CN102914514A - Hollow gold nano particle sensing membrane and preparation method thereof - Google Patents
Hollow gold nano particle sensing membrane and preparation method thereof Download PDFInfo
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- CN102914514A CN102914514A CN2012104435041A CN201210443504A CN102914514A CN 102914514 A CN102914514 A CN 102914514A CN 2012104435041 A CN2012104435041 A CN 2012104435041A CN 201210443504 A CN201210443504 A CN 201210443504A CN 102914514 A CN102914514 A CN 102914514A
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Abstract
The invention discloses a preparation method of a hollow gold nano particle sensing membrane, and the method comprises the following steps of: (a) adopting an electrochemical method to directly deposit silver nano particles on an ITO (Indium Tin Oxide) conductive glass surface to be used as a template; and (b) adopting HAuCl4 to displace the silver nano particles and depositing gold on the surfaces of the silver nano particles; and meanwhile, dissolving the silver nano particles to obtain the hollow gold nano particle sensing membrane. According to the preparation method disclosed by the invention, a hollow nano gold shell is immobilized on the surface of the transparent conductive glass surface, and any organic stabilizing agent and bonding agent do not need to be added; and the surface is clean and the gold surface is further functionalized to prepare an LSPR (Localized Surface Plasmon Resonance) biosensor.
Description
Technical field
The present invention relates to a kind of hollow golden nanometer particle sensing membrane and preparation method thereof, it is a kind of local surface plasma resonance spectrum sensing film, can further make up chemistry and biology sensor.
Background technology
Local surface plasma resonance (localized surface plasmon resonance is called for short LSPR) is an important character of noble metal nano particles, shows strong absorption peak such as golden nanometer particle at ultraviolet-visible spectrum.Outside the Pass local surface plasma resonance absorption spectrum not only has with kind, composition, shape, structure, the size of precious metal material, and extremely responsive to the surrounding environment medium, therefore can be used for sensory field.Local surface plasma resonance sensor volume is little, it is integrated to be easy to, cost is low, can realize bio-sensing (such as various spectrophotometers) by simple equipment, to temperature-insensitive, have high sensitivity, high selectivity, detect and the advantage such as unmarked operation in real time.Therefore, the local surface plasma resonance sensor has wide practical use at aspects such as clinical medicine, clinical examination and medical diagnosis on disease, biological chemistry, environmental chemistry, food fast detecting.
Usually, the local surface plasma resonance peak position of color of spherical gold is in about 520 nm, and its prepared LSPR transducer sensitivity is low, and analytical performance is relatively poor.And the LSPR peak of the golden nanometer particle of hollow structure moves to near-infrared region (approximately 800 nm), is conducive to improve the sensing sensitivity of gold nano film, reduces the interference to measuring of biological tissue and blood sample background, can be used for the direct-detection of the biological sample such as blood sample.
The existing method for preparing hollow golden nanometer particle sensing membrane is: the hollow golden nanometer particle with organic stabilizer that adopts organic adhesive to prepare in advance is fixed in solid substrate (such as glass) surface.Yet, because the method need to be used organic stabilizer and bonding agent, be unfavorable for the further functionalization on golden nanometer particle surface, limited its application on biology sensor.
Summary of the invention
The object of the invention provides a kind of hollow golden nanometer particle sensing membrane and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of hollow golden nanometer particle sensing membrane comprises the steps:
(a) adopt electrochemical process directly at ITO conductive glass surface depositing silver nano particle; As template;
(b) adopt HAuCl
4Replace Nano silver grain, gold is deposited on the surface of Nano silver grain, dissolve simultaneously Nano silver grain, can obtain hollow golden nanometer particle sensing membrane.
Above, in the described step (b), gold is in the process of displacement Nano silver grain, and Nano silver grain dissolves simultaneously, and it is residual that final Nano silver grain may have part, removes such as the available nitric acid of needs or perchloric acid.
