CN104330397A - Surface enhanced Raman scattering substrate with ordered crystal structure and application of surface enhanced Raman scattering substrate - Google Patents
Surface enhanced Raman scattering substrate with ordered crystal structure and application of surface enhanced Raman scattering substrate Download PDFInfo
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- CN104330397A CN104330397A CN201410578179.9A CN201410578179A CN104330397A CN 104330397 A CN104330397 A CN 104330397A CN 201410578179 A CN201410578179 A CN 201410578179A CN 104330397 A CN104330397 A CN 104330397A
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Abstract
The invention discloses a surface enhanced Raman scattering substrate with an ordered crystal structure. The surface enhanced Raman scattering substrate with the ordered crystal structure is assembled by monodispersity spherical nano materials by a marginal evaporation method. The invention also discloses a preparation method of the surface enhanced Raman scattering substrate with the ordered crystal structure and an application of the surface enhanced Raman scattering substrate with the ordered crystal structure. Compared with the SERS substrate in the prior art, the SERS substrate disclosed by the invention has a height ordered structure of a crystal, so that the SERS of the structure has the characteristics of high uniformity and high repeatability; high-accuracy quantitative detection in quantitative analysis of biomarkers is facilitated.
Description
Technical field
The present invention relates to a kind of technical field strengthening Raman substrate and prepare, more specifically, relate to a kind of surface enhanced Raman scattering substrate having crystalline organized structure and its preparation method and application.
Background technology
Surface enhanced raman spectroscopy (SERS) is becoming biological and that medical research is powerful analysis tool.The main advantage of Surface enhanced raman spectroscopy is huge enhancing Raman signal, from the characteristic fingerprint spectrum analyzing thing, can get rid of non-specific molecules interference from complex sample matrix.But the low cost manufacture with high sensitivity and reproducible SERS matrix remains a challenge.In order to obtain the SERS substrate arranged equably, diverse ways such as photoetching, ink jet printing or multipolymer template assembly adopt.But also have when obtaining high-quality SERS substrate, repeatability or the simplicity aspect of said method still have certain difficulty.Evaporation self-assembling method has the advantage of low, the repeatable and unwanted additional agents box consumptive material of cost.Therefore, the various methods based on the manufacturing array of evaporation are used.Convection current assembling has been used to guide well orderly two and three dimensions polystyrene assembly array.Vertical deposition also provides a kind of simple method to assemble colloidal crystal, causes scale large, is formed into multilayer film from the good reappearance silicon array of individual layer.But for metal nano material, because its density refractory is to use above-mentioned the method.
Summary of the invention
Goal of the invention: first object of the present invention there is provided a kind of surface enhanced Raman scattering substrate with crystalline organized structure.Second object of the present invention there is provided the above-mentioned preparation method with the surface enhanced Raman scattering substrate of crystalline organized structure.3rd object of the present invention there is provided a kind of application of surface enhanced Raman scattering substrate in SERS input with crystalline organized structure.
In the present invention, prepared a kind of SERS substrate with crystalline organized structure according to marginal evaporative effect, it has excellent Surface enhanced raman spectroscopy character, SERS signal homogeneity and repeatability etc.Preparation method have simple to operate, without any need for instrument and equipment and low cost and other advantages.This SERS substrate is the prerequisite that SERS detects and respective sensor is developed.
Technical scheme: in order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of surface enhanced Raman scattering substrate with crystalline organized structure, described in there is crystalline organized structure surface enhanced Raman scattering substrate be assembled by the method for the ball shaped nano material of monodispersity by limit evaporation.
Further, the ball shaped nano material of above-mentioned monodispersity be the gold, silver of monodispersity, copper, platinum nanosphere or possess the nanosphere of metal nano shell of monodispersity.
Preparation method about the gold, silver of monodispersity, copper, platinum nanosphere is ripe, report also a lot, below lists part list of references.See list of references: Phootehem.Photobiol. 1994,60,605; Chem.Mater. 1997,9,3083; Langmuir 1998,14,726; Chem. Mater. 2000,12,306; J. Phys. Chme. B 1999,103,9533; Langmuir 1999,15,6738; Chem. Mater. 1998,10,594; J. Phys. Chme. B 1999,103,3818; Chem. Mater. 2001,13,2313; Langmuir 2001,17,6782.
