CN103884756A - Preparation method and application of a TiO2 nanorod array thin-film electrode material - Google Patents
Preparation method and application of a TiO2 nanorod array thin-film electrode material Download PDFInfo
- Publication number
- CN103884756A CN103884756A CN201410050663.4A CN201410050663A CN103884756A CN 103884756 A CN103884756 A CN 103884756A CN 201410050663 A CN201410050663 A CN 201410050663A CN 103884756 A CN103884756 A CN 103884756A
- Authority
- CN
- China
- Prior art keywords
- array thin
- tio
- electrode material
- nano
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention discloses a preparation method and application of a TiO2 nanorod array thin-film electrode material. The method comprises the following steps: soaking a pure titanium sheet in a HCl solution or H2SO4 solution with the concentration of 8-10mmol/L for 12-24h under normal temperature and normal pressure conditions, cleaning the pure titanium sheet by using deionized water after the reaction is ended until the PH value is 7, drying at the temperature of 70-110 DEG C, calcining at the temperature of 400-600 DEG C for 1-2 hours, and thus obtaining the TiO2 nanorod array thin-film electrode material. The invention also discloses application of the TiO2 nanorod array thin-film electrode material in disease attribute miRNA related electrochemical biological sensing detectors or biological sensing devices. The TiO2 nanorod array thin film is uniform in thickness, controllable in shape, firm in structure and simple in electrode preparation process, adhesion of an adhesive is not needed, and standard mass production is easily realized.
Description
Technical field
The invention belongs to microelectronics biosensor technique field, relate to a kind of TiO
2the preparation method of nano-stick array thin film electrode material and application thereof, particularly a kind of TiO
2the preparation method of nano-stick array thin film electrode material and in the application of genius morbi miRNA associated electrical chemical-biological sensing detection or bio-sensing device.
Background technology
Research shows microRNA (miRNAs), in the pathologic processes such as inflammation and canceration generation, brings into play key effect.Set up quick, sensitive, easy, accurately, genius morbi small molecular core ribosomal ribonucleic acid (miRNA) detection method that can be satisfied with the practical application in life science and medical science and clinical diagnosis field is necessary, is also the important topic in life science.At present, DNA chip be because can detect RNA or DNA, and is widely used in gene and molecular biological research, as the detection of large scale measurement rna expression, genomic DNA sudden change, gene diagnosis, pharmacogenomics and medicine etc.And the development of RNA chip is in the starting stage.But no matter DNA chip or RNA chip technology, all needs expensive optical instrument and fluorescent color-developing agent, needs complicated pre-service, and only utilize fluorescence intensity to be difficult to realize the quantitative measurment of micro-example before detection.
Electrochemical test method is easy and simple to handle because of it, economical fast, instantaneity, high sensitivity etc. and be widely used in environmental protection and biological medicine monitoring, the fields such as food hygiene monitoring and material science research.Wherein, electrochemica biological sensing detection is the focus of current concern, is also the key areas of electro-chemical test application.Conventionally, Electrochemical Detection is active material to be connected to the upper formation of basal electrode (glass carbon, gold electrode, glass-carbon electrode, graphite electrode, carbon paste electrode etc.) detecting electrode realize.For electrode, resistance is one of important parameter affecting test electrode performance quality, and resistance requires the smaller the better (tens ohm).The cementing agent that electrode is conventional has polyvinyl alcohol (PVA) (PVA), naphthols (Nafion), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), and its non-conductive son is the main source of electrode resistance; And binders for electrodes suitable amounts is difficult to hold, how many its consumptions directly affects the stability of electrode and the stable output of serviceable life and electric signal.That is to say, connect and prepare detecting electrode with binders for electrodes traditionally, not only increased the resistance of electrode itself, and increased preparation technology's difficulty and numerous and diverse property.
In addition, activity is also one of important parameter affecting test electrode performance quality, and General Requirements activity is more high better.Titania is a kind of good chemical characteristic that has, the multifunctional material of electronics, photoelectricity and photovoltaic property.Wherein, one of most important purposes of titania is as sensing active material, is conventionally prepared into thin-film device, is applied to sensor.Function titanium deoxid film is generally the surface effect of utilizing titania nanoparticles, so people have adopted a lot of methods to prepare porous titanium dioxide thin-film, as sol-gel process, organic chemical vapor deposition method, pulsed laser deposition etc., and obtained good experimental result.But what these methods had must adopt expensive equipment, some needs are accurate to be controlled, the membrane pore size obtaining is difficult to uniformity, and, in many cases, because the partial density being connected with substrate is large, the porosity is low, can have a strong impact on its physical property or catalysis sensing activity.
