CN108802143A - A kind of preparation and application research based on myoglobins and titanium dioxide-carbon fiber nanometer composite material modified electrode - Google Patents

A kind of preparation and application research based on myoglobins and titanium dioxide-carbon fiber nanometer composite material modified electrode Download PDF

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CN108802143A
CN108802143A CN201810527014.7A CN201810527014A CN108802143A CN 108802143 A CN108802143 A CN 108802143A CN 201810527014 A CN201810527014 A CN 201810527014A CN 108802143 A CN108802143 A CN 108802143A
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cnfs
cile
electrode
nafion
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牛燕燕
谢慧
罗贵铃
李晓燕
阮承祥
孙伟
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Hainan Normal University
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Abstract

The invention discloses one kind being based on myoglobins and titanium dioxide-carbon fiber（TiO2-CNFs）The preparation and application of nanocomposite modified electrode are studied.Titanium dioxide-the carbon fiber（TiO2-CNFs）Composite nano materials use TiO2Nano particle and polyacrylonitrile（PAN）High temperature cabonization after prepared by method of electrostatic spinning is blended to form.The protein electrochemistry transducer production method includes the following steps：With Ionic Liquid Modified carbon paste electrode（CILE）For basal electrode, TiO is coated successively2- CNFs dispersion liquids, myoglobins（Mb）Modified electrode Nafion/Mb/TiO is made in solution and Nafion solution2-CNFs/CILE.The result shows that Mb is in TiO2Original secondary protein structure and bioactivity, phosphate buffer solution of the modified electrode in pH=4 is kept to show electrochemical behavior that will definitely be inverse in-CNFs films.Modified electrode has further been probed into trichloroacetic acid（TCA）And sodium nitrite（NaNO2）Electro-catalysis behavior, show high sensitivity, the wider range of linearity and lower detection limit.

Description

One kind is based on myoglobins and titanium dioxide-carbon fiber nanometer composite material modification electricity The preparation and application of pole are studied
Technical field
The present invention relates to bioelectrochemistry and nano electrochemical field of sensing technologies, more particularly to one kind being based on titanium dioxide The preparation and application of titanium-carbon fiber nanometer composite material and the electrochemical sensor of myoglobins modification.
Background technology
Electrochemica biological sensor be it is a kind of by the biological components such as enzyme, antibody, DNA introduce electrode interface, with these biology Material is as sensing element, and various working electrodes are as conversion element, the electrifications such as record current, conductance, current potential, resistance or capacitance The sensor for learning feature detection signal, has many advantages, such as single-minded, quick, sensitive, has been widely used in clinical detection, biochemical has divided The fields such as analysis and environmental monitoring.Myoglobins（Myoglobin, Mb）It is a kind of water solubility being primarily present in muscle cell Albumen, relative molecular mass 17800 play storage oxygen and oxygen carrier containing there are one heme groups in structure in cell Effect, in addition can also be with H2O、CO、OH-, NO plasmas or molecular complexes or bonding.It is at low cost since Mb molecular structures are simple It is honest and clean to be easy to get, become the important models molecule for exploring electron mechanism in life process.Study the direct electrification of protein and enzyme Scholarship and moral conduct is that important theoretical foundation has been established in the exploitation of Electrochemical enzyme biosensor of new generation.
Method of electrostatic spinning is the processing method that spinning is carried out under the action of electrostatic field force, is a kind of continuous Nanowire of acquisition The direct method of dimension, manufacturing process is simple, is easy to largely prepare, of low cost, is easy to functional modification.Pass through electrostatic spinning Method can prepare the nonwoven material with unique reticular structure and high porosity, can after heat treatment be formed unique Conductive network structure shortens ion transmission path, improves the conductivity of material.It is received so that the doping of method of electrostatic spinning preparation is other The carbon fiber nanometer composite material of rice corpuscles not only has the good electronic transmission performance of carbon fiber, and can improve doping The dispersion degree of material shows the property of composite material, in many necks such as catalysis, biomedicine, sensor, environment remediation Domain is widely used.
