CN108414595A - Utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution - Google Patents

Utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution Download PDF

Info

Publication number
CN108414595A
CN108414595A CN201710492759.XA CN201710492759A CN108414595A CN 108414595 A CN108414595 A CN 108414595A CN 201710492759 A CN201710492759 A CN 201710492759A CN 108414595 A CN108414595 A CN 108414595A
Authority
CN
China
Prior art keywords
tio
glucose
ito
electrode
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710492759.XA
Other languages
Chinese (zh)
Other versions
CN108414595B (en
Inventor
程宏英
周灿
汲中玲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University of Science and Technology
Original Assignee
Suzhou University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University of Science and Technology filed Critical Suzhou University of Science and Technology
Priority to CN201710492759.XA priority Critical patent/CN108414595B/en
Publication of CN108414595A publication Critical patent/CN108414595A/en
Application granted granted Critical
Publication of CN108414595B publication Critical patent/CN108414595B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • 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
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Nanotechnology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Abstract

The present invention provides utilize TiO2The method of glucose, synthesizes TiO with hydro-thermal method in nanometer tube modified ito determination of electrode aqueous solution2Nanotube, in its surface graft OH, with electrochemical method by TiO2Nano material and catechol are modified simultaneously forms composite membrane on ito electrodes, then ferrocenecarboxylic acid is modified again on the surface of the composite membrane, and in the superficies drop coating glucose oxidase of ito electrodes, chronoamperometry is finally used to measure the content of glucose in aqueous solution.The assay method of the present invention uses the TiO with catalytic activity2Nanotube, it is coupled modified electrode with catechol, it selects ferrocenecarboxylic acid to cooperate with the electron mediator as glucose oxidase again, enhances the electron transmission and reaction signal during glucose assays, the superiority of this method is particularly shown for the microdetermination of sample.