It is solid substrate that the present invention adopts transparent ITO electro-conductive glass, adopts first electrochemical reducing with the surface of Nano silver grain Direct precipitation in solid substrate, then with the gold displacement, obtains the hollow golden nanometer particle, finally makes hollow golden nanometer particle sensing membrane.
In the technique scheme, in the described step (b), the temperature of displacement reaction is 45 ~ 55 ℃, and the reaction time is 20 ~ 40 min.
The present invention asks for protection the hollow golden nanometer particle sensing membrane that is obtained by above-mentioned preparation method simultaneously.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention has realized the immobilization of hollow golden nanometer particle at transparent conductive glass surface, need not to add any organic stabilizer and bonding agent, and cleaning surfaces is conducive to the further functionalization of gold surface, preparation LSPR biology sensor.
2. experiment showed, that hollow golden nanometer particle sensing membrane that the present invention makes has reached 277nm/RIU to the response of different solvents index of refraction, compare with solid gold or the silver nano-grain of formed objects, its sensitivity is enhanced about more than once.
3. the local surface plasma resonance peak position of hollow golden nanometer particle of the present invention has entered the clear area of biological tissue and blood sample in about 800 nm, is conducive to the mensuration to these biological samples, reduces the impact of background.
4. preparation method of the present invention is simple, and easy operating is suitable for applying.
Description of drawings
Fig. 1 is the ultraviolet-visible light spectrogram of Nano silver grain in the embodiment of the invention one (AgNPs) and hollow golden nanometer particle (HGNs);
Fig. 2 is scanning electron microscope (SEM) figure of Nano silver grain in the embodiment of the invention one;
Fig. 3 is scanning electron microscope (SEM) figure of hollow golden nanometer particle in the embodiment of the invention one;
Fig. 4 is Nano silver grain in the embodiment of the invention one (AgNPs) and the LSPR peak shift curve map of hollow golden nanometer particle (HGNs) in the solvent of different indexs of refraction;
Fig. 5 is the LSPR displacement of sensing membrane in the embodiment of the invention one and the graph of a relation of 11-sulfydryl undecane concentration;
Fig. 6 be in the embodiment of the invention one hollow golden nanometer particle (a) and modify AMTPS(b), biotin (c), and in conjunction with the ultraviolet-visible light spectrogram behind the Streptavidin (d);
Fig. 7 is the working curve diagram of the mensuration Streptavidin of Fig. 6;
Fig. 8 be in the embodiment of the invention one hollow golden nanometer particle (a) and modify goat-anti anti-h-IgG(b), and conjugated antigen h-IgG(c) after the ultraviolet-visible light spectrogram;
Fig. 9 is the working curve diagram of the mensuration h-IgG of Fig. 8.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment one
Shown in Fig. 1 ~ 9, a kind of preparation method of hollow golden nanometer particle sensing membrane comprises the steps:
(1) preparation of template: length 4.0 cm that the ITO electro-conductive glass is made, the rectangle substrate of wide 0.6 cm, (water: behind strong aqua=30:1), absolute ethyl alcohol, inferior boiling water ultrasonic cleaning 10 min, (plating bath forms: 2 mL, 1 mmol AgNO at 7.0 mL silver plating solutions to use successively ammoniacal liquor
3, 0.3 M KNO
3) in, with cyclic voltammetry Electrodeposited Silver nano particle, mode of deposition: 30 ℃ of temperature, fast 0.05V/s is swept in nitrogen protection, the scanning number of turns 100 circles;
(2) (displacement liquid forms: 1 mL, 0.1 mmol HAuCl at displacement liquid with the above-mentioned Nano silver grain ito glass template for preparing
4, the inferior boiling water solution of 4mL) in, take the mode of water-bath (50 ℃ of bath temperatures) to replace generation hollow golden nanometer particle structure, the time is 30min approximately; Can obtain hollow golden nanometer particle sensing membrane.