Cholorination is the common sterilization method in waterworks, for ensureing water outlet micro-biology experiment to prevent infectious disease Propagation.Trichloroacetic acid（TCA）As the Main By product of cholorination, it is frequently present in the drinking water sterilized with hypochlorous acid In, it is very big to human health damage, have the function of " carcinogenic, teratogenesis, mutagenesis ".What the Ministry of Construction of China and the Ministry of Public Health formulated 《National urban water supply water standard》It provides the concentration of dichloroacetic acid and trichloroacetic acid and is no more than 0.06 mgL-1, the world defends The security presence amount of trichloroacetic acid is 100 μ gL in raw tissue clear stipulaties water environment-1。
Nitrite generally existing in food, drinking water and environment, the normal hemoglobin oxidation of human body can be made and The ability of transport oxygen molecule is lost, and can be acted on protein and generate high carcinogenic nitrosamine, is had to human health prodigious Harm.Excess free enthalpy nitrite can cause such as gastric cancer and cancer of the esophagus, baby's methemoglobinemia, therefore to nitrite Measurement and monitoring have great importance.China's national Specification nitrite can be used as color stabilizer and preservative, salt down Maximum usage amount is 0.15 gkg in the food such as bacon and dry fruit beetle-1。
To sum up, research and development are a kind of being based on nano material and can quick and precisely respond, highly sensitive detection trichloroacetic acid（TCA） And sodium nitrite（NaNO2）Model electrochemical enzyme sensor, it appears it is particularly important.
Invention content
It is repaiied based on titanium dioxide-carbon fiber nanometer composite material and myoglobins in view of this, the present invention provides one kind The preparation method of the electrochemical sensor of decorations and application study, prepared modified electrode have trichloroacetic acid and sodium nitrite Good electro-catalysis reducing property shows the advantages that range of linearity is wide, detection limit is low, high sensitivity, can be applied to such object The quantitative determination of matter.
The present invention provides a kind of electrochemistry biography modified based on titanium dioxide-carbon fiber nanometer composite material and myoglobins The preparation method and application and research of sensor, it is characterised in that：The modified electrode is with Ionic Liquid Modified carbon paste electrode （CILE）For basal electrode, titanium dioxide-carbon fiber nanometer composite material is fixed successively（TiO2-CNFs）Coating, myoglobins （Mb）Modified electrode Nafion/Mb/TiO is made in coating, Nafion coatings2- CNFs/CILE includes the following steps：
（1）Take appropriate TiO2- CNFs dispersant liquid drops are coated in CILE basal electrodes surface, and room temperature naturally dry obtains TiO2- CNFs/CILE electrodes；
（2）Take appropriate Mb solution drop coating in TiO2- CNFs/CILE electrode surfaces, room temperature naturally dry, obtain Mb/TiO2- CNFs/CILE electrodes；
（3）Take appropriate Nafion ethanol solutions drop coating in Mb/TiO2- CNFs/CILE electrode surfaces, room temperature after natural drying, i.e., Obtain Nafion/Mb/TiO2- CNFs/CILE electrodes.
Step（1）The preparation method of the CILE basal electrodes includes the following steps：Take appropriate graphite powder and N- hexyl pyrroles Pyridine hexafluorophosphate（HPPF6）It is placed in mortar and grinds uniformly to get carbon paste, carbon paste is inserted in vitreous electricity pole pipe and is compacted, is inserted Copper wire is as conducting wire, obtained Ionic Liquid Modified carbon paste electrode（CILE）For basal electrode.Wherein graphite powder and HPPF6Matter Amount is than being 1.5 ~ 2.5:1, the time of grinding is 2.0 ~ 4.0 h, and glass electrode bore is 4 mm.
