CN108061710A - A kind of plasmon dual-functional sensor based on triangle gold-nano-piece and its preparation method and application - Google Patents
A kind of plasmon dual-functional sensor based on triangle gold-nano-piece and its preparation method and application Download PDFInfo
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- CN108061710A CN108061710A CN201711146648.XA CN201711146648A CN108061710A CN 108061710 A CN108061710 A CN 108061710A CN 201711146648 A CN201711146648 A CN 201711146648A CN 108061710 A CN108061710 A CN 108061710A
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N2021/258—Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension
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Abstract
The present invention provides a kind of plasmon dual-functional sensors based on triangle gold-nano-piece and its preparation method and application, the sensor includes substrate slide and the triangle gold-nano-piece being fixed in substrate slide, the triangle gold-nano-piece surface modification horseradish peroxidase.Its preparation method is first under the conditions of CTAB is as surfactant, obtains gold nano seed using sodium borohydride reduction gold chloride, then further the reaction in growth-promoting media prepares triangle gold-nano-piece by gold nano seed；Then triangle gold-nano-piece is fixed on using physisorption in substrate slide, and functionalization is carried out with sulfydryl covalent bond coupling horseradish peroxidase on triangle gold-nano-piece, so as to which sensor be made.The sensor chemical etching reaction can occur with hydrogen peroxide and its pattern is changed into disc by triangle, so as to fulfill the detection to trace molecules such as halogen ion, glucose under the conditions of existing for halogen ion.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of plasmon based on triangle gold-nano-piece
Dual-functional sensor and its preparation method and application.
Background technology
In recent years, noble metal nano particles are because its is suitably sized, pattern and composition have shown very perfect object
Characteristic is managed, it is special that gold nanoparticle all presents very strong local surface plasma resonance in the specific regions such as visible ray or near-infrared
Property, this causes gold nanoparticle to achieve extensively in every field and effectively apply.And in numerous nano particles respectively to
The triangle gold-nano-piece of the opposite sex is with its structure and the optical property of condition depended, anisotropic surface energy, the length of side and thickness
Controllable synthesis and it is especially prominent.
Free radical is the research hotspot of preclinical medicine and life science in recent years, in the metabolic process of vital movement
Various active oxygen radicals are constantly generated, such as superoxide radical (O2-), hydrogen peroxide (H2O2) and hydroxyl radical free radical
(HO.-)。H2O2It is a kind of reactive oxygen metabolite of energy penetration cell film, numerous studies show that it is served as in cell signalling
The physiology role of second messenger.
Due to H2O2It is played an important role in life entity, designs a kind of effective H2O2Detection method, for some
The major disease of oxidative stress and wound inducement realizes early diagnosis and prevention, its physiology and disease is probed on individual cell level
Reason effect and metabolism etc. will be with important directive significances.
The content of the invention
The object of the present invention is to provide a kind of plasmon dual-functional sensor based on triangle gold-nano-piece and its
Preparation method and application, the sensor under the conditions of existing for halogen ion, can with hydrogen peroxide occur chemical etching reaction and incite somebody to action
Its pattern changes into disc by triangle, so as to fulfill the detection to trace molecules such as halogen ion, glucose.
A kind of plasmon dual-functional sensor based on triangle gold-nano-piece including substrate slide and is fixed on base
Triangle gold-nano-piece on the slide of bottom, the triangle gold-nano-piece surface modification horseradish peroxidase.
Further, the substrate slide is selected from ito glass, glass slide, FTO glass or quartz plate.
The preparation method of the sensor, comprises the following steps：
Step 1, triangle gold-nano-piece solution is prepared by dispersant of CTAB, the length of side of gained triangle gold-nano-piece is 50-
80nm；
Step 2, by the triangle gold-nano-piece solution of step 1 with 1:1-1:It is added drop-wise to after 50 dilution proportion in substrate slide,
Drying；
Step 3, the PBS buffer solution of 1-10 μm of ol/L horseradish peroxidase is added dropwise in the substrate slide of step 2, stands, obtains
To sensor.
Further, the pH of the PBS buffer solution is 4.0.
Application of the sensor in concentration of hydrogen peroxide is detected.
Application of the sensor in concentration of glucose is detected.
Application of the sensor in halide ion concentration is detected.
Further, the halogen ion is chlorion, bromide ion or iodide ion.
The present invention obtains gold nano first under the conditions of CTAB is as surfactant using sodium borohydride reduction gold chloride
Seed, then further the reaction in growth-promoting media prepares triangle gold-nano-piece by gold nano seed, then by triangle gold nano
Piece is fixed on using physisorption in substrate slide, and couples horseradish peroxidase on gold-nano-piece with sulfydryl covalent bond
Enzyme carries out functionalization, so as to prepare plasmon sensor.The characteristics of sensor, mainly includes：Size is small, reaches nanometer
Grade, available for the environmental monitoring in cell, bacterium；Good light stability, compared to fluorescent material without photobleaching, unglazed blink.