Further, the above-mentioned nanosphere possessing the metal nano shell of monodispersity is organic or inorganic nanosphere kernel and the metal nano skin with monodispersity, and described metal nano skin is one or more in gold nano layer, silver nanoparticle layer, copper nanometer layer or platinum nano-layers.
Further, the ball shaped nano material diameter of above-mentioned monodispersity is 40-800 nanometer.
Further, in the organic or inorganic nanosphere of above-mentioned monodispersity, nuclear diameter is 20-500 nanometer, and described metal nano outer layer thickness is 20-500 nanometer.
Further, the above-mentioned preparation method possessing the nanosphere of the metal nano shell of monodispersity is as follows:
1) NaOH of 1 ~ 25 ml fresh configuration 1M adds in 500 ~ 1000 ml water, stir, and then 50-1000 μ l THPC is added, mixed liquor is obtained after magnetic agitation 2-20 minute, 5-100 ml 1% gold chloride adds in mixed liquor, namely magnetic agitation obtains the gold nano grain of 2 ~ 3 nm for 10 ~ 50 minutes, and 4 DEG C keep in Dark Place;
2) the 3-aminopropyl triethoxysilane of the alcohol suspension of monodispersed organic or inorganic nanosphere and 100 ~ 400 μ l is stirred 1 ~ 4 h by 60 ~ 80 DEG C and carry out amination, ethanol washing is removed free 3-aminopropyl triethoxysilane and is namely obtained amination nanosphere;
3) by through step 2) the amination nanosphere that processes adds the gold nano grain of step 1) process, and namely the magnetic agitation gold nano grain that after 10 ~ 50 minutes, centrifugal segregation does not adsorb obtains the nanosphere precursor of the metal nano shell possessing monodispersity;
4) the nanosphere precursor possessing the metal nano shell of monodispersity through step 3) process is added in the salt solusion of gold, silver, copper or platinum, adding reductive agent magnetic agitation after 10 ~ 50 minutes, centrifugal collecting precipitation is resuspended in water the suspension of nanoglobules namely obtaining the metal nano shell possessing monodispersity.
Further, above-mentioned organic or inorganic nanosphere is silica nanosphere, titanium dioxide nano-sphere, polystyrene nanospheres, polytetrafluorethylenano nano ball.
Further, above-mentioned steps 4) in reductive agent be formaldehyde, hydrogen peroxide or hydroxylammonium chloride.
Above-mentioned a kind of preparation method with the surface enhanced Raman scattering substrate of crystalline organized structure, described preparation method is the method for being evaporated by limit, specifically comprises the following steps:
1) microslide is immersed in volume ratio be 0.1-5% there is 0.5-12 hour in the ethanolic solution of the silylating reagent of amino or sulfydryl, then to wash with ethanol;
2) by the dry process 5-60 minute under 60-120 DEG C of condition of the microslide through step 1) process;
3) will through step 2) angle in 3-45 ° between the microslide that processes and surface level is placed, and is 1 × 10 by the concentration of the monodispersity of 1-500 microlitre
6-1 × 10
10the hanging drop of the ball shaped nano material of individual/mL is added on microslide, dry down to liquid evaporation the condition of 4-45 DEG C.
The above-mentioned application of the surface enhanced Raman scattering substrate with crystalline organized structure in SERS input.
Beneficial effect: compared with prior art, tool of the present invention has the following advantages:
(1) the present invention is compared with the SERS substrate of inventing in the past, formed by monodispersity spherical metal nanomaterial assembly based on substrate of the present invention, there is the same higher order structures of crystal, have very good homogeneity and repeatable characteristic as SERS material, this point is particularly important for SERS base material.
