CN115849726A - Surface-enhanced Raman scattering composite substrate and preparation method and application thereof - Google Patents

Surface-enhanced Raman scattering composite substrate and preparation method and application thereof Download PDF

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CN115849726A
CN115849726A CN202211292488.0A CN202211292488A CN115849726A CN 115849726 A CN115849726 A CN 115849726A CN 202211292488 A CN202211292488 A CN 202211292488A CN 115849726 A CN115849726 A CN 115849726A
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cyanamide
composite substrate
hexylthiophene
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徐林
陈正件
李宣
费玉清
杨岳
刘凌雯
孔晶
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Zhuhai Institute Of Advanced Technology Chinese Academy Of Sciences Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00Cyanogen; Compounds thereof
    • C01C3/16Cyanamide; Salts thereof
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering

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Abstract

The invention belongs to the technical field of Raman detection, and discloses a surface-enhanced Raman scattering composite substrate, and a preparation method and application thereof. The preparation method comprises the following steps: dissolving cyanamide salt and poly-3-hexylthiophene in a solvent to obtain a mixed solution; coating the mixed solution on a glass sheet, and drying to obtain a composite substrate; the cyanamide salt is at least one of silver cyanamide, zinc cyanamide and silver dicyanamide. The composite membrane prepared by selecting the poly-3-hexylthiophene and the cyanamide salt is used as the composite substrate for surface enhanced Raman scattering, and the composite substrate is used for Raman spectrum detection, so that the detection sensitivity is high, the stability is high, the reusability is high, and the composite membrane can be widely applied to detection of organic dye molecules, such as methylene blue, crystal violet or azure I. The composite substrate provided by the invention is low in preparation cost and simple in preparation method.

Description

Surface-enhanced Raman scattering composite substrate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of Raman detection, and particularly relates to a surface-enhanced Raman scattering composite substrate, and a preparation method and application thereof.
Background
With the rapid development of modern industrialization, various organic pollutants generated from agriculture, industry and human life are discharged into the natural environment, cause serious harm to the environment, and gradually threaten the health of human beings as time elapses. Organic dye molecules such as methylene blue, crystal violet and the like are widely applied to the fields of dyed fabrics, medicines and the like, have complex aromatic structures, are extremely stable in the air, have extremely high risks such as carcinogenesis and teratogenicity after being taken for a long time, cause serious harm to human bodies even if extremely trace residues exist, and seriously affect the life health of people. Therefore, it is desirable to provide an effective detection technique that can realize rapid detection of environmental and food safety. The traditional trace detection technology comprises thin layer chromatography, spectrophotometry, high performance liquid chromatography and the like, the technologies are mature, the reproducibility is good, but the sample preparation process is complex and the time consumption is long. The Surface Enhanced Raman Spectroscopy (SERS) is used as an excellent trace detection tool and can realize rapid, nondestructive and efficient detection, wherein the selection of an SERS substrate is the key point for exerting high-quality SERS response.
The SERS technique is an effective tool for trace detection because of its high sensitivity, fast response, and convenience. The selection of the substrate is the key point for realizing the high-efficiency SERS response, and the traditional SERS substrate has noble metal nano-particles, and the practical application of the substrate is limited by the defects of instability in air, high cost and the like although the substrate has the sensitive and high-efficiency response. The inorganic semiconductor substrate has the advantages of high selectivity, low cost, high stability and the like, so that the inorganic semiconductor substrate becomes a research hotspot of the SERS substrate, but the Raman enhancement signal of the inorganic semiconductor substrate still has a great difference compared with the noble metal nanoparticles. In recent years, the discovery of an organic small-molecule semiconductor SERS substrate develops a new field for the development of the SERS substrate, and besides the common advantages of the organic small-molecule semiconductor SERS substrate and the inorganic semiconductor substrate, the organic small-molecule semiconductor SERS substrate can also realize the high enhancement of probe molecules, but the preparation process is complex, the aggregation structure is not tunable, and the reutilization property is poor.
