CN110849953B - Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor - Google Patents
Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor Download PDFInfo
- Publication number
- CN110849953B CN110849953B CN201911155065.2A CN201911155065A CN110849953B CN 110849953 B CN110849953 B CN 110849953B CN 201911155065 A CN201911155065 A CN 201911155065A CN 110849953 B CN110849953 B CN 110849953B
- Authority
- CN
- China
- Prior art keywords
- composite material
- nanowire array
- loaded
- cuo
- biosensor
- 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
Images
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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
Abstract
The invention belongs to the field of new nano materials, and particularly relates to a Cu-loaded nano material 2 The invention relates to a composite material of O-CuO nanowire array, a preparation method thereof, a biosensor and application thereof 2 Nanowire array, annealing in air by precisely controlling time and temperature to obtain three-dimensional Cu-loaded substrate 2 The preparation method of the composite material of the O-CuO nanowire array is simple and easy to operate, and CuO can consume Cu in the composite material under illumination 2 Electrons on O conduction band, decrease the rate of photon-generated electron-hole recombination, cu 2 The O-CuO nanowire array is used as a three-dimensional electrode, has large surface area, high active site density and low series resistance, is favorable for generating photoelectric signals, and the prepared composite material biosensor is used for detecting tyrosinase.
Description
Technical Field
The invention belongs to the field of new nano materials, and particularly relates to Cu loaded copper 2 O-CuO nanowire array composite material, preparation method thereof, biosensor and application thereof.
Background
Cu 2 O is a p-type semiconductor with a narrow band gap of 2.0-2.2eV and controllable morphology. Due to its advantages in terms of reasonable price, environmental friendliness, abundant reserves and unique optical and electrical properties, it is used in many fields, including lithium ion batteries, supercapacitors, CO 2 Photocatalytic reduction, photocatalytic degradation, a photoelectric chemical sensor and the like. However, cu 2 O has the disadvantage of high recombination rate of photo-generated electron-hole pairs.
Tyrosinase is a cupreous enzyme, is derived from embryonic nerve kurtosis cells, and is a key enzyme for melanin metabolism and catecholamine. There are many methods for detecting Tyr, such as immunoblotting for detecting Tyr antibody. However, this method is relatively insensitive and cannot be detected quantitatively. The ELISAF method is sensitive to the detection of Tyr antibody, but the homology of the Tyr of the mushroom and the human Tyr is low.
Disclosure of Invention
In view of the above technical problems, the present invention has been madeIs to provide a Cu-supported catalyst 2 The invention provides a composite material of an O-CuO nanowire array and a preparation method thereof, and also provides a biosensor and application thereof.
In the invention, cu is loaded 2 Composite material of O-CuO nanowire array, cu is loaded on foam copper 2 An array of O-CuO nanowires.
The Cu-supported catalyst of the present invention 2 The preparation method of the composite material of the O-CuO nanowire array comprises the steps of putting pretreated foamy copper into a mixed solution of a sodium hydroxide solution and an ammonium persulfate solution, standing for reaction, taking out the foamy copper after the reaction, washing and drying to obtain the Cu (OH) loaded composite material 2 Copper foam of nanowire arrays to be loaded with Cu (OH) 2 Placing the copper foam of the nanowire array in a tube furnace for annealing to obtain the Cu-loaded copper 2 A composite of O-CuO nanowire arrays.
The pretreatment process of the foamy copper comprises the steps of carrying out ultrasonic treatment for 1-2min by using dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid is 1mol/mL.
The concentration of the sodium hydroxide solution is 4-6mol/mL.
The concentration of the ammonium persulfate solution is 0.2-0.3mol/mL.
The annealing process comprises the following steps: at 2-5 deg.C for min -1 The temperature is raised to 300-450 ℃ at the heating rate, and the temperature is kept for 10-20min.
And (3) dropwise adding the chitosan solution to the surface of the composite material, and drying at room temperature to obtain the chitosan composite material, wherein the concentration of the chitosan solution is 0.2-0.5 wt%.
The biosensor is applied to photoelectrochemical detection of tyrosinase, the biosensor is placed in an incubation liquid for incubation for 0.5-2.5 hours, the incubation liquid is a mixed liquid of the tyrosinase, the tyrosine and deionized water, the incubation liquid can enhance a photocurrent signal of the biosensor, and the concentration of the tyrosinase in the incubation liquid during detection has a linear relation with the photocurrent intensity generated by the biosensor.
Compared with the prior art, the invention has the following beneficial effects.