(2) compared with existing SERS substrate technology of preparing, the present invention has the SERS substrate of the higher order structures of crystal by marginal evaporative effect preparation, simple to operate, does not need extra instrument and equipment, most importantly at the bottom of cost.
Accompanying drawing explanation
The extinction spectra of the hollow copper nanosphere of Fig. 1 (A) monodispersity and scanning electron microscopic picture; (B) the particle diameter statistic histogram of the hollow copper nanosphere of monodispersity;
Schematic diagram prepared by the SERS substrate that Fig. 2 has the higher order structures of crystal;
Fig. 3 gold nanoshell suspension drop dried SEM image: (a) wide-field SEM figure, wherein in the visual field, half moon-shaped region is the SERS substrate of the higher order structures with crystal, other are unordered gold nanoshell arrange regional (illustration is a typically dry optical photograph dripping diameter 4 millimeters), the SEM figure of the gold nanoshell arrangement amplification that b border (C) that () is the SERS substrate and unordered gold nanoshell arrange regional with the higher order structures of crystal is unordered, the SEM figure that the SERS substrate that (D) has the higher order structures of crystal is amplified;
Fig. 4 is that the SERS substrate with the higher order structures of crystal of the platinum nanosphere assembling of preparation and unordered platinum nanosphere arrange regional are at the SERS spectrum of the Nile blue A of different excitation light source excites, show that the enhancing effect of the SERS substrate of the higher order structures with crystal is better than unordered platinum nanosphere arrange regional (a:785 nm, b:632 nm, c:533 nm);
Fig. 5 is that the SERS substrate with the higher order structures of crystal of the copper nanoshell assembling of preparation and unordered copper nanoshell arrange regional strengthen the Raman image of effect under 785 nm exciting light conditions, show that the enhancing homogeneity of the SERS substrate of the higher order structures with crystal is better than unordered arrange regional (a: the Raman image figure with the SERS substrate of the higher order structures of crystal, b: there is the SERS spectrum that the SERS basal signal of the higher order structures of crystal is minimum, c: there is the SERS spectrum that the SERS basal signal of the higher order structures of crystal is the highest, d: unordered copper nanoshell arrange regional Raman image figure, e: the SERS spectrum that unordered copper nanoshell arrange regional signal is minimum, f: the SERS spectrum that unordered copper nanoshell arrange regional signal is the highest),
Fig. 6 has the nerve specificity olefinic alcohol enzyme examination criteria curve (a: the SERS spectrum that variable concentrations nerve specificity olefinic alcohol enzyme is corresponding, b: typical curve) of the surface enhanced Raman scattering substrate of crystalline organized structure;
In the serum that the surface enhanced Raman scattering substrate that Fig. 7 has crystalline organized structure detects, variable concentrations nerve specificity olefinic alcohol enzyme adds detection figure; Serum is serum.
Embodiment
Embodiment 1: the preparation possessing the nanosphere of the gold nanoshell of monodispersity
The nanosphere possessing the metal nano shell of monodispersity is organic or inorganic nanosphere kernel and the metal nano skin with monodispersity, and described metal nano skin is gold nano layer.In the organic or inorganic nanosphere of monodispersity, nuclear diameter is 20 nanometers, and described metal nano outer layer thickness is 20 nanometers.Organic or inorganic nanosphere is silica nanosphere.
The preparation method possessing the nanosphere of the gold nanoshell of monodispersity is as follows:
1) NaOH of 1 ml fresh configuration 1M adds in 500 ml water, stir, and then add 50 μ l THPCs, magnetic agitation after 2 minutes 5ml 1% gold chloride add in mixed liquor, namely magnetic agitation obtains the gold nano grain of 2 ~ 3 nm for 10 minutes, and 4 DEG C keep in Dark Place;
2) the 3-aminopropyl triethoxysilane of the alcohol suspension of monodispersed silica nanosphere and 100 μ l is stirred 4 h by 60 DEG C and carry out amination, ethanol washing is removed free 3-aminopropyl triethoxysilane and is namely obtained amination nanosphere.
