CN104849258A - Flexible erasable SERS (surface-enhanced Raman scattering) active substrate and preparation method thereof - Google Patents
Flexible erasable SERS (surface-enhanced Raman scattering) active substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an SERS (surface-enhanced Raman scattering) substrate comprising a flexible supporting layer and a metal nano-film which is adhered to the flexible supporting layer, wherein the flexible supporting layer is a flexible material with a porous structure, and the metal nano-film is subjected to surface modification treatment. According to a prepared flexible porous SERS substrate for wipe sampling, disclosed by the invention, a surface-enhanced Raman substrate can be used for rapidly detecting organic chemical substances particularly 2,4,6-trinitrotoluene on the surfaces of solid materials.
Description
Technical field
The present invention relates to a kind of base material detecting (SERS) for surface-enhanced Raman, particularly a kind of for realizing the SERS substrate that solid surface micro substance detects fast.SERS substrate of the present invention may be used for the quick detection of solid surface trace explosive, has high sensitivity and high reappearance.
Background technology
In recent years, along with the continuous generation of terrorist violence, social event and hi-tech explosive release the factor impacts such as use, cause international and domestic security situation to be tending towards severe.The life security of passenger in the explosive serious threat of particularly hiding in public place hand baggage.How in safety check process, detect whether passenger carries, contacted explosive has become current problem demanding prompt solution fast.
Surface enhanced raman spectroscopy (Surface Enhanced Raman Scattering, calls SERS in the following text) technology finds at 20 century 70s, a kind of new type of high sensitivity spectral analysis technique full-fledged after the nineties.The basis of SERS technology is that the raman spectral signal of material molecule can be strengthened greatly on specific metal nano material (as gold, silver, copper) surface, and its enhancer can reach 10
6~ 10
10doubly.The outstanding advantages of SERS shows three aspects: 1) have high sensitivity; 2) similar to infrared spectrum, can be used for material qualitative analysis; 3) can portable application be realized and not sacrifice analytical performance, being applied to the detection of trace explosive.
SERS analyzes and forms primarily of two parts: Raman spectrometer and SERS substrate.Wherein, the physical and chemical performance of SERS substrate directly determines the mode that detects and the concentration of sample.Substrate functional, then the concentrations of sample is lower, is more conducive to practical application.Usually, SERS substrate major part is structured on the hard material such as glass, silicon chip.Such SERS substrate is mainly used in the detection of solution example.Such as, F. A. Calzzani Jr.(Optics and Photonics in Global Homeland Security IV, 2008,69451O1 ~ 9) etc. PS Nano microsphere is deposited on glass and with golden nanometer particle and covers preparation SERS substrate, the trimethylene trintriamine and 1 of the TNT of 10 ppm, 100 ppm successfully detected, 3,5,7-tetranitro-1,3,5,7-tetraazacyclododecane octane.
Although above-mentioned SERS substrate has higher sensitivity, detect for reality and also have certain limitation.This is because, utilizing before above-mentioned SERS substrate analyzes, needing to use suitable solvent to be extracted from solid surface by detected sample, then dripping in SERS substrate, after solution bone dry, carry out SERS test again.But in safety check process, time and condition do not allow loaded down with trivial details Sample Preparation Procedure and solution dry run.Chang H. Lee(analytical chemistry, 2011,8953 ~ 8958) etc. people commonly uses filter paper for carrier with laboratory, and the gold nanorods particle of assembling 3-D solid structure builds SERS substrate, and the mode sampled by wiping successfully detects Isosorbide-5-Nitrae-BDT.
Chinese patent CN 103293142 A reports and adopts template and vapour deposition method to prepare flexible raman spectrum substrate, and successfully detects dyestuff R6G aqueous solution.Chinese patent CN 103575720 A reports a kind of Raman substrate with pliability and light transmission, adopts this substrate to detect 10
-5the isothiocyanic acid malachite green of M.But all there is the low shortcoming that maybe can not detect explosive of detectability in above-mentioned substrate.This is because above-mentioned substrate exists larger limitation in metal nanoparticle adsorbance, and explosive molecules can not, with the direct complexing of metal nanoparticle, cause above-mentioned substrate not detect explosive.Therefore, for day by day complicated safety check environment and surface enhanced Raman technique problems faced, be necessary the SERS substrate of developing a kind of direct wiping sampling.