Therefore, it is desirable to provide a method for preparing a surface-enhanced raman scattering composite substrate, which has low preparation cost, high sensitivity and high stability in detection, and can be recycled.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a surface-enhanced Raman scattering composite substrate, and a preparation method and application thereof. The composite substrate provided by the invention is low in preparation cost, high in sensitivity and strong in stability in Raman spectrum detection, and can be repeatedly used.
The invention provides a preparation method of a surface-enhanced Raman scattering composite substrate.
Specifically, the preparation method of the surface-enhanced Raman scattering composite substrate comprises the following steps:
dissolving cyanamide salt and poly-3-hexylthiophene (P3 HT) in a solvent to obtain a mixed solution; coating the mixed solution on a glass sheet, and drying to obtain a composite substrate; the cyanamide salt is at least one of silver cyanamide, zinc cyanamide and silver dicyanamide.
Preferably, the mass ratio of the cyanamide salt to the poly-3-hexylthiophene is 1: (0.5-15); further preferably, the mass ratio of the cyanamide salt to the poly-3-hexylthiophene is 1: (1-10); more preferably, the mass ratio of the cyanamide salt to the poly-3-hexylthiophene is 1: (1-5).
Preferably, the total mass concentration of the cyanamide salt and the poly-3-hexylthiophene in the mixed solution is 3-10mg/mL; further preferably, the total mass concentration of the cyanamide salt and the poly-3-hexylthiophene in the mixed solution is 5-10mg/mL.
Preferably, the cyanamide salt is a nano cyanamide salt.
Further preferably, the preparation process of the nano cyanamide salt is as follows:
adding ammonia water into silver nitrate or zinc nitrate solution, then adding cyanamide or dicyandiamide aqueous solution for reaction, filtering and separating to obtain cyanamide salt filter residue after the reaction generates complete precipitation, and cleaning and drying the filter residue to obtain the nano cyanamide salt.
Preferably, the concentration of the silver nitrate or the zinc nitrate is 15-20g/L.
Preferably, the concentration of the ammonia water is 1-3mol/L.
Preferably, the mass fraction of the cyanamide or dicyandiamide aqueous solution is 0.5% -1.5%; such as 0.8%, 0.9%, 1.2%, etc.
In order to further optimize the crystal structure of cyanamide salts such as silver cyanamide, zinc cyanamide, silver dicyanamide and the like, precipitates generated by the reaction are treated at high temperature for 4 to 12 hours at 160 to 200 by using a hydrothermal kettle, and the specific process is as follows: adding the precipitate generated by the reaction into the inner liner of the reaction kettle, adding ultrapure water, stirring into a slurry, assembling, putting into an oven, heating, keeping the temperature constant, and performing suction filtration, washing and drying after natural cooling.
Preferably, the solvent is chloroform.
Preferably, the coating process is to spin-coat the mixed solution on the glass sheet by using a spin-coater.
Further preferably, during the coating, the spin-coating revolution of the spin coater is 2000-6000rpm, such as 2500rpm, 4000rpm and 5500 rpm; the spin coating time is 20-40 seconds, such as 25 seconds, 30 seconds, 35 seconds, 40 seconds, and the like.
Preferably, the glass sheet is pretreated before coating, and the pretreatment process is as follows: cleaning the glass sheet by using water, acetone and ethanol in sequence, then placing the glass sheet into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and heating the glass sheet to 150-170 ℃; and finally, cleaning with water and drying for later use.
Preferably, in the mixed solution, the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is (5-8): (2-4); further preferably, the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 7:3.
preferably, the drying process is drying the coated glass sheet in vacuum at 50-70 ℃ for 20-30 hours. The drying process is to remove excess solvent.
In a second aspect, the invention provides a surface-enhanced raman scattering composite substrate.
Specifically, the composite substrate with the surface enhanced Raman scattering is prepared by the preparation method.
In a third aspect, the invention provides a use of a surface enhanced raman scattering composite substrate.
Specifically, the composite substrate with surface enhanced Raman scattering is applied to surface enhanced Raman spectroscopy detection; the detected object is an organic dye molecule.