Description

Utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of to utilize TiO2Nanometer tube modified ito determination of electrode aqueous solution The method of middle glucose.
Background technology
Analysis for glucose, it will be a very popular research of future biological medical domain.Currently, in the market For the measurement of glucose in solutions, using glucose oxidase film detection device, i.e., glucose oxidase is in aerobic item Can be glycoxidative by grape under part, the substance with certain chemical property is generated, the signal detector in detection device can will have The amount of the substance of chemical property detected, and the power of signal is detected by analysis and research, so that it may to extrapolate in sample The content of glucose.But due to market conventional method to determination sample in the stability of dissolved oxygen and complex sample impurity it is dry It is less to disturb exclusion, leads to have significant limitation in terms of the assay method range of linearity and Monitoring lower-cut.Especially in micro-example Measurement in terms of, limitation seems more apparent.
Invention content
The purpose of the present invention is to solve the above problem, provides and a kind of utilizing TiO2Nanometer tube modified ito determination of electrode The method of glucose in aqueous solution, operability is more preferably.
To achieve the above object, present invention offer is a kind of utilizing TiO2Grape in nanometer tube modified ito determination of electrode solution The method of sugar, specifically, in TiO2Nanotube surface grafting-OH, with electrochemical method by TiO2Nanotube and catechol are same When modification composite membrane is formed on ito electrodes, then modify ferrocenecarboxylic acid again on the surface of the composite membrane, and in ito electricity The superficies drop coating glucose oxidase of pole finally uses i-t methods to measure the content of glucose in solutions.
Further, the TiO2Nanotube is prepared using hydro-thermal method.
Further, the electrochemical method includes using cyclic voltammetry, Electrode with Electrochemical Impedance Spectroscopy or chrono-amperometric Method.
The specific method for measuring glucose in solutions is as follows:
Step 1) contains TiO2Catechol solution preparation:By TiO2Alcohol dispersion liquid is extracted using micro-sampling pin It has directly squeezed into catechol solution afterwards, it is uniform then to have carried out ultrasonic disperse, wherein TiO2TiO in alcohol suspending liquid2For The TiO of surface graft-OH2Nanotube;
Step 2) modifies TiO on ito electrodes2Nanotube and catechol:Naked ito electrodes are prepared by step 1) Contain TiO2Catechol solution in carry out cyclic voltammetry, the scanning number of turns is set as at least 15 circles so that TiO2It receives Mitron and catechol, which are fully modified, arrives ito electrode surfaces;
Step 3) modifies ferrocenecarboxylic acid on ito electrodes:Ferrocene is added dropwise in the ito electrode surfaces of step 2) modified Formic acid solution makes its abundant volatile dry;
Step 4) modifies glucose oxidase on ito electrodes:Portugal is added in the ito electrode surfaces that step 3) is prepared into Grape oxidase solution stands, makes its abundant volatile dry;
The content of step 5) ito determination of electrode glucose in solutions:By ito electrodes made from step 4), using galvanometer When method (i-t methods) measure aqueous solution in glucose content.
Further, naked ito electrodes are pre-processed before use, and specific processing method is, by naked ito electrodes according to In the secondary mixed liquor for being immersed in sodium hydroxide and ethyl alcohol and acetone and the mixed liquor of deionized water, respectively in supersonic cleaning machine Then ultrasound is cleaned with deionized water.
Further, in step 1), the TiO2The preparation method of nanotube is as follows:By titanium dioxide solids powder and hydrogen Sodium hydroxide solution stirs evenly, and is added in autoclave and reacts 24 hours, after reaction, obtained wadding under 130 DEG C of high temperature Shape mixture ultra-pure water and dilute hydrochloric acid solution wash repeatedly, until solution is in neutrality, i.e., after pH value reaches 7.0, suction filtration obtains Solid matter in 70 DEG C of baking ovens dry to get TiO2Nanotube.
Further, in step 1) surface graft-OH TiO2The preparation method of alcohol suspending liquid is as follows:It is suitable being placed with It closes in the flask of size magneton and TiO is added2Nanotube is added ammonium hydroxide and ethyl alcohol, is placed on magnetic stirring apparatus and stirs, obtain table The TiO of face grafting-OH2Alcohol suspending liquid.
Further, containing TiO2Catechol solution in, TiO2Content with catechol is about than being 1: 1.
Further, in step 3), the solvent of ferrocenecarboxylic acid solution is methanol.
Further, in step 3) and step 4), the ferrocenecarboxylic acid solution and glucose that ito electrode surfaces are added The volume for aoxidizing enzyme solutions is equal.
Compared with prior art, assay method of the invention uses the TiO with catalytic activity2Nanotube, with adjacent benzene two Phenol is coupled modified electrode, then ferrocenecarboxylic acid is selected to cooperate with the electron mediator as glucose oxidase, enhances glucose Electron transmission in continuous mode and reaction signal particularly show the microdetermination of sample the superiority of this method.
Description of the drawings
Attached drawing described herein is used to provide further understanding of the present invention, and constitutes the part of the present invention, this hair Bright illustrative embodiments and their description are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings:
Fig. 1 is catechol and catechol+TiO2Scanning modify collection of illustrative plates.
Fig. 2 is multiple electrodes respectively at the Fe of 0.125mmol/L (CN)4-/3-CV in solution compares figure.
Fig. 3 is multiple electrodes in PBS, PBS-H2O2CV in buffer solution compares figure.
Fig. 4 is Fe (CN) of the multiple electrodes in 0.125mmol/L4-/3-EIS in solution compares figure.
Fig. 5 is comparison figure of the multiple electrodes on i-t figures.
Fig. 6 is the Linear equations of tested component glucose assays.
