CN103913499A - Preparation method of molecular imprinting electrochemical sensor for detecting bovine hemoglobin - Google Patents
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Abstract
The invention discloses a preparation method of a molecular imprinting electrochemical sensor for detecting bovine hemoglobin. The preparation method comprises the following steps: carrying out surface treatment on a glassy carbon electrode (GCE); dispensing a dispersed graphene (GR) water solution on the surface of the glassy carbon electrode and dispensing an ion liquid (IL) water solution; immersing the electrode into an oxygen-removed phosphate buffer solution containing the bovine hemoglobin (BHb) and a pyrrole monomer; scanning by using a cyclic voltammetry and carrying out electric polymerization; then immersing the electrode into an eluting solution to elute template molecules BHb to obtain an MIPs/IL/GR/CGE; taking the MIPs/IL/GR/CGE as a working electrode; connecting the working electrode, a reference electrode and a counter electrode on an electrochemical work station to form the molecular imprinting electrochemical sensor. According to the preparation method, more template molecules BHb can be fixed on the surface of the electrode based on IL so as to generate more imprinting holes to improve the sensitivity; the re-bonding balancing time can be shortened and the molecular imprinting electrochemical sensor can be successfully used for electrochemical detection of the BHb; the molecular imprinting electrochemical sensor has excellent sensitivity, high selectivity and rapid balance responses and provides the possibility of immunoassay and clinical detection of the BHb.
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 detecting for bovine hemoglobin.
Background technology
Molecular imprinting (molecular imprinting technology, MIT) is because its good chemical stability and thermal stability, reappearance, preparation are cheap and provide huge potential to the high specific recognition capability of template molecule for the identification of biomolecule in sensory field.In recent years, as the synthetic material of the biomolecule recognition system of the natural Ag-Ab of an analoglike, molecularly imprinted polymer (molecular imprinting polymers, MIPs) is widely used in electrochemical sensing field.The sensitivity that molecularly imprinted polymer not only can be assembled template molecule and improves sensor at electrode surface, and can from similar analysis thing, isolate template molecule to improve the selectivity of sensor.So far, molecular imprinting electrochemical sensor (molecular imprinting electrochemical sensors, MIECSs) is by successfully for trace biological micromolecule.Meanwhile, especially trace protein molecule be applied to Electrochemical Detection and caused that researchers are increasing and pay close attention to of trace biomacromolecule.Although can improve its selectivity by molecularly imprinted polymer being modified to electrode surface for the molecular imprinting electrochemical sensor of identifying biological micromolecule, trace the electrochemical sensor of protein molecule or the sensitivity of biology sensor because the large molecular dimension of protein, bonding efficiency again that structure is changeable and lower are faced with stern challenge 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 detecting for bovine hemoglobin.
The technology used in the present invention solution is:
A preparation method for the molecular imprinting electrochemical sensor detecting for bovine hemoglobin, comprises the following steps:
(1) preparation of GR/GCE
Choose glass-carbon electrode, it is carried out to surface treatment, then get scattered graphene aqueous solution and drip and be coated in glass-carbon electrode surface, be placed under infrared lamp and dry, make GR/GCE;
(2) preparation of IL/GR/GCE
The GR/GCE surface obtaining in step (1) is dripped and is coated with ionic liquid aqueous solution, after drying, obtains IL/GR/GCE;
(3) preparation of BHb@MIPs/IL/GR/GCE
The IL/GR/GCE that step (2) is obtained immerses in the phosphate buffer (pH=7.0) of the deoxygenation that contains bovine hemoglobin and pyrrole monomer, and the concentration of bovine hemoglobin is 1g/L, and pyrroles's concentration is 1.0 × 10
-3mol/L-2.0 × 10
-2mol/L, in-0.2V～1.2V potential range, to take out and to dry after fast cyclic voltammetry scan 4～7 circles of sweeping of 80～120mV/s, obtains BHb@MIPs/IL/GR/GCE;
(4) preparation of MIPs/IL/GR/GCE
The BHb@MIPs/IL/GR/GCE that step (3) is obtained immerses wash-out 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 is 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 glass-carbon electrode is polished on abrasive paper for metallograph, then on chamois leather, use successively 0.3 μ m and 0.05 μ m Al
2o
3powder is polished to minute surface, then rinses glass-carbon electrode surface with redistilled water, and is placed in respectively redistilled water and ethanol supersound washing 20s, 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 glass-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 glass-carbon electrode surface.Ionic liquid also can form the ionic liquid of specific interaction for glyoxaline ion liquid or with protein molecule.