Preferably, the organic dye molecule is methylene blue, crystal violet or azure i.
The fourth aspect of the invention provides a surface enhanced raman spectrometer.
Specifically, the surface enhanced Raman spectrometer comprises the composite substrate for surface enhanced Raman scattering.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite film prepared by selecting the pi-conjugated conductive polymer poly-3-hexylthiophene (P3 HT) and cyanamide salt (such as cyanamide silver) is used as a composite substrate for surface enhanced Raman scattering, the heterojunction structure of the organic semiconductor material poly-3-hexylthiophene and the inorganic semiconductor material cyanamide salt is utilized to enhance the charge transfer efficiency, and the inorganic semiconductor cyanamide salt can further improve the stability and the photocatalytic performance. The composite substrate layer is used in Raman spectrum detection, and has high detection sensitivity, strong stability and strong reusability.
(2) The surface-enhanced Raman scattering composite substrate provided by the invention is low in preparation cost and simple in preparation method, and solves the problems of high cost and complex preparation process of the traditional SERS substrate.
(3) The surface-enhanced Raman scattering composite substrate prepared by the invention can be widely applied to detection of organic dye molecules, such as methylene blue, crystal violet or azure I.
Drawings
FIG. 1 is an SEM image of a composite substrate prepared in example 3.
FIG. 2 is a Raman spectrum of different concentrations of methylene blue on a composite substrate prepared in example 3.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
The embodiment provides a composite substrate for surface enhanced raman scattering, which is a composite film formed on the basis of poly-3-hexylthiophene/silver cyanamide, and the preparation method of the composite substrate is as follows:
(1) Pretreating the glass sheet: firstly, a glass slide is cut into glass sheets with the size of 20mm multiplied by 20mm by a glass knife and placed in a beaker, the glass sheets are washed for 2 times by ultra-pure water, and then the glass sheets are washed by acetone and absolute ethyl alcohol in sequence by ultrasonic waves so as to remove residual organic pollutants on the glass sheets. And (3) cleaning for 3 times by using ultrapure water after the ultrasonic treatment, and then mixing concentrated sulfuric acid and hydrogen peroxide according to a volume ratio of 7:3 were added sequentially to the beaker followed by heating on a 160 ℃ hot plate until the bubbles gradually disappeared. Ultrasonic cleaning with ultrapure water for several times, and then using N 2 Blow-drying, and placing in a clean cuvette for later use.
(2) Preparing nano silver cyanamide: firstly weighing 5g of silver nitrate, dissolving the silver nitrate in 300mL of ultrapure water, then slowly dropwise adding 600mL of ammonia water with the concentration of 3mol/L, wherein the solution can precipitate in the dropwise adding process and then immediately disappear; and (3) continuously and slowly dropwise adding 300mL of cyanamide aqueous solution with the mass fraction of 0.9%, wherein precipitation immediately occurs along with the addition of the cyanamide aqueous solution in the process, and continuously adding the cyanamide aqueous solution until the precipitation is complete. And after stirring for half an hour, carrying out suction filtration, washing for several times by using ultrapure water, and drying in a vacuum drying oven at 60 ℃ to obtain the nano silver cyanamide.
(3) Preparing a composite film: firstly, dispersing poly-3-hexylthiophene and silver cyanamide in a chloroform solution, wherein the mass ratio of nano silver cyanamide to poly-3-hexylthiophene is 1: and 9, preparing a mixed solution with the total concentration of 8mg/mL, and placing the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 10 minutes until the poly-3-hexylthiophene is completely dissolved. And (3) spreading the mixed solution on a cleaned glass sheet (the thickness of the glass sheet is 3 mm) by using a spin coater, wherein the spin rotation speed is 4000rpm, the spin coating time is 30 seconds, placing the glass sheet which is subjected to spin coating with the mixed solution in a vacuum drying box, and placing the glass sheet at room temperature for 24 hours to remove the redundant solvent to obtain the composite substrate.