Fig. 1 is the nano grain of silver subtemplate of deposition and the uv-visible absorption spectra figure of hollow golden nanometer particle, and the LSPR peak position of Nano silver grain (AgNPs) is in about 480 nm, and the LSPR peak red shift of hollow golden nanometer particle (HGNs) is to about 800 nm.
Fig. 2 and 3 is respectively the nano grain of silver subtemplate of deposition and the SEM figure of hollow golden nanometer particle, as seen from the figure, the size of Nano silver grain is about 110 nm, according to the estimation of the stoichiometry of displacement reaction, the thick approximately 5 nm(shells of the shell of golden shell are thick be about the Nano silver grain radius 1/10).
One, the sensitivity test of hollow golden nanometer particle sensing membrane
The fixing ito glass sheet of hollow golden nanometer particle sensing membrane is fixed in the cuvette that fills solvent, adjust suitable height, make light source over against sensing membrane, carry out length scanning, obtain Nano silver grain shown in Figure 4 and the LSPR peak shift curve of hollow golden nanometer particle in the solvent of different indexs of refraction, as seen from the figure, the sensing sensitivity of Nano silver grain is 123 nm/RIU, and the sensitivity of hollow golden nanometer particle sensing membrane is 277 nm/RIU.
Two, hollow golden nanometer particle sensing membrane is to the research of 11-sulfydryl undecane self-assembly system
The fixing ito glass sheet of hollow golden nanometer particle sensing membrane is dipped in the undecanoic solution of 11-sulfydryl of a series of variable concentrations approximately 10 h of self assembly, takes out and dry after cleaning, as reference, measure its uv-visible absorption spectra with ito glass.Referring to shown in Figure 5, sulfhydryl compound can make its LSPR Dependent Red Shift in the absorption of gold surface.11-sulfydryl undecane can be used for detecting the performance of sensing membrane in the self assembly of gold surface.
Three, hollow golden nanometer particle sensing membrane is to the research of biotin-Streptavidin system
Ito glass sheet with hollow golden nanometer particle sensing membrane is soaked in 2 h in the APTMS solution first, makes electrode surface with amino; And then will connect amino test piece and be immersed in biotin solution (2 * 10
-4Mol/L) 4 h in are fixed in golden surface with biotin, and the variation of its ultraviolet-ray visible absorbing peak position of rear observation is dried in flushing.At last test piece is immersed in 4 h in the solution of streptavidin of the variable concentrations that configures, the variation (Fig. 6) of rear observation modified electrode ultraviolet-ray visible absorbing peak position is dried in flushing.Fig. 7 is for measuring the working curve of Streptavidin, and measurement range is 10
-6~ 10
-10Mol/L.
Four, hollow golden nanometer particle sensing membrane is to the response investigations of Ag-Ab
Ito glass sheet with hollow golden nanometer particle sensing membrane is soaked in 12 h in the goat-anti anti-h IgG solution (100 μ g/ml) first, cleans and dries rear record ultraviolet-ray visible absorbing peak position at this moment; Then be immersed in the h-IgG solution of variable concentrations and hatch 3 h, clean and dry the rear record ultraviolet-ray visible absorbing peak position (Fig. 8) of this moment, Fig. 9 is working curve.The method can be used for the preparation of unmarked immunosensor.
Claims (3)
1. the preparation method of a hollow golden nanometer particle sensing membrane is characterized in that, comprises the steps:
(a) adopt electrochemical process directly at ITO conductive glass surface depositing silver nano particle; As template;
(b) adopt HAuCl
4Replace Nano silver grain, gold is deposited on the surface of Nano silver grain, dissolve simultaneously Nano silver grain, can obtain hollow golden nanometer particle sensing membrane.
2. the preparation method of hollow golden nanometer particle sensing membrane according to claim 1, it is characterized in that: in the described step (b), the temperature of displacement reaction is 45 ~ 55 ℃, and the reaction time is 20 ~ 40 min.