Fig. 7 is the scanning spectra influenced on electric current on modified electrode under different scanning rates.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the specific embodiment of the invention and Technical solution of the present invention is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only the present invention one Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing The every other embodiment obtained under the premise of going out creative work, shall fall within the protection scope of the present invention.
TiO is utilized the present invention provides a kind of2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution is surveyed Relevant instrument and reagent are first got out before fixed, specifically,
Instrument includes:Supersonic wave cleaning machine, electronic balance, Superpure water machine, intelligent magnetic force heating stirrer, reinforcement electric mixing Device, electrochemical analyser, electric heating constant-temperature blowing drying box, beaker, conical flask, round-bottomed flask, constant volume bottle, graduated cylinder, EP is mixed to manage, is micro- Measure sample introduction needle, universal meter, pan paper, rubber head dropper, iron stand, tweezers, ito working electrodes, stirring rod, rubber gloves, wiping Mirror paper, label adhesive paper and magneton etc..Wherein, ito electrodes also known as indium-tin oxide electrode are a kind of transparent conductive films.
Reagent includes:C2H5OH (ethyl alcohol), NaOH (sodium hydroxide), CH3COCH3(acetone), CH4O (methanol), K3[Fe (CN)6] (potassium ferricyanide), K4[Fe(CN)6]·3H2O2(potassium ferrocyanide), KCl (potassium chloride), NaHPO4(disodium hydrogen phosphate), KH2PO4(potassium dihydrogen phosphate), TiO2(titanium dioxide), C6Hl2O6·H2O2(glucose), catechol, ferrocenecarboxylic acid, Portugal Grape carbohydrate oxidase and H2O2(hydrogen peroxide) etc..
Specific assay method is as follows:
The pretreatment of the naked ito electrodes of step 1):
1, one, 50mL beakers, the mixed liquor of the sodium hydroxide and ethyl alcohol of configuration about 40mL1: 1 are taken;
2, one, 50mL beakers, the mixed liquor of the acetone and deionized water of configuration about 40mL1: 1 are taken again;
3, several ito electrodes to be measured are immersed in successively in the mixed liquor of 1 and 2 configurations, respectively in supersonic cleaning machine It is 15min/ times ultrasonic, finally, in the beaker of another 50mL, it is packed into the deionized water of about 40mL, carries out the clear of last time It washes;
4, after waiting for wash clean, the droplet of ito electrode surfaces wipe up to dry, then by ito with lens wiping paper Electrode placing flat is on the table.Ito electrode surfaces are tested with universal meter, it is just to test out the surface that electric current is shown It places up, for use.
Step 2) contains TiO2Catechol solution preparation:
TiO2The preparation of dispersion liquid:0.25 gram of titanium dioxide solids powder and 40 milliliters of 10mol L-1Sodium hydroxide solution It stirs evenly, is added in autoclave and is reacted 24 hours under 130 DEG C of high temperature.After reaction, the cloud mixture obtained is used Ultra-pure water and dilute hydrochloric acid solution wash repeatedly, until solution is in neutrality, i.e., after pH value reaches 7.0, and the solid matter that filters The TiO to get caliber about 10nm is dried in 7 DEG C of baking ovens2Nanotube.
The TiO of surface graft-OH2The preparation of nanotube alcoholic dispersion system:In the round bottom for being placed with suitable size magneton The TiO of 0.5g or so is added in flask2Nanotube is added the ammonium hydroxide of a concentration of 1mol/L of 1mL, and is added about 2-3mL's or so Ethyl alcohol is placed on magnetic stirring apparatus and stirs, and the TiO of surface graft-OH is made2Alcohol suspending liquid.It is at least stirred before every time 15min or more.
The preparation of catechol solution:Catechol solid 0.005g is weighed with electronic balance, is dissolved in 10mL pH=7 PBS buffer solutions, ultrasound about 10min.
Contain TiO2The catechol solution of nanotube:Sufficient TiO will be stirred2Alcohol suspending liquid uses micro-sampling pin It extracts 20 μ L directly to have squeezed into catechol solution, ultrasound about 10min, configuration terminates.
Step 3) modifies TiO on ito electrodes2Nano material and catechol:
Naked ito electrodes are contained into TiO what is prepared by step 2)2Catechol solution in carry out cyclic voltammetry survey Fixed, the scanning number of turns is set as at least 15 circles so that TiO2Nanotube and catechol, which are fully modified, arrives ito electrode surfaces.
Step 4) modifies ferrocenecarboxylic acid on ito electrodes:
The ito electrode surfaces of step 3) modified are added dropwise to the ferrocenecarboxylic acid solution of 10 μ L, make its abundant volatile dry. Wherein, the solvent of ferrocenecarboxylic acid solution is methanol.
Step 5) modifies glucose oxidase on ito electrodes:
The glucose oxidase solution of 10 μ L is added dropwise again in the ito electrode surfaces that step 4) is prepared into, stands, makes it fully Volatile dry.
The content of glucose in step 6) ito determination of electrode aqueous solutions:
By ito electrodes made from step 5), the content of glucose in aqueous solution is measured using i-t methods.
Then, to containing TiO in surface modification film2TiO is not contained in the ito electrodes and surface modification film of nanotube2It receives The ito electrodes of mitron are compared under these electrochemical methods such as Fe-CV, PBS-CV, EIS.
It is as follows:
Step 1) prepares several naked ito electrodes.
The preparation of step 2) auxiliary reagent:
1, the PBS buffer solutions of PH=7:Weigh 71.628g disodium hydrogen phosphates and 27.218 phosphoric acid respectively with electronic balance Potassium dihydrogen carries out constant volume, a concentration of 0.2mol/L with the volumetric flask of 1000mL to them.According to disodium hydrogen phosphate: biphosphate The volume ratio that potassium is 61: 39 is configured to the buffer solution of PH=7, a concentration of 0.1mol/L.
2, Fe solution:Potassium ferrocyanide 0.026g, potassium ferricyanide 0.0206g and potassium chloride are weighed with electronic balance Then 0.1864g adds the phosphate buffer of 25mL, the Fe solution for being configured to 5mmol/L to be placed in volumetric flask in conical flask For use.
3, glucose solution:Glucose is weighed with electronic balance and deionized water is added, and 1mol/L is configured in volumetric flask Glucose solution, place for use.