The embodiment also provides a method for applying the composite substrate to surface-enhanced raman spectroscopy detection to detect methylene blue dye, which comprises the following specific steps:
5 mu L of methylene blue dye is dripped on the composite substrate, a Raman experiment is carried out after the solution is dried, and the surface Raman enhancement performance of the composite substrate is evaluated by using the enhancement factor and the lowest detected concentration. The Raman experiment selects a 532-nanometer laser source, the laser power is 50 microwatts, the exposure time is 5 seconds, and the test wavelength range is 200cm -1 To 2200cm -1 . Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 3800, and the detection limit concentration is 10 -6 Mol/l.
Example 2
Example 2 differs from example 1 in that the mass ratio of silver cyanamide to poly-3-hexylthiophene was 1:6, the rest of the preparation method and the detection process are the same as those of example 1.
Through testing, the enhancement factor of the composite substrate prepared in the embodiment is 3500, and the detection limit concentration is 10 -6 Mol/l.
Example 3
Example 3 differs from example 1 in that the mass ratio of silver cyanamide to poly-3-hexylthiophene was 1:4, the rest of the preparation method and the detection process are the same as those of example 1.
Fig. 1 is an SEM image of the composite substrate prepared in example 3. As can be seen from fig. 1, silver cyanamide nanoparticles are present on the substrate, which are relatively uniformly distributed, and the surface and corners of the silver cyanamide nanoparticles become blurred, which may be due to the P3HT film covering the silver cyanamide particles. Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 6100, and the detection limit concentration is 10 -9 Mol/l. FIG. 2 is a Raman spectrum of different concentrations of methylene blue on a composite substrate. As can be seen from FIG. 2, when the concentration of methylene blue is 10 -9 At M, there is still a strong signal intensity.
Example 4
Example 4 differs from example 1 in that the mass ratio of silver cyanamide to poly-3-hexylthiophene was 1:3, the rest of the preparation method and the detection process are the same as those of example 1.
Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 5500, and the detection limit concentration is 10 -8 Mol/l.
Example 5
Example 5 differs from example 1 in that the mass ratio of silver cyanamide to poly-3-hexylthiophene is 1:2, the rest of the preparation method and the detection process are the same as those of example 1.
Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 5400, and the detection limit concentration is 10 -8 Mol/l.
Example 6
Example 6 differs from example 1 in that the mass ratio of silver cyanamide to poly-3-hexylthiophene was 1:1, the rest of the preparation method and the detection process are the same as those of example 1.
Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 5000, and the detection limit concentration is 10 -8 Mol/l.
Example 7
Example 7 differs from example 3 in that the total concentration of nano silver cyanamide and poly 3-hexylthiophene is 5mg/mL, the mass ratio of silver cyanamide to poly 3-hexylthiophene is still 1:4, the rest of the preparation method and the detection process are the same as those of example 3.
Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 5900, and the detection limit concentration is 10 -9 Mol/l.
Example 8
Example 8 differs from example 3 in that the total concentration of nano silver cyanamide and poly 3-hexylthiophene was 10mg/mL, the mass ratio of silver cyanamide to poly 3-hexylthiophene was still 1:4, the rest of the preparation method and the detection process are the same as those of example 3.
Through tests, the enhancement factor of the composite substrate prepared in the embodiment is 5800, and the detection limit concentration is 10 -9 Mol/l.
Example 9
Example 9 is different from example 3 in that the prepared composite substrate is applied to surface enhanced raman spectroscopy for detecting azure I, and the rest of the preparation method and the detection process are the same as example 3.
Through tests, the enhancement factor for detecting azure I in the embodiment is 4500, and the detection limit concentration is 10 -8 Mol/l.
Example 10
Example 10 is different from example 3 in that the prepared composite substrate is applied to surface enhanced raman spectroscopy for detecting crystal violet dye, and the rest of the preparation method and detection process are the same as example 3.
Through tests, the enhancement factor of the crystal violet dye detected by the embodiment is 5000, and the detection limit concentration is 10 -8 Mol/l.
