CN104730062A - Transparent flexible surface-enhanced Roman spectroscopy substrate (SERS) and preparation method and application thereof - Google Patents

Transparent flexible surface-enhanced Roman spectroscopy substrate (SERS) and preparation method and application thereof Download PDF

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Publication number
CN104730062A
CN104730062A CN201510180681.9A CN201510180681A CN104730062A CN 104730062 A CN104730062 A CN 104730062A CN 201510180681 A CN201510180681 A CN 201510180681A CN 104730062 A CN104730062 A CN 104730062A
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sers
transparent
substrate
preparation
film
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CN201510180681.9A
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姚建林
王伟伟
张晨杰
金琦
夏迪
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Suzhou University
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Suzhou University
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Abstract

The invention discloses a transparent flexible surface-enhanced Roman spectroscopy (SERS) substrate and a preparation method and application thereof. The preparation method includes: firstly utilizing a sodium citrate method to prepare gold nanoparticles and then utilizing an ammonia propyl trimethoxy silane self-assembly method or liquid-liquid two-phase film formation method to obtain a gold nanoparticle monolayer film loaded on a silicon slice or a glass slide; finally coating the adhesive transparent film on the gold nanoparticles and uncovering the film to obtain the flexible transparent SERS substrate attached with the monolayer gold nanoparticles. The surface-enhanced Roman spectroscopy substrate is good in flexibility and adhesivity and can be attached to the surface of a solid to be tested. The transparent flexible SERS is prepared by the aid of the transferring technique of the nanoparticles, the method is simple and easy to implement and highly operability. The surface of the solid can be rapidly sampled and analyzed by the aid of the adhesive function through the gold nanoparticles contained adhesive tape formed by adhering and stripping of the adhesive film, and a new method is provided for sampling analysis in the fields of environmental monitoring, criminal investigation and the like.