When the hydrogen peroxide and sodium halide solution containing various concentration of sensor surface covering certain volume, thus solution
The halogen free radical of middle generation will generate strong corrasion with plasmon, and triangle gold-nano-piece is made to be gradually varied to circle
Shape nanometer sheet, as shown in Figure 1.This process can be by real-time monitored under dark field microscope, and in its individual particle scattering spectrum
Peak position on show significant difference, pattern change spectroscopic studying is influenced it is big.So as to fixed hydrogen peroxide concentration or
Halide ion concentration scatters darkfield image by individual particle plasma and single scattering spectrum realizes another substance（Hydrogen peroxide
Or halogen ion）Highly sensitive detection.
Description of the drawings
Fig. 1 is gradually etched for intermediate cam shape gold-nano-piece of the present invention and the TEM of final molding figures；
Fig. 2 is the TEM figures of triangle gold-nano-piece obtained in embodiment 1；
Fig. 3 is the ultra-violet absorption spectrum and darkfield image of triangle gold-nano-piece obtained in embodiment 1；
Fig. 4 is the ultra-violet absorption spectrum and darkfield image, pair of TEM that 2 intermediate cam shape gold-nano-piece of embodiment is gradually etched
Than；
Fig. 5 is influence and corresponding ultraviolet spectrogram of the concentration of hydrogen peroxide to etching degree in embodiment 2.
Specific embodiment
Technical scheme is described further below, but these embodiments not limit embodiments of the present invention.
The present invention has a variety of different embodiments, is not only limited in content described in this specification.Those skilled in the art exists
In the case of the present application spirit, the scheme completed should be within the scope of the invention.
Embodiment 1
Step 1, the preparation of gold nano seed：Take 42.5 μ L concentration 1%（g/g）Gold chloride is added to 4.7 mL, 0.1 M CTAB
In solution, 300 μ L, 0.01 M sodium borohydride solutions are added, stirs 2 minutes, 2h is stood at 25 DEG C.
Step 2,8 mL water is taken to add in 1.6 mL, 0.1 M CTAB, add the gold chloride of 68 μ L concentration 1% (g/g)
With 15 μ L, 0.01 M IodineSodium Solutions.
Step 3,7.487 mL water is taken to add in 0.513 μ L, 0.78 M CTAB, are then added to 170 μ L concentration, 1% (g/
G) in chlorauric acid solution.
Step 4,40 μ L, 0.1 M ascorbic acid solutions is taken to add in the solution prepared by step 2, take 80 μ L, 0.1 M
Ascorbic acid solution is added in the solution prepared by step 3, hand to clear, colorless.
Step 5, gold nano seed prepared in step 1 is diluted 10 times, and the seed after 50 μ L dilutions is taken to be added to
It has been mixed into step 4 in the solution prepared by the step 2 of ascorbic acid solution, has rocked a moment and take out 640 μ L immediately and be added to
Be mixed into the solution prepared by the step 3 of ascorbic acid solution, rocked manually 50 seconds, be stored at room temperature 1 it is small when, obtain triangle
Gold-nano-piece solution.
As shown in Fig. 2, gained triangle gold-nano-piece solution intermediate cam shape gold-nano-piece pattern is homogeneous, the length of side is in 70nm.
As shown in figure 3, the ultraviolet peak value of gained triangle gold-nano-piece solution intermediate cam shape gold-nano-piece is left in 650nm
The right side, gained darkfield image are shown in red.
Embodiment 2
Step 1, the ito glass piece for cleaning up and being dried up with nitrogen is taken, in order to show influence of the various concentration to spectral region,
By the triangle gold-nano-piece solution obtained by embodiment 1 with 1:1-1:20 point are added drop-wise on sheet glass after 50 dilution proportion
Zhong Houyong ultrapure waters, and dried up with nitrogen.
Step 2,100 μ L 1-10 μm ol/L horseradish peroxidases are added dropwise in the ito glass on piece obtained by step 1
PH4.0 PBS buffer solution stands 30 min-2 h, and sensor is made.
Step 3,10-50 μ L fixed concentrations are added dropwise on step 2 gained sensor（0.1-20 μmol/L）Peroxidating
Then hydrogen solution adds in 5-20 μ L various concentrations（1-10 μmol/L）Halogen ion solution, redox reaction 40 minutes
The scattering spectrum of particle is gathered afterwards.
