CN108918623A - A kind of preparation method and application of the Electrochemical enzyme biosensor based on zinc-base metal-organic framework materials and nanogold composite material - Google Patents

A kind of preparation method and application of the Electrochemical enzyme biosensor based on zinc-base metal-organic framework materials and nanogold composite material Download PDF

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CN108918623A
CN108918623A CN201810807252.3A CN201810807252A CN108918623A CN 108918623 A CN108918623 A CN 108918623A CN 201810807252 A CN201810807252 A CN 201810807252A CN 108918623 A CN108918623 A CN 108918623A
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zif
electrode
cile
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nafion
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孙伟
刘娟
殷春晓
翁文举
罗贵铃
牛燕燕
李光九
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Hainan Normal University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
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    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

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Abstract

The present invention relates to a kind of preparation method and application of Electrochemical enzyme biosensor based on zinc-base metal-organic framework materials (ZIF-8) and nanogold (Au) composite material.It is basal electrode with Ionic Liquid Modified carbon paste electrode (CILE), first by zinc-base metal-organic framework materials (ZIF-8) drop coating on basal electrode surface, then electro-deposition nanogold is to ZIF-8 modified electrode surface, finally by Hb and Nafion, successively drop coating is to above-mentioned modified electrode surface, so that modified electrode (Nafion/Hb/Au/ZIF-8/CILE) be made.The influence of pH and scanning speed to electrochemical behavior is probed into, prepared Electrochemical enzyme biosensor is to KBrO3And NaNO2Good electro-catalysis effect is shown, the range of linearity is respectively 0.5 ~ 10.0 mmol/L and 0.1 ~ 0.8 mmol/L, and detection is limited to 0.83 mmol/L and 0.03 mmol/L.