Step（1）The TiO2- CNFs nanocomposites are through TiO2Nano particle and polyacrylonitrile（PAN）Electrostatic is blended High temperature cabonization is prepared after spinning：1. taking appropriate TiO2Nano particle and PAN are dissolved in a certain amount of DMF, and magnetic force stirs at room temperature 10 ~ 15 h are mixed, uniform spinning solution is obtained.Electrostatic spinning process uses the external high pressures of 15 ~ 25 kV, syringe stainless steel syringe needle High-voltage power cathode is connected, cathode is connect with the roller bearing that aluminium foil coats, and the distance between syringe needle and collector are 15 ~ 20 Cm, receiver roller rotation rate are 400 ~ 800 rpm, and the speed that pushes away of spinning solution is 0.2 ~ 1.0 mLh in syringe-1, it is prepared into To TiO2- PAN composite nano fibers.2. by TiO2- PAN composite nano fibers, which are placed in tube furnace, leads to nitrogen protection, with 5 ~ 15oThe heating rate of C/min is heated to 600 ~ 1000oC carries out high temperature cabonization, and keeps 1 ~ 3 h, obtains TiO2- CNFs is compound to be received Rice fiber.
Step（1）Described in TiO2- CNFs dispersion liquid concentrations are 0.5 ~ 2.0 mgmL-1, drop coating volume is 6 ~ 10 μ L.
Step（2）Described in Mb solution concentrations be 10.0 ~ 20.0 mgmL-1, drop coating volume is 6 ~ 10 μ L.
Step（3）Described in Nafion volumes of aqueous ethanol a concentration of 0.2 ~ 0.8%, drop coating volume is with 6 ~ 10 μ L.
Another embodiment of the present invention provides above-mentioned titanium dioxide-carbon fiber nanometer composite material and myoglobins modification Electrode（It is preferred that Nafion/Mb/TiO2- CNFs/CILE electrodes）Electrochemical behavior research with electro-catalysis restore TCA and NaNO2's Using.
Titanium dioxide-carbon fiber nanometer composite material and myoglobins modified electrode of the present invention（It is preferred that Nafion/ Mb/TiO2- CNFs/CILE electrodes）It is in 4.0 phosphate buffer solutions of pH to detect environment.
The above-mentioned preparation method step of the present invention（1）-（3）Middle TiO2- CNFs dispersion liquids, Mb solution, Nafion ethanol solutions Dosage, be advisable so that electrode surface can be uniformly coated on, generally 6 ~ 10 μ L.Those skilled in the art can be according to electrode And the property of coating solution, reasonably select TiO2The dosage of-CNFs dispersion liquids, Mb solution and Nafion ethanol solutions.
In the present invention, CILE is Ionic Liquid Modified carbon paste electrode, HPPF6For N- hexyl pyridine hexafluorophosphates, TiO2- CNFs is titanium dioxide-carbon fiber nanometer composite material, and Mb is myoglobins, and Nafion is that perfluorinated sulfonic acid-polytetrafluoroethylene (PTFE) is total Polymers, TCA are trichloroacetic acid, NaNO2For sodium nitrite, PBS is phosphate buffer solution, the solution being related to（That has indicated removes Outside）It is redistilled water.
Compared with the prior art, the advantages of the present invention are as follows：（1）Utilize TiO2- CNFs nanocomposites are prepared A kind of third generation Electrochemical enzyme biosensor part（Nafion/Mb/TiO2-CNFs/CILE）, which not only maintains Mb's Original conformation and bioactivity, and TiO2The addition of-CNFs nanocomposites promotes transmission of the electronics in electrode interface Process；（2）Nafion/Mb/TiO2- CNFs/CILE electrodes are to TCA and NaNO2Good electro-catalysis reducing property is all shown, Effectively amplification current signal, the detection range of linearity is wide, and detection limits low, high sensitivity.