(1) The invention takes the foam copper as the substrate and prepares Cu (OH) by the room temperature solvothermal method 2 Array of nanowires, thenAnnealing in air by accurately controlling time and temperature to prepare three-dimensional Cu-loaded 2 The preparation method of the composite material of the O-CuO nanowire array is simple and easy to operate;
(2) Cu-loaded prepared by the invention 2 In the composite material of O-CuO nanowire array, cuO can consume Cu under illumination 2 Electrons on O conduction band, decrease the rate of photon-generated electron-hole recombination, cu 2 The O-CuO nanowire array is used as a three-dimensional electrode, has larger surface area, high active site density and low series resistance, and is beneficial to generating photoelectric signals;
(3) The invention provides a biosensor based on a prepared composite material, which is used for detecting tyrosinase, wherein the photocurrent of the biosensor has a linear relation with the concentration of the tyrosinase, the lower limit of the detection of the tyrosinase is 0.023U/mL when S/N =3, and the biosensor has good selectivity during detection.
Drawings
FIG. 1 shows Cu-supported catalyst prepared in example 1 2 O-CuO nanowire array composite (Cu) 2 O/CuO NA/CF) experimental schematic diagram for detecting Tyr;
FIG. 2 shows Cu (OH) prepared in example 1 2 Scanning electron microscopy images of nanowire arrays;
FIG. 3 shows Cu prepared in example 1 2 Scanning electron microscope images of O-CuO nanowire arrays;
FIG. 4A is a curve showing the variation of photocurrent intensity with the concentration of Tyr, and B is a calibration curve corresponding thereto;
FIG. 5 is a graph showing the selectivity of a sensor for detecting Tyr, which is prepared in example 2.
Detailed Description
The invention is further illustrated by the following examples and figures of the specification.
Example 1
(1) Taking the foam copper, and cutting the foam copper into 2 x 4cm by using scissors 2 And then sonicated with dilute hydrochloric acid for 1-2 minutes. Washing with deionized water, weighing 3.204g sodium hydroxide in 15mL water, weighing 0.89g ammonium persulfate in 15mL waterMixing a dissolved sodium hydroxide solution with an ammonium persulfate solution, then putting a foamed copper sheet subjected to ultrasonic treatment by dilute hydrochloric acid into the mixed solution, standing and reacting for 20min, taking out the foamed copper sheet after the reaction is finished, washing the foamed copper sheet by deionized water, and drying the foamed copper sheet by an oven to obtain the Cu-loaded copper sheet 2 A composite of O-CuO nanowire arrays;
(2) Loading Cu obtained in the step (1) 2 Placing the composite material of the O-CuO nanowire array into a tube furnace for annealing, wherein the annealing process is carried out at 2 ℃ for min -1 Heating to 350 ℃ at the heating rate, and keeping the temperature for 15min to obtain the Cu-loaded material 2 O-CuO nanowire array composite material.
Example 2
The composite material obtained in example 1 was cut into 0.5X 1.0cm pieces 2 The sheet of (1) was fixed with a raw tape to an area of 0.5 x 0.5cm 2 . 0.25wt% chitosan solution was added dropwise to a fixed area of Cu using a 50 μ L format pipette 2 And drying the O-CuO nanowire array at room temperature to obtain an electrode, and putting the electrode into a 2mL centrifugal tube containing 100 muL Tyr,100 muL tyrosine and 100 muL deionized water for incubation for 1.5h to obtain the signal-enhanced biosensor for detecting Tyr.
FIG. 1 shows the preparation of a composite material (Cu) 2 O/CuO NA/CF) for detecting Tyr. As shown in the figure, a three-dimensional Cu is synthesized 2 O-CuO nanowire array composite material. Because the chitosan has good adhesiveness, the chitosan can be adhered to Cu after the chitosan is dripped 2 On the electrode surface of the O-CuO nanowire array. Cu deposition of chitosan 2 And placing the O-CuO nanowire array in an incubation liquid of Tyr and tyrosine for incubation. According to Cu 2 Band diagram of O-CuO, cu under light 2 The photo-generated electrons on the Conduction Band (CB) of O can be transferred to the CB of CuO. As the chitosan has a plurality of amino structures, 1, 2-benzoquinone or derivatives thereof generated by Tyr catalyzing tyrosine are covalently connected with amino, and the amino is used as an electron acceptor to consume a photogenerated carrier, and a photogenerated hole of CuO is transferred to Cu 2 Valence band of O, and then to the substrate, thereby realizing Cu 2 And the separation of the O-CuO photo-generated electron-hole pairs enhances the photocurrent signals. Thus can be used for testingDetecting Tyr;
FIG. 2 shows Cu (OH) 2 Scanning electron micrograph of the nanowire array, from which Cu (OH) can be observed 2 The nano wires cover the whole foam copper;
FIG. 3 is Cu 2 Scanning electron microscope image of O-CuO nanowire array, from which Cu can be observed 2 The O-CuO nanowire array covers the whole foam copper;
fig. 4A is a graph showing the change of photocurrent intensity with the Tyr concentration, and fig. 4B is a calibration curve corresponding thereto. As shown in the figure, as the concentration of Tyr increases from 0U/mL to 10U/mL, the generated photocurrent also linearly increased. FIG. 4B is the interpolation graph corresponding to the calibration curve with the linear regression equation of y =53.793x +170.517 (R) 2 = 0.993), wherein y (μ a) is the photocurrent signal and x (U/mL) is the concentration of Tyr; the lower detection limit is 0.023U/mL when S/N = 3;
FIG. 5 is a graph showing the selectivity of a sensor for detecting Tyr, which is prepared in example 2. By detecting relatively high concentrations of potentially interfering substances, for example: bovine Serum Albumin (BSA), trypsin, alkaline phosphatase (ALP), glucose oxidase (GOx), glucose, thrombin, zinc ion (Zn) 2+ ) Potassium ion (K) + ) We can see this Cu 2 The PEC response signal of the O-CuO nanowire array is strongest, which indicates that the PEC enzyme biological analysis method has good selectivity.
