CN106596673B - Application of nano titanium dioxide/graphite fiber composite electrode in electrochemical biosensor - Google Patents
Application of nano titanium dioxide/graphite fiber composite electrode in electrochemical biosensor Download PDFInfo
- Publication number
- CN106596673B CN106596673B CN201510827357.1A CN201510827357A CN106596673B CN 106596673 B CN106596673 B CN 106596673B CN 201510827357 A CN201510827357 A CN 201510827357A CN 106596673 B CN106596673 B CN 106596673B
- Authority
- CN
- China
- Prior art keywords
- composite electrode
- titanium dioxide
- electrochemical
- electrode material
- tetrabutyl titanate
- 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.)
- Active
Links
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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an application of a nano titanium dioxide/graphite fiber composite electrode in an electrochemical biosensor, wherein the composite electrode comprises a composite electrode material and biomolecules assembled on the surface of the composite electrode material, the composite electrode material comprises graphite fibers and nano titanium dioxide attached to the surfaces of the graphite fibers, and the nano titanium dioxide is generated in situ on the surfaces of the graphite fibers. The electrode provided by the invention is applied to an electrochemical biosensor, and the sensitivity and repeatability of the sensor are greatly improved.
Description
Technical Field
The invention relates to an application of a nano titanium dioxide/graphite fiber composite electrode in an electrochemical biosensor.
Background
The biosensor plays an important role in clinical diagnosis, bioengineering, epidemic prevention and treatment, environmental protection and the like. Among them, electrochemical methods are gaining increasing favor in terms of their rapidity, simplicity, low cost, and high sensitivity. Various methods for constructing electrochemical biosensors have been developed, such as electrochemical biosensors based on various nanomaterials, biomacromolecules, and polymer materials, etc. Various electrochemical detection means have also been applied in electrochemical biosensors, including square wave voltammetry, differential pulse voltammetry, cyclic voltammetry, electrochemical impedance, etc.
In recent years, scientists in the fields of physics, chemistry, materials and the like have attracted great interest for one-dimensional nano titanium dioxide inorganic materials due to excellent biocompatibility, better electron transmission capability and mature preparation methods, and some sensing devices taking the one-dimensional nano titanium dioxide inorganic materials as construction materials have come into play. In the current research, the titanium dioxide one-dimensional nano material is mainly prepared by a hydrothermal method and a sol-gel method, and then is dripped on an electrode, and a biological molecule is modified and designed into a biosensor by physical adsorption and chemical assembly. The diameter of a conventional electrode such as a glassy carbon electrode or a gold electrode is only 1-3mm generally, the surface area is small, the number of parts for assembling or modifying is small, meanwhile, the conventional electrode is assembled layer by layer and is complex, unstable and easy to fall off, and the sensitivity and the repeatability of the sensor are greatly influenced.
Therefore, there is a need in the art to develop an electrode material with a large specific surface area, easy assembly or modification, and stable and high sensitivity for use in a sensor.
Disclosure of Invention
The invention aims to overcome the defects of small specific surface area, few parts for assembling or modifying, complex surface assembly and poor stability after assembly of the existing electrode material, and provides the application of the nano titanium dioxide/graphite fiber composite electrode in the electrochemical biosensor, wherein the nano titanium dioxide/graphite fiber composite electrode has large specific surface area, more assembling or modifying parts, simple surface assembly and good stability after assembly.
The inventor of the present invention found in research that, after graphite fibers are contacted with a solution containing tetrabutyl titanate and sintered to obtain graphite fibers with a titanium dioxide seed layer growing on the surface, the obtained graphite fibers with the titanium dioxide seed layer growing on the surface are mixed with an aqueous solution of tetrabutyl titanate in the presence of acid and subjected to hydrothermal reaction, so that one-dimensional nano titanium dioxide can be generated in situ on the surfaces of the graphite fibers, and the composite material as an electrode material has a large specific surface area and is easy to assemble or modify. The electrode material is applied to an electrochemical biosensor, and can greatly improve the sensitivity and repeatability of the sensor.
