CN109884026A - A kind of liquid phase in-situ SERS detection method - Google Patents
A kind of liquid phase in-situ SERS detection method Download PDFInfo
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- CN109884026A CN109884026A CN201910054272.2A CN201910054272A CN109884026A CN 109884026 A CN109884026 A CN 109884026A CN 201910054272 A CN201910054272 A CN 201910054272A CN 109884026 A CN109884026 A CN 109884026A
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Abstract
The present invention provides a kind of liquid phase in-situ SERS detection methods, belong to detection and analysis technical field.The present invention mixes inducer and organic solvent, obtains oil and mixes liquid；The test side that will test optical fiber is immersed oil and is mixed in liquid, is infiltrated, and so that test side is wrapped up one layer of oil and mixes liquid；The other end of the detection fiber is of coupled connections with Raman spectrometer；Detection fiber after infiltration is immersed in prepare liquid, under the action of inducer, noble metal nano particles and determinand molecule form local water-oil interface self assembly in the end face of test side, then acquire Raman spectrum；The prepare liquid is the aqueous solution containing determinand and noble metal nano particles.The present invention realizes the stabilization of determinand molecule SERS spectra, original position, highly sensitive detection in liquid phase environment using the above method, has the advantages that easy to operate, low in cost, reproducible.
Description
Technical field
The present invention relates to test and analyze technical field more particularly to a kind of liquid phase in-situ SERS detection method.
Background technique
Surface enhanced Raman scattering (surface enhanced Raman scattering, SERS) is presently most used
A kind of Raman enhance technology, its local surface plasma resonance effect based on noble metal nano particles is capable of providing 106~
1010The Raman signal of magnitude enhances, and all has important application prospect in fields such as biomedicine, environmental monitoring, Internet of Things.Liquid phase
Stabilization, the in situ detection of SERS spectra are an important directions of current SERS technical research.
Water-oil interface self assembly is to prepare large area, the simple and effective method of one kind of equally distributed SERS substrate,
This method reduces the surface charge of noble metal nano particles or circumgranular electric double layer thickness in solution using inducer, realizes
Noble metal nano particles form a film in water-oil interface self assembly to provide big SERS enhancement factor.In order to realize liquid phase SERS spectra
In situ detection, people attempt raman excitation light is directly focused to water-oil interface carry out Raman spectrum acquisition；However, due to water
The noble metal nano particles film quality of oil interface is lighter, and in the case where focusing raman excitation light irradiation, light momentum causes nano particle
Drift, thus the detection stability of larger impact SERS spectra.Currently, more commonly used method is to construct water-oil interface
Noble metal nano particles film is transferred on planar substrates (such as sheet glass, silicon wafer), then carries out SERS spectra detection, to obtain
Reliable and stable SERS spectra；But the film transfer method is difficult to realize the in situ detection of liquid phase SERS spectra.
Summary of the invention
The purpose of the present invention is to provide a kind of liquid phase in-situ SERS detection method, this method has easy to operate, cost
Cheap, reproducible advantage.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of liquid phase in-situ SERS detection methods, include the following steps:
Inducer and organic solvent are mixed, oil is obtained and mixes liquid；
The test side that will test optical fiber is immersed oil and is mixed in liquid, is infiltrated；The other end of the detection fiber and drawing
Graceful spectrometer is of coupled connections；
Test side after infiltration is immersed in prepare liquid, self assembly is carried out, then acquires Raman spectrum；The prepare liquid is
Aqueous solution containing determinand and noble metal nano particles.
Preferably, the inducer includes ethyl alcohol or acetone.
Preferably, the organic solvent includes thiacyclohexane, hexane or n-butanol.
Preferably, the volume ratio of the inducer and organic solvent is 1:1~10.
Preferably, the test side of the detection fiber is naked fibre.
Preferably, the time of the infiltration is 10~30min.
Preferably, the mode being of coupled connections be in the way of the fiber coupling of FC/PC or SMA905 optical fiber interface, or
By the way of space optical path coupling.
Preferably, the Raman spectrometer is Portable Raman spectrometer.
Preferably, the noble metal nano particles are at least one of gold nano grain and silver nano-grain；It is described expensive
The partial size of metal nanoparticle is 10~60nm.
The present invention provides a kind of liquid phase in-situ SERS detection methods, include the following steps: inducer and organic solvent
Mixing, obtains oil and mixes liquid；The test side that will test optical fiber is immersed oil and is mixed in liquid, is infiltrated；The detection fiber
The other end be of coupled connections with Raman spectrometer；Detection fiber after infiltration is immersed in prepare liquid, self assembly is carried out, acquisition is drawn
Graceful spectrum；The prepare liquid is the aqueous solution containing determinand and noble metal nano particles.The present invention will test one layer of end package
The oil of inducer and organic solvent composition mixes liquid, then contains the test side insertion of surface package a thin layer oil-phase solution
In the aqueous solution of determinand and noble metal nano particles, under the action of inducer, noble metal nano particles and determinand molecule
Local water-oil interface self assembly is formed in the end face of test side, has constructed highly sensitive SERS substrate, is realized to be measured in liquid phase environment
The stabilization of object molecule SERS spectra, original position, highly sensitive detection have the advantages that easy to operate, low in cost, reproducible.