3) by through step 2) the amination nanosphere that processes adds the gold nano grain of step 1) process, and namely the magnetic agitation golden nanometer particle that after 10 minutes, centrifugal segregation does not adsorb obtains the nanosphere precursor of the metal nano shell possessing monodispersity;
4) the nanosphere precursor possessing the metal nano shell of monodispersity through step 3) process is added in the salt solusion of gold, adding reductive agent formaldehyde magnetic agitation after 10 minutes, centrifugal collecting precipitation is resuspended in the suspension of nanoglobules namely obtaining the gold nanoshell possessing monodispersity in water.
Embodiment 2 possesses the preparation of the nanosphere of the silver nanoparticle shell of monodispersity
The nanosphere possessing the metal nano shell of monodispersity is organic or inorganic nanosphere kernel and the metal nano skin with monodispersity, and described metal nano skin is silver nanoparticle layer.In the organic or inorganic nanosphere of monodispersity, nuclear diameter is 500 nanometers, and described metal nano outer layer thickness is 500 nanometers.Organic or inorganic nanosphere is titanium dioxide nano-sphere.
The preparation method possessing the nanosphere of the metal nano shell of monodispersity is as follows:
1) NaOH of 25 ml fresh configuration 1M adds in 1000 ml water, stir, and then add 1000 μ l THPCs, magnetic agitation after 20 minutes 100 ml 1% gold chlorides add in mixed liquor, namely magnetic agitation obtains the gold nano grain of 2 ~ 3 nm for 50 minutes, and 4 DEG C keep in Dark Place;
2) the 3-aminopropyl triethoxysilane of the alcohol suspension of monodispersed titanium dioxide nano-sphere and 400 μ l is stirred 4 h by 80 DEG C and carry out amination, ethanol washing is removed free 3-aminopropyl triethoxysilane and is namely obtained amination nanosphere.
3) by through step 2) the amination nanosphere that processes adds the gold nano grain of step 1) process, and namely the magnetic agitation golden nanometer particle that after 50 minutes, centrifugal segregation does not adsorb obtains the nanosphere precursor of the metal nano shell possessing monodispersity;
4) the nanosphere precursor possessing the metal nano shell of monodispersity through step 3) process is added in the salt solusion of silver, adding reductive agent hydrogen peroxide magnetic agitation after 50 minutes, centrifugal collecting precipitation is resuspended in water the suspension of nanoglobules namely obtaining the silver nanoparticle shell possessing monodispersity.
Embodiment 3 possesses the preparation of the nanosphere of the copper nanoshell of monodispersity
The nanosphere possessing the metal nano shell of monodispersity is organic or inorganic nanosphere kernel and the metal nano skin with monodispersity, and described metal nano skin is copper nanometer layer.In the organic or inorganic nanosphere of monodispersity, nuclear diameter is 250 nanometers, and described metal nano outer layer thickness is 250 nanometers.Organic or inorganic nanosphere is polystyrene nanospheres.
The preparation method possessing the nanosphere of the metal nano shell of monodispersity is as follows:
1) NaOH of 12 ml fresh configuration 1 M adds in 750 ml water, stir, and then add 500 μ l THPCs, magnetic agitation after 10 minutes 50 ml 1% gold chlorides add in mixed liquor, namely magnetic agitation obtains the gold nano grain of 2 ~ 3 nm for 30 minutes, and 4 DEG C keep in Dark Place;
2) the 3-aminopropyl triethoxysilane of the alcohol suspension of monodispersed polystyrene nanospheres and 250 μ l is stirred 2 h by 70 DEG C and carry out amination, ethanol washing is removed free 3-aminopropyl triethoxysilane and is namely obtained amination nanosphere.
3) by through step 2) the amination nanosphere that processes adds the gold nano grain of step 1) process, and namely the magnetic agitation golden nanometer particle that after 30 minutes, centrifugal segregation does not adsorb obtains the nanosphere precursor of the metal nano shell possessing monodispersity;
4) the nanosphere precursor possessing the metal nano shell of monodispersity through step 3) process is added in the salt solusion of copper, adding reductive agent hydroxylammonium chloride magnetic agitation after 30 minutes, centrifugal collecting precipitation is resuspended in water the suspension of nanoglobules (as shown in Figure 1) namely obtaining the copper nanoshell possessing monodispersity.