In order to achieve the above object, the present invention provides a use of a nano titanium dioxide/graphite fiber composite electrode in an electrochemical biosensor, wherein the composite electrode comprises a composite electrode material and a biomolecule assembled on a surface of the composite electrode material, the composite electrode material comprises graphite fibers and nano titanium dioxide attached to surfaces of the graphite fibers, and the nano titanium dioxide is generated in situ on the surfaces of the graphite fibers.
The composite electrode material provided by the invention has a large specific surface area, so that the surface of the electrode is easier to assemble or modify, and the composite electrode material has good stability after being assembled and is not easy to fall off. The composite electrode formed by assembling the electrode material and the biomolecules is applied to an electrochemical biosensor, so that the sensitivity and the repeatability of the sensor are greatly improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a scanning electron microscope SEM image of the nano titanium dioxide/graphite fiber composite electrode material a1 and a commercially available graphite fiber in preparation example 1 of the present invention, wherein a and b are commercially available graphite fibers, and c and d are the nano titanium dioxide/graphite fiber composite electrode material a 1.
FIG. 2 is an X-ray diffraction chart of titanium dioxide, graphite fibers and a nano titanium dioxide/graphite fiber composite electrode material A1 in preparation example 1 of the present invention, wherein a is titanium dioxide, b is graphite fibers, and c is a nano titanium dioxide/graphite fiber composite electrode material A1.
FIG. 3 is a graph showing the results of cyclic voltammetry measurements for example 1 (FIG. 3 a) and comparative example 1 (FIG. 3 b) of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, the term "in situ generation" refers to nucleation growth on the surface of graphite fibers.
The invention provides an application of a nano titanium dioxide/graphite fiber composite electrode in an electrochemical biosensor, wherein the composite electrode comprises a composite electrode material and biomolecules assembled on the surface of the composite electrode material, the composite electrode material comprises graphite fibers and nano titanium dioxide attached to the surfaces of the graphite fibers, and the nano titanium dioxide is generated in situ on the surfaces of the graphite fibers.
According to the invention, the composite electrode is a working electrode of the sensor, which is prepared by using a nano titanium dioxide/graphite fiber composite electrode material as a composite electrode material and assembling biomolecules on the surface of the composite electrode material. Preferably, the composite electrode material consists of graphite fibers and nano titanium dioxide attached to the surfaces of the graphite fibers. In the present invention, a method for preparing such a working electrode is not particularly limited, and may be a method conventionally used in the art, and may include, for example: the nano titanium dioxide/graphite fiber composite electrode material is adhered to FTO glass through silver colloid and connected with an electrode lead, then epoxy resin and tetrafluoroethylene tape are used for packaging, and biomolecules are assembled.
According to the present invention, the content of the nano titanium dioxide and the graphite fiber may be varied in a wide range, and preferably, the content of the nano titanium dioxide is 7 to 21 wt% and the content of the graphite fiber is 79 to 93 wt% based on the total amount of the composite electrode material. More preferably, the content of the nano titanium dioxide is 12 to 16 wt% and the content of the graphite fiber is 84 to 88 wt% based on the total amount of the composite electrode material.
According to the present invention, the nano titanium dioxide generated in situ on the surface of the graphite fiber may be a one-dimensional nano titanium dioxide, and the application is not particularly limited to such one-dimensional nano titanium dioxide, for example, the nano titanium dioxide may be one or more of a titanium dioxide nanowire, a titanium dioxide nanorod, and a titanium dioxide nanotube. In order to further improve the comprehensive performance of the electrode material, preferably, the nano titanium dioxide is one or more of a titanium dioxide nanowire, a titanium dioxide nanorod and a titanium dioxide nanotube. Wherein, in a preferred embodiment of the invention, the nano titanium dioxide is a nanowire with a diameter of 15-20nm and a length of 400-500 nm. Wherein, in another preferred embodiment of the invention, the nano titanium dioxide is a nano rod with a diameter of 100-150nm and a length of 1-1.5 μm. Wherein, in another preferred embodiment of the invention, the nano titanium dioxide is a nanotube with an inner diameter of 50-80nm, an outer diameter of 100-150nm and a length of 1-1.5 μm.