Summary of the invention
The object of the invention is, for above deficiency, to propose a kind of TiO
2the preparation method of nano-stick array thin film electrode material is covered with TiO by normal temperature and pressure aciding on titanium sheet
2nano-stick array thin film,
TiO of the present invention
2the preparation method of nano-stick array thin film electrode material is:
Under normal temperature and pressure conditions, the HCl solution or the H that are 8～10mol/L in concentration by pure titanium sheet
2sO
4in solution, soak 12～24h, after completion of the reaction, by washed with de-ionized water, be washed till pH value and be 7,70～110 DEG C dry, 400～600 DEG C of calcining 1～2h, make the surface of pure titanium sheet be covered with TiO
2nano-stick array thin film, this is covered with TiO
2the titanium sheet of nano-stick array thin film is TiO
2nano-stick array thin film electrode material.
Another object of the present invention is to provide above-mentioned TiO
2nano-stick array thin film electrode material is in the application of genius morbi miRNA associated electrical chemical-biological sensing detection or bio-sensing device, with this TiO that is covered with
2the titanium sheet of nano-stick array thin film, directly as electrode, becomes the TiO of single-stranded probe DNA or RNA modification through surface modification
2nano-stick array thin film sensing detection electrode, taking the simulated body fluid phosphate buffer solution (PBS damping fluid) of pH=7.4 as electrolyte solution, utilizes electrochemical techniques means, realizes the miRNA electrochemica biological sensing detection of genius morbi.Specifically:
Step (1). by TiO
2nano-stick array thin film electrode material, directly as electrode, by amido or silylation or carboxyl or isothiocyano organic molecule functional group, is connected with single-stranded probe DNA or RNA, forms the TiO that nucleic acid probe is modified
2nano-stick array thin film sensing detection electrode.
Step (2). the TiO that nucleic acid probe is modified
2in the simulated body fluid phosphate buffer (PBS damping fluid) that nano-stick array thin film sensing detection electrode is 7.4 in pH value, according to base complementrity pair principle (A-U, G-C, A-T), make DNA probe or RNA and there is the target miRNA hydridization of genius morbi, double-stranded DNA-the RNA or the RNA-RNA that form hydridization, carry out electrochemical techniques detection.
The present invention utilizes normal temperature and pressure aciding to be covered with TiO on titanium sheet
2nano-stick array thin film, and using this titanium sheet directly as electrode, carry out the miRNA electrochemica biological sensing detection of genius morbi.The TiO being covered with on titanium sheet of the present invention
2nano-stick array thin film thin and thick is even, and pattern is controlled, sound construction, and technology for preparing electrode is simple, without cementing agent bonding, can realize TiO
2the standardization of nanosensor device and mass production, advantageously promote the practical application in life science and medical science and clinical diagnosis field.
Except the miRNA electrochemica biological sensing detection of genius morbi, the present invention is also suitable for the sensing detection of other biomolecule.
Brief description of the drawings
Fig. 1 is TiO
2nano-stick array thin film electrode material micrograph;
Fig. 2 is TiO
2nano-stick array thin film sensing electrode detects dengue fever virus miRNA volt-ampere scanning curve: (a) blank sample; (b) dengue fever virus miRNA(10
-18mol);
Fig. 3 is TiO
2nano structure membrane sensing electrode detection adenine phosphoric acid (
6pA) volt-ampere scanning curve: (a) blank sample; (b) 0.1 μ M adenine phosphoric acid.
Embodiment
Below in conjunction with example, the present invention will be further described:
Embodiment 1.
After pure titanium sheet is smooth with sand papering, use successively tap water, ultrapure water, acetone ethanol mixed liquor and ultrapure water ultrasonic cleaning clean, under normal temperature and pressure, put into 8mol/L HCl solution and soak 12h, after completion of the reaction, thoroughly clean with deionized water, being washed till pH value is 7,80 DEG C dry, and 500 DEG C of calcining 1h, are covered with TiO on the surface of pure titanium sheet
2nano-stick array thin film (as shown in Figure 1).To be covered with TiO
2the titanium sheet of nano-stick array thin film is directly as electrode, in 5 mmol/L 3-aminopropyl trimethoxysilane and 5 mmol/L diisothio-cyanates, leave standstill successively and soak 1h, the single-stranded probe DNA again amino-contained being modified or RNA solution drop in the titanic oxide nano-membrane electrode surface of above-mentioned surface-functionalized modification, form the TiO that single-stranded probe DNA or RNA modify
2nanometer film sensing detection electrode, then taking the simulated body fluid phosphate buffer solution (PBS) of pH=7.4 as electrolyte solution, dengue fever miRNA virus is carried out to electrochemical sensing detection, electrochemical sensing testing result as shown in Figure 2, dengue fever miRNA virus characteristic electrochemical potential is respectively 2.65V and 3.0V, and sensitivity is high, can detect 10
-18mol; To medicine adenine phosphoric acid (
6pA) carry out electrochemical sensing detection, its characteristic electrochemical potential be 0.91V(as shown in Figure 3).