Description

A kind of electrochemistry based on zinc-base metal-organic framework materials and nanogold composite material The preparation method and application of enzyme sensor
Technical field
The invention belongs to the preparations of nanocomposite and electrochemical sensing assays technical field.
More particularly to a kind of system of Electrochemical enzyme biosensor based on zinc-base metal organic framework and nanogold composite material Preparation Method.
Background technique
Metal-organic framework materials (MOFs) are also referred to as Porous coordination polymer, are a kind of novel porous materials.MOFs It is the crystalline material with topological structure generated by metal center and organic ligand by self assembly, specific surface with higher Product, aperture is adjustable, can functional modification, there are the characteristics such as ligand unsatuated metal, structure diversity, separation, gas absorption, The fields such as drug conveying, catalysis, optics, electricity are applied.Reported MOFs has Antoine Lavoisier framework material (MILs), net Shape-metal-organic framework materials (IRMOFs), class zeolitic imidazolate framework material (ZIFs), hole-channel-type framework material (PCNs) etc. series, novel MOFs material have caused the interest of domestic and international researcher.ZIFs is by configuration metal ions Zn2+Or Co2+ A kind of topological structure with space net structure formed with imidazoles ylidene ligands or derivatives thereof, this structure and zeolite molecular sieve Quite similar with the topological structure of MOFs, bond angle is quite similar in the bond angle and zeolite molecular sieve of metal ion and ligand, about 145°.ZIF-8 is by configuration metal ions Zn as the Typical Representative in metal-organic framework materials ZIFs series2+Match with imidazole radicals A kind of porous material with topological structure that body is constituted has unique property, such as traditional inorganic material The specific surface area of superelevation, stable hydro-thermal, regulatable aperture structure.Existing various metals at present(As Cu, Ru, Pd, Au, Ag, Pt etc.)Material can be carried in different MOFs, and can be used as a variety of heavy catalyst to be reacted.
The development of nanotechnology is that the research of biosensor is filled with new vitality.Nano material has specific surface area Greatly, the excellent characteristics such as adsorption capacity is strong, electric conductivity is high, good biocompatibility, the addition of nano material can greatly improve Stability, sensitivity and working efficiency of electrochemica biological sensor etc. have become Electroanalytical Chemistry and biosensor neck The research hotspot in domain.Common metal nano material has nanogold, Technique of Nano Pd, Platinum Nanoparticles and nano silver etc. in building sensor, Wherein nanogold electric conductivity with higher, surface energy, biggish specific surface area and good good biocompatibility, can make a living Object molecule(Such as enzyme, protein and DNA)One good immobilization platform is provided, and has unique optically and electrically property The features such as matter, good biocompatibility, preferable stability, can be used for molecular labeling and detection signal amplification etc., can Greatly to improve detection speed, sensitivity and the stability of biosensor.
Hemoglobin(Hb)It is a kind of oxidation-reduction type protein, is the chief component of red blood cell, primary biological Function is storage and transport oxygen.Oxygen and carbon dioxide can be transported, content can be well reflected poor in conjunction with oxygen in human body Blood degree.Hb is made of peptide chain, globin and ferroheme, and peptide chain encompasses one and is similar to spherical three-dimensional structure, Internal hole embeds ferroheme, and relative molecular mass is about 64500.Each ferroheme is made of 4 pyrrole rings again, in ring Between there is Fe2+/3+, that is, electro-chemical activity center, so Hb is often chosen to as protein Direct Electrochemistry and electrification Learn the Model Molecule of sensor.
Bromate (BrO3 ) it is a kind of genotoxic carcinogens matter, it is that a variety of open water supplies such as mineral water and mountain spring water exist The by-product generated after ozonization.Bromate also there is oxidation characteristic can be used as food additives, for flour Mature, alec and fermented beverage production.Studies have shown that bromate, which is excessively used, can lead to rat kidney cell tumour and thyroid gland Follicular cells tumour.
NaNO2Appearance is similar with salt, preservative is commonly used in meat processed, but content is excessively a kind of toxic articles.Mesh It includes photometry, oscilloscopic polarography, fluorescence analysis, chromatography, capillary that the method for nitrite is detected in preceding food industry The methods of electrophoresis.These detection method measurement results accuracy are high, but have that detection time is longer, process is loaded down with trivial details, cost simultaneously The disadvantages of high.
Therefore, the highly sensitive method with selective enumeration method bromate and sodium nitrite of research has important meaning.This hair It is bright to be prepared for a kind of Electrochemical enzyme biosensor based on organic framework material and nanogold composite material, it can be to bromate and Asia Sodium nitrate carries out electro-catalysis reduction, and achievees the purpose that Electrochemical Detection.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind to be based on zinc-base metal organic framework and nanogold composite wood The preparation method of the Electrochemical enzyme biosensor of material.