According to the present invention, the graphite fiber is also not particularly limited, and may be a graphite fiber that is conventional in the art, for example, the graphite fiber may be commercially available. In the present invention, the graphite fibers may be filamentous, and for example, may be filamentous fibers having a diameter of 5 to 6 μm.
According to the present invention, the preparation method of the nano titanium dioxide/graphite fiber composite electrode material preferably comprises:
(1) contacting the graphite fiber with a solution containing tetrabutyl titanate, and calcining a product obtained by the contact to obtain the graphite fiber with a titanium dioxide seed layer growing on the surface;
(2) and (2) in the presence of acid, mixing the graphite fiber with the titanium dioxide seed layer growing on the surface obtained in the step (1) and tetrabutyl titanate in water, and carrying out hydrothermal reaction.
According to the present invention, in the step (1), the amount of the solution containing tetrabutyl titanate used is not particularly limited, and in order to sufficiently contact the graphite fiber with the solution containing tetrabutyl titanate, the amount of the solution containing tetrabutyl titanate is preferably 30 to 40ml per 1g of the graphite fiber. The solution containing tetrabutyl titanate can be an alcohol solution containing tetrabutyl titanate, and the alcohol can be one or more of ethanol, methanol, ethylene glycol and the like. In order to prevent hydrolysis of tetrabutyl titanate, the solution containing tetrabutyl titanate may further contain a hydrolysis inhibitor, which may be a hydrolysis inhibitor conventionally used in the art, such as diethanolamine. Preferably, the solution containing tetrabutyl titanate is an ethanol solution containing tetrabutyl titanate and diethanolamine. More preferably, in the solution containing tetrabutyl titanate, the volume ratio of tetrabutyl titanate, diethanolamine and ethanol is 1: 0.1-0.5: 3-5.
According to the present invention, in the step (1), preferably, the contacting conditions include: the temperature is 15-35 deg.C, and the time is 30-40 min. The contact process is not particularly limited, and for example, the graphite fibers may be added to a solution containing tetrabutyl titanate to be brought into contact by immersion.
Preferably, the conditions of the calcination include: the temperature is 450-500 ℃ and the time is 1-3 h. The calcination may be carried out in a muffle furnace as is conventional in the art.
According to the present invention, in the step (2), the amount of the graphite fiber having a titanium dioxide seed layer grown on the surface thereof and tetrabutyl titanate is not particularly limited, and in order to sufficiently contact the graphite fiber having a titanium dioxide seed layer grown on the surface thereof and tetrabutyl titanate, the amount of tetrabutyl titanate is preferably 0.5 to 2mL, more preferably 0.5 to 1.5mL, based on 1g of the graphite fiber having a titanium dioxide seed layer grown on the surface thereof.
According to the present invention, it is preferable that, in the step (2), the volume ratio of tetrabutyl titanate to water is 1: 15-20.
According to the present invention, the process of mixing the graphite fiber having the titanium dioxide seed layer grown on the surface thereof with tetrabutyl titanate in the presence of acid in water is not particularly limited, and for example, the graphite fiber having the titanium dioxide seed layer grown on the surface thereof may be added to a mixed solution of tetrabutyl titanate, acid and water and mixed.
According to the present invention, the acid is not particularly limited, but preferably, the acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, and more preferably hydrochloric acid. Preferably, the amount of the acid used is 5 to 6mol/L relative to the system of the hydrothermal reaction (i.e., relative to the entire reaction solution of the hydrothermal reaction system). The concentration of the hydrochloric acid may be, for example, 10 to 12 mol/L.
According to the invention, in the step (2), the conditions of the hydrothermal reaction are such that the nano titanium dioxide is generated in situ on the surface of the graphite fiber in the form of one-dimensional nano structures, and preferably, the conditions of the hydrothermal reaction comprise: the temperature is 130-180 ℃, and the time is 8-12 h. The hydrothermal reaction may be carried out in a vessel conventionally used in the art, such as a polytetrafluoroethylene reaction vessel.