Summary of the invention
The object of the invention is to overcome the deficiency that SERS in prior art is difficult to be applied to the quick detection case of needs, provide a kind of SERS substrate, this SERS substrate is that flexible erasable samples, and can be used in quick, the on-the-spot trace detection of explosive.The present invention additionally provides a kind of method preparing this surface enhanced Raman substrate simultaneously.
In order to realize foregoing invention object, the invention provides following technical scheme:
A kind of SERS substrate, comprise flexible support layers and metal nano film attached thereto, described flexible support layers is the flexible material with porous structure, and described metal nano film is through finishing process.
Surface enhanced Raman substrate of the present invention is the porous SERS substrate of flexible erasable sampling, forms by having the flexible support layers of porous structure, metal nano film and finishing coat.Porous structure is mainly used in the specific surface area improving flexible support layers, and then improves the detectability of surface enhanced Raman substrate; Flexible support layers carried metal nanometer film forms deformable flexible layer (shape) material Convenient scrubber swabbing sample and detects; Finishing coat is mainly used in adsorbing explosive molecules, is applicable to explosive detection to make surface enhanced Raman substrate.
Further, the material of described flexible support layers is at least one in polyacrylamide, polyvinyl alcohol (PVA) and shitosan.Select the raw material possessing functional group to prepare porous flexible material, be conducive to the specific surface area increasing material, be conducive in subsequent handling thereon in conjunction with more metal nano film.Described porous structure pore size is 40 ~ 150 μm, and porosity is 70 ~ 90%.
Further, described metal nano film is the layer of nanomaterial that the material with surface reinforced Raman active is made, and is preferably the metal Nano structure that at least one in gold, silver, copper, nickel is formed.The nanometer film surface that known gold, silver, copper, nickel etc. are formed strengthens for the signal of trace materials in SERS testing process the facilitation having and give prominence to very much.Preferably, the size of the single metal nanostructured in described metal nano film is 10 ~ 2000nm, the size of screening metal Nano structure is 10 ~ 200nm, facilitation for Raman signal is comparatively outstanding, and in described metal nano film, the pattern of single nanostructured is at least one in nano particle, nanometer pyrometric cone, nanometer rods, nano wire.
Further, the coating material of described metal nano film containing sulfydryl or amino carries out modification.The load of metal nano film, in flexible support layers, enhances the signal response intensity of metal nano film to TNT.Preferably, described coating material can be at least one in ethylenediamine, Cys, D-Cys, mercaptopropionic acid, DL-methionine.Above-mentioned coating material has good reactivity, and wherein sulfydryl can form firmly bonding structure with metal nano film, amino can with testing molecule 2,4,6-trinitro-toluene forms chelation structure, thus ensures that Raman method can detect 2,4,6-trinitro-toluene.
The Raman method that is used for above-mentioned surface enhanced Raman substrate detects and analyzes.After being preferably direct wiping solid surface, Raman method direct-detection is adopted to analyze.Especially for organic compounds such as explosive detection TNT, dyestuffs.
Above-mentioned Raman substrate can be used for trace amounts of substances and detects in surface-enhanced Raman method, and the TNT being specially adapted to wiping sampling detects.
The present invention additionally provides a kind of method preparing above-mentioned SERS substrate simultaneously, comprises the following steps:
(1) flexible support layers with porous structure is prepared by cryodesiccated method.
(2) the above-mentioned flexible support layers with porous structure is immersed in metal nano solution, and ultrasonic disperse, obtain the flexible support layers of carried metal nanometer film.
(3) flexible support layers of above-mentioned carried metal nanometer film is dipped in finishing agent solution, leaves standstill, take out postlyophilization, obtained surface enhanced Raman substrate.
