/GR/GCE at electrode surface.
Above-mentioned molecular imprinting electrochemical sensor is prepared with optimal conditions, and in preferably phosphoric acid salt buffer, pyrrole concentrations is 5.0 × 10
-3mol/L, in-0.2V ~ 1.2V potential range, encloses with the fast cyclic voltammetry scan 5 of sweeping of 100mV/s, obtains polymer-modified IL/GR/GCE(BHbMIPs/IL/GR/GCE).Certainly, also can choose pyrrole concentrations when preparing molecular imprinting electrochemical sensor is 1.0 × 10
-3mol/L-2.0 × 10
-2arbitrary value in mol/L, as pyrrole concentrations can be chosen for 1.0 × 10
-3mol/L, 3.0 × 10
-3mol/L, 1.0 × 10
-2mol/L, 2.0 × 10
-2mol/L etc., sweeping speed can at 80 ~ 120mV/
sscope in choose, as can 80mV/s, 90mV/s, 120mV/s etc. be chosen for, scanning the number of turns also can be 3,4,6 or 7 circle etc.But the activity of the molecular imprinting electrochemical sensor that above-mentioned condition obtains should be poor compared with performance of electrochemical sensors obtained under optimal conditions.Below choosing of optimal conditions is described.
Monomer concentration affects the deposit thickness of polymkeric substance and the quantity of microsphere in the course of the polymerization process, will affect the electrochemical behavior of sensor further.In order to study the impact of pyrrole concentrations on MIECS, electrode is in pyrroles's aqueous solution of variable concentrations (1.0 × 10
-3mol/L-2.0 × 10
-2mol/L, BHb concentration is definite value 1g/L) carry out electropolymerization.As Fig. 4 A, when pyrrole concentrations is 5.0 × 10
-3during mol/L, [Fe (CN)
6]
3-/4-response peak electric current on MIECS is maximum, when pyrrole concentrations is less than 5.0 × 10
-3during mol/L, with the reduction of concentration, peak current diminishes, and may be to cause in electropolymerization process, do not have so much BHb molecule to fix because pyrrole concentrations is too low.When pyrrole concentrations is greater than 5.0 × 10
-3during mol/L, along with the increase of concentration, the current-responsive on MIECS obviously reduces, should be the imprinted polymer that causes because the concentration of pyrroles is excessive being formed too consolidation be unfavorable for the formation in trace hole after wash-out.Therefore, the optimal concentration preparing the pyrroles of MIECES is 5.0 × 10
-3mol/L.
The electropolymerization scanning number of turns and to sweep speed be also affect key factor prepared by MIECS, can affect thickness and the tight ness rating of molecularly imprinted polymer.In order to investigate the scanning number of turns to the impact of polymer film thickness, investigate the impact of 3,4,5,6,7 circles respectively, as Fig. 4 B.The polymerization number of turns too much causes the thickness of polymer film too large, decreases effective trace hole.According to [Fe (CN)
6]
3-/4-the size of peak current, the best polymerization number of turns is decided to be 5 circles.Shown in Fig. 4 C is the impact of sweeping speed in electropolymerization process.Sweep speed too small, cause the polymer film too consolidation prepared, be unfavorable for that eluted template molecule forms trace hole; If but sweep fast too fast, cause the polymer film of formation too loose, the hole formed after making wash-out easily caves in.Therefore, the speed of sweeping in electropolymerization process is set to 100mV/s.
The MIPs/IL/GR/GCE prepared in optimal conditions can provide more trace hole thus make more template (target) molecule can be bonded to the surface of trace electrode when balancing.In order to study the usefulness of molecular engram electrode further, be immersed in 1.0 × 10 by record MIPs/IL/GR/GCE
-3the kinetics of adsorption of trace electrode is investigated in DPV peak current response in g/LBHb solution after different time, and MIPs/GR/GCE is electrode as a comparison.As shown in Figure 5, MIPs/IL/GR/GCE(curve a under the same conditions, 32.4 μ A and 20min) than MIPs/GR/GCE(curve b, 19.8 μ A and 120min) show higher, current-responsive faster, the MIPs/IL/GR/GCE prepared by expression has excellent sensitivity.Ionic liquid BmimBF
4not only reduce the electron transmission resistance of trace electrode and accelerate template molecule BHb and be bonded to speed on trace electrode again, thus improve trace electrode sensitivity, decrease the time that bonding again reaches balance.This electrochemical detection method is that the online of protein detects the means providing a kind of novelty real-time.