Description

A kind of transparent flexible Raman spectrum base, preparation method and application
Technical field
The present invention relates to a kind of surface enhancement Raman spectroscopy substrate material, preparation method and application thereof.
Background technology
From the seventies in last century, Surface enhanced raman spectroscopy (Surface Enhanced-Raman Spectroscopy is found in the silver electrode surface of electrochemical roughening, SERS) after phenomenon, SERS technology is due to the testing result of the finger print information and fast high-sensitive that can provide molecular structure, and the fields such as environmental monitoring, life science and Homeland Security that are widely used in are (see document: Brosseau C L et al. j Raman Spectrosc.2011,42,1305.).Owing to preparing the short-lived of the with high costs and Basal Activity of SERS substrate, so be also only confined in laboratory about the detect delay of SERS.In order to promote the transformation of SERS from fundamental research to practical application, scientists has made a large amount of unremitting effort in cheap SERS substrate easy to prepare.SERS substrate based on the Cheap highly effective of plastics, paper and PDMS is developed in succession, researcher also constantly it to be optimized and the SERS substrate exploring more closing to reality (see document: Yu W W and White I M. analyst.2012,137,1168; Lee K L, Chen P W, Wu S H, Huang J B, Yang S Y, Wei P K. aCS Nano.2012,6,2931.).
2011, prepare loaded down with trivial details to make up Tip-Enhanced Raman Spectroscopy (TERS) and strengthen the limited defect of signal, document provides a kind of at dimethyl silicone polymer (PDMS) finishing one deck aminopropyl trimethoxysilane (APTMS) molecule, again at its surface self-organization one deck gold (silver) nano particle, obtain non-transparent flexible substrate (the Lu G with SERS activity, Li H, Zhang H. chem. Commun.2011,47,8560.); The SERS substrate obtained is covered object under test surface simply, just can obtain the Raman signal being adsorbed on molecule in solid substrate.Document there was reported a kind of non-transparent flexible substrate (Xu W G, Ling X, Xiao J Q, Dresselhaus M S, Kong J, Xu H X, Liu Z F, Zhang J. based on polymethylmethacrylate (PMMA) proc. Natl. Acad. Sci. USA.2012,109,9281.), and above nano level metal, be provided with monoatomic layer Graphene separation layer, directly contact with metal in order to the reappearance and isolated probe molecule ensureing the cleanliness signal of substrate.
In sum, the SERS substrate of flexible and transparent is all be attached to transparent polymer surface by coarse metal film to be formed, therefore, complicated polymer polymerizing film forming procedure must be carried out, even if the film cost sometimes making this polymkeric substance is not high, longer (PDMS film preparation needs a few hours usually) but consuming time, and when carrying out incident laser and carrying on the back into formula Information Monitoring, substrate can not contact well with object under test surface, by the surface of the means such as extruding often slight damage object, thus affect test result, there is certain limitation.On the other hand, in fields such as environmental monitoring, food security and criminal investigations, how to realize the quick grab sampling of sample (as illegal adjuvant, drugs etc.), very crucial to subsequent analysis.Therefore, simple, that price is cheap, workable transparent flexible SERS substrate is used in the urgent need to developing and providing a kind of.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, provide a kind of easy to use efficient, prepare transparent flexible Raman spectrum base simple, with low cost, preparation method and application thereof.
The technical scheme realizing the object of the invention is to provide a kind of preparation method of transparent flexible Raman spectrum base, first obtain golden nanometer particle with Citrate Buffer, the Gold nanoparticle monofilm of load on silicon chip or microslide is obtained again by aminopropyl trimethoxysilane self-assembly method or liquid-liquid diphase membrane formation process, again viscosity transparent membrane is pasted on above Gold nanoparticle monofilm, single layer of gold nano particle is made to be attached on transparent membrane, after taking transparent membrane off, a kind of surface attachment can be obtained and have single layer of gold nano particle, the sticking transparent flexible Raman spectrum base of tool.
Technical solution of the present invention also comprises a kind of transparent flexible Raman spectrum base obtained by above-mentioned preparation method; Also comprising the application of described substrate, substrate being pasted on solids to be checked surface, for carrying out Surface enhanced raman spectroscopy detection after sampling.
Compared with prior art, technical solution of the present invention adheres to the golden nanometer particle of fine and close individual layer on the film of transparent flexible, and method is simple, workable.Because film has excellent flexibility and adhesiveness, nearly all solid surface to be measured can be sticked to and carry out SERS detection, and fast sampling analysis can be realized simultaneously.
Accompanying drawing explanation
The golden nanometer particle SEM that Fig. 1 is 55nm for particle diameter that the embodiment of the present invention provides schemes;
Fig. 2 is to the SERS spectrogram that single-crystal surface adsorbing species is analyzed in the embodiment of the present invention;
Fig. 3 is the test to solution species in the embodiment of the present invention, and namely Pyridine Molecules is adsorbed on the SERS spectrogram of flexible SERS activity gel strip substrate;
Fig. 4 is to the analysis result figure after the sampling of solid objects surface species in the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1