Preferably, in step (3): described pyrroles's concentration is 5.0 × 10
-3mol/L, sweeps speed for 100mV/s, and 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.
Useful technique effect of the present invention is:
Molecular imprinting electrochemical sensor prepared by the present invention, based on ionic liquid BmimBF
4thereby can produce more trace hole to improve its sensitivity at the fixing more template molecule BHb in modified electrode surface, and can shorten again the time of Binding equilibrium, to bovine hemoglobin template molecule can be fast bonding again, can be successfully used to the Sensitive Detection of BHb, there is excellent sensitivity, high selectivity and fast equilibrium response, for immunoassay and the clinical detection of BHb provide possibility.
Accompanying drawing explanation
Fig. 1 is that Different electrodes is containing the [Fe (CN) of 0.1mmol/L
6]
3-/4-the phosphate buffer of pH=7.0 in EIS figure, frequency is 0.01-10
5hz, a is BHb@MIPs/IL/GR/GCE, and b is MIPs/IL/GR/GCE, and c is that BHb@MIPs/GR/GCE and d are MIPs/GR/GCE.
Fig. 2 is that different trace electrodes are containing the [Fe (CN) of 0.1mmol/L
6]
3-/4-the phosphate buffer of pH=7.0 in differential pulse voltammetry figure, sweep speed for 100mV/s, a is MIPs/IL/GR/GCE, b is MIPs/IL/GCE, c is that MIPs/GR/GCE and d are MIPs/GCE.
Fig. 3 be 1.0g/L BHb in aqueous solution, 1.0g/L BHb neutralizes the ultraviolet-visible light spectrogram of pure ionic liquid mutually at ionic liquid, wherein: Fig. 3 A illustrates 300-750nm, Fig. 3 B illustrates 450-750nm; In Fig. 3 A, 3B, a is the ultraviolet-visible light spectrogram of BHb molecule in aqueous solution, the b ultraviolet-visible light spectrogram in mutually that is BHb molecule at ionic liquid;
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 and sweeps fast impact;
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
-3g/L BHb, the selectivity of 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
A preparation method for the molecular imprinting electrochemical sensor detecting for bovine hemoglobin, comprises the following steps:
(1) preparation of GR/GCE
Choose glass-carbon electrode, first it is polished on abrasive paper for metallograph, then on chamois leather, use successively 0.3 μ m and 0.05 μ m Al
2o
3powder is polished to minute surface, then rinses glass-carbon electrode surface with redistilled water, and is placed in respectively redistilled water and ethanol supersound washing 20s, dries for subsequent use under room temperature.Be scattered in water ultrasonic Graphene, compound concentration is the graphene aqueous solution of 1mg/mL, get the scattered graphene aqueous solution of 5.0 μ L and drip and be coated in glass-carbon electrode after treatment surface, be then placed under infrared lamp and dry, make the glass-carbon electrode (GR/GCE) of graphene modified.
(2) preparation of IL/GR/GCE
It is 1.0 × 10 that painting 5.0 μ L concentration are dripped on the GR/GCE surface obtaining in step (1)
-41-butyl-3-methyl imidazolium tetrafluoroborate (BmimBF of g/L
4) aqueous solution, after drying, obtain the glass-carbon electrode (IL/GR/GCE) of ionic liquid and graphene modified.