Example 11
In this example, the composite substrate film used in the detection in example 3 is washed with purified water and dried, and then irradiated with visible light for 4 hours, and then a raman experiment is performed to test the reusability of the composite substrate. The specific operation is as follows: dripping 5 μ L of methylene blue dye on the cleaned and dried composite substrate, drying the solution, and performing Raman experiment under the same detection conditions as in example 4, wherein the enhancement factor of the second detection is 6100, and the detection limit concentration is 10 -9 Mole/liter. Repeating the above method for 6 times, wherein the detection limit concentration is 10 -9 Mole/liter, third enhancement factor 6050, fourth enhancement factor 6080, fifth enhancement factor 6030 and sixth enhancement factor 6010. The composite substrate provided by the invention can be recycled, and after the composite substrate is recycled, the SERS performance is still excellent.
Comparative example 1
Comparative example 1 provides a surface-enhanced raman scattering substrate, which is a base film formed based on poly-3-hexylthiophene. Comparative example 1 is different from example 1 in that in comparative example 1, poly-3-hexylthiophene was dispersed in a chloroform solution without adding silver cyanamide to prepare a poly-3-hexylthiophene solution having a total concentration of 8mg/mL, and then the poly-3-hexylthiophene solution was spin-coated. The rest of the preparation method and the detection process are the same as those of example 1.
The enhancement factor of the substrate prepared by the comparative example is 800 and the detection limit concentration is 10 through testing -4 Mol/l.
Comparative example 2
Comparative example 2 provides a surface-enhanced raman scattering substrate, which is a substrate film formed based on silver cyanamide. Comparative example 2 is different from example 1 in that in comparative example 2, silver cyanamide was dispersed in a chloroform solution without adding poly-3-hexylthiophene to prepare a silver cyanamide solution having a total concentration of 8mg/mL, and then the silver cyanamide solution was spin-coated. The rest of the preparation method and the detection process are the same as in example 1.
The enhancement factor of the substrate prepared in the comparative example was 200 and the detection limit concentration was 10 -3 Mol/l.
Comparative example 3
Comparative example 3 is different from example 3 in that poly-3-hexylthiophene was replaced with the same amount of polythiophene, and the remaining preparation method and detection process were the same as in example 3.
The composite substrate prepared by the comparative example is tested to have the enhancement factor of 2500 and the detection limit concentration of 10 -5 Mol/l.
Comparative example 4
Comparative example 4 differs from example 1 in that the mass ratio of silver cyanamide to poly-3-hexylthiophene was 1:19, the rest of the preparation method and the detection process are the same as those of example 1.
The composite substrate prepared by the comparative example is tested to have the enhancement factor of 1200 and the detection limit concentration of 10 -4 Mol/l.

Claims (10)

1. A preparation method of a surface-enhanced Raman scattering composite substrate is characterized by comprising the following steps:
dissolving cyanamide salt and poly-3-hexylthiophene in a solvent to obtain a mixed solution; coating the mixed solution on a glass sheet, and drying to obtain a composite substrate; the cyanamide salt is at least one of silver cyanamide, zinc cyanamide and silver dicyanamide.
2. The method according to claim 1, wherein the mass ratio of the cyanamide salt to the poly-3-hexylthiophene is 1: (0.5-15); preferably, the mass ratio of the cyanamide salt to the poly-3-hexylthiophene is 1: (1-10).
3. The preparation method according to claim 1, wherein the total mass concentration of the cyanamide salt and the poly-3-hexylthiophene in the mixed solution is 3-10mg/mL; preferably, the total mass concentration of the cyanamide salt and the poly-3-hexylthiophene in the mixed solution is 5-10mg/mL.
4. The production method according to any one of claims 1 to 3, characterized in that the cyanamide salt is a nano cyanamide salt; the preparation process of the nano cyanamide salt is as follows:
adding ammonia water into silver nitrate or zinc nitrate solution, then adding cyanamide or dicyandiamide aqueous solution for reaction, filtering and separating to obtain cyanamide salt filter residue after the reaction generates complete precipitation, and cleaning and drying the filter residue to obtain the nano cyanamide salt.