Adopt above-mentioned Freeze Drying Technique to prepare SERS substrate, preparation process is easy, has clean pure feature, can control the cleanliness factor of substrate well, be extremely important in trace materials testing process.The porous structure formed in cryodesiccated process is very trickle, and the good pliability of flexible support layers itself can touch the residuals of complex surface in wiping process, is applied to actual detection better.
Further, the flexible material (i.e. flexible support layers) of the porous structure that step (1) prepares, through cleaning, cleans to eluent in neutrality, preferably uses water cleaning to aqueous solution pH=6 ~ 8.Because freeze drying just can be good at freezing removing for moisture usually; in the flexible support layers of the porous structure that freeze drying obtains, non-volatile or difficult volatile component can remain in porous structure usually; the cleaning unreacted starting material of removing and other material that metal nano rete may be disturbed to be formed are carried out to it, is more conducive to the lifting of the effect stability reliability that follow-up nano-solution load is combined.
compared with prior art, beneficial effect of the present invention: the flexible, porous SERS substrate of wiping sampling prepared by the present invention, this surface enhanced Raman substrate can realize the organic chemicals to solid material surface, especially to the quick detection of TNT.
Strengthening Raman substrate with traditional hard surface detects compared with organic chemicals, and use the Raman detection method of this substrate without the need to carrying out extraction pre-service to sample, sample time is short, and sampling procedure is easy.
Accompanying drawing illustrates:
Fig. 1 is the flexible support layers scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 porous structure;
Fig. 2 is the embodiment of the present invention 1 flexible gold goal surface enhanced Raman substrate scanning electron microscope (SEM) photograph;
Fig. 3 is the embodiment of the present invention 2 flexible ping-pong ball surface enhanced Raman substrate scanning electron microscope (SEM) photograph;
Fig. 4 is the flexible golden excellent surface enhanced Raman substrate scanning electron microscope (SEM) photograph of the embodiment of the present invention 3;
Fig. 5 is the embodiment of the present invention 4 Nai Erlan surface increasing Raman spectrum figure;
Fig. 6 is the surface increasing Raman spectrum figure of the embodiment of the present invention 5 wiping sampling Nai Erlan;
Fig. 7 is the surface-enhanced Raman stability spectrogram of the embodiment of the present invention 5 wiping sampling Nai Erlan;
Fig. 8 is the surface increasing Raman spectrum figure of the embodiment of the present invention 6 wiping sampling TNT;
Fig. 9 is the surface increasing Raman spectrum figure that comparative example 1 does not use the flexible, porous SERS substrate wiping sampling TNT of finishing coat.
Embodiment
Further specifically, the surface enhanced Raman substrate preparation method of flexible erasable of the present invention, comprises the following steps:
(1) to select in polyacrylamide, polyvinyl alcohol (PVA) and shitosan starting material based at least one, starting material are dissolved and obtains aqueous solution, if use shitosan, acetic acid aqueous solution can be used to dissolve.Suitably can heat in course of dissolution and promote raw-material dissolution velocity, dissolution rate.Solution after dissolving completely, in freezing 4 ~ 24 hours of less than-20 DEG C temperature, makes moisture wherein be frozen into ice completely.Freeze drier vacuum freeze drying process 4 ~ 96 hours put into by freezing raw material completely, preferably freeze drying 24 ~ 72 hours, is prepared into the flexible support material (flexible support layers) of porous structure.
(102) flexible support layers of above-mentioned porous structure is put into deionized water for ultrasonic cleaning 5 ~ 60 minutes, preferably 10 ~ 30 minutes, or rinse above-mentioned flexible support layers to aqueous solution pH=6 ~ 8, preferably pH ≈ 7, for subsequent use.Step (102) is the optional operation between step 1,2, mainly controls the degree of purity of flexible support layers, is beneficial to the load of subsequent metal nano material, improves the effect that SERS signal strengthens response.
(2) flexible support layers of the porous structure handled well to be immersed in metal nano solution and ultrasonic process 5 ~ 60 minutes, preferably 10 ~ 30 minutes.