Claims (6)
1. Loaded with Cu 2 The application of the sensor prepared from the O-CuO nanowire array composite material in the detection of the casamino acid enzyme is characterized in that: cu is loaded on the foam copper 2 An O-CuO nanowire array;
said supported Cu 2 The preparation method of the O-CuO nanowire array composite material comprises the following steps: putting the pretreated foamy copper into a mixed solution of a sodium hydroxide solution and an ammonium persulfate solution, standing for reaction, taking out the foamy copper after reaction, washing and drying to obtain the loaded Cu (OH) 2 Copper foam of nanowire arrays to be loaded with Cu (OH) 2 Placing the foamy copper of the nanowire array in a tube furnace for annealing to obtain Cu-loaded copper 2 Of arrays of O-CuO nanowiresA composite material;
the annealing process comprises the following steps: at 2-5 deg.C for min -1 Heating to 300-450 deg.C at a heating rate, and maintaining the temperature for 10-20min;
loaded with Cu 2 The biosensor prepared from the O-CuO nanowire array composite material comprises the following steps: dripping chitosan solution on the surface of the composite material, and drying at room temperature to obtain the chitosan composite material, wherein the concentration of the chitosan solution is 0.2-0.5wt%;
the biosensor is applied to photoelectrochemical detection of tyrosinase.
2. Cu-loaded according to claim 1 2 The application of the sensor prepared from the O-CuO nanowire array composite material in the detection of the casamino acid enzyme is characterized in that: the pretreatment process of the foamy copper adopts dilute hydrochloric acid to carry out ultrasonic treatment for 1-2m1in, and the concentration of the dilute hydrochloric acid is 1mol/mL.
3. Cu-loaded according to claim 2 2 The application of the sensor prepared from the O-CuO nanowire array composite material in the detection of the casamino acid enzyme is characterized in that: the concentration of the sodium hydroxide solution is 4-6mol/mL.
4. Cu-loaded according to claim 2 2 The application of the sensor prepared from the composite material of the O-CuO nanowire array in the detection of the tyrosinase is characterized in that: the concentration of the ammonium persulfate solution is 0.2-0.3mol/mL.
5. Cu-loaded according to claim 1 2 The application of the sensor prepared from the composite material of the O-CuO nanowire array in the detection of the tyrosinase is characterized in that: and placing the biosensor in an incubation liquid for incubation for 0.5-2.5h, wherein the incubation liquid is a mixed liquid of tyrosinase, tyrosine and deionized water, and the incubation liquid can enhance the photocurrent signal of the biosensor.