1, the cleaning of silicon chip
(1) oil removing: by silicon chip difference ultrasonic cleaning 20 min in ethanol, acetone;
(2) oxide on surface is removed: silicon chip is placed in alkaline hydrogen peroxide solution (NH 4oH, H 2o 2and H 2the volume ratio 1:1:4 of O) middle oxidation 10 min;
(3) oxide on surface and damaged thin layer is removed: silicon chip is placed in HF solution (pH=5) etching about 10 min and even curface can be obtained;
(4) metallic ion on complexing surface: silicon chip is placed in acid hydrogen peroxide (HCl, H 2o 2and H 2the volume ratio of O is 1:1:4) middle oxidation 10 min.
2, the preparation of Au nano particle
Prepare the gold seeds colloidal sol that particle diameter is 15 nm: be 1.0 × 10 by 100 mL concentration -4gmL -1hAuCl 4aqueous solution (the HAuCl of 1 mL 1% 44H 2o is dissolved to 100 mL) under magnetic stirring heating be back to boiling, stirring while, add rapidly freshly prepared 2 mL 1.0 × 10 -2gmL -1trisodium citrate aqueous solution (1.14g Na 3c 6h 5o 72H 2o is dissolved to 100 mL), within 3 min, solution went from clear is faint yellow becomes the last pulverize redness of black, and continue stirring and refluxing 30 min, detaching device treats that colloidal sol naturally cools to room temperature.
Prepare the gold nano colloidal sol of 55 nm particle diameters: the 15 nm gold seedses adding 3 mL in the ultrapure water of 96 mL, then add 220 μ L 1.0 × 10 -2gmL -1trisodium citrate aqueous solution, adds the HAuCl of 1 mL 1% 44H 2o, the p-dihydroxy-benzene aqueous solution (33 mg are dissolved in the water of 10 mL, now with the current) finally adding 33 mM continues stirring 60 min, can obtain the golden nanometer particle colloidal sol of required 55 nm.
3, the preparation of transparent flexible SERS substrate
The silicon chip of the cleaning after process is left standstill 12 h in the APTMS aqueous solution of 1 mM, and taking-up ultrapure water nitrogen dries up, and is placed in 120 DEG C of baking ovens and solidifies half an hour.After taking-up, in golden nanometer particle colloidal sol silicon chip being placed in 55 nm, leave standstill 1 ~ 2 h, with ultrapure water for several times and after drying, silicon chip adheres to one deck nano particle, and tool SERS is active.See accompanying drawing 1, the golden nanometer particle SEM that it is 55nm for particle diameter that the present embodiment provides schemes.
A face of transparent fexible film applies viscoloid, after drying, obtains viscosity transparent membrane, also can replace with transparent adhesive tape.Above Gold nanoparticle monofilm viscosity transparent membrane being covered gently silicon chip, golden nanometer particle is made to be attached on viscosity transparent membrane, after taking film off, can obtain the flexible and transparent SERS substrate film being attached with single layer of gold nano particle, this substrate also has viscosity.
Test to single-crystal surface adsorbing species: see accompanying drawing 2, it is to the SERS spectrogram that single-crystal surface adsorbing species is analyzed in the present embodiment; In figure, a is SERS spectrum mercaptobenzoic acid being adsorbed on to single-crystal surface; B is the SERS spectrum of the single-crystal surface being stained with the active adhesive tape of SERS.As shown in a in Fig. 2, the gold surface of monocrystalline is considered to do not have SERS to strengthen, when on the monocrystalline gold plaque SERS substrate of transparent flexible being covered adsorption analysis thing, analysis thing is in the enhancing hot spot region between nano particle and gold plaque, its Raman signal is exaggerated, finally can capture high-quality SERS spectrogram, as shown in b in Fig. 2.
Test to solution species: adhesive tape substrate tiling is come, testing molecule in dropping, as Pyridine Molecules (as the SERS substrate of rigidity), good SERS signal can be obtained equally, its result is see accompanying drawing 3, Fig. 3 is the test to solution species in the present embodiment, and namely Pyridine Molecules is adsorbed on the SERS spectrogram of flexible SERS activity gel strip substrate; The characteristic that substrate that the present embodiment provides has stiff base equally and has is described.
Test as follows the flexible and transparent SERS substrate film that the present embodiment obtains, result is see accompanying drawing 4.
(1) be close on smooth monocrystalline gold plaque, the probe molecule p-Mercaptoaniline (PATP) of individual layer has been expired in absorption, after tested, only can obtain faint SERS signal, as shown in a figure;
(2) flexible transparent film with SERS activity prepared by the present embodiment is attached on above-mentioned gold plaque, laser is injected from the transparent membrane back side, be irradiated to the binding molecule on nano particle and gold plaque through film, the SERS signal at once obtained at least promotes two orders of magnitude, as shown in b figure;
(3) gently film is taken off from gold plaque, then SERS detection is carried out to original solid phase gold plaque, find signal weaker, almost only have original 1/4th, as shown in c figure, can think thus, most probe molecule adhere to by the sticking film of tool;
(4) on the adhesive membrane adhesive tape taken off, very strong SERS signal detected, as shown in d figure, illustrate in tape-stripping and stripping process, achieve the sampling to solid state surface molecule.
The invention provides a kind of adhered to transparent flexible SERS substrate of convenient and efficient.The monofilm of self assembly is transferred to adhesive membrane surface, the base material obtained has the active advantage with having adhesive character of SERS concurrently, the rear strange land of sampling on solid sample can be realized and carry out SERS analysis, for fast sampling and the High Sensitive Analysis of the sample such as field, strange land, provide new resolving ideas.