(3) preparation of BHb@MIPs/IL/GR/GCE
The IL/GR/GCE that step (2) is obtained immerses in the phosphate buffer of the deoxygenation that contains bovine hemoglobin and pyrrole monomer (pH=7.0), and the concentration of bovine hemoglobin in solution (BHb) is 1g/L, and pyrroles's concentration is 5.0 × 10
-3mol/L, in-0.2V～1.2V potential range, to take out and to dry after fast cyclic voltammetry scan 5 circles of sweeping of 100mV/s, obtains polymer modified electrode IL/GR/GCE(BHb@MIPs/IL/GR/GCE).
(4) preparation of MIPs/IL/GR/GCE
Wash-out template molecule bovine hemoglobin (BHb) in the sulfuric acid solution of the BHb@MIPs/IL/GR/GCE immersion 1mol/L that step (3) is obtained, obtains trace electrode MIPs/IL/GR/GCE.
(5) preparation of molecular imprinting electrochemical sensor
The MIPs/IL/GR/GCE that step (4) is obtained is 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.
The electrical property of the molecular imprinting electrochemical sensor of below by corresponding experiment being prepared by the present invention characterizes, as a comparison, adopt said method to prepare respectively corresponding polymer modified electrode BHb@MIPs/GR/GCE with different modified electrodes, BHb@MIPs/IL/GCE and BHb@MIPs/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 of analyzing modified electrode interfacial property, can be used in the building process that characterizes sensor.Fig. 1 is that EIS investigation different modifying electrode is containing the [Fe (CN) of 0.1mmol/L
6]
3-/4-the phosphate buffered solution of pH=7.0 in AC impedance curve.As curve a and c, there is larger Nyquist circular arc, illustrate that the molecular imprinted polymer membrane obtaining after electropolymerization produces large charge transfer resistance to redox probe.But the Nyquist arc radius in curve b and d sharply reduces, should be owing to having produced trace hole after template molecule wash-out, be [Fe (CN)
6]
3-/4-probe reaches electrode surface by imprinted polymer film to carry out redox reaction infiltration lane is provided.Relatively before and after template protein molecular wash-out, (a → b, the changing value of the Nyquist circular arc of c → d), can find that MIPs/IL/GR/GCE has larger changing value than MIPs/GR/GCE to two trace electrodes (MIPs/IL/GR/GCE and MIPs/GR/GCE).This is because ionic liquid can be in conjunction with more template molecule, thereby obtains 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, further test the DPV figure (MIPs/GCE, MIPs/GR/GCE, MIPs/IL/GCE and MIPs/IL/GR/GCE) of different trace electrodes.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 that the specific surface area large due to Graphene and excellent electronics transmission capacity have produced larger redox conversion.When IL modifies behind glass-carbon electrode surface, with MIPs/GCE(curve d) compared with, MIPs/IL/GCE(curve b) has larger peak current, this should be the high ionic conductivity due to IL, the electric conductivity of glass-carbon electrode that IL modifies significantly improves.When IL is modified GR/GCE upper after, MIPs/IL/GR/GCE(curve peak current a) is maximum, this may be because the bigger serface of GR and IL can be in the synergies of the fixing more BHb of electrode surface.
In order to further illustrate ionic liquid BmimBF
4with the effect of bovine hemoglobin molecule BHb, investigate 1.0g/L BHb in aqueous solution, 1.0g/L BHb neutralizes the ultraviolet-visible spectrum of pure ionic liquid mutually at ionic liquid.As Fig. 3 A, in aqueous solution (curve a) BHb molecule has a sharp-pointed Soret absorption peak at 416nm place, have Q band absorption peak at 539nm place, 575 and 630nm have two characteristic absorption peaks; When BHb ionic liquid mutually in time (curve b), Soret absorption peak is from 416nm blue shift to 406nm, and Q band absorption peak is from 539nm red shift to 550nm, and the characteristic absorption peak red shift at 575nm place is to 646nm, and the disappearance of the characteristic absorption peak at 630nm place.Iron atom four-coordination in aqueous solution in protoheme, the 5th coordination site and water molecules; In the time that 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
4thereby the sensitivity that can improve MIPs/IL/GR/GCE at the fixing more BHb of electrode surface.