4, ferrocenecarboxylic acid solution:The ferrocene that 0.005g is weighed with electronic balance takes the methanol of 1mL or so, uniformly mixed It closes in EP pipes, if dissolving is not enough, puts it into and carry out ultrasound in supersonic cleaning machine, accelerate its dissolving.
5, glucose oxidase solution:The glucose oxidase that 0.005g is weighed with electronic balance takes the PH of 1mL or so =7 PBS buffer solutions are dissolved, and are shaken up in EP pipes, if dissolving, which is not enough, can still place it in ultrasound Ultrasound is carried out in cleaning machine, accelerates its dissolving.
The characterization of step 3) electrode:
1, cyclic voltammetry of the naked ito electrodes in Fe and PBS
The cyclic voltammetry about naked ito electrodes is carried out in the PBS buffer solutions of the test solution of Fe and pH=7 first (CV) it measures, the foundation drawing as reference.
Wherein, cyclic voltammetry (CV) can be categorized into reduction parsing characterization on this basis, capacitance meter is sought peace resistance Hinder effect characterization etc..Cyclic voltammetry is the method analyzed by current -voltage curve, it is by potential value from starting One scanning to one of terminal, again from terminal one scan one to starting again.Cyclic voltammetry not only possesses Unique ability of the intermediate product of electrode process can be excavated, be differentiated, can also be easy to capture the electricity of in-between product The information of chemical and other properties.In addition to this, cyclic voltammetry or a kind of sensitive electrochemical method of comparison.Emphasis shows The information such as the shortcomings that this method can decidedly provide all about film and pin hole in membrane structure very much.This method not only may be used For characterization of membrane, it can also be used to processing update electrode etc..
2, ito electrodes are modified
Next, being in catechol solution and to contain TiO respectively by other two ready clean ito electrode2Point Cyclic voltammetry scanning is carried out in the catechol solution of granular media system, the setting scanning number of turns is 15 circles so that TiO2Nanotube and Catechol can fully modify ito electrode surfaces.Obtain catechol as shown in Figure 1 and catechol+TiO2It receives Collection of illustrative plates is modified in the scanning of mitron, wherein a indicates ito electrodes in catechol+TiO2Sweeping in the PBS buffer solutions of nanotube Tracing spectrum, b indicate scanning spectra of the ito electrodes in the PBS buffer solutions of catechol.Two curves of a from Fig. 1, b In comparing, hence it is evident that can obtain, prodigious variation occur in catechol oxidation peak current on the electrode and current potential, in solution Contain TiO2Catechol oxidation peak current (in a curves) ratio of nanotube dispersion system does not contain TiO2Nanotube dispersion system Catechol oxidation peak current be higher by about 3 times, illustrate TiO2Nanotube just plays well the oxidation of catechol Electronic catalytic acts on;Also occur shuffling phenomenon in simultaneous oxidation spike potential a curves, shows TiO2Nanotube is participating in being catalyzed While, also assist in the modification of electrode.
3, cyclic voltammetry of the modification ito electrodes in Fe solution
Wait for the surface liquid of two ito electrodes of modified all evaporate it is dry after, they are sequentially placed into The Fe (CN) of 0.125mmol/L4-/3The measurement that cyclic voltammetry is carried out in solution, compares the size of its redox peak current.
4, the cyclic voltammetry in PBS solution
Above-mentioned two pieces of electrodes are respectively put into the measurement for carrying out cyclic voltammetry in the PBS buffer solutions of pH=7, carry out electricity Flow the comparison of position.
5, in PBS+H2O2In cyclic voltammetry
Above-mentioned two pieces of electrodes are respectively put into the PBS buffer solutions of PH=7, and are rapidly added the H of 10 μ L2O2It is followed Ring voltammetric determination, then carry out the comparison of Current Position.
6, AC impedance (EIS) is carried out in Fe solution to test
Above-mentioned two pieces of electrodes are subjected to ac impedance measurement in Fe solution respectively.
Wherein, AC impedence method is EIS, and entire electrode system is investigated by the impedance spectrum in the wideband field that measures System, therefore it can be more than the acquisition of other electrochemical methods additional about interfacial structure and dynamic (dynamical) information.Exchange Impedance method (EIS) can use it for the transmission activity of the electronics of characterization electrode surface, and it can also effectively obtain electrode Reactive kinetics parameters.It not only will appreciate that the resistance characteristic of film itself by AC impedence method (EIS) and also have to solution and hinder Between substrate the effect of electron transmission, moreover it is possible to which the performance of qualitative and quantitative investigation self-assembled film, it is existed by studying different molecular Lead to the change of impedance and its behavior between different film layers, thus it will be seen that going out the pass between RCt, Cdt and film layer number Connection.
7, the modification characterization of ferrocenecarboxylic acid
With before, prepares ito electrodes (respectively bare electrode, in catechol-PBS solution the electrode of modified with contain There is TiO2Catechol-PBS buffer solutions in modified electrode) surface be added dropwise 10 μ L ferrocenecarboxylic acid solution, due to The solvent of ferrocenecarboxylic acid solution is methanol, so volatility is very high, when surface evaporation is completely dry, is carried out in Fe solution The measurement of cyclic voltammetry, the measurement that cyclic voltammetry is carried out in PBS, H is added in PBS buffer solutions2O2Carry out cycle volt The measurement of peace method, and in Fe solution carry out EIS measurement.
8, the modification characterization of glucose oxidase
With before, prepares ito (respectively bare electrode, in catechol-PBS buffer solutions the electrode of modified with contain There is TiO2The electrode of modified in the catechol-PBS buffer solutions of nanotube) surface be added 10 μ L ferrocenecarboxylic acid it is molten After liquid, after waiting for its evaporation completely, continue that the 10 μ L of glucose oxidase solution configured are added dropwise on its surface, standing is about 24H, after making its abundant volatile dry, carry out respectively in Fe solution the measurement of cyclic voltammetry, in PBS buffer solutions into H is added in PBS buffer solutions in the measurement of row cyclic voltammetry2O2The measurement of cyclic voltammetry is carried out, and in Fe solution Carry out the measurement of EIS.