5. The method according to claim 1, wherein the solvent is chloroform.
6. A method of manufacturing as claimed in any one of claims 1 to 3 wherein the glass sheet is pre-treated prior to coating by the following steps: cleaning the glass sheet by using water, acetone and ethanol in sequence, then placing the glass sheet into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and heating the glass sheet to 150-170 ℃; and finally, cleaning with water and drying for later use.
7. A surface-enhanced Raman scattering composite substrate produced by the production method according to any one of claims 1 to 6.
8. Use of the composite substrate of claim 7 for surface enhanced raman spectroscopy detection wherein the object of detection is an organic dye molecule.
9. Use according to claim 8, wherein the organic dye molecule is methylene blue, crystal violet or azure i.
10. A surface enhanced raman spectrometer comprising the surface enhanced raman scattering composite substrate of claim 7.
CN202211292488.0A 2022-10-21 2022-10-21 Surface-enhanced Raman scattering composite substrate and preparation method and application thereof Pending CN115849726A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024082952A1 (en) * 2022-10-21 2024-04-25 珠海中科先进技术研究院有限公司 Surface-enhanced raman scattering composite substrate, and preparation method therefor and use thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103526291A (en) * 2013-10-28 2014-01-22 中国工程物理研究院化工材料研究所 Surface enhanced Raman scattering substrate, preparation method therefor and application thereof
CN106525808A (en) * 2016-09-21 2017-03-22 北京科技大学 Method for preparing flexible surface-enhanced raman base with polymer substrate
WO2018030785A1 (en) * 2016-08-09 2018-02-15 한양대학교 에리카산학협력단 Bimetal-conductive polymer janus composite nanostructure having electrical stimulus response, colloid self-assembled structure thereof, preparing method, and bio-sensing, bio-imaging, drug delivery, and industrial application
CN109799220A (en) * 2018-12-21 2019-05-24 中国科学院合肥物质科学研究院 Method based on histamine in metallo-chelate Raman tag technology detection tissue fluid
CN112683877A (en) * 2020-12-03 2021-04-20 苏州大学 Surface-enhanced Raman substrate based on silver pyramid-shaped nanoparticles and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105158229B (en) * 2015-08-13 2018-10-02 南京理工大学 A kind of recyclable Raman spectrum base preparation method of high sensitivity
CN114965423A (en) * 2022-05-10 2022-08-30 江南大学 Method for detecting melamine in milk based on Ag-COF-COOH substrate surface enhanced Raman spectroscopy
CN115849726A (en) * 2022-10-21 2023-03-28 珠海中科先进技术研究院有限公司 Surface-enhanced Raman scattering composite substrate and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103526291A (en) * 2013-10-28 2014-01-22 中国工程物理研究院化工材料研究所 Surface enhanced Raman scattering substrate, preparation method therefor and application thereof
WO2018030785A1 (en) * 2016-08-09 2018-02-15 한양대학교 에리카산학협력단 Bimetal-conductive polymer janus composite nanostructure having electrical stimulus response, colloid self-assembled structure thereof, preparing method, and bio-sensing, bio-imaging, drug delivery, and industrial application
CN106525808A (en) * 2016-09-21 2017-03-22 北京科技大学 Method for preparing flexible surface-enhanced raman base with polymer substrate
CN109799220A (en) * 2018-12-21 2019-05-24 中国科学院合肥物质科学研究院 Method based on histamine in metallo-chelate Raman tag technology detection tissue fluid
CN112683877A (en) * 2020-12-03 2021-04-20 苏州大学 Surface-enhanced Raman substrate based on silver pyramid-shaped nanoparticles and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王涛: "P3HT复合薄膜的制备及其SERS性能研究", 中国学位论文全文数据库, 21 September 2022 (2022-09-21), pages 33 - 34 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024082952A1 (en) * 2022-10-21 2024-04-25 珠海中科先进技术研究院有限公司 Surface-enhanced raman scattering composite substrate, and preparation method therefor and use thereof

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