According to the present invention, the method may further comprise the steps of washing and drying the product obtained from the hydrothermal reaction. The washing may be washing the product with deionized water. The drying may be natural drying.
In the application of the nano titanium dioxide/graphite fiber composite electrode material in the preparation of the electrochemical biosensor, the electrochemical biosensor can be an electrochemical DNA sensor, an electrochemical immunosensor or an electrochemical glucose sensor.
As described above, the composite electrode refers to a working electrode of a sensor prepared by using a nano titanium dioxide/graphite fiber composite electrode material as a composite electrode material and assembling biomolecules on the surface of the composite electrode material. The surface treatment process of the prepared working electrode can be included for the purpose of assembling or modifying the electrode. The surface treatment method may be a method conventionally used in the art, such as surface hydroxylation, silanization, amination, and modification of electrode surface film forming property with a substance having good film forming property. The surface hydroxylation may be achieved by contacting the working electrode with concentrated sulfuric acid. The silylation and amination can be achieved by contacting the above surface hydroxylated working electrode with 3-Aminopropyltriethoxysilane (APTES). The change of the film forming property of the electrode surface can be realized by contacting the prepared working electrode with chitosan solution.
According to the present invention, in order to reduce the influence of the residual surface treatment solution on the assembly of the subsequent biomolecules, it is preferable to wash the surface-treated working electrode with water.
According to the present invention, the application may further include a process of assembling the surface-treated working electrode with biomolecules, for example, the silanized and aminated working electrode may be crosslinked with glutaraldehyde and then contacted with a solution of amino-containing biomolecules, such as terminally aminated DNA probe molecules, antibody molecules, or enzymes; the prepared working electrode can also be contacted with chitosan solution containing protein molecules such as enzyme or antibody. When the working electrode assembled with the antibody is used as an immunosensor, the electrode may be washed with a phosphate buffer solution, and then brought into contact with Bovine Serum Albumin (BSA) to block the same.
According to the invention, the application can be used for detecting biomolecules by using an electrochemical impedance technology, because the immobilization of the biomolecules on the surface of the electrode or the identification of the biomolecules can change the capacitance and the electron transfer impedance on the surface of the electrode. According to the application provided by the invention, the cyclic voltammetry technology can be used for detecting the biological molecules, because the biological molecules are fixed on the surface of the electrode and can undergo redox reaction in an electrochemical system.
In the present invention, when the electrochemical biosensor is an electrochemical DNA sensor, wherein in the electrochemical DNA sensor, the composite electrode is preferably prepared by cross-linking a composite electrode material with 3-aminopropyltriethoxysilane and glutaraldehyde and then assembling a DNA probe molecule with an aminated end, and the composite electrode is used as a working electrode to perform detection in complementary DNA solutions of different concentrations by an electrochemical impedance technique using a three-electrode system. Specifically, the method may include: (1) immersing the prepared working electrode in concentrated sulfuric acid overnight, then immersing in 1-3 wt% APTES solution for reaction for 1-3h, and then drying at 100-120 ℃ for 1-2 h. (2) Then, the working electrode treated in the above (1) was crosslinked with 1 to 5 wt% of glutaraldehyde for 2 hours and washed with secondary water. Then contacting with a solution of DNA probe molecules (1-100 mu M) with aminated ends, and reacting for 16-20h at the temperature of 2-8 ℃. (3) And (3) immersing the working electrode treated in the step (2) into complementary DNA solutions with different concentrations, reacting for 0.5-1.5h, taking out, washing with a phosphate buffer solution with the pH value of 7-7.4, adopting a platinum sheet or a platinum wire as a counter electrode and adopting a three-electrode system with Ag/AgCl (saturated KCl) as a reference electrode, and detecting by an electrochemical impedance technology.