Embodiment 4 possesses the preparation of the nanosphere of the platinum nanoshell of monodispersity
In the same manner as in Example 1, difference is, the salt solusion of what step 4) added is platinum, and what obtain is the suspension of nanoglobules of the platinum nanoshell possessing monodispersity, and organic or inorganic nanosphere is polytetrafluorethylenano nano ball.
Embodiment 5 has the preparation of the surface enhanced Raman scattering substrate of crystalline organized structure
1) microslide is immersed in have in the ethanolic solution of the silylating reagent of amino or sulfydryl 0.5 hour that volume ratio is 0.1%, then washs with ethanol;
2) 60 minutes are processed by dry under 60 DEG C of conditions for the microslide through step 1) process;
3) will through step 2) angle in 3 ° between the microslide that processes and surface level places (as shown in Figure 2), is 1 × 10 respectively by the concentration in the embodiment 1 of 1 microlitre
6the suspension of nanoglobules possessing the gold nanoshell of monodispersity of individual/mL is added drop-wise on microslide, gets final product (as shown in Figure 3) the conditions of 4 DEG C down to liquid evaporation is dry.
Embodiment 6
There is the preparation of the surface enhanced Raman scattering substrate of crystalline organized structure
1) microslide is immersed in have in the ethanolic solution of the silylating reagent of amino or sulfydryl 12 hours that volume ratio is 5%, then washs with ethanol;
2) 5 minutes are processed by dry under 120 DEG C of conditions for the microslide through step 1) process;
3) will through step 2) angle in 45 ° between the microslide that processes and surface level places, and is 1 × 10 respectively by the concentration in the embodiment 2 of 500 microlitres
10the suspension of nanoglobules possessing the silver nanoparticle shell of monodispersity of individual/mL is added drop-wise on microslide, dry down to liquid evaporation the conditions of 45 DEG C.
Embodiment 7
There is the preparation of the surface enhanced Raman scattering substrate of crystalline organized structure
1) microslide is immersed in have in the ethanolic solution of the silylating reagent of amino or sulfydryl 6 hours that volume ratio is 2.5%, then washs with ethanol;
2) 30 minutes are processed by dry under 90 DEG C of conditions for the microslide through step 1) process;
3) will through step 2) angle in 24 ° between the microslide that processes and surface level places, and is 0.5 × 10 respectively by the concentration in the embodiment 3 of 250 microlitres
10the suspension of nanoglobules possessing the copper nanoshell of monodispersity of individual/mL is added drop-wise on microslide, dry down to liquid evaporation the conditions of 25 DEG C.
Embodiment 8 has the preparation of the surface enhanced Raman scattering substrate of crystalline organized structure
Substantially the same with embodiment 7, difference is that what to adopt be the concentration of embodiment 4 is 1 × 10
8the surface enhanced Raman scattering substrate with crystalline organized structure that the suspension of nanoglobules possessing the platinum nanoshell of monodispersity of individual/mL is prepared from.
Embodiment 9
Substantially the same with embodiment 5, difference is the surface enhanced Raman scattering substrate with crystalline organized structure that the gold nanosphere suspending liquid of the common monodispersity adopted is prepared from.
Embodiment 10
Substantially the same with embodiment 6, difference is the surface enhanced Raman scattering substrate with crystalline organized structure that the silver nanoparticle ball suspending liquid of the common monodispersity adopted is prepared from.
Embodiment 11
Substantially the same with embodiment 7, difference is the surface enhanced Raman scattering substrate with crystalline organized structure that the copper suspension of nanoglobules of the common monodispersity adopted is prepared from.
Embodiment 12
Substantially the same with embodiment 8, difference is the surface enhanced Raman scattering substrate with crystalline organized structure that the platinum suspension of nanoglobules of the common monodispersity adopted is prepared from.
