CN103278544B - Working electrode of electrochemical biosensor - Google Patents
Working electrode of electrochemical biosensor Download PDFInfo
- Publication number
- CN103278544B CN103278544B CN201310160204.7A CN201310160204A CN103278544B CN 103278544 B CN103278544 B CN 103278544B CN 201310160204 A CN201310160204 A CN 201310160204A CN 103278544 B CN103278544 B CN 103278544B
- Authority
- CN
- China
- Prior art keywords
- working electrode
- tio
- substrate
- silk
- enzyme
- 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.)
- Expired - Fee Related
Links
Landscapes
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The invention discloses a Tio2 nanorod array-based working electrode of an electrochemical biosensor. A layer of evenly distributed and compact TiO2 nanorod array grows on a Ti substrate or a Ti wire surface through a hydrothermal method, and after being modified by Nafion and enzyme, the previously formed electrode can be used as the working electrode of the electrochemical biosensor. According to the working electrode of the electrochemical biosensor, a variety of working electrodes of electrochemical biosensor can be prepared, the working electrodes of electrochemical biosensor are high in sensitivity, wide in detection range and excellent in stability, and can be widely used in the fields of biomedicine, environment monitoring, food detection, and so on.
Description
Technical field
The present invention relates to a kind of electrochemica biological sensor working electrode.
Background technology
Electrochemica biological sensor is that reacting with electrical signal form that biological identification molecule is occurred with substrate reads out, and has the advantages such as signals collecting is convenient, detection sensitivity is high, is to study a class biology sensor the most extensive and with the fastest developing speed.Wherein, the working electrode of enzyme modification is the important component part in electrochemica biological sensor, the working electrode of current state-of-the-art third generation electrochemica biological sensor need to be realized enzyme and interelectrode Direct electron transfer, the electrochemical sensor of this medialess can improve greatly sensor performance and serviceable life (N.J. Ronkainen et al.
chem. Soc. Rev.,39 (2010) 1747).But because the electric activity center of enzyme is all buried inner at one deck protein molecular, the Direct electron transfer of enzyme active center and electrode surface is difficult to occur.
Nano material is owing to having high-specific surface area, high surface free energy and a lot of other properties, can improve the avtive spot of enzyme immobilization and greatly improve catalytic capability, realizing Direct electron transfer (the A. Kaushik et al. of enzyme electric activity center and electrode surface
biosens. Bioelectron., 24 (2008) 676; S.W. Tan et al.
j. Electroanal. Chem., 668 (2012) 113).The preparation of the electrochemica biological sensor working electrode based on nano material at present, major part is all to use Powdered nano material, can have a strong impact on stability and the serviceable life of electrode, and nano material is easily reunited simultaneously, can reduce the immobilized of enzyme, affect the performance of sensor.Therefore, the advantage of combining nano material and the high-biocompatibility of titanic oxide material, the single crystal titanium dioxide nanometer rods with high-specific surface area is directly prepared at surface of metal electrode, utilizing the high conductivity of titanic oxide nanorod array, efficient enzyme adsorptive power and stability to improve the sensing capabilities of working electrode, is the biological sensor electrode material that has very much application prospect.
Summary of the invention
The object of this invention is to provide that a kind of highly sensitive, sensing range is wide, the electrochemica biological sensor working electrode of good stability.
Electrochemica biological sensor working electrode of the present invention obtains by following preparation process:
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, Ti substrate or Ti silk are placed in to water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h under 160 C °, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2ti substrate or the superficial growth of nanometer stick array have TiO
2the Ti silk of nanometer stick array;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti substrate of nanometer stick array, exposes 0.3 * 0.3 cm2 area as working electrode; Or there is TiO with epoxy encapsulation superficial growth
2the Ti silk of nanometer stick array, exposes the Ti silk of 3 mm length as working electrode;
3) enzyme is dissolved in 0.01M PBS to preparation 10 mg mL
-1enzyme solutions, by through step 2) packaged working electrode soaks 4 h in enzyme solutions, after drying at room temperature, then the Nafion solution that is placed in mass concentration 0.5 % soaks 1 h, after drying at room temperature, at 4 ° of C, preserves 12 h.