Above-mentioned molecular imprinting electrochemical sensor is prepared under optimal conditions, and in preferably phosphoric acid salt buffer, pyrroles's concentration 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(BHb@MIPs/IL/GR/GCE).Certainly while, preparing molecular imprinting electrochemical sensor, also can choose pyrroles's concentration is 1.0 × 10
-3mol/L-2.0 × 10
-2arbitrary value in mol/L, as pyrroles's concentration 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 be at 80～120mV/
sscope in choose, as being chosen for 80mV/s, 90mV/s, 120mV/s etc., 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 makes should be poor compared with the performance of electrochemical sensors making under optimal conditions.Below choosing of optimal conditions described.
Monomer concentration affects the quantity of deposit thickness and the microsphere of polymkeric substance in polymerization process, will further affect the electrochemical behavior of sensor.In order to study the impact of pyrroles's concentration 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 pyrroles's concentration is 5.0 × 10
-3when mol/L, [Fe (CN)
6]
3-/4-response peak electric current maximum on MIECS, when pyrroles's concentration is less than 5.0 × 10
-3when mol/L, with reducing of concentration, peak current diminishes, and may be to cause not having so much BHb molecule to be fixed in electropolymerization process because pyrroles's concentration is too low.When pyrroles's concentration is greater than 5.0 × 10
-3when mol/L, along with the increase of concentration, the current-responsive on MIECS obviously reduces, should be concentration due to pyrroles excessive cause the imprinted polymer that forms too consolidation be unfavorable for the formation in trace hole after wash-out.Therefore, the pyrroles's of preparation MIECES optimal concentration is 5.0 × 10
-3mol/L.
The electropolymerization scanning number of turns is also to affect key factor prepared by MIECS with sweeping speed, can affect thickness and the tight ness rating of molecularly imprinted polymer.In order to investigate the impact of the scanning number of turns on polymer film thickness, investigate respectively the impact of 3,4,5,6,7 circles, as Fig. 4 B.The polymerization number of turns too much causes the thickness of polymer film too large, has reduced 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 in electropolymerization process, to sweep fast impact.Sweep speed too small, cause the too consolidation of polymer film of preparation, be unfavorable for that wash-out template molecule forms trace hole; If but sweep speed too fast, cause form polymer film too loose, the hole forming after wash-out is easily caved in.Therefore, the speed of sweeping in electropolymerization process is made as 100mV/s.
Thereby the MIPs/IL/GR/GCE preparing under optimal conditions can provide more trace hole in the time of balance, to make more template (target) molecule can be bonded to the surface of trace electrode.In order further to study the usefulness of molecular engram electrode, be immersed in 1.0 × 10 by recording MIPs/IL/GR/GCE
-3dPV peak current in g/L BHb solution after different time responds to investigate the kinetics of adsorption of trace electrode, 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, represent that prepared MIPs/IL/GR/GCE has excellent sensitivity.Ionic liquid BmimBF
4the electronics that has not only reduced trace electrode transmits resistance but also accelerated template molecule BHb and being bonded to the speed on trace electrode again, thus improved trace electrode sensitivity, reduced again bonding and reached time of balance.The online means that a kind of novelty is provided that detect real-time that this electrochemical detection method is protein.
In order to investigate the selectivity of MIPs/IL/GR/GCE, with 1.0 × 10
-3g/L BHb, BSA and HSA, as competition albumen, adopt DPV method to measure the peak current changing value (Δ I) of corresponding protein molecule on MIPs/IL/GR/GCE.As shown in Figure 6, the Δ I maximum of MIPs/IL/GR/GCE to BHb molecule, is respectively 6.2 times of BSA, 8.1 times of HSA, and this all shows the selectivity that MIPs/IL/GR/GCE is high to template molecule BHb.