9, i-t is tested
I-t methods are chronoamperometry, are by applying unipotential step or double electricity to the working electrode of electrochemical system After the step of position, the functional relation of current-responsive and time is measured.
Specifically, prepare fresh ito electrodes (bare electrode, in catechol-PBS solution the electrode of modified with contain Have the electrode of modified in catechol-PBS solution of TiO2), one layer of ferrocenecarboxylic acid solution is modified at it, evaporates exsiccation Modify one layer of glucose oxidase again afterwards, it is about that 24H is placed on the pH of 10mL after making its abundant volatile dry to stand In=7 PBS solution, at interval of one minute, 10 μ L, 15 μ L, 20 μ L, 25 μ L, 30 μ L, 35 μ L, 40 μ are added in the solution successively L, the glucose solution of 45 μ L, 50 μ L observes pulse change.
Analysis and summary:
1, the comparison of CV figures:
First, CV figure of the comparison multiple electrodes in Fe solution.Such as Fig. 2, multiple electrodes are respectively 0.125mmol/L's Fe(CN)4-/3-CV in solution compares.From figure, it can be clearly seen that by TiO2Scanning modified electrode current be It is maximum.Secondly the TiO to smear2The electrode current of modification and without TiO2The electrode current of modification.
Then compare in PBS, PBS-H2O2Middle CV figures.See Fig. 3, multiple electrodes are in PBS, PBS-H2O2In buffer solution CV compares.From figure, by TiO2No matter the electrode that nanotube scans modified is all obviously to be higher by PBS, PBS-H2O2 Smear the electrode of TiO2 modifications and no TiO2The electric current of the electrode of modified.It has been investigated that there is TiO2The electrode of modification Electric current, which has, obviously to be increased, and illustrates TiO2Nanotube is in the solution for H2O2Electrochemical behavior have well catalysis Effect, TiO2Nanotube accelerates the transmission capacity of electronics.
2, the comparison of EIS figures:
The electrode of modified and contain TiO by bare electrode, in catechol-PBS solution2The catechol-of nanotube EIS of these three electrodes of the electrode of modified in Fe solution is compared in PBS solution.
The electrode of modified and contain TiO by bare electrode, in catechol-PBS solution again2The adjacent benzene two of nanotube The electrode of modified in phenol-PBS solution, the EIS after electrode surface added ferrocenecarboxylic acid respectively in Fe solution are carried out Comparison.
Finally the electrode of modified and contain TiO by bare electrode, in catechol-PBS solution2The adjacent benzene two of nanotube Three electrodes difference of the electrode of modified after successively adding ferrocenecarboxylic acid and glucose oxidase in phenol-PBS solution EIS in Fe solution is compared.
After chosen superposition, as shown in Figure 4, Fe (CN) of the multiple electrodes in 0.125mmol/L4-/3-EIS in solution Compare.
By contrast it can be found that there is TiO2For nanometer tube modified electrode in terms of impedance, impedance value is smaller, so more Confirmation has TiO2The catalytic action of nanotube, the transmission for sufficiently lowering electronics hinder ability.
3, the comparison of i-t figures
The electrode of modified and contain TiO by bare electrode, in catechol-PBS solution2The catechol-of nanotube These three electrodes of the electrode of modified added the comparison of progress i-t after ferrocenecarboxylic acid and glucose oxidase in PBS solution. As shown in Figure 5
As a result, it has been found that the electric current of a is the largest relative to other electrode currents, and because due to glucose oxidase There is catalytic action to the oxidation of glucose, oxidation product is H2O2, TiO in experiment2The nanotube product glycoxidative to grape is gathered around There is good catalytic action.
The range of linearity of glucose is 0.1 μm of ol~2.0mmol, linear equation y=0.03072+0.06406x, detection limit For 0.05 μm of ol.As shown in Figure 6.
4, the comparison of rate
By the surfaces ito in catechol and TiO2One layer of ferrocene first is added dropwise on its surface after being modified in nanotube Acid, it is to be evaporated that one layer of glucolase is added dropwise completely and then by its surface.Ito obtained is put into PBS buffer solutions by us In, carry out the measurement of influence of the different rates to its electric current.As shown in Figure 7.
Take out everywhere peak position current value, make the linearity curve of corresponding LogV and I, obtained straight line compared with For success, it is higher that its linear dependence can be obtained.
Contain TiO it can be seen from above-mentioned relatively figure2The ito of nanotube no matter Fe-CV, PBS-CV, EIS etc. these Electrochemical method has compared to without containing TiO2The unsurpassed electronic catalytic superiority of ito of nanotube.In the outer of electrode Layer surface drop coating glucose oxidase measures the content of glucose in aqueous solution using i-t methods, and detection range is wider, detection limit It reduces.
Due to TiO2Nanotube possesses so outstanding catalytic, so the electronics that it is measured as glucose oxidase Carrier is transmitted, the measurement of glucose in aqueous solution is applied to.
The assay method of the present invention selects the TiO with catalytic activity2Nanotube, on the basis of laboratory synthesizes, with Catechol is coupled modified electrode, then ferrocenecarboxylic acid is selected to cooperate with the electron mediator as glucose oxidase, enhances Electron transmission during glucose assays and reaction signal particularly show the superior of this method for the microdetermination of sample Property.
Above-described specific example has carried out further in detail the purpose of the present invention, technical solution and advantageous effect Illustrate, it should be understood that the above is only a specific embodiment of the present invention, be not intended to restrict the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention Within the scope of.