Detailed description of the invention
Fig. 1 liquid phase in-situ SERS detection method schematic diagram provided by the invention；
The liquid phase in-situ SERS testing result of Fig. 2 melamine molecule.
Specific embodiment
The present invention provides a kind of liquid phase in-situ SERS detection methods, include the following steps:
Inducer and organic solvent are mixed, oil is obtained and mixes liquid；
The test side that will test optical fiber is immersed oil and is mixed in liquid, is infiltrated；The other end of the detection fiber and drawing
Graceful spectrometer is of coupled connections；
Test side after infiltration is immersed in prepare liquid, self assembly is carried out, acquires Raman spectrum；The prepare liquid be containing
The aqueous solution of determinand and noble metal nano particles.
The present invention contains determinand and noble metal nano by the way that surface to be wrapped up to the test side insertion of a thin layer oil-phase solution
In the aqueous solution of particle, local water-oil interface is formed certainly in the end face of test side using noble metal nano particles and determinand molecule
Highly sensitive SERS substrate is constructed in assembling, realizes the detection of liquid phase in-situ SERS, has easy to operate, low in cost, reproducible
Advantage.
The present invention mixes inducer and organic solvent, obtains oil and mixes liquid.
In the present invention, the inducer preferably includes ethyl alcohol or acetone.In the present invention, the inducer can reduce
The surface charge of noble metal nano particles or circumgranular electric double layer thickness in solution realize noble metal nano in subsequent step
Particle forms a film in water-oil interface self assembly to provide big SERS enhancement factor.
In the present invention, the organic solvent preferably includes thiacyclohexane, hexane or n-butanol.In the present invention, described to have
Solvent is used to form oil-water interfaces in the next steps.
In the present invention, the volume ratio of the inducer and organic solvent is preferably 1:1~10.In the present invention, above-mentioned
The survivable oily phase environment of ratio, while being also conducive to subsequent induction noble metal nano particles and carrying out self assembly in water-oil interface.
It obtains after oil mixes liquid, the test side that the present invention will test optical fiber is immersed oil and mixed in liquid, is infiltrated；Institute
The other end and Raman spectrometer for stating detection fiber are of coupled connections.In the present invention, it will test after holding immersion oil to mix in liquid,
Under the action of surface tension, oil, which mixes solution, can be wrapped in test side, form one layer of oil and mix solution, be subsequent detection
Process forms noble metal nano particles and the self assembly of determinand provides condition.
In the present invention, the test side of the detection fiber is preferably naked fibre.Material of the present invention to the detection fiber
It is not particularly limited, using conventional optical fiber.
The present invention is not particularly limited the structure of the test side, and in embodiments of the present invention, the test side is preferred
For planar end surface or pyramidal structure.
In the present invention, the time of the infiltration is preferably 10~30min.
In the present invention, the mode being of coupled connections is preferably the optical fiber coupling for utilizing FC/PC or SMA905 optical fiber interface
Conjunction mode, or by the way of space optical path coupling.
In the present invention, the Raman spectrometer is preferably Portable Raman spectrometer.In the present invention, use is portable
Raman spectrometer in situ, the highly sensitive detection to determinand Molecular Raman spectrum can be realized, it is more convenient, quick.
After the completion of infiltration, the present invention immerses the test side after infiltration in prepare liquid, carries out self assembly, then acquires Raman
Spectrum；The prepare liquid is the aqueous solution containing determinand and noble metal nano particles.In the present invention, test side is immersed to be measured
After in liquid, due to the presence of organic solvent, the end face of test side nearby will form local water-oil interface；Under inducer effect,
Noble metal nano particles and determinand molecular motion to interface in water phase carries out self assembly (as shown in Figure 1), forms your gold
Metal nano-particle film is to provide big SERS enhancement factor.
The angle that the present invention immerses in prepare liquid the test side is not particularly limited, in embodiments of the present invention, institute
Test side is stated to be preferably perpendicular in prepare liquid liquid level immersion prepare liquid.
The present invention is not particularly limited the time of the self assembly, and those skilled in the art can be with experimental reality
Situation adjustment.In embodiments of the present invention, the time of the self assembly is preferably 30s~20min.