(3) further, the wherein metal nano solution described in step (2), concentration is 0.1 ~ 10mM, is preferably 1 ~ 5mM; Volume is 0.5 ~ 20mL, and be preferably 2 ~ 10mL, the concentration of metal nano solution can adjust accordingly according to the volumetric porosity etc. of porous flexible supporting layer, more than can as better preferable case.
(4) compound concentration is the coating material aqueous solution of 0.005 ~ 5mg/mL, the flexible support layers of the porous structure of carried metal nanometer film is dipped in coating material aqueous solution, leaves standstill 15 ~ 90 minutes.The refrigerator and cooled putting into-20 DEG C after taking-up freezes 4 ~ 12 hours, is then placed in freeze drier process 24 ~ 72 hours, obtained surface enhanced Raman substrate.
Further, the wherein aqueous solution described in step (1), it is 1 ~ 30 % by weight that raw material dissolving obtains solution concentration, is preferably 1 ~ 15 % by weight.
Further, wherein the coating material described in step (4) is at least one in ethylenediamine, Cys, D-Cys, mercaptopropionic acid, DL-methionine.
Preferably, its coating material solution concentration is 0.001 ~ 10 mg/mL, is preferably 0.005 ~ 5 mg/mL.
Below in conjunction with test example and embodiment, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on content of the present invention all belong to scope of the present invention.The experimental technique used in following embodiment if no special instructions, is conventional method.The material used in following embodiment, reagent, if no special instructions, all can obtain from commercial channels.Number percent not specified in the present invention is all weight percentage.
embodiment 1
Prepare flexible nano gold goal surface enhanced Raman substrate:
1) the flexible support layers preparation of porous structure
By water-soluble for polyvinyl alcohol (PVA) powder solution, be placed in water-bath heating and be stirred to and dissolve completely, obtained massfraction is the poly-vinyl alcohol solution of 8%.Take the disk that appropriate poly-vinyl alcohol solution puts into plastic material, slowly drip concentration and be the borax solution of 4% and constantly stir, treat that poly-vinyl alcohol solution forms the refrigerator and cooled that gel state is placed on-20 DEG C and freezes 4 hours.Freezing polyvinyl alcohol (PVA) is completely put into freeze drier process after 24 hours, be prepared into the flexible support material of porous structure.The flexible support layers of above-mentioned porous structure is put into deionized water for ultrasonic and cleans 30 minutes, to aqueous solution pH ≈ 7, take out the flexible support layers of porous structure, for subsequent use.The flexible support layers of this porous structure detected by scanning electron microscope and analyze, as shown in Figure 1, the supporting layer obtained through freeze drying as seen has large number of orifices gap structure to result, and hole size is suitable can carry out load with various different metal Nano structure body.
2) preparation of gold nanosphere solution
The preparation of seed solution: compound concentration is 0.1M(volumetric molar concentration, i.e. 0.1 mol/L, lower with) sodium borohydride aqueous solution, be placed in ice bath.Getting above-mentioned solution 0.6mL joins in the cetyl trimethyl ammonium bromide mixed aqueous solution of gold chloride that concentration is 0.01M and 0.1M fast, leaves standstill 1 hour after rapid mixing.
Appropriate above-mentioned three kinds of aqueous solution are added to the water and mix by the preparation of growth solution: prepare the cetyl trimethyl ammonium bromide of 0.1M, the gold chloride of 0.01M, the aqueous ascorbic acid of 0.1M respectively.
The preparation of gold nanosphere: after the cetyl trimethyl ammonium bromide solution dilution seed solution 10 times of 0.1M, join in growth solution and mix, leaves standstill 24 hours.
3) preparation of flexible Raman substrate
Get step 2) in gold nanosphere solution 2mL in beaker, the flexible support layers of the polyvinyl alcohol cellular structure handled well in step 1) to be immersed in gold nanosphere solution and ultrasonic process 10 minutes.