The present invention also provides a kind of application of Electrochemical enzyme biosensor, it can be used for the electrification to potassium bromate and sodium nitrite Learn catalysis and laboratory originally BrO in water sample3 Detection.The Electrochemical enzyme biosensor of preparation is to BrO3 Detection have very well Response, detection range is wide, detection limit it is low.
The technical solution adopted in the present invention is as follows:
1, a kind of preparation method and use of the Electrochemical enzyme biosensor based on zinc-base metal organic framework and nanogold composite material On the way, it is characterised in that the method for preparing electrode, the electrode face finish zinc-base metal organic framework (ZIF-8) of the electrode are received The method of meter Jin (Au), Hb and Nafion, the method for testing the electrochemical behavior of the Electrochemical enzyme biosensor, feature exist In including the following steps:
(1)Basal electrode (CILE) is prepared according to claims 1;
(2)In step(1)The 1.0 mg/mL ZIF-8 dispersion liquids of 8 μ L of drop coating on basal electrode obtained, naturally dry are made Obtain ZIF-8/CILE electrode;
(3)By step(2)Obtained ZIF-8/CILE electrode is placed in 1.0 mmol/L HAuCl4In solution, electro-deposition nanometer Gold obtains Au/ZIF-8/CILE electrode;
(4)Take the 15.0 mg/mL Hb solution drop coatings of 8 μ L in step again(3)Prepared Au/ZIF-8/CILE electrode surface, Hb/Au/ZIF-8/CILE electrode can be obtained in naturally dry at room temperature;
(5)Finally take 6 μ L, 0.3 ~ 0.7% Nafion ethanol solution drop coating in step again(4)Prepared Hb/Au/ZIF-8/ CILE electrode surface, Nafion/Hb/Au/ZIF-8/CILE electrode can be obtained in naturally dry at room temperature.
2, the preparation method as described in claims 1, step(1)Specific method be:By 1.6 g graphite powders and 0.8 g HPPF6 mixing, then plus 500 μ L atoleines, with mortar grinder uniformly afterwards insert vitreous electricity pole pipe (Φ=4mm) in simultaneously Conducting wire of the copper wire as electrode is inserted into compacting, and electrode obtained is basal electrode (CILE), is being beaten electrode surface using preceding Mirror surface is polished on mill paper.
3, the preparation method of the Nafion/Hb/Au/ZIF-8/CILE modified electrode as described in claims 1, feature It is, it is described(2)In step, the ZIF-8 dispersion liquid of preparation uses preceding sonic oscillation.
4, the preparation method of the Nafion/Hb/Au/ZIF-8/CILE modified electrode as described in claims 1, feature It is, it is described(3)In step, -0.3 V of sedimentation potential, 100 s of sedimentation time.
5, the preparation method of the Nafion/Hb/Au/ZIF-8/CILE modified electrode as described in claims 1, feature It is, it is described(4)In step, electrode surface drying is generally required 2 ~ 3 hours.
6, such as described in any item Nafion/Hb/Au/ZIF-8/CILE modified electrodes of claims 1 ~ 5 are for electrification Learn catalysis reduction potassium bromate and sodium nitrite.
7, the detection environment of Electrochemical enzyme biosensor as claimed in claim 6 is the phosphate buffer solution in pH 3.0 In.
Compared with prior art, the beneficial effects of the invention are as follows:The present invention utilizes zinc-base metal-organic framework materials (ZIF- 8) and nanogold (Au) composite material, fixed hemoglobin prepare Electrochemical enzyme biosensor.The modification of ZIF-8 and nanometer Au are effective Increase the specific surface area and electric conductivity of working electrode, accelerate electron transfer rate, modified electrode made to have good electricity Chemical property.Electrochemical enzyme biosensor prepared by the present invention has good response to the detection of potassium bromate and sodium nitrite, detection Range is 0.5 ~ 10.0 mmol/L and 0.1 ~ 0.8 mmol/L, and detection is limited to 0.83 mmol/L and 0.03 mmol/L, shows Detection range is wide, detection limits low feature.Therefore it is expected to be used for BrO in different samples3 Detection.
Detailed description of the invention
Fig. 1 is cyclic voltammogram of the different modifying electrode in the PBS buffer solution of pH 3.0, and sweeping speed is 0.1 V/s, Hb's Concentration is 15.0 mg/mL.(a)Nafion/CILE;(b)Nafion/Hb/CILE;(c)Nafion/Hb/Au/ZIF-8/CILE.
Fig. 2 is cyclic voltammogram of the Nafion/Hb/Au/ZIF-8/CILE modified electrode under different scanning speed, and (a is arrived K is respectively 50,100,200,300,400,500,600,700,800,900,1000 mV/s).
Fig. 3 is the cyclic voltammogram of Nafion/Hb/Au/ZIF-8/CILE in different pH buffer solutions, and sweeping speed is 0.1 V/ S, (a to f is respectively 3.0,4.0,5.0,6.0,7.0,8.0).
Fig. 4 is Nafion/Hb/Au/ZIF-8/CILE modified electrode in various concentration KBrO3In the presence of cyclic voltammetric Figure, sweep speed be 0.1 V/s, (a to h is respectively 0.0,0.5,1.0,2.0,4.0,6.0,8.0,10.0 mmol/L, Middle illustration is reduction peak current and KBrO3Concentration between relation curve).
Fig. 5 is Nafion/Hb/Au/ZIF-8/CILE modified electrode in various concentration NaNO2In the presence of cyclic voltammetric Figure, sweep speed be 0.1 V/s, (a to h is respectively 0.0,0.1,0.2,0.3,0.4,0.6,0.7,0.8 mmol/L, Middle illustration is reduction peak current and NaNO2Relation curve between concentration).
Specific embodiment
Present invention will be further explained below with reference to specific examples.These embodiments are merely to illustrate the present invention and do not have to In being limited to the scope of the present invention.
The Direct Electrochemistry of 1 Hb of example