In addition detect, the sensitivity of the MIPs/IL/GR/GCE of preparation 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 curent change value Δ I on MIPs/IL/GR/GCE reduces gradually.Linear equation is Δ I (μ A)=32.37+3.08log C
bHb(g/L), R=0.998, detects and is limited to 3.09 × 10
-11g/L(3 σ).These results show the MIPs/IL/GR/GCE of preparation can high sensitivity, highly selective detects 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 that contains template molecule BHb by electropolymerization under 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
-3in g/L BHb concentration range, present good linearity, R=0.998, and detection is limited to 3.09 × 10
-11g/L.Therefore the quantitative detection that, this technology is 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 to contain 0.1mmol/L[Fe (CN) at pH=7.0
6]
3-/4-phosphate buffered solution in carry out.
Below be only concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, within all dropping on rights protection scope of the present invention.
Claims (7)
1. a preparation method for the molecular imprinting electrochemical sensor detecting for bovine hemoglobin, is characterized in that comprising the following steps:
(1) preparation of GR/GCE
Choose glass-carbon electrode, it is carried out to surface treatment, then get scattered graphene aqueous solution and drip and be coated in glass-carbon electrode surface, be placed under infrared lamp and dry, make GR/GCE;
(2) preparation of IL/GR/GCE
The GR/GCE surface obtaining in step (1) is dripped and is coated with ionic liquid aqueous solution, after drying, obtains IL/GR/GCE;
(3) preparation of BHb@MIPs/IL/GR/GCE
The IL/GR/GCE that step (2) is obtained immerses in the phosphate buffer of the deoxygenation that contains bovine hemoglobin and pyrrole monomer, and the concentration of bovine hemoglobin is 1g/L, and pyrroles's concentration is 1.0 × 10
-3mol/L-2.0 × 10
-2mol/L, in-0.2V～1.2V potential range, to take out and to dry after fast cyclic voltammetry scan 4～7 circles of sweeping of 80～120mV/s, obtains BHb@MIPs/IL/GR/GCE;
(4) preparation of MIPs/IL/GR/GCE
The BHb@MIPs/IL/GR/GCE that step (3) is obtained immerses wash-out 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 is as working electrode, and contrast electrode, to electrode exact connect ion on electrochemical workstation with ingredient trace electrochemical sensor.
2. the preparation method of a kind of molecular imprinting electrochemical sensor detecting for bovine hemoglobin 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 glass-carbon electrode is polished on abrasive paper for metallograph, then on chamois leather, use successively 0.3 μ m and 0.05 μ m Al
2o
3powder is polished to minute surface, then rinses glass-carbon electrode surface with redistilled water, and is placed in respectively redistilled water and ethanol supersound washing 20s, dries for subsequent use under room temperature.
3. the preparation method of a kind of molecular imprinting electrochemical sensor detecting for bovine hemoglobin 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 glass-carbon electrode surface.
4. the preparation method of a kind of molecular imprinting electrochemical sensor detecting for bovine hemoglobin according to claim 1, it is characterized in that, 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 glass-carbon electrode surface.
5. the preparation method of a kind of molecular imprinting electrochemical sensor detecting for bovine hemoglobin according to claim 1, is characterized in that, in step (3): described pyrroles's concentration is 5.0 × 10
-3mol/L, sweeps speed for 100mV/s, and the scanning number of turns is 5 circles, and the pH of phosphate buffer is 7.0.
6. the preparation method of a kind of molecular imprinting electrochemical sensor detecting for bovine hemoglobin according to claim 1, is characterized in that, in step (4): described eluent is sulfuric acid solution, its concentration is 1mol/L.
7. the preparation method of a kind of molecular imprinting electrochemical sensor detecting for bovine hemoglobin 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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