In order to investigate the selectivity of MIPs/IL/GR/GCE, with 1.0 × 10
-3g/LBHb, BSA and HSA, as competition albumen, adopt DPV method to measure the peak current changing value of corresponding protein molecule on MIPs/IL/GR/GCE (Δ I).As shown in Figure 6, the Δ I of MIPs/IL/GR/GCE to BHb molecule is maximum, is 6.2 times of BSA respectively, 8.1 times of HSA, and this all shows the selectivity that MIPs/IL/GR/GCE is high to template molecule BHb.
In addition, the sensitivity of the MIPs/IL/GR/GCE of preparation is detected with the BHb solution of variable concentrations.As Fig. 7, along with the increase of BHb concentration is (from 1.0 × 10
-10to 1.0 × 10
-3g/L), the current variation value Δ I on MIPs/IL/GR/GCE reduces gradually.Linear equation is Δ I (μ A)=32.37+3.08logC
bHb(g/L), R=0.998, detects and is limited to 3.09 × 10
-11g/L(3 σ).These results show that the MIPs/IL/GR/GCE prepared can high sensitivity, highly selective detection BHb.
In sum, the present invention has successfully prepared the graphene-based bovine hemoglobin molecular engram electrode of Ionic Liquid Modified.This trace electrode is that the pyrrole monomer solution containing template molecule BHb by electropolymerization with optimal conditions obtains.In the Electrochemical Detection of template protein molecule, this trace electrode shows excellent sensitivity, and high selectivity and fast equilibrium response, 1.0 × 10
-10-1.0 × 10
-3present good linear in g/LBHb concentration range, R=0.998, and detect and be limited to 3.09 × 10
-11g/L.Therefore, this technology is that the quantitative detection of clinical middle BHb provides a kind of possible method.
Above material: bovine hemoglobin, is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Bovine serum albumin(BSA) and human serum albumins, be purchased from sea blue season development in science and technology company limited; 1-butyl-3-methyl-tetrafluoro boric acid imidazole salts (BmimBF
4), be purchased from the prompt Chemical Co., Ltd. of marine origin; It is pure that other reagent are analysis.In experiment, solution used is prepared by redistilled water.Instrument: Shanghai occasion China CHI660C electrochemical workstation, three electrode work system: MIPs/IL/GR/GCE are as working electrode, and saturated potassium chloride mercurous chloride electrode is as contrast electrode, and platinum electrode is as to electrode; SK5200H type ultrasonic washing instrument (Shanghai section leads ultrasonic instrument); UV755B ultraviolet-visible pectrophotometer (Shanghai You Ke instrument and meter company limited); Infrared lamp.All electrochemistry experiments are all contain 0.1mmol/L [Fe (CN) at pH=7.0
6]
3-/4-phosphate buffered solution in carry out.
Below be only embody rule example of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all drops within rights protection scope of the present invention.