Step 4,10-50 μ L fixed concentrations are added dropwise on step 2 gained sensor（0.1-20 μmol/L）Halogen ion
Then solution adds in 5-20 μ L various concentrations（1-100 μmol/L）Hydrogenperoxide steam generator, redox reaction is after forty minutes
Gather the scattering spectrum of particle.
As shown in figure 4, under the conditions of existing for sodium halide, sensor and hydrogen peroxide occur chemical etching reaction and by its
Pattern changes into disc by triangle, and scattering spectrum peak value is also by the notable blue shifts of 680 nm to 600 nm, darkfield image face
Color can also gradually become yellow from red, and concentration of hydrogen peroxide has direct relation with peak value and color, by individual particle etc. from
Son scattering darkfield image and single scattering spectrum can realize the highly sensitive detection of hydrogen peroxide.
As shown in figure 5, under the conditions of existing for sodium halide, sensor and hydrogen peroxide occur chemical etching reaction and by its
Pattern changes into disc by triangle, when concentration of hydrogen peroxide is respectively 0,5 μm of ol/L, 10 μm of ol/L, 15 μm of ol/L, 20 μ
During mol/L, blue shift occurs for scattering spectrum summit, and as concentration increases, blue shift becomes more；The pattern of gold-nano-piece is also changed by triangle
Become disc, as concentration increases, change degree and deepen.
Claims (8)
1. a kind of plasmon dual-functional sensor based on triangle gold-nano-piece, it is characterised in that：Including substrate slide
With the triangle gold-nano-piece being fixed in substrate slide, the triangle gold-nano-piece surface modification horseradish peroxidase.
2. sensor according to claim 1, it is characterised in that：The substrate slide is selected from ito glass, glass slide, FTO
Glass or quartz plate.
3. the preparation method of sensor described in claim 1, it is characterised in that：Comprise the following steps：
Step 1, triangle gold-nano-piece solution is prepared by dispersant of CTAB, the length of side of gained triangle gold-nano-piece is 50-
80nm；
Step 2, by the triangle gold-nano-piece solution of step 1 with 1:1-1:It is added drop-wise to after 50 dilution proportion in substrate slide,
Drying；
Step 3, the PBS buffer solution of 1-10 μm of ol/L horseradish peroxidase is added dropwise in the substrate slide of step 2, stands, obtains
To sensor.
4. the preparation method of sensor according to claim 3, it is characterised in that：The pH of the PBS buffer solution is 4.0.
5. application of the sensor described in claim 1 in concentration of hydrogen peroxide is detected.
6. application of the sensor described in claim 1 in concentration of glucose is detected.
7. application of the sensor described in claim 1 in halide ion concentration is detected.
8. application according to claim 7, it is characterised in that：The halogen ion is chlorion, bromide ion or iodide ion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108594341A (en) * | 2018-06-13 | 2018-09-28 | 中国工程物理研究院应用电子学研究所 | The preparation of gold-nano-piece-gold nanosphere dimer and its application resonated in strong polarization independent method promise |
| CN113004887A (en) * | 2021-02-23 | 2021-06-22 | 南京医科大学 | Gold nano disc crown-shaped nano probe, preparation method thereof and application thereof in biological detection |
-
2017
- 2017-11-17 CN CN201711146648.XA patent/CN108061710A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| LAURA SAA等: "Enzymatic etching of gold nanorods by horseradish peroxidase and application to blood glucose detection", 《NANOSCALE》 * |
| SHANSHAN SUN等: "Visually monitoring the etching process of gold nanoparticles by KI/I2 at single-nanoparticle level using scattered-light dark-field microscopic imaging", 《NANO RESEARCH》 * |
| 冯宁等: "辣根过氧化氢酶催化刻蚀金纳米三角片实现对双氧水和葡萄的单颗粒水平生物传感检测", 《中国化学会第30届学术年会摘要集-第四分会：生物分析和生物传感器》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108594341A (en) * | 2018-06-13 | 2018-09-28 | 中国工程物理研究院应用电子学研究所 | The preparation of gold-nano-piece-gold nanosphere dimer and its application resonated in strong polarization independent method promise |
| CN108594341B (en) * | 2018-06-13 | 2020-08-04 | 中国工程物理研究院应用电子学研究所 | Preparation of gold nanosheet-gold nanosphere dimer and application of gold nanosheet-gold nanosphere dimer in strong polarization-dependent Fano resonance |
| CN113004887A (en) * | 2021-02-23 | 2021-06-22 | 南京医科大学 | Gold nano disc crown-shaped nano probe, preparation method thereof and application thereof in biological detection |
| CN113004887B (en) * | 2021-02-23 | 2022-12-23 | 南京医科大学 | Gold nano disc crown-shaped nano probe, preparation method thereof and application thereof in biological detection |
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Application publication date: 20180522 |