In the present invention, the noble metal nano particles are preferably at least one in gold nano grain and silver nano-grain
Kind；The partial size of the noble metal nano particles is preferably 10nm~60nm.Source of the present invention to the noble metal nano particles
It is not particularly limited, is prepared using commercial product or laboratory oneself；In embodiments of the present invention, it is preferred to use commercially available
Noble metal nano particles colloidal sol；The optical density (OD) OD value of the noble metal nano particles colloidal sol is preferably 5~20；The present invention is to institute
The content for stating noble metal nano particles in prepare liquid is not particularly limited, and those skilled in the art can pass through routine test means
The content of suitable noble metal nano particles is adjusted, in embodiments of the present invention, the prepare liquid is preferably the water-soluble of determinand
Liquid is mixed to get in equal volume with noble metal granule Nano sol.
The present invention is not particularly limited the concentration of determinand in the prepare liquid, and those skilled in the art can be according to drawing
Graceful spectrometer adjusts to obtain suitable concentration by conventional technical means to the sensitivity of different material.
In the present invention, complete one-time detection after, the detection tip cut-off after preferably using, then with new test side into
Row detects next time.
A kind of liquid phase in-situ SERS detection method provided by the invention is described in detail below with reference to embodiment, but
It is that they cannot be interpreted as limiting the scope of the present invention.
Embodiment
Choose ethyl alcohol as inducer, thiacyclohexane as organic solvent, the two is mixed in equal volume, obtain oil mix it is molten
Liquid；It is 2 × 10 by concentration-5The melamine aqueous solution and gold nano particle colloidal sols of M mixes in equal volume, obtains prepare liquid, Jenner
The optical density (OD) OD value of rice grain colloidal sol is 10；Using fibre core and cladding diameter be respectively 200 μm and 220 μm optical fiber as detection
Optical fiber；The covering removal that will test one end of optical fiber, as test side；The other end that will test optical fiber is connect using FC/PC optical fiber
Mouth is of coupled connections with Portable Raman spectrometer；It is cut into planar end surface using the end face that optical fiber cutter will test end, is then immersed in
Above-mentioned oil mixes in solution, takes out after infiltrating 15min；Test side after infiltration is inserted into prepare liquid, noble metal nano
Grain and testing molecule open Portable Raman spectrometer and carry out Raman light in the local water-oil interface progress self assembly of fiber end face
Spectrum acquisition.
The SERS spectra for the melamine molecule that Fig. 2 is collected after being water-oil interface self assembly 5min is as a result, can by Fig. 2
Know, in characteristic peak 682cm-1Place obtains higher SERS signal, to show that the method for the invention realizes liquid phase in situ detection
Feasibility.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of liquid phase in-situ SERS detection method, which comprises the steps of:
Inducer and organic solvent are mixed, oil is obtained and mixes liquid；
The test side that will test optical fiber is immersed oil and is mixed in liquid, is infiltrated；The other end and Raman light of the detection fiber
Spectrometer is of coupled connections；
Test side after infiltration is immersed in prepare liquid, self assembly is carried out, then acquires Raman spectrum；The prepare liquid be containing
The aqueous solution of determinand and noble metal nano particles.
2. detection method according to claim 1, which is characterized in that the inducer includes ethyl alcohol or acetone.
3. detection method according to claim 1, which is characterized in that the organic solvent includes thiacyclohexane, hexane or just
Butanol.
4. any one detection method according to claim 1~3, which is characterized in that the body of the inducer and organic solvent
Product is than being 1:1~10.
5. detection method according to claim 1, which is characterized in that the test side of the detection fiber is naked fibre.
6. detection method according to claim 1, which is characterized in that the time of the infiltration is 10~30min.
7. detection method according to claim 1, which is characterized in that the mode being of coupled connections be using FC/PC or
The fiber coupling mode of SMA905 optical fiber interface, or by the way of space optical path coupling.
8. detection method according to claim 1 or claim 7, which is characterized in that the Raman spectrometer is portable Raman light
Spectrometer.
9. detection method according to claim 1, which is characterized in that the noble metal nano particles be gold nano grain and
At least one of silver nano-grain；The partial size of the noble metal nano particles is 10nm~60nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113008871A (en) * | 2021-04-07 | 2021-06-22 | 东莞理工学院 | Phase-change crystallization-based optical fiber tweezers molecule capture method and Raman spectrum detection method for persistent organic pollutants |
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| CN108120709A (en) * | 2017-12-25 | 2018-06-05 | 合肥工业大学 | A kind of capillary microlayer model metal ball detection method for Surface enhanced Raman spectroscopy |
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2019
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Patent Citations (4)
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| CN102944543A (en) * | 2012-11-05 | 2013-02-27 | 中物院成都科学技术发展中心 | Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy |
| CN105241864A (en) * | 2015-10-21 | 2016-01-13 | 中国科学院合肥物质科学研究院 | Laser-induce self-assembly method for preparing high-sensitivity optical fiber SERS probe |
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| CN113008871A (en) * | 2021-04-07 | 2021-06-22 | 东莞理工学院 | Phase-change crystallization-based optical fiber tweezers molecule capture method and Raman spectrum detection method for persistent organic pollutants |
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