Compound concentration is the Cys coating material aqueous solution of 0.01mg/mL.Load there is the flexible support layers of the porous structure of gold nanosphere to be dipped in Cys coating material aqueous solution, leave standstill 15 minutes.The refrigerator and cooled putting into-20 DEG C after taking-up freezes 4 hours, is then placed in freeze drier process 24 hours, obtained flexible nano gold goal surface enhanced Raman substrate.Adopt scanning electron microscope to gained SERS substrate scanning, as shown in Figure 2, metal Nano structure distributes in a large number result in the hole of supporting layer, presents good nanometer system, has good signal strengthen potentiality as SERS active-substrate.
embodiment 2
Prepare flexible nano ping-pong ball surface enhanced Raman substrate:
1) preparation of the flexible support layers of porous structure
By water-soluble for shitosan powder solution, be placed in water-bath heating and be stirred to and dissolve completely, obtained massfraction is the chitosan solution of 3%.Take the disk that appropriate chitosan solution puts into plastic material, the refrigerator and cooled being then placed in-20 DEG C freezes 12 hours.Freezing shitosan is completely put into freeze drier process after 48 hours, be prepared into the flexible support material of porous structure.The flexible support layers of above-mentioned porous structure is put into deionized water for ultrasonic and cleans 10 minutes, to aqueous solution pH ≈ 7, take out the flexible support layers of porous structure, for subsequent use.
2) preparation of silver nanoparticle ball solution
Take 0.2g silver nitrate dissolution of solid in the deionized water of 250mL, adopt microwave reactor heated solution to 98 DEG C.The trisodium citrate aqueous solution of preparation massfraction 10%, then adds trisodium citrate aqueous solution in above-mentioned liquor argenti nitratis ophthalmicus fast, continues maintenance 98 DEG C reaction 30 minutes, becomes after silver gray stop heating, obtained silver nanoparticle ball solution until solution colour.
3) preparation of flexible Raman substrate
Get 10mL silver nanoparticle ball solution in beaker, the flexible support layers of the chitosan multi-porous structure handled well in step 1) to be immersed in silver nano solution and ultrasonic process 30 minutes.
Compound concentration is the mercaptopropionic acid finishing agent solution of 1mg/mL.Load there is the flexible support layers of the porous structure of silver nanoparticle ball to be dipped in mercaptopropionic acid finishing agent solution, leave standstill 60 minutes.The refrigerator and cooled putting into-20 DEG C after taking-up freezes 12 hours, is then placed in freeze drier process 48 hours, obtained flexible nano ping-pong ball surface enhanced Raman substrate.Adopt scanning electron microscope to gained SERS substrate scanning, result as shown in Figure 3.
embodiment 3
Prepare the excellent surface enhanced Raman substrate of flexible nano gold
1) preparation of the flexible support layers of porous structure
By water-soluble for polyvinyl alcohol (PVA) powder solution, be placed in water-bath heating and be stirred to and dissolve completely, obtained massfraction is the poly-vinyl alcohol solution of 10%.Take the disk that appropriate poly-vinyl alcohol solution puts into plastic material, slowly drip concentration and be the borax solution of 4% and constantly stir, treat that poly-vinyl alcohol solution forms the refrigerator and cooled that gel state is placed on-20 DEG C and freezes 12 hours.Freezing polyvinyl alcohol (PVA) is completely put into freeze drier process after 72 hours, be prepared into the flexible support material of porous structure.The flexible support layers of above-mentioned porous structure is put into deionized water for ultrasonic and cleans 30 minutes, to aqueous solution pH ≈ 7, take out the flexible support layers of porous structure, for subsequent use.
2) preparation of gold nanorods solution
The preparation of seed solution: compound concentration is the sodium borohydride aqueous solution of 0.01M, is placed in ice bath.Getting above-mentioned solution 0.6mL joins in the cetyl trimethyl ammonium bromide mixed aqueous solution of gold chloride that concentration is 0.01M and 0.1M fast, leaves standstill 2 hours after rapid mixing.
