CN103234951B - A kind of noble metal nano particles coat photonic crystal coding microball preparation method - Google Patents

A kind of noble metal nano particles coat photonic crystal coding microball preparation method Download PDF

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CN103234951B
CN103234951B CN201310115308.6A CN201310115308A CN103234951B CN 103234951 B CN103234951 B CN 103234951B CN 201310115308 A CN201310115308 A CN 201310115308A CN 103234951 B CN103234951 B CN 103234951B
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photonic crystal
coding microball
noble metal
nano particles
crystal coding
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CN103234951A (en
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李娟�
戚华梅
王欢
刁国旺
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Yangzhou University
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Yangzhou University
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Abstract

The present invention relates to a kind of noble metal nano particles cladding photonic crystal coding microball preparation method.The present invention on the surface of photonic crystal coding microball after carrying out chemical bond modification, noble metal nano particles are coated on photonic crystal coding microball surface using the method for fabricated in situ, noble metal nano particles are introduced on photonic crystal coding microball surface to realize strengthening Surface Raman Spectra effect, using the feature reflection peak of photonic crystal coding microball, various testing samples are detected simultaneously, the unmarked multi-element biologic immune detection of hypersensitivity is realized.Cause stability not high instant invention overcomes easily being limited by illumination, temperature, storage time etc. existing for fluorescence spectrum, the problems such as biocompatibility, and the defect such as solvent effect on environment.Sensitivity degree of the present invention, detection is simple and quick, and with low cost, property is sufficiently stable, and detection efficiency is improved.