Embodiment 2.
After pure titanium sheet is smooth with sand papering, use successively tap water, ultrapure water, acetone ethanol mixed liquor and ultrapure water ultrasonic cleaning clean, under normal temperature and pressure, put into 9mol/L HCl solution and soak 23h, after completion of the reaction, thoroughly clean with deionized water, being washed till pH value is 7,80 DEG C dry, and 500 DEG C of calcining 1h, are covered with TiO on the surface of pure titanium sheet
2nano-stick array thin film (shown in similar accompanying drawing 1).To be covered with TiO
2the titanium sheet of nano-stick array thin film is directly as electrode, in 5 mmol/L polyethyleneimine: amine aqueous solutions and 5 mmol/L glutaraldehyde solutions, leave standstill successively and soak 1h, the single-stranded probe DNA again amino-contained being modified or RNA solution drop in the titanic oxide nano-membrane electrode surface of above-mentioned surface-functionalized modification, form the TiO that single-stranded probe DNA or RNA modify
2nanometer film sensing detection electrode, then taking the simulated body fluid phosphate buffer solution (PBS) of pH=7.4 as electrolyte solution, to dengue fever miRNA virus and medicine adenine phosphoric acid (
6pA) carry out electrochemical sensing detection, the similar accompanying drawing 2 of electrochemical sensing testing result, shown in Fig. 3.
Embodiment 3.
After pure titanium sheet is smooth with sand papering, use successively tap water, ultrapure water, acetone ethanol mixed liquor and ultrapure water ultrasonic cleaning clean, under normal temperature and pressure, put into 10mol/L HCl solution and soak 24h, after completion of the reaction, thoroughly clean with deionized water, being washed till pH value is 7,70 DEG C dry, and 600 DEG C of calcining 1h, are covered with TiO on the surface of pure titanium sheet
2nano-stick array thin film (shown in similar accompanying drawing 1).To be covered with TiO
2the titanium sheet of nano-stick array thin film is directly as electrode, at 5 mmol/L 3-aminopropyl trimethoxysilane solution and 10 mmol/L 1, in 4-phenylene two isothiocyanic acid ester solutions, leave standstill successively and soak 1h, the single-stranded probe DNA again amino-contained being modified or RNA solution drop in the titanic oxide nano-membrane electrode surface of above-mentioned surface-functionalized modification, form the TiO that single-stranded probe DNA or RNA modify
2nanometer film sensing detection electrode, then taking the simulated body fluid phosphate buffer solution (PBS) of pH=7.4 as electrolyte solution, to dengue fever miRNA virus and medicine adenine phosphoric acid (
6pA) carry out electrochemical sensing detection, the similar accompanying drawing 2 of electrochemical sensing testing result, shown in Fig. 3.
Embodiment 4.
After pure titanium sheet is smooth with sand papering, use successively tap water, ultrapure water, acetone ethanol mixed liquor and ultrapure water ultrasonic cleaning clean, under normal temperature and pressure, put into 8mol/L H
2sO
4in solution, soak 20h, after completion of the reaction, thoroughly clean with deionized water, be washed till pH value and be 7,110 DEG C dry, 400 DEG C of calcining 2h, are covered with TiO on the surface of pure titanium sheet
2nano-stick array thin film (shown in similar accompanying drawing 1).To be covered with TiO
2the titanium sheet of nano-stick array thin film is directly as electrode, at 5 mmol/L 3-aminopropyl trimethoxysilane solution and 10 mmol/L 1,4-phenylene two isothiocyanic acid ester solutions leave standstill successively and soak 1h, the single-stranded probe DNA again amino-contained being modified or RNA solution drop in the titanic oxide nano-membrane electrode surface of above-mentioned surface-functionalized modification, form the TiO that single-stranded probe DNA or RNA modify
2nanometer film sensing detection electrode, then taking the simulated body fluid phosphate buffer solution (PBS) of pH=7.4 as electrolyte solution, to dengue fever miRNA virus and medicine adenine phosphoric acid (
6pA) carry out electrochemical sensing detection, the similar accompanying drawing 2 of electrochemical sensing testing result, shown in Fig. 3.