When the electrochemical biosensor is an electrochemical immunosensor, in the electrochemical immunosensor, the composite electrode is preferably prepared by assembling a terminal aminated antibody molecule after cross-linking a composite electrode material with 3-aminopropyltriethoxysilane and glutaraldehyde, and the composite electrode is used as a working electrode to perform detection in antigen solutions of different concentrations by adopting a three-electrode system through an electrochemical impedance technology. Specifically, the method may include: (1) immersing the prepared working electrode in concentrated sulfuric acid overnight, then immersing in 1-3 wt% APTES solution for reaction for 1-3h, and then drying at 100-120 ℃ for 1-2 h. (2) Then, the working electrode treated in the above (1) was crosslinked with 1 to 5 wt% of glutaraldehyde for 2 hours and washed with secondary water. Then contacting with antibody molecule (1-100 μ M) solution, and reacting at 2-8 deg.C for 16-20 h. The working electrode after the reaction was washed with phosphate buffer at pH 6-7, and then contacted with Bovine Serum Albumin (BSA) to block it. (3) And (3) immersing the working electrode treated in the step (2) into antigen solutions with different concentrations, reacting for 0.5-1.5h at 37-55 ℃, taking out, washing with a phosphate buffer solution with the pH value of 6-7, and detecting by an electrochemical impedance technology by using a three-electrode system with a platinum sheet or a platinum wire as a counter electrode and Ag/AgCl (saturated KCl) as a reference electrode.
When the electrochemical biosensor is an electrochemical glucose sensor, in the electrochemical glucose sensor, the composite electrode is preferably prepared by contacting a composite electrode material with glucose oxidase and chitosan so as to assemble the glucose oxidase on the composite electrode material, and the composite electrode is used as a working electrode to detect glucose analysis solution containing different concentrations by adopting a three-electrode system through an electrochemical timing current technology. Specifically, the method may include: (1) immersing the prepared working electrode into a solution containing 10-20mg/ml glucose oxidase and 0.3-0.5 wt% of chitosan, and reacting for 0.5-1h at 15-35 ℃. (2) Then naturally drying at 2-8 ℃ overnight. (3) The glucose concentration in Phosphate Buffer Solution (PBS) is changed to carry out oxidation-reduction reactions of different degrees, a platinum sheet or a platinum wire is used as a counter electrode, Ag/AgCl (saturated KCl) is used as a three-electrode system of a reference electrode, and the detection is carried out by an electrochemical impedance technology.
The present invention will be described in detail below by way of examples.
In the present invention:
graphite fibers are available from east-li japan under the designation M40-JB 12k, filamentous fibers with a diameter of 5-6 μ M.
Tetrabutyl titanate is purchased from national pharmaceutical companies and has a purity of 99% by weight.
Diethanolamine, available from national medicine, is 99% pure by weight.
APTES solutions are available from sigma.
Silver glue is available from new Bailey.
FTO glass is available from emerging bairy corporation.
The electron micrograph was obtained by scanning electron microscopy of a model S-8020 from Hitachi.
The X-ray diffraction pattern was measured by an X-ray diffractometer model D8-advance of Bruker AXS.
Preparation example 1
The preparation example is used to illustrate the nano titanium dioxide/graphite fiber composite electrode material of the invention.
(1) Adding 1g of graphite fiber into an ethanol solution containing tetrabutyl titanate (7ml of tetrabutyl titanate, 2ml of diethanolamine and 27ml of absolute ethanol), carrying out ultrasonic treatment for 3 minutes, then contacting for 30 minutes, and calcining a product obtained by contacting at 500 ℃ for 1 hour to obtain the graphite fiber with a titanium dioxide seed layer growing on the surface;
(2) and (2) adding 1g of the graphite fiber with the titanium dioxide seed layer growing on the surface obtained in the step (1) into a polytetrafluoroethylene reaction kettle filled with a mixed solution of 1ml of tetrabutyl titanate, 20ml of deionized water and 20ml of hydrochloric acid (the concentration is 12mol/L), and carrying out hydrothermal reaction for 8 hours at 150 ℃. And washing and naturally drying a product obtained by the hydrothermal reaction to obtain a nano titanium dioxide/graphite fiber composite electrode material A1 (the content of nano titanium dioxide is 20 wt%, and the content of graphite fiber is 80 wt%), wherein the nano titanium dioxide is in a nanorod structure, the diameter of the nano titanium dioxide is 100nm, and the length of the nano titanium dioxide is 1.2 mu m. The SEM images of a1 are shown in c and d of fig. 1 (in addition, SEM images of commercially available graphite fibers are shown in a and b of fig. 1), and the X-ray diffraction pattern is shown in c of fig. 2 (in addition, X-ray diffraction patterns of titanium dioxide and commercially available graphite fibers are shown in a and b of fig. 2, respectively).