It (is almost that straight line without redox peaks shows electrode table on curve a) from figure 1 it appears that Nafion/CILE Electroactive material is not present in face.In Nafion/Hb/CILE, (there are a pair of asymmetrical redox peaks in curve b), illustrates Hb Electron transfer rate between CILE is slower.And Nafion/Hb/Au/ZIF-8/CILE (have on curve c) it is a pair of good and Redox peaks that will definitely be inverse occur, and redox current also increases.Spike potential, which can directly be read, from curve c is respectively Epa=- 0.117 V and Epc=- 0.227 V, spike potential poor (Δ Ep) are 110 mV, Middle Eocene (E0') it is -0.172 V, oxygen Change the ratio between reduction peak current and be equal to 0.98, close to 1.
Influence of 2 scanning speed of example to Hb electrochemical behavior
Scanning speed is had studied to the shadow of Nafion/Hb/Au/ZIF-8/CILE electrode electro Chemical signal used in the present invention It rings, as a result as shown in Figure 2.Within the scope of 50 ~ 1000 mV/s different scanning speeds, the symmetrical oxidation of a pair of Hb has been obtained Reduction peak shows that the Direct Electrochemistry of Hb is a electrode process that will definitely be inverse.Redox peak current with scanning speed increasing It is big and increases, equation of linear regression for Ipa (μ A)=- 379.28 υ (V/s)+5.89 (n=10, γ=0.996) and Ipc (μ A)=261.40 υ (V/s)+14.35 (n=10, γ=0.992), shows that the reaction of the Hb of electrode surface belongs to The thin layer electrochemistry behavior of adsorption process control, this electrode reaction swept in fast range are controlled by adsorption process.With scanning speed The increase of degree, spike potential poor (Δ Ep) are gradually increased, and the equation of linear regression of E and ln υ are Epc (V)=- 0.055 ln υ (V/s) -0.320 (n=10, γ=0.992) and Epa (V)=0.044 ln υ (V/s) -0.032 (n=10, γ= 0.991).According to Laviron theory and respective formula, calculating electron transfer number (n) is 1.06, and electron transmission coefficient (α) is 0.44, reaction rate constant (ks) it is 1.13 s-1
Influence of 3 pH of example to Hb electrochemical behavior
Influence of the acid-base property of buffer solution to Nafion/Hb/Au/ZIF-8/CILE electrode Direct Electrochemistry behavior is had studied, As a result as shown in Figure 3.With the increase of the pH value of buffer solution, it is mobile that negative direction occurs for the redox spike potential of Hb.It is real It tests and show that the electrochemical behavior of Hb is more stable and is Quasi-reversible process, and redox is anti-when pH is in 3.0 ~ 8.0 ranges Answer Middle Eocene (E0') it with the size of pH value can be in good linear relationship, obtained equation of linear regression is E0' = -0.04211 pH + 0.005 (n=6, γ=0.993).Equation slope is -42.1 mV/pH, less than 25 DEG C under the conditions of in reversible system As a result theoretical value (- 59 mV/pH) out can determine whether Hb on the modified electrode while an electronics and proton occur Transfer.
4 modified electrode of example is to KBrO3Electro-catalysis behavior
Nafion/Hb/Au/ZIF-8/CILE electrode electro-catalysis of the invention restores KBrO3Catalytic effect, as a result such as Fig. 4 institute Show.KBrO is added in the PBS buffer solution of pH 3.03After record cyclic voltammetry curve, there is reduction in -0.199 V in discovery Peak, reduction peak current is with KBrO3The increase of concentration and increase.Work as KBrO3Concentration in the range of 0.5 ~ 10.0 mmol/L When, reduction peak current and KBrO3Concentration at good linear relationship, equation of linear regression is I (μ A)=9.209 C (mmol/L)+57.988 (n=8, γ=0.994), detection are limited to 0.16 mmol/L (3 σ).Work as KBrO3Concentration be greater than Peak current will appear a platform when 10.0 mmol/L and current value remains unchanged, this is Michaelis-Menten dynamics The characteristic feature of process.Apparent K_m (KM app) it is that investigation enzyme-substrate reactions are dynamic (dynamical) important in enzymic catalytic reaction Index, according to Lineweaver-Burk equation:
Above in formula each parameter meaning:Iss is steady-state current when forming good linear relationship after adding substrate, and C is to be added Concentration of the substrate in 10 mL PBS, ImaxIt is in KBrO3Concentration saturation of substrates state for being formed when being greater than 10.0 mmol/L Lower measured maximum current.It can be according to double-reciprocal plot method (1/Iss ~ 1/ [KBrO3]) calculate Nafion/Hb/Au/ZIF- 8/CILE is to KBrO3Catalysis reaction KM appFor 0.83 mmol/L, show Nafion/Hb/Au/ZIF-8/CILE to potassium bromate Catalytic effect it is good.
Example 5
Detection of the Nafion/Hb/Au/ZIF-8/CILE to actual sample has been probed into, has been used for the modified electrode of preparation to detect reality Test the KBrO in the water sample of room3Content, as a result as shown in table 1 below, testing result show in water sample without KBrO3Residual.Utilize standard Addition method has studied the actual sample rate of recovery, and the rate of recovery is within the scope of the % of 98.18 % ~ 99.75.
Table 1 is to KBrO in actual sample3Test result (n=3).
6 modified electrode of example is to NaNO2Electro-catalysis behavior
Nafion/Hb/Au/ZIF-8/CILE electrode electro-catalysis of the invention restores NaNO2Catalytic effect, as a result such as Fig. 5 institute Show.NaNO is added in the PBS buffer solution of pH 3.02After record cyclic voltammetry curve, -0.624 V occur one it is new also Parent peak, reduction peak current is with NaNO2The increase of concentration and increase.Work as NaNO2Concentration in the range of 0.1 ~ 0.8 mmol/L When, reduction peak current and NaNO2Concentration at good linear relationship, equation of linear regression is I (μ A)=152.806 C (mmol/L)+3.034 (n=7, γ=0.995), detection are limited to 0.03 mmol/L (3 σ).Work as NaNO2Concentration be greater than Peak current will appear a platform when 0.8 mmol/L and current value remains unchanged.It can be according to double-reciprocal plot method (1/Iss ~ 1/ [NaNO2]) Nafion/Hb/Au/ZIF-8/CILE is calculated to NaNO2Catalysis reaction KM appFor 4.96 mmol/L.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.