Embodiment 5.
After pure titanium sheet is smooth with sand papering, use successively tap water, ultrapure water, acetone ethanol mixed liquor and ultrapure water ultrasonic cleaning clean, under normal temperature and pressure, put into 9mol/L H
2sO
4in solution, soak 15h, after completion of the reaction, thoroughly clean with deionized water, be washed till pH value and be 7,100 DEG C dry, 550 DEG C of calcining 2h, are covered with TiO on the surface of pure titanium sheet
2nano-stick array thin film (shown in similar accompanying drawing 1).To be covered with TiO
2the titanium sheet of nano-stick array thin film is directly as electrode, at 5 mmol/L 3,3 '-bis-thiodipropionic acid solution and 5 mmol/L N-ethyl-N '-(3-dimethylamine propyl) carbodiimide solution and 5 mmol/L N-hydroxy-succinamide solution leave standstill successively and soak 1h, the single-stranded probe DNA again amino-contained being modified or RNA solution drop in the titanic oxide nano-membrane electrode surface of above-mentioned surface-functionalized modification, form the TiO that single-stranded probe DNA or RNA modify
2nanometer film sensing detection electrode, then taking the simulated body fluid phosphate buffer solution (PBS) of pH=7.4 as electrolyte solution, to dengue fever miRNA virus and medicine adenine phosphoric acid (
6pA) carry out electrochemical sensing detection, the similar accompanying drawing 2 of electrochemical sensing testing result, shown in Fig. 3.
Embodiment 6.
After pure titanium sheet is smooth with sand papering, use successively tap water, ultrapure water, acetone ethanol mixed liquor and ultrapure water ultrasonic cleaning clean, under normal temperature and pressure, put into 10mol/L H
2sO
4in solution, soak 18h, after completion of the reaction, thoroughly clean with deionized water, be washed till pH value and be 7,90 DEG C dry, 450 DEG C of calcining 2h, are covered with TiO on the surface of pure titanium sheet
2nano-stick array thin film (shown in similar accompanying drawing 1).To be covered with TiO
2the titanium sheet of nano-stick array thin film is directly as electrode, at 5 mmol/L mercaptopropionic acid solution, in 5 mmol/L N-ethyl-N '-(3-dimethylamine propyl) carbodiimide solution and 5 mmol/L N-hydroxy-succinamide solution, leave standstill successively and soak 1h, the single-stranded probe DNA again amino-contained being modified or RNA solution drop in the titanic oxide nano-membrane electrode surface of above-mentioned surface-functionalized modification, form the TiO that single-stranded probe DNA or RNA modify
2nanometer film sensing detection electrode, then taking the simulated body fluid phosphate buffer solution (PBS) of pH=7.4 as electrolyte solution, to dengue fever miRNA virus and medicine adenine phosphoric acid (
6pA) carry out electrochemical sensing detection, the similar accompanying drawing 2 of electrochemical sensing testing result, shown in Fig. 3.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.
Claims (2)
1. a TiO
2the preparation method of nano-stick array thin film electrode material, is characterized in that the method is:
Under normal temperature and pressure conditions, the HCl solution or the H that are 8～10mol/L in concentration by pure titanium sheet
2sO
4in solution, soak 12～24h, after completion of the reaction, by washed with de-ionized water, be washed till pH value and be 7,70～110 DEG C dry, 400～600 DEG C of calcining 1～2h, obtain TiO
2nano-stick array thin film electrode material.