Above-mentioned enzyme can be horseradish peroxidase, glucose oxidase, myoglobins, cholesterol oxidase or haemoglobin.
In the present invention, said Ti substrate thickness is generally 0.1 mm, the TiO on Ti substrate working electrode
2nanometer rods mean diameter is 40 nm, is highly 1 μ m.
Said Ti filament diameter is 1 mm, the TiO on Ti silk working electrode
2nanometer rods mean diameter is 40 nm, is highly 1 μ m.
The present invention by hydro-thermal method at Ti substrate or Ti silk superficial growth one deck, be evenly distributed, fine and close TiO
2nanometer stick array, by just can be used as electrochemica biological sensor working electrode after Nafion and enzyme modification, preparation method is simple and repeatability is high.The abundant species of electrochemica biological sensor working electrode prepared by the present invention, highly sensitive, sensing range are wide, good stability, can be widely used in the fields such as biomedicine, environmental monitoring and food inspection.
Accompanying drawing explanation
Fig. 1 is the TiO that is grown in Ti substrate surface
2the SEM picture of nanometer stick array; Wherein: figure a is low power SEM figure, illustration is section S EM figure, and figure b is high power SEM figure;
Fig. 2 is the TiO that is grown in Ti silk surface
2the SEM picture of nanometer stick array; Wherein scheming a is low power SEM figure, and figure b is high power SEM figure.
Embodiment
Embodiment 1
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, the Ti substrate that is 0.1 mm by thickness is placed in water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h under 160 C °, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2the Ti substrate of nanometer stick array, Fig. 1 is shown in by its SEM picture;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti substrate of nanometer stick array, exposes 0.3 * 0.3 cm2 area as working electrode;
3) haemoglobin is dissolved in 0.01M PBS, makes 10 mg mL
-1enzyme solutions, by through step 2) packaged working electrode soaks 4 h in enzyme solutions, and after drying at room temperature, then the Nafion solution that is placed in mass concentration 0.5 % soaks 1 h, after drying at room temperature, in 4 ° of C refrigerators, preserve 12 h, obtain the working electrode of modified hemoglobin.
This working electrode bio-sensing sensitivity is 1780 μ A mM
-1cm
-2, linear test specification is 5 ~ 865 μ M.
Embodiment 2
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, the Ti substrate that is 0.1 mm by thickness is placed in water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h under 160 C °, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2the Ti substrate of nanometer stick array;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti substrate of nanometer stick array, exposes 0.3 * 0.3 cm2 area as working electrode;
3) cholesterol oxidase is dissolved in 0.01M PBS, makes 10 mg mL
-1enzyme solutions, by through step 2) packaged working electrode soaks 4 h in enzyme solutions, and after drying at room temperature, then the Nafion solution that is placed in mass concentration 0.5 % soaks 1 h, after drying at room temperature, in 4 ° of C refrigerators, preserve 12 h, obtain the working electrode that cholesterol oxidase is modified.Its bio-sensing sensitivity is 732 μ A mM
-1cm
-2, linear test specification is 36 ~ 1038 μ M.
Embodiment 3
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, Ti silk is placed in to water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h under 160 C °, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2the Ti silk of nanometer stick array, Fig. 2 is shown in by its SEM picture;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti silk of nanometer stick array, exposes the Ti silk of 3 mm length as working electrode;
3) horseradish peroxidase is dissolved in 0.01M PBS, makes 10 mg mL
-1enzyme solutions, by through step 2) packaged working electrode soaks 4 h in enzyme solutions, and after drying at room temperature, then the Nafion solution that is placed in mass concentration 0.5 % soaks 1 h, after drying at room temperature, in 4 ° of C refrigerators, preserve 12 h, obtain the working electrode that horseradish peroxidase is modified.This working electrode bio-sensing sensitivity is 3520 μ A mM
-1cm
-2, linear test specification is 2 ~ 578 μ M.