6. The Cu-supporting alloy according to claim 1 2 Casein enzyme of sensor prepared from O-CuO nanowire array composite materialUse in detection, characterized by: the concentration of tyrosinase in the incubation liquid has a linear relationship with the photocurrent intensity generated by the biosensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155065.2A CN110849953B (en) | 2019-11-22 | 2019-11-22 | Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155065.2A CN110849953B (en) | 2019-11-22 | 2019-11-22 | Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110849953A CN110849953A (en) | 2020-02-28 |
| CN110849953B true CN110849953B (en) | 2022-10-25 |
Family
ID=69603522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911155065.2A Active CN110849953B (en) | 2019-11-22 | 2019-11-22 | Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110849953B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111705315B (en) * | 2020-06-28 | 2021-08-06 | 北京理工大学 | Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery |
| CN113036151B (en) * | 2021-03-08 | 2022-12-27 | 江汉大学 | Nitride modified current collector and preparation method and application thereof |
| CN114791452A (en) * | 2022-06-02 | 2022-07-26 | 江西鑫德新科技有限公司 | Preparation method of copper oxide nanowire electrode material and application of copper oxide nanowire electrode material in preparation of glucose sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888167A (en) * | 2019-02-21 | 2019-06-14 | 三峡大学 | A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10280525B2 (en) * | 2014-01-17 | 2019-05-07 | The Board Of Regents Of The University Of Texas System | Photoelectrochemical devices, methods, and systems with a cupric oxide/cuprous oxide coated electrode |
| CN110237564B (en) * | 2019-05-24 | 2022-02-01 | 深圳中拓天达环境工程有限公司 | Preparation method of self-heating nanowire array foam |
-
2019
- 2019-11-22 CN CN201911155065.2A patent/CN110849953B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888167A (en) * | 2019-02-21 | 2019-06-14 | 三峡大学 | A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material |
Non-Patent Citations (2)
| Title |
|---|
| Enzyme-Initiated Quinone-Chitosan Conjugation Chemistry: Toward A General in Situ Strategy for High-Throughput Photoelectrochemical Enzymatic Bioanalysis;Guang-Li Wang等;《Anal. Chem》;20180118;第90卷;第1492页ABSTRACT，第1494页右栏第一段，Supporting Information * |
| Nanoporous CuO layer modified Cu electrode for high performance enzymatic and non-enzymatic glucose sensing;Changli Li等;《Nanotechnology》;20141210;第26卷;第015503-1至015503-8页Experimental section、Results and discusion * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110849953A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110849953B (en) | Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor | |
| Zhao et al. | Enhanced biosensing platform constructed using urchin-like ZnO-Au@ CdS microspheres based on the combination of photoelectrochemical and bioetching strategies | |
| Zhang et al. | Porous hollow carbon nanobubbles@ ZnCdS multi-shelled dodecahedral cages with enhanced visible-light harvesting for ultrasensitive photoelectrochemical biosensors | |
| Wang et al. | Solar driven electrochromic photoelectrochemical fuel cells for simultaneous energy conversion, storage and self-powered sensing | |
| Feng et al. | Self-powered cathodic photoelectrochemical aptasensor comprising a photocathode and a photoanode in microfluidic analysis systems | |
| US20090111681A1 (en) | Electrocatalysts Based on Mono/Plurimetallic Carbon Nitrides for Fuel Cells Fueled with Hydrogen | |
| Zhang et al. | Novel Bi2+ x WO6 p–n Homojunction Nanostructure: Preparation, Characterization, and Application for a Self-Powered Cathodic Photoelectrochemical Immunosensor | |
| Mai et al. | Non-enzymatic fluorescent biosensor for glucose sensing based on ZnO nanorods | |
| CN107422012B (en) | Electrochemical biosensor electrode, sensor and preparation method thereof | |
| CN109706478A (en) | The thin layer titanium carbide of hydrogen reducing loads photoelectrolysis water cuprous oxide photocathode material and preparation method thereof | |
| CN110297023B (en) | Preparation method and application of self-enhanced photoelectrochemical immunosensor for detecting procalcitonin electrochemical catalysis assistance | |
| Gu et al. | Light-driven ultrasensitive self-powered cytosensing of circulating tumor cells via integration of biofuel cells and a photoelectrochemical strategy | |
| CN107271518B (en) | A kind of amperometric electrochemical sensor and its preparation method and application | |
| CN108414599B (en) | Preparation method of copper nanoparticle enzyme-free electrochemical glucose sensor | |
| Lai et al. | A tandem photoelectrochemical water splitting cell consisting of CuBi 2 O 4 and BiVO 4 synthesized from a single Bi 4 O 5 I 2 nanosheet template | |
| Tapia et al. | Laccase-catalyzed bioelectrochemical oxidation of water assisted with visible light | |
| CN110308187A (en) | A kind of preparation method and application of porous nano pucherite/bismuth sulfide optical electro-chemistry aptamer sensor based on zinc and cobalt doped | |
| Zhao et al. | ZnAgInS quantum dot-decorated BiOI heterostructure for cathodic photoelectrochemical bioanalysis of glucose oxidase | |
| CN109580746B (en) | Preparation and application of molybdenum sulfide-titanium oxide nano composite material | |
| CN110841664B (en) | Cu2O @ BiOI composite material and preparation method and application thereof | |
| Lu et al. | Self-powered molecular imprinted photoelectrochemical sensing platform of sialic acid employing WO3/Bi2S3 photoanode and CuInS2 photocathode | |
| CN110890554A (en) | High-power flexible single-enzyme glucose fuel cell and preparation method thereof | |
| EP0387026A2 (en) | Biosensor device | |
| Beigi et al. | Use of an Electrogenerated Chemiluminescence Sensor Modified with Sm2O3 Nanoparticles/Chitosan for the Analysis of Phenylalanine | |
| CN105758849B (en) | A kind of preparation method and application of the difunctional stilbestrol without enzyme sensor based on Two-dimensional Composites structure |
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 |