Description of the drawings
Fig. 1 is different modifying electrode in 10.0 mmolL-1 [Fe(CN)6]3-/4-With 0.1 molL-1KCl is mixed Scan frequency is 10 in solution4To the electrochemical AC impedance collection of illustrative plates of 0.1 Hz, wherein curve d is 1 Nafion/Mb/ of comparative example CILE impedance curves, curve c are 1 Nafion/Mb/TiO of embodiment2- CNFs/CILE impedance curves, curve b are comparative example 2 Nafion/TiO2- CNFs/CILE impedance curves, curve a are 3 Nafion/CILE impedance curves of comparative example.
Fig. 2 is cyclic voltammogram of the different modifying electrode in 4.0 PBS buffer solutions of pH（Sweep speed is 100 mV·s-1）, wherein curve d is 1 Nafion/Mb/TiO of embodiment2- CNFs/CILE cyclic voltammetry curves, curve c are comparative example Nafion/Mb/CILE cyclic voltammetry curves in 1, curve b are Nafion/TiO in comparative example 22The cycle of-CNFs/CILE lies prostrate Pacify curve, curve a is the cyclic voltammetry curve of Nafion/CILE in comparative example 3.
Fig. 3 is Nafion/Mb/TiO2Cyclic voltammograms of-the CNFs/CILE under different scanning speed（A to k sweeps speed point It Wei not 50,100,200,300,400,500,600,700,800,900,1000 mVs-1）.
Fig. 4 is Nafion/Mb/TiO in different pH buffer solutions2(a to f bufferings are molten for the cyclic voltammogram of-CNFs/CILE Liquid pH is followed successively by 3.0,4.0,5.0,6.0,7.0,8.0).
Fig. 5 is Nafion/Mb/TiO2Cyclic voltammetry curves of-CNFs/CILE in the presence of various concentration TCA（A to p： TCA concentration is followed successively by 0,3,6,10,15,20,26,32,38,44,50,60,70,80,90,105 mmol·L-1, wherein illustration is the relation curve of reduction peak current and TCA concentration）.
Fig. 6 is Nafion/Mb/TiO2- CNFs/CILE is in various concentration NaNO2In the presence of cyclic voltammetry curve（A to j： NaNO2Concentration is followed successively by 0,6,9,12,20,30,40,50,60,70 mmolL-1, wherein illustration is reduction peak Electric current and NaNO2The relation curve of concentration）.
Specific implementation mode
For the ease of being further understood to the present invention, embodiment is provided below, more detailed description is done to it.But these Embodiment is only for being better understood from invention rather than range for the purpose of limiting the invention or implementation principle, and embodiments of the present invention are not It is limited to the following contents.
Embodiment 1
（1）Take 1.6 g graphite powders and 0.8 g ionic liquids HPPF6It is placed in mortar and grinds 3 h, obtain carbon paste, then by carbon paste It is compacted and is polishing to minute surface in the vitreous electricity pole pipe that filling internal diameter is 4 mm, interpolation copper wire obtains CILE as conducting wire；
（2）Take 0.3 g TiO2Nano particle and 0.5 g PAN are dissolved in 9.5 g DMF, at room temperature 12 h of magnetic agitation, Obtain uniform spinning solution.Electrospinning is carried out using electrospinning device：Syringe stainless steel syringe needle connects high-voltage power cathode, bears Pole is connect with the roller bearing that aluminium foil coats, and the distance between syringe needle and collector are 18 cm, and external voltage is 18 kV；It connects Receipts device roller rotation rate is 600 rpm, and the speed that pushes away of spinning solution is 0.5 mLh in syringe-1, TiO is prepared2- PAN is compound Nanofiber；
（3）By TiO2- PAN composite nano fibers, which are placed in tube furnace, leads to nitrogen protection, with 10oThe heating rate of C/min heats To 800oC simultaneously keeps 2 h to be carbonized, and obtains TiO2- CNFs composite nano fibers；
（4）Take a concentration of 1.5 mgmL of 8 μ L-1TiO2- CNFs dispersant liquid drops are coated in the surfaces CILE, and room temperature naturally dry obtains To TiO2- CNFs/CILE electrodes；
（5）Take a concentration of 15 mgmL of 8 μ L-1Mb solution drop coatings in TiO2- CNFs/CILE electrode surfaces, room temperature are dried in the air naturally It is dry, obtain Mb/TiO2- CNFs/CILE electrodes；
（6）Take 6 μ L, 0.5% Nafion ethanol solution drop coatings in Mb/TiO2- CNFs/CILE electrode surfaces, room temperature naturally dry Afterwards to get to Nafion/Mb/TiO2- CNFs/CILE electrodes.