Claims (10)

1. utilizing TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, which is characterized in that in TiO2Nanometer Pipe surface grafting-OH, with electrochemical method by TiO2Nanotube and catechol modification simultaneously form compound on ito electrodes Then film modifies ferrocenecarboxylic acid again on the surface of the composite membrane, and glycoxidative in the superficies drop coating grape of ito electrodes Enzyme finally uses chronoamperometry to measure the content of glucose in aqueous solution.
2. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, the TiO2Nanotube is prepared using hydro-thermal method.
3. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, the electrochemical method includes using cyclic voltammetry, Electrode with Electrochemical Impedance Spectroscopy or chronoamperometry.
4. utilizing TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, which is characterized in that including walking as follows Suddenly:
Step 1) contains TiO2Catechol solution preparation:By TiO2Alcohol suspending liquid is straight after being extracted using micro-sampling pin It has taken in catechol solution, has then carried out ultrasound, wherein TiO2TiO in alcohol suspending liquid2For surface graft-OH's TiO2Nanotube;
Step 2) modifies TiO on ito electrodes2Nanotube and catechol:Naked ito electrodes are contained what is prepared by step 1) TiO2Catechol solution in carry out cyclic voltammetry scanning, scanning the number of turns be set as at least 15 circle so that TiO2Nanotube and Catechol, which is fully modified, arrives ito electrode surfaces;
Step 3) modifies ferrocenecarboxylic acid on ito electrodes:Ferrocenecarboxylic acid is added dropwise in the ito electrode surfaces of step 2) modified Solution makes its abundant volatile dry;
Step 4) modifies glucose oxidase on ito electrodes:Glucose is added dropwise again in the ito electrode surfaces that step 3) is prepared into Enzyme solutions are aoxidized, stands, makes its abundant volatile dry;
The content of glucose in step 5) ito determination of electrode aqueous solutions:By ito electrodes made from step 4), using electrochemistry work Chronoamperometry on standing measures the content of glucose in aqueous solution.
5. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, naked ito electrodes are pre-processed before use, and specific processing method is that naked ito electrodes are immersed in hydrogen successively It is ultrasonic in supersonic cleaning machine respectively in the mixed liquor and acetone of sodium oxide molybdena and ethyl alcohol and the mixed liquor of deionized water, then use Deionized water is cleaned.
6. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, in step 1), TiO2The preparation method of nanotube is as follows:
By TiO2Solid powder is stirred evenly with sodium hydroxide solution, and reaction 24 is small under 130 DEG C of high temperature in addition autoclave When, after reaction, obtained cloud mixture ultra-pure water and dilute hydrochloric acid solution wash repeatedly, until solution is in neutrality, i.e., After pH value reaches 7.0, the solid matter filtered is dried in 70 DEG C of baking ovens to get TiO2Nanotube.
7. according to claim 6 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, the TiO of surface graft-OH in step 1)2The preparation method of nanotube alcohol suspending liquid is as follows:
TiO is added in the flask for being placed with suitable size magneton2Nanotube is added ammonium hydroxide and ethyl alcohol, is placed on magnetic stirring apparatus Stirring, obtains the TiO of surface graft-OH2Nanotube alcohol suspending liquid.
8. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, contains TiO2In the catechol solution of nanotube, TiO2Content ratio with catechol is 1: 1.
9. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, in step 3), the solvent of ferrocenecarboxylic acid solution is methanol.
10. according to claim 1 utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution, It is characterized in that, in step 3) and step 4), the ferrocenecarboxylic acid solution and glucose oxidase that ito electrode surfaces are added are molten The volume of liquid is equal.
CN201710492759.XA 2017-06-18 2017-06-18 By using TiO2Method for determining glucose in aqueous solution by nanotube modified ito electrode Expired - Fee Related CN108414595B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710492759.XA CN108414595B (en) 2017-06-18 2017-06-18 By using TiO2Method for determining glucose in aqueous solution by nanotube modified ito electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710492759.XA CN108414595B (en) 2017-06-18 2017-06-18 By using TiO2Method for determining glucose in aqueous solution by nanotube modified ito electrode