Embodiment 4
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, Ti silk is placed in to water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h under 160 C °, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2the Ti silk of nanometer stick array;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti silk of nanometer stick array, exposes the Ti silk of 3 mm length as working electrode;
3) glucose oxidase thing enzyme is dissolved in 0.01M PBS, makes 10 mg mL
-1enzyme solutions.By through step 2) packaged working electrode soaks 4 h in enzyme solutions, and after drying at room temperature, then the Nafion solution that is placed in 0.5 wt.% soaks 1 h, after drying at room temperature, in 4 ° of C refrigerators, preserves 12 h, obtains the working electrode of glucose oxidase thing enzyme modification.Its bio-sensing sensitivity is 115 μ A mM
-1cm
-2, linear test specification is 45 ~ 974 μ M.
Embodiment 5
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, Ti substrate is placed in to water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h under 160 C °, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2the Ti substrate of nanometer stick array;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti substrate of nanometer stick array, exposes 0.3 * 0.3 cm2 area as working electrode;
3) myoglobins is dissolved in 0.01M PBS, makes 10 mg mL
-1enzyme solutions, by through step 2) packaged working electrode soaks 4 h in enzyme solutions, and after drying at room temperature, then the Nafion solution that is placed in mass concentration 0.5 % soaks 1 h, after drying at room temperature, in 4 ° of C refrigerators, preserve 12 h, obtain the working electrode that myoglobins is modified.Its bio-sensing sensitivity is 1443 μ A mM
-1cm
-2, linear test specification is 32 ~ 1142 μ M.
Claims (4)
1. an electrochemica biological sensor working electrode, described working electrode obtains by following preparation process:
1) 0.29g picric acid is dissolved in 9.6mL ethanol, then add successively hydrochloric acid and 150 μ L butyl titanates that 36mL deionized water, 24mL mass concentration are 37%, stir and be placed in water heating kettle, Ti substrate or Ti silk are placed in to water heating kettle, sealing, naturally is cooled to room temperature after reacting 4 h at 160 ℃, taking-up, with deionized water and ethanol, repeatedly rinse successively, obtaining superficial growth has TiO
2ti substrate or the superficial growth of nanometer stick array have TiO
2the Ti silk of nanometer stick array;
2) with epoxy encapsulation superficial growth, there is TiO
2the Ti substrate of nanometer stick array, exposes 0.3 * 0.3 cm2 area as working electrode; Or there is TiO with epoxy encapsulation superficial growth
2the Ti silk of nanometer stick array, exposes the Ti silk of 3 mm length as working electrode;
3) enzyme is dissolved in 0.01M PBS to preparation 10 mg mL
-1enzyme solutions, by through step 2) packaged working electrode soaks 4 h in enzyme solutions, after drying at room temperature, then the Nafion solution that is placed in mass concentration 0.5 % soaks 1 h, after drying at room temperature, at 4 ℃, preserves 12 h.
2. electrochemica biological sensor working electrode according to claim 1, is characterized in that said enzyme is horseradish peroxidase, glucose oxidase or cholesterol oxidase.
3. electrochemica biological sensor working electrode according to claim 1, is characterized in that said Ti substrate thickness is 0.1 mm, the TiO on Ti substrate working electrode
2nanometer rods mean diameter is 40 nm, is highly 1 μ m.