Example 1
This example is used to illustrate the application of the nano titanium dioxide/graphite fiber composite electrode material of the present invention in an electrochemical glucose sensor.
(1) A nano titanium dioxide/graphite fiber composite electrode material A1 prepared by 1cm is cut out, the nano titanium dioxide/graphite fiber composite electrode material A1 is adhered to FTO glass through silver colloid, a copper wire is adhered to one end of the FTO glass through the silver colloid to serve as an electrode lead, and the rest part of the FTO glass is sealed through epoxy resin and a polytetrafluoroethylene tape. Obtaining a working electrode of the electrochemical glucose sensor;
(2) then, immersing the working electrode treated in the step (1) into a mixed solution of glucose oxidase and chitosan (wherein the concentration of the glucose oxidase is 15mg/ml, and the mass fraction of the chitosan is 0.3 wt%), stirring for 1h at room temperature (20 ℃), and drying the working electrode obtained after reaction at 4 ℃ overnight;
(3) immersing the working electrode processed in the step (2) in Phosphate Buffered Saline (PBS) with glucose concentration of different concentrations, detecting by electrochemical cyclic voltammetry using a three-electrode system with a platinum sheet as a counter electrode and Ag/AgCl (saturated KCl) as a reference electrode, and the result is shown in FIG. 3 a.
Comparative example 1
According to the method of example 1, except that the nano titanium dioxide/graphite fiber composite electrode material a1 was replaced by commercial graphite fiber, the cyclic voltammetry test results are shown in fig. 3 b.
As described above, the nano titanium dioxide/graphite fiber composite electrode material provided by the invention has a larger specific surface area, is easier to assemble or modify, has ordered arrangement of titanium dioxide with a one-dimensional nano structure, does not agglomerate, is applied to a working electrode of a biosensor, and can remarkably improve the stability and sensitivity of the electrode.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various technical features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations of the features described in the present invention are not described again.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. The application of a nano titanium dioxide/graphite fiber composite electrode in an electrochemical biosensor is characterized in that the composite electrode comprises a composite electrode material and biomolecules assembled on the surface of the composite electrode material, wherein the composite electrode material comprises graphite fibers and nano titanium dioxide attached to the surfaces of the graphite fibers, and the nano titanium dioxide is generated in situ on the surfaces of the graphite fibers;
the preparation method of the composite electrode material comprises the following steps:
(1) contacting the graphite fiber with a solution containing tetrabutyl titanate, and calcining a product obtained by the contact to obtain the graphite fiber with a titanium dioxide seed layer growing on the surface;
(2) in the presence of acid, mixing the graphite fiber with the titanium dioxide seed layer growing on the surface obtained in the step (1) and tetrabutyl titanate in water and carrying out hydrothermal reaction;
in the step (1), the dosage of the solution containing tetrabutyl titanate is 30-40ml relative to 1g of graphite fiber, and the solution containing tetrabutyl titanate is an ethanol solution containing tetrabutyl titanate and diethanolamine; in the solution containing tetrabutyl titanate, the volume ratio of tetrabutyl titanate to diethanolamine to ethanol is 1: 0.1-0.5: 3-5; the conditions of the contacting include: the temperature is 15-35 ℃, the time is 30-40min, and the calcining conditions comprise: the temperature is 450-500 ℃, and the time is 1-3 h;
in the step (2), the using amount of tetrabutyl titanate is 0.5-2m relative to 1g of graphite fiber with a titanium dioxide seed layer growing on the surface; the volume ratio of tetrabutyl titanate to water is 1: 15-20 parts of; the conditions of the hydrothermal reaction include: the temperature is 130-180 ℃, and the time is 8-12 h.