Claims (3)

1. the preparation method of a transparent flexible Raman spectrum base, first obtain golden nanometer particle with Citrate Buffer, the Gold nanoparticle monofilm of load on silicon chip or microslide is obtained again by aminopropyl trimethoxysilane self-assembly method or liquid-liquid diphase membrane formation process, it is characterized in that: again viscosity transparent membrane is pasted on above Gold nanoparticle monofilm, single layer of gold nano particle is made to be attached on transparent membrane, after taking transparent membrane off, a kind of surface attachment can be obtained and have single layer of gold nano particle, the sticking transparent flexible Raman spectrum base of tool.
2. by a kind of transparent flexible Raman spectrum base that claim 1 preparation method obtains.
3. the application of a kind of transparent flexible Raman spectrum base according to claim 2, is characterized in that: substrate is pasted on solids to be checked surface, for carrying out Surface enhanced raman spectroscopy detection after sampling.
CN201510180681.9A 2015-04-16 2015-04-16 Transparent flexible surface-enhanced Roman spectroscopy substrate (SERS) and preparation method and application thereof Pending CN104730062A (en)

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CN105424676A (en) * 2015-11-24 2016-03-23 郭秋泉 Preparation method of flexible surface enhanced Raman spectrum substrate and application thereof
CN105436516A (en) * 2015-12-03 2016-03-30 南昌大学 Preparing method of multi-branch colloidal gold nano particles with controllable grain diameter and high light absorbing intensity
CN107116231A (en) * 2017-06-01 2017-09-01 云南大学 A kind of preparation method of individual layer self-assembling of gold nanoparticles/molybdenum disulfide composite membrane
CN107688015A (en) * 2017-07-13 2018-02-13 北京工业大学 A kind of preparation method for being used to strengthen the transparent dielectric microballoon fexible film of Raman diffused light spectral intensity
CN107727640A (en) * 2017-12-08 2018-02-23 浙江中烟工业有限责任公司 A kind of method for differentiating essence spice for cigarette using SERS method
CN108226135A (en) * 2018-01-26 2018-06-29 江南大学 A kind of compound film sensors and its method for detecting vibrio parahemolyticus
CN109030453A (en) * 2018-07-04 2018-12-18 浙江工业大学 A kind of preparation method and application of flexible and transparent SERS substrate
CN109342398A (en) * 2018-11-27 2019-02-15 浙江工业大学 The SERS detection method of trace Ciprofloxacin in a kind of flesh of fish
CN111999279A (en) * 2020-07-21 2020-11-27 北京邮电大学 Flexible SERS substrate based on small ball array and preparation method thereof
CN112893865A (en) * 2021-03-26 2021-06-04 江苏师范大学 Double-layer gold nanoparticle modified flexible SERS substrate and preparation method thereof
CN113125409A (en) * 2021-03-25 2021-07-16 云南省烟草质量监督检测站 Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
CN105424676A (en) * 2015-11-24 2016-03-23 郭秋泉 Preparation method of flexible surface enhanced Raman spectrum substrate and application thereof
CN105436516A (en) * 2015-12-03 2016-03-30 南昌大学 Preparing method of multi-branch colloidal gold nano particles with controllable grain diameter and high light absorbing intensity
CN107116231B (en) * 2017-06-01 2018-07-20 云南大学 A kind of single layer self-assembling of gold nanoparticles/molybdenum disulfide composite membrane and preparation method thereof
CN107116231A (en) * 2017-06-01 2017-09-01 云南大学 A kind of preparation method of individual layer self-assembling of gold nanoparticles/molybdenum disulfide composite membrane
CN107688015A (en) * 2017-07-13 2018-02-13 北京工业大学 A kind of preparation method for being used to strengthen the transparent dielectric microballoon fexible film of Raman diffused light spectral intensity
CN107727640A (en) * 2017-12-08 2018-02-23 浙江中烟工业有限责任公司 A kind of method for differentiating essence spice for cigarette using SERS method
CN108226135A (en) * 2018-01-26 2018-06-29 江南大学 A kind of compound film sensors and its method for detecting vibrio parahemolyticus
CN108226135B (en) * 2018-01-26 2020-12-29 江南大学 Composite membrane sensor and method for detecting vibrio parahaemolyticus by using same
CN109030453A (en) * 2018-07-04 2018-12-18 浙江工业大学 A kind of preparation method and application of flexible and transparent SERS substrate
CN109342398A (en) * 2018-11-27 2019-02-15 浙江工业大学 The SERS detection method of trace Ciprofloxacin in a kind of flesh of fish
CN111999279A (en) * 2020-07-21 2020-11-27 北京邮电大学 Flexible SERS substrate based on small ball array and preparation method thereof
CN111999279B (en) * 2020-07-21 2021-09-21 北京邮电大学 Flexible SERS substrate based on small ball array and preparation method thereof
CN113125409A (en) * 2021-03-25 2021-07-16 云南省烟草质量监督检测站 Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering
CN113125409B (en) * 2021-03-25 2023-12-19 云南省烟草质量监督检测站 Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering
CN112893865A (en) * 2021-03-26 2021-06-04 江苏师范大学 Double-layer gold nanoparticle modified flexible SERS substrate and preparation method thereof

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Application publication date: 20150624