Comparative example 1
（1）Take 1.6 g graphite powders and 0.8 g ionic liquids HPPF6It is placed in mortar and grinds 3 h, obtain carbon paste, then by carbon paste It is compacted and is polishing to minute surface in the vitreous electricity pole pipe that filling internal diameter is 4 mm, interpolation copper wire obtains CILE as conducting wire；
（2）Take a concentration of 15 mgmL of 8 μ L-1Mb solution drop coating in CILE electrode surfaces, room temperature naturally dry obtains Mb/ CILE electrodes；
（3）Take 6 μ L, 0.5% Nafion ethanol solutions drop coatings in Mb/CILE electrode surfaces, room temperature after natural drying to get to Nafion/Mb/CILE electrodes.
Comparative example 2
（1）Take 1.6 g graphite powders and 0.8 g ionic liquids HPPF6It is placed in mortar and grinds 3 h, obtain carbon paste, then by carbon paste It is compacted and is polishing to minute surface in the vitreous electricity pole pipe that filling internal diameter is 4 mm, interpolation copper wire obtains CILE as conducting wire；
（2）Take a concentration of 1.5 mgmL of 8 μ L-1TiO2- CNFs dispersant liquid drops are coated in CILE electrode surfaces, and room temperature is dried in the air naturally It is dry, obtain TiO2- CNFs/CILE electrodes；
（3）Take 6 μ L, 0.5% Nafion ethanol solution drop coatings in TiO2- CNFs/CILE electrode surfaces, room temperature after natural drying, Obtain Nafion/TiO2- CNFs/CILE electrodes.
Comparative example 3
（1）Take 1.6 g graphite powders and 0.8 g ionic liquids HPPF6It is placed in mortar and grinds 3 h, obtain carbon paste, then by carbon paste It is compacted and is polishing to minute surface in the vitreous electricity pole pipe that filling internal diameter is 4 mm, interpolation copper wire obtains CILE as conducting wire；
（2）Take 6 μ L, 0.5% Nafion ethanol solutions drop coatings in CILE electrode surfaces, room temperature after natural drying to get to Nafion/CILE electrodes.
One, electrochemical AC impedance collection of illustrative plates is studied
Electrochemical alternate impedance spectrum（EIS）It is a kind of characterizing method being used for describing the variation of modified electrode surface impedance, high frequency region Semicircle arc dia indicate electronics transfer impedance（Ret）.Experimental result as shown in Figure 1,3 Nafion/CILE of comparative example impedance Value is minimum（25.71 Ω）, show that the carbon paste electrode of Ionic Liquid Modified has fabulous electric conductivity；Composite Nano material is modified After material（Nafion/TiO2-CNFs/CILE）Comparative example 2, impedance slightly increase（29.31 Ω）, show semi-conducting material TiO2 It cancels out each other electric conductivity effect with conductive CNFs, therefore generates certain inhibition to electron transmission, interface resistance is made to become larger； And the electrode of Mb is modified（Nafion/Mb/CILE）1 impedance value of comparative example is maximum（72.37 Ω）, show that electrode surface is not led The large biological molecule Mb of electricity hinders the transmission of electronics, increases the electron transmission resistance at interface.1 Nafion/Mb/ of embodiment TiO2The impedance value of-CNFs/CILE（46.86 Ω）It is obviously reduced than Nafion/Mb/CILE, shows TiO2- CNFs is nano combined The synergistic effect of material can effectively reduce the electron transmission resistance at interface.