Description

A kind of noble metal nano particles coat photonic crystal coding microball preparation method
Technical field
The present invention relates to the technical field of biomedical research, environmental monitoring and clinical detection, more particularly to a kind of your gold Category nano-particle cladding photonic crystal coding microball preparation method.
Background technology
With the fast development of progressively implementation and molecular biology etc. the related discipline that human genome (sequencing) is planned, Increasing animals and plants, microbial genome sequence are determined, and gene sequence data is fast at an unprecedented rate Speed increases.Meanwhile, all it is often to detect many index in a sample, particularly new disease in clinical immunology detection Pathogenic microorganism is constantly found that the new amynologic index related to disease is also constantly being found, and clinical detection project also must Can so be continuously increased.Therefore, setting up new hybridization and sequence measurement so as to realize carrying out substantial amounts of hereditary information, clinical sample Efficiently, quickly detection, analysis just seem increasingly important.
At present, flowing code carrier due to its preparation it is simple, encoding amount is big, receives significant attention the features such as react quick. Photonic crystal coding wherein based on spectral technique is easy to detect to be intuitively able to universal due to its coding, detection technique maturation Using.Additionally, relative to the carrier of other solid phase forms, microballoon has more significant advantage:First, the specific surface area ratio of microballoon It is larger, by increasing capacitance it is possible to increase the ratio between the surface area and volume of effecting reaction, therefore the chemical reaction on surface can be made smaller Carried out in volume range;The carrier for secondly, being used as solid phase form using microballoon can utilize related supplementary means as stirred, Ultrasound, liquid wash away etc. to realize the reaction system of multi-form, such that it is able to accelerate the reaction speed of system;Finally, with The change of microsphere surface functionalization group, can extend the purposes of microballoon.
But, fluorescence spectrum is relied primarily on currently with the multivariate detection of photonic crystal coding microball.The suction of fluorescence spectrum Peak is received, the chemical constitution of molecule, the i.e. chemical constitution by molecule in itself is typically from and is determined, therefore be highly prone to illumination, The limitation of the factors such as temperature, storage time, therefore stability is not high, usual spectrum peak scope is relatively wide to be difficult to differentiate between, and There are problems that, additionally, the detection of fluorescence spectrum is generally required being carried out in specific solvent, solvent may Fluorescence to material produces important ambient influnence, can make fluorescent weakening, even disappears completely, therefore is typically made using fluorescence spectrum Also to there is certain limitation in the foundation of detection.
The content of the invention
It is an object of the invention to provide drawbacks described above is overcome, develop a kind of noble metal nano particles cladding photonic crystal and compile Code method for preparing microsphere.
The technical scheme is that:
A kind of noble metal nano particles coat photonic crystal coding microball preparation method, and it is mainly characterized by and passes through After the surface of photonic crystal coding microball carries out chemical bond modification, using the method for fabricated in situ by noble metal nano particles bag Photonic crystal coding microball surface is overlayed on, i.e., introduces noble metal nano particles on photonic crystal coding microball surface to realize enhancing Surface Raman Spectra effect, using the feature reflection peak of photonic crystal coding microball, while detecting various testing samples, realizes super Highly sensitive unmarked multi-element biologic immune detection.
Further technical scheme of the invention is:
(1) the photonic crystal coding microball of different coding is chosen, its surface is processed, with microsphere surface functionalization The change of group, obtains the photonic crystal coding microball with amino group modification;
(2) using the method for fabricated in situ, deionized water and contain to being added in the container for filling photonic crystal coding microball The precursor solution of precious metal ion, the reducing agent made configured in advance is added after slow intensification, that is, obtain noble metal nano grain The photonic crystal coding microball that attached bag is covered;
(3) hot conditions are placed in after the photonic crystal coding microball washing of the noble metal nano particles cladding that will be prepared Lower calcining, for removing the impurity introduced in experimentation, and further enhances the mechanical strength of photonic crystal coding microball.
In the middle of the technical program, the coding of described photon crystal micro-ball is the feature in photonic crystal reflectance spectrum The wavelength values of reflection peak.The structure of described photon crystal micro-ball is the albumen of colloidal particle long-range order ground self assembly The photonic crystal of stone structure;The photon crystal micro-ball of opal structural has the ability of the light of reflection specific wavelength, its reflected light Spectrum has its feature reflection peak, and wave-length coverage covers ultraviolet, it is seen that with infrared region.
The present invention introduces noble metal nano particles by chemical method on photon crystal micro-ball surface, such that it is able to be had The nano composite material of standby three-dimensional structure, as a kind of new and with the substrate of enhancing surface-enhanced raman scattering, has concurrently The property of the optics of noble metal nano particles, electricity, catalysis and the aspect such as immune, has photon crystal micro-ball as substrate again Flowing code carrier characteristic, can simultaneously detect various testing samples, realize the multi-element biologic immune detection of hypersensitivity.
The present invention has advantages below:
1) noble metal nano particles cladding photonic crystal coding microball, can be micro- by choosing the photonic crystal of different coding Ball carries out efficient coding to testing sample, meets detect multiple indexs simultaneously the need for, additionally, in photonic crystal coding microball table Face introduces noble metal nano particles to realize strengthening Surface Raman Spectra effect, can effectively be increased using SERS The sensitivity of strong detection, realizes the multi-element biologic immune detection of hypersensitivity;
2) this noble metal nano particles cladding photonic crystal coding microball, both can effectively using photon crystal micro-ball Feature reflection peak learns the species of testing sample, can be detected using the intensity of SERS again and treat test sample The content of product.The detection process is simple, and quickly.
3) this noble metal nano particles cladding photonic crystal coding microball preparation method is simple, is compiled by photonic crystal After the surface of code microballoon carries out chemical bond modification, noble metal nano particles are coated on photonic crystal using the method for fabricated in situ Coding microball surface, the synthetic method is easily controlled, and cost of manufacture is cheap, simple efficient;