4. electrochemica biological sensor working electrode according to claim 1, is characterized in that said Ti filament diameter is 1 mm, the TiO on Ti silk working electrode
2nanometer rods mean diameter is 40 nm, is highly 1 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310160204.7A CN103278544B (en) | 2013-05-03 | 2013-05-03 | Working electrode of electrochemical biosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310160204.7A CN103278544B (en) | 2013-05-03 | 2013-05-03 | Working electrode of electrochemical biosensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103278544A CN103278544A (en) | 2013-09-04 |
| CN103278544B true CN103278544B (en) | 2014-11-26 |
Family
ID=49061125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310160204.7A Expired - Fee Related CN103278544B (en) | 2013-05-03 | 2013-05-03 | Working electrode of electrochemical biosensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103278544B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104076077B (en) * | 2014-06-25 | 2016-07-06 | 东南大学 | A kind of nitrogen-doped titanium dioxide nanotube array enzyme electrode and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497427A (en) * | 2009-02-27 | 2009-08-05 | 南京航空航天大学 | Method for preparing titanic oxide nanorod array combination electrode by low-temperature hydrothermal process |
| CN101813660B (en) * | 2010-04-02 | 2013-04-24 | 北京工业大学 | Method for preparing fixed enzyme electrode by using TiO2 as carrier |
| CN102645475A (en) * | 2012-04-25 | 2012-08-22 | 浙江大学 | Surface treated TiO2 nano lattice array based working electrode for electrochemical biosensor |
-
2013
- 2013-05-03 CN CN201310160204.7A patent/CN103278544B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103278544A (en) | 2013-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | TiO 2 nanotube arrays: intrinsic peroxidase mimetics | |
| Zhong et al. | Ultrasensitive non-enzymatic glucose sensors based on different copper oxide nanostructures by in-situ growth | |
| Emran et al. | Facile synthesis of microporous sulfur-doped carbon spheres as electrodes for ultrasensitive detection of ascorbic acid in food and pharmaceutical products | |
| Zhao et al. | Highly sensitive uric acid biosensor based on individual zinc oxide micro/nanowires | |
| Niu et al. | Recent advances in non-enzymatic electrochemical glucose sensors based on non-precious transition metal materials: opportunities and challenges | |
| Yang et al. | NiO/SiC nanocomposite prepared by atomic layer deposition used as a novel electrocatalyst for nonenzymatic glucose sensing | |
| Wang et al. | Solvothermal synthesis of Cu/Cu 2 O hollow microspheres for non-enzymatic amperometric glucose sensing | |
| Niu et al. | Platinum nanoparticle-decorated carbon nanotube clusters on screen-printed gold nanofilm electrode for enhanced electrocatalytic reduction of hydrogen peroxide | |
| Weina et al. | A novel β-MnO2 micro/nanorod arrays directly grown on flexible carbon fiber fabric for high-performance enzymeless glucose sensing | |
| US9725332B2 (en) | Transition metal dichalcogenide aerogels and methods of preparation and use | |
| Chu et al. | An amperometric glucose biosensor based on the immobilization of glucose oxidase on the platinum electrode modified with NiO doped ZnO nanorods | |
| Qu et al. | Nanoflower-like CoS-decorated 3D porous carbon skeleton derived from rose for a high performance nonenzymatic glucose sensor | |
| Lou et al. | A simple sonochemical assisted synthesis of NiMoO4/chitosan nanocomposite for electrochemical sensing of amlodipine in pharmaceutical and serum samples | |
| Zhang et al. | Construction of titanium dioxide nanorod/graphite microfiber hybrid electrodes for a high performance electrochemical glucose biosensor | |
| CN106324059B (en) | A kind of preparation method of glucose sensor electrode without enzyme material | |
| Ding et al. | A promising biosensing-platform based on bismuth oxide polycrystalline-modified electrode: characterization and its application in development of amperometric glucose sensor | |
| Fallatah et al. | Cerium oxide based glucose biosensors: influence of morphology and underlying substrate on biosensor performance | |
| Liu et al. | Mesoporous ZnO-NiO architectures for use in a high-performance nonenzymatic glucose sensor | |
| Fan et al. | Flower-like Bi2Se3 nanostructures: synthesis and their application for the direct electrochemistry of hemoglobin and H2O2 detection | |
| Wang et al. | A nonenzymatic glucose sensing platform based on Ni nanowire modified electrode | |
| Cao et al. | ISFET‐based sensors for (bio) chemical applications: A review | |
| CN109778172A (en) | One kind is for non-enzymatic glucose sensor composite nano materials and preparation method thereof | |
| Zhao et al. | Zinc oxide nanowires-based electrochemical biosensor for L-lactic acid amperometric detection | |
| Hong et al. | Immobilization of glucose oxidase on graphene oxide for highly sensitive biosensors | |
| CN103412000A (en) | ZnO/NiO single bending nanowire heterojunction biosensor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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: 20141126 Termination date: 20200503 |