Two, the research of Mb Direct Electrochemistries behavior
Mb is had studied in 4.0 PBS buffer solutions of pH, 100 mVs of sweep speed using cyclic voltammetry-1When it is directly electric Chemical behavior, the results are shown in Figure 2.Curve (a) Nafion/CILE（Comparative example 3）With curve (b) Nafion/TiO2- CNFs/CILE（Comparative example 2）Upper no apparent redox peaks, illustrate that electrode surface does not have electroactive material presence；Curve (c) Nafion/Mb/CILE（Comparative example 1）On there are a pair of of redox peaks, peak current is smaller, illustrates Mb molecules and CILE Between electrode there is electronics transfer but speed it is slower；In curve (d) Nafion/Mb/TiO2-CNFs/CILE（Embodiment 1） On, there are the redox peaks that a pair of of peak shape is good and stabilization will definitely be inverse, illustrates TiO2The presence of-CNFs composite nano materials adds Electron transfer rate between fast Mb and CILE electrodes, has effectively facilitated electronic transfer process.TiO used in the present invention2- CNFs has good biocompatibility, larger specific surface area and good electric conductivity, can adsorb more Mb molecules, fine Dimension shape structure can form faster electron transmission channel, be conducive to accelerate electronics transfer.By curve d it is found that oxidation spike potential （Epa）With reduction spike potential（Epc）Respectively -0.18 V and -0.30 V (vsSCE), poor (the △ E of spike potentialp) it is 0.12 V, Middle Eocene (E0’) be -0.24 V (vsSCE), it is auxiliary to show myoglobins ferroheme close to 1 for the ratio between redox peak current The characteristic electrochemical behavior of base Fe (III)/Fe (II) electricity pair, illustrates TiO2- CNFs composite nano materials are deposited electrode surface In the Direct Electrochemistry behavior for effectively promoting Mb.
Three, influence of the sweep speed to Mb electrochemical responses
Sweep speed is had studied to 1 Nafion/Mb/TiO of embodiment2The influence of-CNFs/CILE cyclic voltammetric electrochemical responses, The results are shown in Figure 3.In 50 ~ 1000 mVs-1Sweep speed within the scope of obtained symmetrical redox peaks, and peak current Increase with the increase of sweep speed, shows that the Direct Electrochemistry behavior of Mb is a process that will definitely be inverse.Peak current and sweep speed Between equation of linear regression be Ipc(μA)=93.23v (V·s-1)+4.28 (R=0.9914) and Ipa(μA)=-63.90v (V·s-1)-1.60 (R=0.9921).The experimental results showed that Nafion/Mb/TiO2Electrochemical behavior category on-CNFs/CILE It is reacted in thin layer electrochemistry, which is by absorption and control.By formula Q=nAF Γ*（Q is the quantity of electric charge, and n is in electrode reaction Electronics transfer number, A are the area of electrode, and F is Faraday constant, Γ*It is electroactive material in electrode surface coverage）, can To calculate Γ* =4.69×10-9 mol·cm-2.With the increase of sweep speed, spike potential difference △ Ep gradually increase, peak electricity Position and ln v equations of linear regression are respectively Epa (V)=0.058lnv (V·s-1) -0.12 (r=0.9890) and Epc (V)=- 0.052lnv (V·s-1)-0.30 (r=0.9955).According to Laviron theories, it is 0.93 that can calculate electron transfer number, electricity Sub- carry-over factorαIt is 0.53, reaction rate constantk s For 1.81 s-1, illustrate Mb in TiO2The electrode surface of-CNFs modifications has Faster electron transfer rate.