4) this code used good stability of photonic crystal coding microball, and after noble metal nano particles are coated with The coding efficiency of photonic crystal coding microball is consistent.The photonic crystal coding microball that the noble metal nano particles are coated is put In under normal temperature, the stable chemical nature of its own is difficult to be influenceed by external conditions such as temperature, illumination, humidity, and property is very steady It is fixed.The coding of stabilization is remained during application;
5) detecting step is simply efficient, because the outer layer of photonic crystal coding microball is coated by noble metal nano particles, and General biological sample contains amino again, therefore need not can be fixed on microballoon with by probe molecule by rhetorical function group again Surface, the step of reduce chemical coupling, improves detection efficiency.
Other specific advantages of the invention and effect will go on to say below.
Specific embodiment
Technical thought of the invention is:
Noble metal nano particles are introduced on photonic crystal coding microball surface by chemical method, such that it is able to be possessed The nano composite material of three-dimensional structure.Test result indicate that, the photonic crystal coding microball particle size range as obtained in this method Can control at 50 μm between 3mm, the particle size range of noble metal nano particles can be controlled between 3nm to 70nm.Its system Preparation Method is simply efficient, and method in photonic crystal coding microball Surface coating noble metal nano particles it is relatively easy and Size, pattern, dispersiveness can be adjusted suitably.
Experimentation of the invention is described in detail below, it is intended to make design cycle of the invention, purpose of design And its innovative point and advantage more understand.
A kind of noble metal nano particles coat the preparation method of photonic crystal coding microball, are the photons for choosing different coding Crystal microballoon, after carrying out chemical bond modification to its surface, is coated noble metal nano particles by the method using fabricated in situ On the surface of photon crystal micro-ball, using the various testing samples of surface Raman enhancement spectral detection, many of hypersensitivity are realized First biological immune detection.
Preparation method is comprised the following steps:
The photon crystal micro-ball of different coding is chosen, its surface is processed, obtain the photon with amino group modification Crystal coding microball.Wherein photonic crystal coding microball can be organic polyvinyls photon crystal micro-ball, i.e. polyphenyl Ethene, polypropylene, polyacrylonitrile, polymethyl methacrylate, polyethylene or polyethyl acrylate, or for inorganic photon crystal is micro- Ball is silica or titanium dioxide.
Using the method for fabricated in situ, to addition deionized water in the container for filling photonic crystal coding microball and containing your gold Belong to the precursor solution of ion, the reducing agent made configured in advance is added after slow intensification, that is, obtain noble metal nano particles bag The photonic crystal coding microball for covering.Noble metal nano particles can be golden nanometer particle, Nano silver grain or nano platinum particle.
It is placed under hot conditions after the photonic crystal coding microball washing of the noble metal nano particles cladding that will be prepared Calcining, for removing the impurity introduced in experimentation, and further enhances the mechanical strength of photonic crystal coding microball.
In the middle of the technical program, the coding of described photon crystal micro-ball is the feature in photonic crystal reflectance spectrum The wavelength values of reflection peak.The structure of described photon crystal micro-ball is the albumen of colloidal particle long-range order ground self assembly The photonic crystal of stone structure;The photon crystal micro-ball of opal structural can reflect the light of specific wavelength, and its reflectance spectrum has Its feature reflection peak, wave-length coverage covers ultraviolet, it is seen that with infrared region.Described Surface coating has the light of noble metal nano particles Sub- crystal coding microball, is to realize strengthening surface Raman light by introducing noble metal on photonic crystal coding microball surface Spectrum effect.
Here is specific embodiment.
Embodiment 1:
The preparation of the silica photonic crystal coding microball of golden nanometer particle cladding
1st, the silica photonic crystal coding microball of different coding is chosen respectively, is dipped in 70% (V/V0) concentrated sulfuric acid With in 30% hydrogen peroxide solution overnight so that the silica photonic crystal coding microball surface of preparation carry oh group. The silica photonic crystal coding microball that hydroxyl will have been modified is immersed in concentration for the ethoxy of 0.015mol/L3- aminopropyls three In the aqueous isopropanol of base silane (APTES), shaken in 80 DEG C of water bath with thermostatic control 2 hours, fully use ultra-pure water after reaction Flush three times, unnecessary APTES is removed, silica photonic crystal coding microball surface is carried amino group.
2nd, the silica photonic crystal coding microball that will modify amino is immersed in 1% gold chloride (HAuCl4) solution In, and slowly heat up up to boiling, 1% sodium citrate aqueous solution made configured in advance is added, it is stirred vigorously until final Solution becomes claret, and ultrapure water is used three times after being cooled to room temperature, finally gives the silica of golden nanometer particle cladding Photonic crystal coding microball.
3rd, the photonic crystal coding microball that will be prepared by above-mentioned condition is calcined under being placed in hot conditions, for removing The impurity introduced in experimentation, and further enhance the mechanical strength of photonic crystal coding microball.The simple synthetic method, it is micro- Ball is stable in properties.It is many using surface Raman enhancement spectral detection using the feature reflection peak of photonic crystal coding microball as coding Testing sample is planted, the multi-element biologic immune detection of hypersensitivity is realized.
Embodiment 2:
The preparation of the polystyrene photon crystal coding microball of Nano silver grain modification
1st, the polystyrene photon crystal coding microball of different coding is chosen respectively, because the polystyrene photon for preparing is brilliant Body microsphere surface carries carboxyl, therefore is placed directly within concentration for 0.015mol/L3- aminopropyltriethoxywerene werenes (APTES) in aqueous isopropanol, shaken in 80 DEG C of water bath with thermostatic control 2 hours, fully use ultrapure water three after reaction It is secondary, unnecessary APTES is removed, polystyrene photon crystal coding microball surface is carried amino group.
2nd, will modify amino polystyrene photon crystal coding microball be immersed in 0.2mg mL silver nitrate (AgNO3) In solution, and slowly heat up until boiling, add 1% sodium citrate aqueous solution made configured in advance, be stirred vigorously up to Reaction is complete, and ultrapure water is used three times after being cooled to room temperature, and the polystyrene photon for finally giving Nano silver grain cladding is brilliant Body coding microball.
3rd, the photonic crystal coding microball that will be prepared by above-mentioned condition is calcined under being placed in hot conditions, for removing The impurity introduced in experimentation, and further enhance the mechanical strength of photonic crystal coding microball.The simple synthetic method, it is micro- Ball is stable in properties.It is many using surface Raman enhancement spectral detection using the feature reflection peak of photonic crystal coding microball as coding Testing sample is planted, the multi-element biologic immune detection of hypersensitivity is realized.