2. a kind of TiO that preparation method as claimed in claim 1 obtains
2nano-stick array thin film electrode material is in the application of genius morbi miRNA associated electrical chemical-biological sensing detection or bio-sensing device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410050663.4A CN103884756B (en) | 2014-02-13 | 2014-02-13 | A kind of TiO2the preparation method and applications of nano-stick array thin film electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410050663.4A CN103884756B (en) | 2014-02-13 | 2014-02-13 | A kind of TiO2the preparation method and applications of nano-stick array thin film electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103884756A true CN103884756A (en) | 2014-06-25 |
| CN103884756B CN103884756B (en) | 2016-08-17 |
Family
ID=50953770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410050663.4A Expired - Fee Related CN103884756B (en) | 2014-02-13 | 2014-02-13 | A kind of TiO2the preparation method and applications of nano-stick array thin film electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103884756B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891245A (en) * | 2010-07-16 | 2010-11-24 | 重庆大学 | Method for preparing titanium dioxide nano-rod array materials at low temperature |
| CN101935015A (en) * | 2010-06-29 | 2011-01-05 | 东华大学 | Method for preparing titanium dioxide nanorod array electrode with mixed crystal structure |
-
2014
- 2014-02-13 CN CN201410050663.4A patent/CN103884756B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935015A (en) * | 2010-06-29 | 2011-01-05 | 东华大学 | Method for preparing titanium dioxide nanorod array electrode with mixed crystal structure |
| CN101891245A (en) * | 2010-07-16 | 2010-11-24 | 重庆大学 | Method for preparing titanium dioxide nano-rod array materials at low temperature |
Non-Patent Citations (3)
| Title |
|---|
| JING ZHOU,ET AL.: "Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method", 《NANOSCALE RESEARCH LETTERS》 * |
| XIANGPING HUANG,ET AL.: "Large-scale synthesis of single-crystalline rutile TiO2 nanorods via a one-step solution route", 《JOURNAL OF CRYSTAL GROWTH》 * |
| ZHENYAO WANG,ET AL.: "The effects of different acids on the preparation of TiO2 nanostructure in liquid media at low temperature", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103884756B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gholizadeh et al. | Fabrication of sensitive glutamate biosensor based on vertically aligned CNT nanoelectrode array and investigating the effect of CNTs density on the electrode performance | |
| Zhang et al. | Construction of titanium dioxide nanorod/graphite microfiber hybrid electrodes for a high performance electrochemical glucose biosensor | |
| Lee et al. | A coral-like macroporous gold–platinum hybrid 3D electrode for enzyme-free glucose detection | |
| CN104698055B (en) | Method for orderly assembling DNA and graphene on gold electrode surface | |
| CN105784796B (en) | A kind of sensitive determination method of the aptamer sensor based on gold/molybdenum disulfide/graphene nanocomposite material to lysozyme | |
| CN102735732B (en) | Preparation and application of nano-cuprous oxide based enzyme-free hydrogen peroxide sensor electrode | |
| CN101315345B (en) | Production method for Modified electrode for detecting grape-sugar concentration in non-enzyme condition | |
| CN104897746A (en) | Preparation method of aptamer photoelectrochemical sensor for high-sensitivity high-selectivity detection of MC-LR | |
| CN103743802A (en) | DNA biosensor based on three-dimensional ordered gold doped nano titanium dioxide electrode as well as preparation method and application of DNA biosensor | |
| Temoçin | Designing of a stable and selective glucose biosensor by glucose oxidase immobilization on glassy carbon electrode sensitive to H 2 O 2 via nanofiber interface | |
| CN102866185A (en) | Method for detecting potassium ion by preparing biosensor based on G-quadruplex and gold nanoparticle | |
| CN103592350A (en) | Melanin nanoparticle-graphene electrochemical sensor as well as preparation method and application thereof | |
| Rajapaksha et al. | Nanoparticles in electrochemical bioanalytical analysis | |
| CN109060915A (en) | A kind of enzyme biologic sensor based on flexible electrode | |
| CN103884755B (en) | A kind of TiO2the preparation method and applications of nano flower thin-film electrode material | |
| CN105911128B (en) | A kind of enzyme-free glucose electrochemical sensor and its application | |
| Jang et al. | Immunosensor based on the ZnO nanorod networks for the detection of H1N1 swine influenza virus | |
| CN103399070A (en) | Preparation method of high-sensitivity electrochemical sensors for glucose detection based on nickel hydroxide and glucose oxidase | |
| Chou et al. | Fabrication and characteristic analysis of a remote real-time monitoring applied to glucose sensor system based on microfluidic framework | |
| CN108663426A (en) | A kind of glucose sensor electrode and the preparation method and application thereof | |
| CN104391021A (en) | Method for detecting phenol compound in solution by tyrosinase biosensor | |
| Ramachandran et al. | High electroactive electrode catalysts and highly sensitive electro analytical techniques for hydrogen peroxide detection | |
| CN103884756B (en) | A kind of TiO2the preparation method and applications of nano-stick array thin film electrode material | |
| CN103884754B (en) | A kind of TiO2the preparation method and applications of nanometer network thin-film electrode material | |
| CN104049011A (en) | Electrochemical biosensor, preparation method and application of electrochemical biosensor and method for detecting platelet-derived growth factor |
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: 20160817 Termination date: 20180213 |