Four, influences of the pH to Mb electrochemical signals
Phosphate buffer solution pH value is studied to 1 Nafion/Mb/TiO of embodiment2- CNFs/CILE Direct Electrochemistry behaviors It influences, the results are shown in Figure 4.With the increase of buffer solution pH, negative shifting occurs for the oxidation-reduction potential of Mb, shows there is proton Participate in electrode reaction.As pH=4.0, redox peak current is maximum, therefore selects the phosphate buffer solution of pH 4.0 as branch Hold electrolyte.When pH is in 3.0 ~ 8.0 range, electrochemical behaviors of the Mb on modified electrode surface is Quasi-reversible process, Middle Eocene （E0′）In a linear relationship with pH value, slope is 53.96 mVpH-1, it is slightly less than 59 mVpH of theoretical value-1, illustrate that Mb is being modified Single electron list proton translocation occurs for electrode surface.
Five, modified electrode（Embodiment 1）Research to TCA electro-catalysis behaviors
Study 1 Nafion/Mb/TiO of embodiment2- CNFs/CILE electro-catalysis reduction TCA in the PBS buffer solutions of pH=4.0 Electrochemical behavior, the results are shown in Figure 5.With the increase of TCA concentration, reduction peak（-0.28 V）Electric current dramatically increases, and aoxidizes Peak then fades away, this is typical TCA electrocatalytic reductions.When the concentration of TCA is in 5.0 ~ 105.0 mmolL-1Range When, reduction peak current and TCA concentration are in good linear relationship, and equation of linear regression is I (μ A)=1.49C (mmolL-1)- 1.73 (n=41, r=0.9961), detection are limited to 1.6 mmolL-1.When TCA concentration is more than 105.0 mmolL-1When, it urges Galvanic current tends towards stability, and illustrates to meet Michaelis-Menten principles of dynamics.According to Lineweaver-Burk equations 1/Iss =(1/Imax)(1+KM app/ C) double-reciprocal plot method（Wherein, IssSteady-state current when being substrate saturation, C are the substrates being added Concentration in PBS electrolyte, ImaxIt is maximum current measured under saturation of substrates state）, catalytic reduction reaction can be solvedK M app For 5.06 mmolL-1, show Nafion/Mb/TiO2- CNFs/CILE has good electro-catalysis effect to TCA.
Six, modified electrode（Embodiment 1）To NaNO2The research of electro-catalysis behavior
Study 1 Nafion/Mb/TiO of embodiment2- CNFs/CILE electro-catalysis in the PBS buffer solutions of pH=4.0 restores NaNO2 Electrochemical behavior, the results are shown in Figure 6, occurs new reduction peak in -0.75 V.NaNO2In 1.0 ~ 14.0 mmolL-1With 14.0~70.0 mmol·L-1In concentration range, reduction peak current is with NaNO2The increase of concentration and linearly increase, linear regression Equation is respectively I (μ A)=0.59C (mmolL-1)+0.45 (n=13, r=0.9670) and I (μ A)=0.076C (mmol L-1)+7.40 (n=16, r=0.9905), it detects and is limited to 0.3 mmolL-1.When concentration is more than 70.0 mmolL-1When, it urges Galvanic current tends towards stability, and meets Michaelis-Menten principles of dynamics, catalytic reduction reactionK M app For 0.98 mmolL-1。

Claims (5)

1. one kind being based on myoglobins and titanium dioxide-carbon fiber（TiO2-CNFs）The modified electrode of nanocomposite, it is special Sign is with Ionic Liquid Modified carbon paste electrode（CILE）For basal electrode, modified titanic oxide-carbon fiber successively（TiO2- CNFs）Nano composite material coating, myoglobins（Mb）Coating, Nafion coatings, obtain modified electrode Nafion/Mb/TiO2- CNFs/CILE。
2. a kind of electrochemica biological sensor part, it is characterised in that using modified electrode described in claim 1 as working electrode.