Claims (2)

1. unmarked multi-element biologic immunologic detection method, it is characterised in that by the surface of photonic crystal coding microball After learning key modification, noble metal nano particles are coated on photonic crystal coding microball surface using the method for fabricated in situ, that is, existed Photonic crystal coding microball surface introduces noble metal nano particles to realize strengthening Surface Raman Spectra effect, using photonic crystal The feature reflection peak of coding microball, while detecting various testing samples, realizes that the unmarked multi-element biologic of hypersensitivity is immunized Detection;Wherein concretely comprising the following steps for chemical bond modification is carried out on the surface of photonic crystal coding microball choose different coding respectively Silica photonic crystal coding microball, is dipped in 70% (V/V0) in the concentrated sulfuric acid and 30% hydrogen peroxide solution overnight, make The silica photonic crystal coding microball surface that must be prepared carries oh group, and the silica photon that will modify hydroxyl is brilliant Body coding microball is immersed in the aqueous isopropanol that concentration is 0.015mol/L APTESs, at 80 DEG C Water bath with thermostatic control in shake 2 hours, fully unnecessary APTES is removed with ultrapure water three times after reaction, make titanium dioxide Silicon photonic crystal coding microball surface carries amino group.
2. unmarked multi-element biologic immunologic detection method according to claim 1, it is characterised in that photonic crystal coding is micro- , at 50 μm between 3mm, the particle size range of noble metal nano particles is between 3nm to 70nm for ball particle size range.
CN201310115308.6A 2013-04-02 2013-04-02 A kind of noble metal nano particles coat photonic crystal coding microball preparation method Expired - Fee Related CN103234951B (en)

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CN105652347A (en) * 2016-01-21 2016-06-08 扬州大学 Preparation method of three-dimensional ordered titanium dioxide photonic crystal microballoons covered by silver nanoparticles
CN106950616B (en) * 2017-05-22 2019-11-01 扬州大学 A kind of preparation method of compound Raman photon crystal microballoon
CN108344713B (en) * 2018-02-06 2021-04-13 军事科学院军事医学研究院环境医学与作业医学研究所 Photonic crystal sensing material and preparation method and application thereof
CN109342392B (en) * 2018-11-09 2021-09-17 中国科学院烟台海岸带研究所 Surface-enhanced Raman scattering nano probe taking polystyrene as coating shell material and preparation method thereof
US20210394440A1 (en) * 2020-06-18 2021-12-23 University Of Massachusetts Fabrication of structure from lost base material
CN114354574A (en) * 2022-01-11 2022-04-15 扬州大学 Multielement SERS biological detection method based on analog enzyme signal amplification

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