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 PDFInfo
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- 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
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- tio
- glucose
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 44
- 239000008103 glucose Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002071 nanotube Substances 0.000 claims abstract description 49
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004366 Glucose oxidase Substances 0.000 claims abstract description 22
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 22
- 229940116332 glucose oxidase Drugs 0.000 claims abstract description 22
- 235000019420 glucose oxidase Nutrition 0.000 claims abstract description 22
- 238000002848 electrochemical method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 238000000970 chrono-amperometry Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000001548 drop coating Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 88
- 238000002484 cyclic voltammetry Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 19
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 5
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 5
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229940088598 enzyme Drugs 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000003556 assay Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000007853 buffer solution Substances 0.000 description 18
- 238000005259 measurement Methods 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000219095 Vitis Species 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- -1 hydrogen Sodium hydroxide Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- 101710128063 Carbohydrate oxidase Proteins 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004082 amperometric method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems 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
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.
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| 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 |
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| 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 |
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| 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 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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