Claims (5)

1. a kind of preparation method of the Electrochemical enzyme biosensor based on zinc-base metal-organic framework materials and nanogold composite material, It is characterized in that, the preparation method comprises the following steps:
(1)Prepare basal electrode (CILE);
(2)In step(1)The zinc-base metal-organic framework materials (ZIF-8) of 6 ~ 8 μ L of drop coating on the electrode of preparation, naturally dry, Up to ZIF-8/CILE;
(3)By step(2)Obtained ZIF-8/CLIE is placed in chlorauric acid solution, electro-deposition nanogold to electrode surface, i.e., Obtain Au/ZIF-8/CILE;
(4)Take 10 ~ 20 mg/mL hemoglobin (Hb) solution drop coatings of 6 ~ 10 μ L in step again(3)Prepared Au/ZIF-8/ CILE electrode surface, Hb/Au/ZIF-8/CILE electrode can be obtained in naturally dry at room temperature;
(5)Finally take 6 ~ 8 μ L, 0.3 ~ 0.7% Nafion ethanol solution drop coating in step again(4)Prepared Hb/Au/ZIF- 8/CILE electrode surface, Nafion/Hb/Au/ZIF-8/CILE electrode can be obtained in naturally dry at room temperature.
2. according to preparation method described in claims 1, which is characterized in that described(2)In step, the concentration of ZIF-8 is 1.0 mg/mL。
3. according to preparation method described in claims 1, which is characterized in that described(3)In step, the concentration of chlorauric acid solution It is 1.0 mmol/L.
4. according to preparation method described in claims 1, which is characterized in that described(3)In step, electro-deposition current potential is -0.3 V, 100 s of sedimentation time.
5. being modified electrode according to the described in any item Nafion/Hb/Au/ZIF-8/CILE of claims 1 ~ 4, platinum filament is pair Electrode, the three-electrode system that silver/silver chlorate is reference electrode building, are collectively disposed in the PBS solution of pH=3.0, are lied prostrate with circulation The performance of peace method research electrochemical sensor, prepares the KBrO of various concentration3And NaNO2Solution is studied using the three-electrode system Its chemical property.
CN201810807252.3A 2018-07-21 2018-07-21 A kind of preparation method and application of the Electrochemical enzyme biosensor based on zinc-base metal-organic framework materials and nanogold composite material Pending CN108918623A (en)

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Application publication date: 20181130