3. the hollow golden nanometer particle sensing membrane that is obtained by preparation method claimed in claim 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357887A (en) * | 2013-07-01 | 2013-10-23 | 西安交通大学 | Sea urchin-shaped hollow gold and silver alloy nano particle and preparation method and application thereof |
| CN103543109A (en) * | 2013-08-12 | 2014-01-29 | 苏州大学 | LSPR (Localized Surface Plasmon Resonance) sensor membrane for measuring mercury ion and preparation method thereof |
| CN103691482A (en) * | 2013-12-04 | 2014-04-02 | 哈尔滨师范大学 | Preparation method of hollow gold nano-sphere and application thereof |
| CN105057694A (en) * | 2015-08-26 | 2015-11-18 | 南京理工大学 | Method for quickly preparing nanogold on conducting glass through electric replacement reaction |
| CN105880623A (en) * | 2016-04-13 | 2016-08-24 | 同济大学 | Precious metal nanocrystalline with adjustable plasma resonance absorption characteristic in visible wave band and preparation method of precious metal nanocrystalline |
| CN107983951A (en) * | 2018-01-08 | 2018-05-04 | 合肥学院 | A kind of preparation method of raspberry shape gold nanoparticle |
| CN108372314A (en) * | 2018-03-29 | 2018-08-07 | 景德镇陶瓷大学 | A kind of preparation method of the hollow gold-silver alloy nanoparticles of high SERS activity |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357887A (en) * | 2013-07-01 | 2013-10-23 | 西安交通大学 | Sea urchin-shaped hollow gold and silver alloy nano particle and preparation method and application thereof |
| CN103357887B (en) * | 2013-07-01 | 2015-12-02 | 西安交通大学 | Hollow gold-silver alloy nano particle of a kind of sea urchin shape and its preparation method and application |
| CN103543109B (en) * | 2013-08-12 | 2016-08-10 | 苏州大学 | For LSPR sensing membrane measuring mercury ion and preparation method thereof |
| CN103543109A (en) * | 2013-08-12 | 2014-01-29 | 苏州大学 | LSPR (Localized Surface Plasmon Resonance) sensor membrane for measuring mercury ion and preparation method thereof |
| CN103691482A (en) * | 2013-12-04 | 2014-04-02 | 哈尔滨师范大学 | Preparation method of hollow gold nano-sphere and application thereof |
| CN103691482B (en) * | 2013-12-04 | 2016-02-24 | 哈尔滨师范大学 | A kind of preparation method of hollow gold nano-sphere and application thereof |
| CN105057694A (en) * | 2015-08-26 | 2015-11-18 | 南京理工大学 | Method for quickly preparing nanogold on conducting glass through electric replacement reaction |
| CN105880623A (en) * | 2016-04-13 | 2016-08-24 | 同济大学 | Precious metal nanocrystalline with adjustable plasma resonance absorption characteristic in visible wave band and preparation method of precious metal nanocrystalline |
| CN105880623B (en) * | 2016-04-13 | 2018-04-13 | 同济大学 | It is a kind of to have in noble metal nanocrystalline of the adjustable plasma resonance absorption characteristic of visible waveband and preparation method thereof |
| CN107983951A (en) * | 2018-01-08 | 2018-05-04 | 合肥学院 | A kind of preparation method of raspberry shape gold nanoparticle |
| CN107983951B (en) * | 2018-01-08 | 2021-01-29 | 合肥学院 | Preparation method of raspberry-shaped gold nanoparticles |
| CN108372314A (en) * | 2018-03-29 | 2018-08-07 | 景德镇陶瓷大学 | A kind of preparation method of the hollow gold-silver alloy nanoparticles of high SERS activity |
| CN108372314B (en) * | 2018-03-29 | 2021-03-12 | 景德镇陶瓷大学 | Preparation method of hollow gold-silver alloy nanoparticles with high SERS activity |
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Application publication date: 20130206 |