Publications (2)

Publication Number Publication Date
CN108414595A true CN108414595A (en) 2018-08-17
CN108414595B CN108414595B (en) 2020-06-16

Family

ID=63125407

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710492759.XA Expired - Fee Related CN108414595B (en) 2017-06-18 2017-06-18 By using TiO2Method for determining glucose in aqueous solution by nanotube modified ito electrode

Country Status (1)

Country Link
CN (1) CN108414595B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111077200A (en) * 2019-12-13 2020-04-28 江苏大学 Method for detecting chemical oxygen demand by constructing photoelectric color change visual sensor based on colorimetric method
CN111725525A (en) * 2020-06-18 2020-09-29 上海交通大学 Carbon-supported monodisperse Pt-Ni nanoparticle catalyst prepared by electrodeposition and preparation and application thereof
CN115356387A (en) * 2022-08-18 2022-11-18 北京大学 Transparent electrochemical sensor and biosensor, and manufacturing method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1346983A (en) * 2001-10-12 2002-05-01 中国科学院长春应用化学研究所 Process for preparing biologic sensor by embedding enzyme with composite titanium oxide sol-gel membrane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1346983A (en) * 2001-10-12 2002-05-01 中国科学院长春应用化学研究所 Process for preparing biologic sensor by embedding enzyme with composite titanium oxide sol-gel membrane