The nerve specificity olefinic alcohol enzyme examination criteria curve that embodiment 13 has the surface enhanced Raman scattering substrate of crystalline organized structure is set up
With the dilution nerve specificity olefinic alcohol enzyme of phosphate buffer (0.01 M, pH=7.4) dilution standard, configuration 0.1,0.5,1,5,10,50,100,500, and the nerve specificity olefinic alcohol enzyme standard solution of 1000 ngs/ml.Mixed solution containing the 2 μ L nerve specificity olefinic alcohol enzyme standard solution 5 μ L SERS probes metal nano shell of antibody modification (detect) to be added drop-wise on the surface enhanced Raman scattering substrate with crystalline organized structure catching antibody modification incubation 40 minutes.SERS probe can be left in conjunction with nerve specificity olefinic alcohol enzyme to be had on the surface enhanced Raman scattering substrate of crystalline organized structure.Being removed by washing not in conjunction with nerve specificity olefinic alcohol enzyme, drying detects the Surface enhanced raman spectroscopy had on the surface enhanced Raman scattering substrate of crystalline organized structure afterwards in atmosphere.According to labeled molecule 592 cm on SERS probe
-1the intensity at place, draws nerve specificity olefinic alcohol enzyme examination criteria curve (as shown in Figure 6).
Embodiment 14 has in the serum of the surface enhanced Raman scattering substrate of crystalline organized structure adds the detection of variable concentrations nerve specificity olefinic alcohol enzyme
Nerve specificity olefinic alcohol enzyme sensing detection is performed by two steps.First, the mixed solution analyzing the sample buffer of things and 5 μ L SERS probes (detecting the metal nano shell of antibody modification) containing 2 μ L be added drop-wise to catch antibody modification the surface enhanced Raman scattering substrate with crystalline organized structure on incubation 40 minutes.SERS probe can be left in conjunction with nerve specificity olefinic alcohol enzyme to be had on the surface enhanced Raman scattering substrate of crystalline organized structure.Being removed by washing not in conjunction with nerve specificity olefinic alcohol enzyme, drying detects the Surface enhanced raman spectroscopy had on the surface enhanced Raman scattering substrate of crystalline organized structure afterwards in atmosphere.According to labeled molecule 592 cm on SERS probe
-1the intensity at place, passes judgment on the content (as shown in Figure 7) of nerve specificity olefinic alcohol enzyme.
Above-mentioned non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Claims (10)
1. one kind has the surface enhanced Raman scattering substrate of crystalline organized structure, it is characterized in that, described in there is crystalline organized structure surface enhanced Raman scattering substrate be assembled by the method for the spherical metal nano material of monodispersity by limit evaporation.
2. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 1, it is characterized in that, the spherical metal nano material of described monodispersity is the gold, silver of monodispersity, copper, platinum nanosphere or possess the metal nano ball of nucleocapsid structure of monodispersity.
3. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 2, it is characterized in that, the described metal nano ball possessing the nucleocapsid structure of monodispersity is organic or inorganic nanosphere kernel and the metal nano skin with monodispersity, and described metal nano skin is one or more in gold nano layer, silver nanoparticle layer, copper nanometer layer or platinum nano-layers.
4. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 1, is characterized in that, the spherical metal nano material diameter of described monodispersity is 40-800 nanometer.
5. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 3, it is characterized in that, in the organic or inorganic nanosphere of described monodispersity, nuclear diameter is 20-500 nanometer, and described metal nano outer layer thickness is 20-500 nanometer.
6. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 3, is characterized in that, described in possess the preparation method of the metal nano ball of the nucleocapsid structure of monodispersity as follows:
1) NaOH of 1 ~ 25 ml fresh configuration 1M adds in 500 ~ 1000 ml water, stir, and then 50-1000 μ l THPC is added, mixed liquor is obtained after magnetic agitation 2-20 minute, 5-100 ml 1% gold chloride adds in mixed liquor, namely magnetic agitation obtains the gold nano grain of 2 ~ 3 nm for 10 ~ 50 minutes, and 4 DEG C keep in Dark Place;
2) the 3-aminopropyl triethoxysilane of the alcohol suspension of monodispersed organic or inorganic nanosphere and 100 ~ 400 μ l is stirred 1 ~ 4 h by 60 ~ 80 DEG C and carry out amination, ethanol washing is removed free 3-aminopropyl triethoxysilane and is namely obtained amination nanosphere;
3) by through step 2) the amination nanosphere that processes adds the gold nano grain of step 1) process, and namely the magnetic agitation gold nano grain that after 10 ~ 50 minutes, centrifugal segregation does not adsorb obtains the nanosphere precursor of the metal nano ball of the nucleocapsid structure possessing monodispersity;
4) the nanosphere precursor possessing the metal nano shell of monodispersity through step 3) process is added in the salt solusion of gold, silver, copper or platinum, adding reductive agent magnetic agitation after 10 ~ 50 minutes, centrifugal collecting precipitation is resuspended in the metal nano ball suspending liquid namely obtaining the nucleocapsid structure possessing monodispersity in water.
7. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 3, it is characterized in that, described organic or inorganic nanosphere is silica nanosphere, titanium dioxide nano-sphere, polystyrene nanospheres, polytetrafluorethylenano nano ball.
8. a kind of surface enhanced Raman scattering substrate with crystalline organized structure according to claim 6, is characterized in that, the reductive agent in described step 4) is formaldehyde, hydrogen peroxide or hydroxylammonium chloride.
9. a kind of preparation method with the surface enhanced Raman scattering substrate of crystalline organized structure described in any one of claim 1 ~ 8, it is characterized in that, described preparation method is the method for being evaporated by limit, specifically comprises the following steps:
1) microslide is immersed in volume ratio be 0.1-5% there is 0.5-12 hour in the ethanolic solution of the silylating reagent of amino or sulfydryl, then to wash with ethanol;
2) by the dry process 5-60 minute under 60-120 DEG C of condition of the microslide through step 1) process;
3) will through step 2) angle in 3-45 ° between the microslide that processes and surface level is placed, and is 1 × 10 by the concentration of 1-500 microlitre
6-1 × 10
10the hanging drop of the spherical metal nano material of the monodispersity of individual/mL is added on microslide, does and obtain the surface enhanced Raman scattering substrate with crystalline organized structure the condition of 4-45 DEG C down to liquid evaporation.
10. the application of the surface enhanced Raman scattering substrate with crystalline organized structure in SERS input described in any one of claim 1 ~ 8.
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| CN105271110A (en) * | 2015-09-18 | 2016-01-27 | 北京工业大学 | Method of manufacturing dense nano granular film and ordered nanowire film by using coffee-ring effects |
| CN108202140A (en) * | 2016-12-16 | 2018-06-26 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | The seed mediated growth method of polyethyleneimine prepares silicon core silver core-shell nanoparticles |
| CN107064101A (en) * | 2017-03-15 | 2017-08-18 | 东南大学 | A kind of enhancing Raman substrate and its preparation and application for detecting streptomycete mycelia |
| CN107064101B (en) * | 2017-03-15 | 2020-03-31 | 东南大学 | Enhanced Raman substrate for detecting streptomyces hyphae and preparation and use methods thereof |
| CN106914630A (en) * | 2017-03-28 | 2017-07-04 | 运城学院 | A kind of preparation method of Cu/SiO 2 core-shell structure nanometer particle |
| CN107132212A (en) * | 2017-06-09 | 2017-09-05 | 天津大学 | The preparation method of the SERS senser element with side effect based on photonic crystal |
| CN107132212B (en) * | 2017-06-09 | 2020-07-10 | 天津大学 | Preparation method of surface-enhanced Raman scattering sensor |
| CN111289493A (en) * | 2020-03-27 | 2020-06-16 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
| CN111289493B (en) * | 2020-03-27 | 2021-08-06 | 电子科技大学 | Surface-enhanced Raman substrate and preparation method thereof |
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