CN103278544A - Working electrode of electrochemical biosensor - Google Patents
Working electrode of electrochemical biosensor Download PDFInfo
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- CN103278544A CN103278544A CN2013101602047A CN201310160204A CN103278544A CN 103278544 A CN103278544 A CN 103278544A CN 2013101602047 A CN2013101602047 A CN 2013101602047A CN 201310160204 A CN201310160204 A CN 201310160204A CN 103278544 A CN103278544 A CN 103278544A
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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 the reaction that biological identification molecule and substrate take place is read out with electrical signal form, has advantages such as signals collecting convenience, detection sensitivity height, 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 the electrochemica biological sensor, the working electrode of present state-of-the-art third generation electrochemica biological sensor need realize that enzyme and interelectrode direct electron shift, 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 all is buried in one deck protein molecular inside, the direct electron of enzyme active center and electrode surface shifts and is difficult to take place.
Nano material is owing to have 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, realize that the direct electron of enzyme electric activity center and electrode surface shifts (A. Kaushik et al.
Biosens. Bioelectron., 24 (2008) 676; S.W. Tan et al.
J. Electroanal. Chem., 668 (2012) 113).At present based on the preparation of the electrochemica biological sensor working electrode of nano material, major part all is 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, influence 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 that will have high-specific surface area directly prepares 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 application prospect is arranged very much.
Summary of the invention
The purpose 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 the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, Ti substrate or Ti silk are placed water heating kettle, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol 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 the epoxy encapsulation superficial growth TiO is arranged
2The Ti substrate of nanometer stick array exposes 0.3 * 0.3 cm2 area as working electrode; Perhaps with the epoxy encapsulation superficial growth TiO is arranged
2The Ti silk of nanometer stick array exposes the Ti silk of 3 mm length as working electrode;
3) enzyme is dissolved among the 0.01M PBS, prepares 10 mg mL
-1Enzyme solutions, will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of mass concentration 0.5 % to soak 1 h again, preserves 12 h at 4 ° of C after the drying at room temperature.
Above-mentioned enzyme can be horseradish peroxidase, glucose oxidase, myoglobins, cholesterol oxidase or haemoglobin.
Among the present invention, said Ti substrate thickness is generally 0.1 mm, the TiO on the Ti substrate working electrode
2The nanometer rods mean diameter is 40 nm, highly is 1 μ m.
Said Ti filament diameter is 1 mm, the TiO on the Ti silk working electrode
2The nanometer rods mean diameter is 40 nm, highly is 1 μ m.
The present invention by hydro-thermal method be evenly distributed at Ti substrate or Ti silk superficial growth one deck, fine and close TiO
2Nanometer stick array, by just can be used as the electrochemica biological sensor working electrode behind Nafion and the enzyme modification, the preparation method is simple and repeatability is high.The kind of the electrochemica biological sensor working electrode of the present invention's preparation is abundant, highly sensitive, sensing range wide, good stability, can be widely used in fields such as biomedicine, environmental monitoring and food inspection.
Description of drawings
Fig. 1 is the TiO that is grown in the Ti substrate surface
2The SEM picture of nanometer stick array; Wherein: figure a is low power SEM figure, and 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 the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, be that the Ti substrate of 0.1 mm places water heating kettle with thickness, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol successively, obtaining superficial growth has TiO
2The Ti substrate of nanometer stick array, its SEM picture is seen Fig. 1;
2) with the epoxy encapsulation superficial growth TiO is arranged
2The Ti substrate of nanometer stick array exposes 0.3 * 0.3 cm2 area as working electrode;
3) haemoglobin is dissolved among the 0.01M PBS, makes 10 mg mL
-1Enzyme solutions, will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of mass concentration 0.5 % to soak 1 h again, in 4 ° of C refrigerators, preserve 12 h after the drying at room temperature, 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 the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, be that the Ti substrate of 0.1 mm places water heating kettle with thickness, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol successively, obtaining superficial growth has TiO
2The Ti substrate of nanometer stick array;
2) with the epoxy encapsulation superficial growth TiO is arranged
2The Ti substrate of nanometer stick array exposes 0.3 * 0.3 cm2 area as working electrode;
3) cholesterol oxidase is dissolved among the 0.01M PBS, makes 10 mg mL