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CURULLI, VALENTINI ET AL.: "Smart (Nano) materials: TiO2 nanostructured films to modify electrodes for assembling of new electrochemical probes", 《SENSORS AND ACTUATORS B: CHEMICAL》 *
LI, LUO ET AL.: "Amperometric Detection of Glucose with Glucose Oxidase Absorbed on Porous Nanocrystalline TiO2 Film", 《ELECTROANALYSIS》 *
PANG, HE ET AL.: "An amperometric glucose biosensor fabricated with Pt nanoparticle-decorated carbon nanotubes/TiO2 nanotube arrays composite", 《SENSORS AND ACTUATORS B: CHEMICAL》 *
WANG, XIE ET AL.: "Glucose biosensor based on glucose oxidase immobilized on unhybridized titanium dioxide nanotube arrays", 《MICROCHIMICA ACTA》 *
WEN, ZHAO ET AL.: "Rapid Photoelectrochemical Method for in Situ Determination of Effective Diffusion Coefficient of Organic Compounds", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *
ZHAO, XU ET AL.: "Electrochemical Biosensors Based on Layer-by-Layer Assemblies", 《ELECTROANALYSIS》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111077200A (en) * 2019-12-13 2020-04-28 江苏大学 Method for detecting chemical oxygen demand by constructing photoelectric color change visual sensor based on colorimetric method
CN111077200B (en) * 2019-12-13 2022-03-22 江苏大学 Method for detecting chemical oxygen demand by constructing photoelectric color change visual sensor based on colorimetric method
CN111725525A (en) * 2020-06-18 2020-09-29 上海交通大学 Carbon-supported monodisperse Pt-Ni nanoparticle catalyst prepared by electrodeposition and preparation and application thereof
CN111725525B (en) * 2020-06-18 2022-03-15 上海交通大学 Carbon-supported monodisperse Pt-Ni nanoparticle catalyst prepared by electrodeposition and preparation and application thereof
CN115356387A (en) * 2022-08-18 2022-11-18 北京大学 Transparent electrochemical sensor and biosensor, and manufacturing method and application thereof

Also Published As

Publication number Publication date
CN108414595B (en) 2020-06-16

Similar Documents

Publication Publication Date Title
Yang et al. Electrochemical sensor based on molecularly imprinted polymer film via sol–gel technology and multi-walled carbon nanotubes-chitosan functional layer for sensitive determination of quinoxaline-2-carboxylic acid
Ensafi et al. A differential pulse voltammetric method for simultaneous determination of ascorbic acid, dopamine, and uric acid using poly (3-(5-chloro-2-hydroxyphenylazo)-4, 5-dihydroxynaphthalene-2, 7-disulfonic acid) film modified glassy carbon electrode
CN105842321B (en) The preparation method of the non-enzymatic glucose electrochemical sensor of cupric oxide nano pin/nitrogen-doped graphene composite
CN103604849B (en) Electrochemical sensor capable of simultaneously detecting dopamine, ascorbic acid and uric acid
Babaei et al. A sensor for simultaneous determination of dopamine and morphine in biological samples using a multi-walled carbon nanotube/chitosan composite modified glassy carbon electrode
CN104634853A (en) Method for detecting concentration of acrylamide in solution
CN108414595A (en) Utilize TiO2The method of glucose in nanometer tube modified ito determination of electrode aqueous solution
CN109580741A (en) It is a kind of to detect the modified electrode of dopamine, preparation method and applications
CN109613083A (en) Nanogold-highly sensitive detection the H of protoporphyrin copper (II)2O2The building and its application of electrochemical sensor
CN110031522A (en) Nickel metal-organic framework material and the preparation method and application thereof
CN111060573B (en) CoFe Prussian blue analogue modified electrode and application thereof in simultaneous determination of dopamine and 5-hydroxytryptamine contents
CN103063717A (en) Application of nickel aluminum layered double metal hydroxide modified electrode to measurement of uric acid
CN105866226A (en) Preparation and using method of glucose oxidase biosensor
CN101576530B (en) Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode
CN105866211B (en) A kind of preparation method and application of ampicillin molecular engram sensor
CN105223260B (en) Electrochemical sensor of trace quick detection butyl p-hydroxybenzoate and preparation method thereof
CN107153088A (en) It is a kind of to be used to detect electrochemical sensor of tyrosine and its preparation method and application
CN108760861A (en) A kind of Ni-MOF based electrochemical sensors for detecting uric acid
CN110261450A (en) It is a kind of to detect dopamine and adrenaline modified glassy carbon electrode, preparation method and application simultaneously
CN107064265A (en) A kind of electrochemica biological sensor for being used for HbA1c detections of MPBA modifications and its preparation and application
Xu et al. Simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid using polybromothymol blue film-modified glassy carbon electrode
CN112010359B (en) NiO/C nano composite electrode material and preparation method and application thereof
CN104049015B (en) Polypyrrole-Hemin-reduced graphene trielement composite material the application of microwave solvent method thermal synthesis
CN107515239B (en) A kind of method of recycling carbon fibre ultramicroelectrode
CN111830103A (en) Preparation and application methods of electrochemical sensor for rapidly detecting hydrogen peroxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200616