Claims (6)
1., for a preparation method for the molecular imprinting electrochemical sensor of bovine hemoglobin detection, it is characterized in that comprising the following steps:
(1) preparation of GR/GCE
Choose glass-carbon electrode, surface treatment is carried out to it, then get scattered graphene aqueous solution and drip and be coated in glassy carbon electrode surface, dry under being placed in infrared lamp, obtained GR/GCE;
(2) preparation of IL/GR/GCE
Drip in the GR/GCE surface that step (1) obtains and be coated with ionic liquid aqueous solution, after drying, obtain IL/GR/GCE;
(3) preparation of BHbMIPs/IL/GR/GCE
IL/GR/GCE step (2) obtained immerses in the phosphate buffer of the deoxygenation containing bovine hemoglobin and pyrrole monomer, and the concentration of bovine hemoglobin is 1g/L, and pyrrole concentrations is 1.0 × 10
-3mol/L-2.0 × 10
-2mol/L, in-0.2V ~ 1.2V potential range, dries with rear taking-up of fast cyclic voltammetry scan 4 ~ 7 circle of sweeping of 80 ~ 120mV/s, obtains BHbMIPs/IL/GR/GCE;
(4) preparation of MIPs/IL/GR/GCE
BHbMIPs/IL/GR/GCE step (3) obtained immerses eluted template molecule bovine hemoglobin in eluent, obtains MIPs/IL/GR/GCE;
(5) preparation of molecular imprinting electrochemical sensor
The MIPs/IL/GR/GCE that step (4) is obtained as working electrode, and contrast electrode, to electrode exact connect ion on electrochemical workstation with ingredient trace electrochemical sensor;
In step (2): described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate, and the concentration of its aqueous solution is 1.0 × 10
-4g/L, gets 5.0 μ L and drips and be coated in glassy carbon electrode surface.
2. the preparation method of a kind of molecular imprinting electrochemical sensor for bovine hemoglobin detection according to claim 1, it is characterized in that, in step (1), the surface treatment process of described glass-carbon electrode is as follows: first polished on abrasive paper for metallograph by glass-carbon electrode, on chamois leather, then use 0.3 μm and 0.05 μm of Al successively
2o
3powder is polished to minute surface, then rinses glassy carbon electrode surface with redistilled water, and is placed in redistilled water and ethanol supersound washing 20s respectively, dries for subsequent use under room temperature.
3. the preparation method of a kind of molecular imprinting electrochemical sensor for bovine hemoglobin detection according to claim 1, it is characterized in that, in step (1): described Graphene is Graphene body or the Graphene through functionalization, the concentration of described graphene aqueous solution is 1mg/mL, gets 5.0 μ L and drips and be coated in glassy carbon electrode surface.
4. the preparation method of a kind of molecular imprinting electrochemical sensor for bovine hemoglobin detection according to claim 1, is characterized in that, in step (3): described pyrrole concentrations is 5.0 × 10
-3mol/L, sweep speed for 100mV/s, the scanning number of turns is 5 circles, and the pH of phosphate buffer is 7.0.
5. the preparation method of a kind of molecular imprinting electrochemical sensor for bovine hemoglobin detection according to claim 1, it is characterized in that, in step (4): described eluent is sulfuric acid solution, its concentration is 1mol/L.
6. the preparation method of a kind of molecular imprinting electrochemical sensor for bovine hemoglobin detection according to claim 1, is characterized in that, in step (5): described contrast electrode is saturated potassium chloride mercurous chloride electrode, is platinum electrode to electrode.
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| CN104833767B (en) * | 2015-06-02 | 2015-12-09 | 青岛大学 | A kind of GR/WS 2-AuNPs-WS 2the preparation method of complex molecule trace sensor and application thereof |
| CN104910411B (en) * | 2015-06-18 | 2018-04-20 | 辽宁师范大学 | The method that electric field-assisted removing template molecule prepares protein-imprinted polymer |
| CN105017476B (en) * | 2015-07-14 | 2017-04-26 | 辽宁师范大学 | Preparation method for hemoglobin molecularly imprinted polymers through autocatalysis of ATRP |
| CN105466987B (en) * | 2015-12-18 | 2019-01-08 | 山东鲁岳检测科技有限公司 | The preparation method of protein molecule engram electrochemical sensor based on metal coordination |
| CN106770570A (en) * | 2016-12-21 | 2017-05-31 | 北京农业信息技术研究中心 | Microelectrode biosensor and its application in plant salicylic acid on-line checking |
| CN108007992B (en) * | 2017-12-04 | 2019-08-09 | 辽宁师范大学 | Detect the preparation method of the poly ion liquid@3D nanogold cluster modified electrode of hemoglobin |
| CN112763553B (en) * | 2020-12-25 | 2023-02-28 | 中北大学 | Electrochemical detection method for protein based on molecular imprinting technology |
| CN113834866B (en) * | 2021-09-15 | 2024-01-05 | 昆明理工大学 | Preparation method and application of molecularly imprinted electrode for electrochemical sensor |
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