The preparation of growth solution: prepare the cetyl trimethyl ammonium bromide of 0.1M, the gold chloride of 0.01M, the silver nitrate aqueous solution of 0.01M respectively, the aqueous ascorbic acid of 0.1M is added after appropriate above-mentioned three kinds of aqueous solution are even, then add the aqueous hydrochloric acid solution of appropriate 1.0M, mix.
The preparation of gold nanosphere: joined in growth solution fast by above-mentioned seed solution and mix, leaves standstill 6 hours.
3) preparation of flexible Raman substrate
Get 6mL gold nanorods solution in beaker, the flexible support layers of the polyvinyl alcohol cellular structure handled well in step 1) to be immersed in gold nano solution and ultrasonic process 10 minutes.
Compound concentration is the Cys coating material aqueous solution of 0.01mg/mL.Above-mentioned load there is the flexible support layers of the porous structure of nanometer gold bar to be dipped in Cys coating material aqueous solution, leave standstill 15 minutes.The refrigerator and cooled putting into-20 DEG C after taking-up freezes 4 hours, is then placed in freeze drier process 24 hours, the excellent surface enhanced Raman substrate of obtained flexible nano gold.Adopt scanning electron microscope to gained SERS substrate scanning, result as shown in Figure 4.
embodiment 4
Flexible nano gold goal surface enhanced Raman substrate is used for Nai Erlan dyestuff and detects
The standard solution of preparation 1mg/g Nai Erlan, prepares the Nai Erlan solution of a series of concentration by the method for stepwise dilution.10 are drawn with liquid-transfering gun
μl concentration is that the solution of 100ppb is added drop-wise in the flexible nano gold surface enhancing Raman substrate of embodiment 1 preparation, and use micro-Raman spectroscopy to detect, testing result as shown in Figure 5.Raman excitation optical wavelength is 633nm, and excitation light power is 500
μw.
Visible employing flexible erasable Raman substrate of the present invention can well be applied to the detection of trace materials, the intensity of signal response in Raman detection process.
embodiment 5
Flexible nano ping-pong ball surface enhanced Raman substrate is used for wiping sampling and detects Nai Erlan dyestuff
The standard solution of preparation 1mg/g Nai Erlan, prepares the Nai Erlan solution of a series of concentration by the method for stepwise dilution.20 are drawn with liquid-transfering gun
μthe solution of L concentration position 100ppb is added drop-wise on glass sheet.After solvent volatilization completely, drip 20 on the glass sheet
μthe deionized water of L, the flexible nano silver surface adopting embodiment 2 to prepare strengthens Raman substrate cleaning glass window sheet.Use micro-Raman spectroscopy to detect, testing result as shown in Figure 6, Figure 7.In Fig. 7, each curve is the Nai Erlan Raman signal at this substrate diverse location place, and signal intensity is close, shows this Raman substrate good stability.Raman excitation optical wavelength is 633nm, and excitation light power is 500
μw.
embodiment 6
Flexible nano ping-pong ball surface enhanced Raman substrate is used for wiping sampling and detects TNT
The TNT methanol solution of 1mM is prepared the solution of a series of concentration by the method for stepwise dilution.20 are drawn with liquid-transfering gun
μthe solution of L variable concentrations is added drop-wise on glass sheet.After solvent volatilization completely, drip 20 on the glass sheet
μthe ethanol of L, the flexible nano silver surface adopting embodiment 2 to prepare strengthens Raman substrate cleaning glass window sheet.Use micro-Raman spectroscopy to detect, as shown in Figure 8, in figure, curve is concentration from top to bottom is successively 1 × 10 to testing result
-4m, 1 × 10
-5m, 1 × 10
-6m, 1 × 10
-7the TNT of M and 0 M.Raman excitation optical wavelength is 633nm, and excitation light power is 500
μw.
comparative example 1
The flexible, porous SERS substrate of finishing coat is not used to detect TNT
1) preparation of the flexible, porous SERS substrate of finishing coat is not used
Step 1), step 2 according in embodiment 2) prepare flexible support layers and the silver nanoparticle ball solution of porous structure respectively, get 10mL silver nanoparticle ball solution in beaker, the flexible support layers of the chitosan multi-porous structure handled well to be immersed in silver nano solution and ultrasonic process 30 minutes.The refrigerator and cooled putting into-20 DEG C after taking-up freezes 12 hours, is then placed in freeze drier process 48 hours, obtained flexible nano ping-pong ball surface enhanced Raman substrate.