2. Use according to claim 1, wherein the electrochemical biosensor is an electrochemical DNA sensor, an electrochemical immunosensor or an electrochemical glucose sensor.
3. The use of claim 2, wherein, in the electrochemical DNA sensor, the composite electrode is prepared by assembling a DNA probe molecule with an aminated terminal after cross-linking a composite electrode material with 3-aminopropyltriethoxysilane and glutaraldehyde, and the composite electrode is used as a working electrode to detect in complementary DNA solutions with different concentrations by an electrochemical impedance technology by using a three-electrode system.
4. The use of claim 2, wherein, in the electrochemical immunosensor, the composite electrode is prepared by assembling a terminal aminated antibody molecule after cross-linking a composite electrode material with 3-aminopropyltriethoxysilane and glutaraldehyde, and the composite electrode is used as a working electrode to detect in antigen solutions with different concentrations by an electrochemical impedance technology by using a three-electrode system.
5. The use according to claim 2, wherein, in the electrochemical glucose sensor, the composite electrode is prepared by contacting a composite electrode material with glucose oxidase and chitosan so that the composite electrode material is assembled with the glucose oxidase, and the composite electrode is used as a working electrode to detect glucose analysis solution containing different concentrations by an electrochemical chronoamperometry current technique by adopting a three-electrode system.
6. The use according to any one of claims 1 to 5, wherein the nano titanium dioxide is present in an amount of 7 to 21 wt% and the graphite fibers are present in an amount of 79 to 93 wt%, based on the total amount of the composite electrode material.
7. The use according to claim 6, wherein the nano titania is present in an amount of 12-16 wt% and the graphite fibers are present in an amount of 84-88 wt%, based on the total amount of the composite electrode material.
8. The use of any one of claims 1-5, wherein the nano titanium dioxide is one or more of a titanium dioxide nanowire, a titanium dioxide nanorod, and a titanium dioxide nanotube.
9. The use as claimed in claim 8, wherein the nano-titania is one or more of nanowires with a diameter of 15-20nm and a length of 400-500nm, nanorods with a diameter of 100-150nm and a length of 1-1.5 μm, and nanotubes with an inner diameter of 50-80nm, an outer diameter of 100-150nm and a length of 1-1.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510827357.1A CN106596673B (en) | 2015-11-24 | 2015-11-24 | Application of nano titanium dioxide/graphite fiber composite electrode in electrochemical biosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510827357.1A CN106596673B (en) | 2015-11-24 | 2015-11-24 | Application of nano titanium dioxide/graphite fiber composite electrode in electrochemical biosensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106596673A CN106596673A (en) | 2017-04-26 |
| CN106596673B true CN106596673B (en) | 2019-12-31 |
Family
ID=58555531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510827357.1A Active CN106596673B (en) | 2015-11-24 | 2015-11-24 | Application of nano titanium dioxide/graphite fiber composite electrode in electrochemical biosensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106596673B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110441366A (en) * | 2018-05-05 | 2019-11-12 | 深圳市贝沃德克生物技术研究院有限公司 | Detect the biosensor and method of concentration of glucose in diabetes biomarker |
| CN109406595B (en) * | 2018-11-26 | 2020-11-03 | 阜阳师范学院 | Preparation method of electrochemical sensor for detecting butyl p-hydroxybenzoate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265502A (en) * | 2008-04-23 | 2008-09-17 | 昆明理工大学 | Method for preparing tantalum doping tin oxide thin film carrier material for gene chip |
| CN103116023A (en) * | 2013-01-25 | 2013-05-22 | 宁波大学 | ECL (electrochemiluminescence) immunosensor for detecting tumor markers and preparation method and applications thereof |
-
2015