-1Enzyme solutions, will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of mass concentration 0.5 % to soak 1 h again, in 4 ° of C refrigerators, preserve 12 h after the drying at room temperature, 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 the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, the Ti silk is placed water heating kettle, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol successively, obtaining superficial growth has TiO
2The Ti silk of nanometer stick array, its SEM picture is seen Fig. 2;
2) with the epoxy encapsulation superficial growth TiO is arranged
2The Ti silk of nanometer stick array exposes the Ti silk of 3 mm length as working electrode;
3) horseradish peroxidase is dissolved among the 0.01M PBS, makes 10 mg mL
-1Enzyme solutions, will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of mass concentration 0.5 % to soak 1 h again, in 4 ° of C refrigerators, preserve 12 h after the drying at room temperature, 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 the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, the Ti silk is placed water heating kettle, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol successively, obtaining superficial growth has TiO
2The Ti silk of nanometer stick array;
2) with the epoxy encapsulation superficial growth TiO is arranged
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 among the 0.01M PBS, makes 10 mg mL
-1Enzyme solutions.Will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of 0.5 wt.% to soak 1 h again, preserves 12 h after the drying at room temperature in 4 ° of C refrigerators, 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 the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, the Ti substrate is placed water heating kettle, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol successively, obtaining superficial growth has TiO
2The Ti substrate of nanometer stick array;
2) with the epoxy encapsulation superficial growth TiO is arranged
2The Ti substrate of nanometer stick array exposes 0.3 * 0.3 cm2 area as working electrode;
3) myoglobins is dissolved among the 0.01M PBS, makes 10 mg mL
-1Enzyme solutions, will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of mass concentration 0.5 % to soak 1 h again, in 4 ° of C refrigerators, preserve 12 h after the drying at room temperature, 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. electrochemica biological sensor working electrode, described working electrode obtains by following preparation process:
1) 0.29g picric acid is dissolved in the 9.6mL ethanol, add 36mL deionized water, 24mL mass concentration then successively and be 37% hydrochloric acid and 150 μ L butyl titanates, stir and be placed in the water heating kettle, Ti substrate or Ti silk are placed water heating kettle, sealing is cooled to room temperature behind reaction 4 h down naturally at 160 C °, takes out, wash repeatedly with deionized water and ethanol 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 the epoxy encapsulation superficial growth TiO is arranged
2The Ti substrate of nanometer stick array exposes 0.3 * 0.3 cm2 area as working electrode; Perhaps with the epoxy encapsulation superficial growth TiO is arranged
2The Ti silk of nanometer stick array exposes the Ti silk of 3 mm length as working electrode;
3) enzyme is dissolved among the 0.01M PBS, prepares 10 mg mL
-1Enzyme solutions, will be through step 2) packaged working electrode soaks 4 h in enzyme solutions, after the drying at room temperature, place the Nafion solution of mass concentration 0.5 % to soak 1 h again, preserves 12 h at 4 ° of C after the drying at room temperature.
2. electrochemica biological sensor working electrode according to claim 1 is characterized in that said enzyme is horseradish peroxidase, glucose oxidase, myoglobins, cholesterol oxidase or haemoglobin.
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 the Ti substrate working electrode
2The nanometer rods mean diameter is 40 nm, highly is 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 the Ti silk working electrode
2The nanometer rods mean diameter is 40 nm, highly is 1 μ m.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104076077A (en) * | 2014-06-25 | 2014-10-01 | 东南大学 | Nitrogen doped titanium dioxide nanotube array enzyme electrode and preparation method and application thereof |
Citations (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 |
| CN101813660A (en) * | 2010-04-02 | 2010-08-25 | 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 |
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Patent Citations (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 |
| CN101813660A (en) * | 2010-04-02 | 2010-08-25 | 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 |
Non-Patent Citations (2)
| Title |
|---|
| QIAN LI ET AL: ""Highly sensitive hydrogen peroxide biosensors based on TiO2 nanodots/ITO electrodes"", 《JOURNAL OF MATERIALS CHEMISTRY》, 31 December 2012 (2012-12-31), pages 9019 - 9026 * |
| 黄闪闪等: ""纯钛表面TiO2纳米棒阵列的制备及其形成机理研究"", 《稀有金属材料与工程》, vol. 41, 30 September 2012 (2012-09-30), pages 67 - 70 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104076077A (en) * | 2014-06-25 | 2014-10-01 | 东南大学 | Nitrogen doped titanium dioxide nanotube array enzyme electrode and preparation method and application thereof |
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