2) the flexible, porous SERS substrate using step 1) to prepare detects TNT
100 are drawn with liquid-transfering gun
μthe TNT solution of L is added drop-wise on glass sheet.After solvent volatilization completely, drip 50 on the glass sheet
μthe ethanol of L, the flexible nano silver surface adopting step 1) to prepare strengthens Raman substrate cleaning glass window sheet.Use micro-Raman spectroscopy to detect, as shown in Figure 9, in figure, curve from top to bottom successively for testing result: have the SERS substrate of decorative layer to detect TNT, the SERS substrate without decorative layer detects TNT.Raman excitation optical wavelength is 633nm, and excitation light power is 500
μw.
By contrasting with embodiment 2, illustrating that the flexible wiping porous SERS substrate not using finishing coat cannot detect TNT, and using the flexible wiping porous SERS substrate of finishing coat TNT to be detected.
Claims (10)
1. a SERS substrate, comprise flexible support layers and metal nano film attached thereto, described flexible support layers is the flexible material with porous structure, and described metal nano film is through finishing.
2. SERS substrate according to claim 1, is characterized in that, the material of described flexible support layers is at least one in polyacrylamide, polyvinyl alcohol (PVA) and shitosan.
3. SERS substrate according to claim 1, is characterized in that, described metal nano film is the layer of nanomaterial that the material with surface reinforced Raman active is made.
4. SERS substrate according to claim 3, is characterized in that, described metal nano film is the nanometer rete that at least one in gold, silver, copper, nickel is formed.
5. SERS substrate according to claim 1, is characterized in that, the coating material of described metal nano film containing sulfydryl or amino carries out modification.
6. SERS substrate according to claim 5, is characterized in that, described coating material is at least one in ethylenediamine, Cys, D-Cys, mercaptopropionic acid, DL-methionine.
7. according to claim 1-6 any one, SERS substrate is used for Raman detection analysis.
8. prepare a method for above-mentioned SERS substrate, comprise the following steps:
(1) flexible support layers with porous structure is prepared by cryodesiccated method;
(2) the above-mentioned flexible support layers with porous structure is immersed in metal nano solution, and ultrasonic disperse, obtain the supporting layer of carried metal nanometer film;
(3) supporting layer of carried metal nanometer film is dipped in finishing agent solution, leaves standstill, take out postlyophilization, obtained surface enhanced Raman substrate.
9. prepare the method for SERS substrate according to claim 8, it is characterized in that, the flexible support layers of the porous structure that step (1) prepares, through cleaning treatment, is cleaned to eluent pH=6 ~ 8.
10. prepare the method for SERS substrate according to claim 8, it is characterized in that, step (1) to select in polyacrylamide, polyvinyl alcohol (PVA) and shitosan starting material based at least one, is dissolved by starting material and obtains aqueous solution, if shitosan then uses acetic acid aqueous solution to dissolve; Solution after dissolving completely was in freezing 4 ~ 24 hours of less than-20 DEG C temperature, and freeze drier vacuum freeze drying process 4 ~ 96 hours put into by freezing raw material completely, is prepared into the flexible support material with porous structure.
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| CN105548134A (en) * | 2015-12-04 | 2016-05-04 | 山东大学 | Wiping extraction-surface-enhanced Raman scattering film for on-site fast detection of explosive and its preparation method and use |
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| CN112525881A (en) * | 2020-11-17 | 2021-03-19 | 宁夏大学 | Polyvinyl alcohol coated surface enhanced Raman scattering substrate and preparation method thereof |
| CN112730372A (en) * | 2020-11-26 | 2021-04-30 | 中国科学院合肥物质科学研究院 | Flexible surface enhanced Raman substrate, preparation method thereof and paraquat detection method |
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