- 2015-11-24 CN CN201510827357.1A patent/CN106596673B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265502A (en) * | 2008-04-23 | 2008-09-17 | 昆明理工大学 | Method for preparing tantalum doping tin oxide thin film carrier material for gene chip |
| CN103116023A (en) * | 2013-01-25 | 2013-05-22 | 宁波大学 | ECL (electrochemiluminescence) immunosensor for detecting tumor markers and preparation method and applications thereof |
Non-Patent Citations (3)
| Title |
|---|
| Hierarchical TiO2 nanowire/graphite fiber photoelectrocatalysis setup powered by a wind-driven nanogenerator:A highly efficient photoelectrocatalytic device entirely based on renewable energy;Xin Yu等;《Nano Energy》;20141028;第11卷;摘要以及第20、25-26页 * |
| Highly sensitive silicon nanowire biosensor with novel liquid gate control for detection of specific single-stranded DNA molecules;Tijjani Adam等;《Biosensors and Bioelectronics》;20141006;第67卷;第656–661页 * |
| Performance of Impedimetric Biosensors Based on Anodically Formed Ti/TiO2 Electrodes;Aikaterini G. Mantzila等;《Electroanalysis》;20051015;第17卷(第20期);摘要，第1879、1885页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106596673A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sapountzi et al. | Recent advances in electrospun nanofiber interfaces for biosensing devices | |
| Esmaeeli et al. | Copper oxide-polyaniline nanofiber modified fluorine doped tin oxide (FTO) electrode as non-enzymatic glucose sensor | |
| Ahmad et al. | A single ZnO nanofiber-based highly sensitive amperometric glucose biosensor | |
| Ahmad et al. | High performance cholesterol sensor based on ZnO nanotubes grown on Si/Ag electrodes | |
| Singh et al. | Biomedical perspective of electrochemical nanobiosensor | |
| Liu et al. | Characterization of immobilization of an enzyme in a modified Y zeolite matrix and its application to an amperometric glucose biosensor | |
| Fang et al. | A glucose oxidase immobilization platform for glucose biosensor using ZnO hollow nanospheres | |
| Castillo et al. | Detection of cancer cells using a peptide nanotube–folic acid modified graphene electrode | |
| Abu-Salah et al. | Nanomaterials as analytical tools for genosensors | |
| JP2010531434A (en) | All-solid contact ion-selective electrode based on carbon nanotubes | |
| Fatemi et al. | Apple–biomorphic synthesis of porous ZnO nanostructures for glucose direct electrochemical biosensor | |
| Willander et al. | Metal oxide nanosensors using polymeric membranes, enzymes and antibody receptors as ion and molecular recognition elements | |
| Zhang et al. | An enzymatic glucose biosensor based on a glassy carbon electrode modified with manganese dioxide nanowires | |
| Ensafi et al. | Multiwall carbon nanotubes decorated with FeCr 2 O 4, a new selective electrochemical sensor for amoxicillin determination | |
| Khazaei et al. | Polyvinyl alcohol as a crucial omissible polymer to fabricate an impedimetric glucose biosensor based on hierarchical 3D-NPZnO/chitosan | |
| Radi et al. | Electrochemical sensors based on molecularly imprinted polymers for pharmaceuticals analysis | |
| Krishna et al. | A review on 2D-ZnO nanostructure based biosensors: From materials to devices | |
| Chen et al. | Immobilization of HRP in mesoporous silica and its application for the construction of polyaniline modified hydrogen peroxide biosensor | |
| Ghanei Agh Kaariz et al. | Fabrication of Au/ZnO/MWCNTs electrode and its characterization for electrochemical cholesterol biosensor | |
| Bai et al. | Voltammetric determination of chloramphenicol using a carbon fiber microelectrode modified with Fe 3 O 4 nanoparticles | |
| Yan et al. | Disposal immunosensor for sensitive electrochemical detection of prostate-specific antigen based on amino-rich nanochannels array-modified patterned indium tin oxide electrode | |
| CN106596673B (en) | Application of nano titanium dioxide/graphite fiber composite electrode in electrochemical biosensor | |
| Muthusankar et al. | Chitosan based nanocomposite biosensors: a recent review | |
| Caglar et al. | 3-Acrylamidopropyl-trimethylammoniumchloride cationic hydrogel modified graphite electrode and its superior sensitivity to hydrogen peroxide | |
| Amirthalingam et al. | Chitosan-based biosensor fabrication and biosensing applications |
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 |