3. the preparation method of working electrode described in claim 1, it is characterised in that include the following steps：
（1）Take appropriate graphite powder and ionic liquid N-hexyl pyridine hexafluorophosphate (HPPF6) be placed in mortar and grind uniformly, i.e., Carbon paste is obtained, carbon paste is inserted in vitreous electricity pole pipe and be compacted and be polishing to minute surface, inserts copper wire as conducting wire, obtained ionic liquid is repaiied Adorn carbon paste electrode（CILE）For basal electrode；Wherein graphite powder and HPPF6Mass ratio be 1.5 ~ 2.5:1, the time of grinding is 2.0 ~ 4.0 h, glass electrode bore are 4 mm；
（2）Using TiO2Nano particle and polyacrylonitrile（PAN）Method of electrostatic spinning is blended, TiO is prepared by high temperature cabonization2-CNFs Nano-composite fiber：1. taking appropriate TiO2Nano particle and PAN are dissolved in a certain amount of N,N-dimethylformamide（DMF）In, room temperature Lower 10 ~ 15 h of magnetic agitation obtains uniform spinning solution；Electrostatic spinning process uses the external high pressures of 15 ~ 25 kV, syringe stainless Draw point head connects high-voltage power cathode, and cathode is connect with the roller bearing that aluminium foil coats, the distance between syringe needle and collector For 15 ~ 20 cm, receiver roller rotation rate is 400 ~ 800 rpm, and the speed that pushes away of spinning solution is 0.2 ~ 1.0 mLh in syringe-1, TiO is prepared2- PAN nano-composite fibers；2. by TiO2- PAN nano-composite fibers, which are placed in tube furnace, leads to nitrogen guarantor Shield, with 5 ~ 15oThe heating rate of C/min is heated to 600 ~ 1000oC carries out high temperature cabonization, and keeps 1 ~ 3 h, obtains TiO2- CNFs nano-composite fibers；
（3）Take appropriate TiO2- CNFs dispersant liquid drops are applied to the surfaces basal electrode CILE, and room temperature condition naturally dry obtains TiO2- CNFs/CILE electrodes；
（4）Take appropriate Mb solution drop coating in TiO2- CNFs/CILE electrode surfaces, room temperature condition naturally dry, obtain Mb/TiO2- CNFs/CILE electrodes；
（5）Take appropriate Nafion ethanol solutions drop coating in Mb/TiO2- CNFs/CILE electrode surfaces, room temperature condition naturally dry, i.e., Obtain Nafion/Mb/TiO2- CNFs/CILE modified electrodes.
4. the method described in claim 3, it is characterised in that：Step（3）Described in TiO2- CNFs dispersion liquid concentrations are 0.5 ~ 2.0 mg·mL-1；Step（4）Described in Mb solution concentrations be 10.0 ~ 20.0 mgmL-1；Step（5）Described in Nafion ethyl alcohol it is molten The volumetric concentration of liquid is 0.2 ~ 0.8%.
5. electrochemica biological sensor part described in claim 1 is in electro-catalysis reduction trichloroacetic acid and sodium nitrite and accordingly Application in substance detection.
CN201810527014.7A 2018-05-29 2018-05-29 A kind of preparation and application research based on myoglobins and titanium dioxide-carbon fiber nanometer composite material modified electrode Pending CN108802143A (en)

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CN110672689A (en) * 2019-08-30 2020-01-10 佛山市南海区里水镇经济促进局 Electrochemical biosensor for detecting sodium nitrite and preparation method and application thereof
CN110672689B (en) * 2019-08-30 2022-05-20 佛山市南海区里水镇经济促进局 Electrochemical biosensor for detecting sodium nitrite and preparation method and application thereof
CN112834589A (en) * 2020-12-31 2021-05-25 陕西师范大学 AuQD @ CNFs composite material and preparation method and application thereof
CN112834589B (en) * 2020-12-31 2023-12-22 陕西师范大学 AuQD@CNFs composite material and preparation method and application thereof

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