CN110790220A - Surface-enhanced Raman scattering substrate, preparation method thereof and in-situ rapid detection method - Google Patents

Surface-enhanced Raman scattering substrate, preparation method thereof and in-situ rapid detection method Download PDF

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CN110790220A
CN110790220A CN201911034538.3A CN201911034538A CN110790220A CN 110790220 A CN110790220 A CN 110790220A CN 201911034538 A CN201911034538 A CN 201911034538A CN 110790220 A CN110790220 A CN 110790220A
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陈晶
王远文
汪国平
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Shenzhen University
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Abstract

The invention discloses a surface-enhanced Raman scattering substrate, a preparation method thereof and an in-situ rapid detection method, wherein the preparation method comprises the steps of adding a solvent into a gold nanoparticle solution, wherein the solvent is immiscible with the gold nanoparticle solution and floats above the gold nanoparticle solution to form a layering phenomenon with a liquid-liquid interface; injecting an alcohol solution into the gold nanoparticle solution, transferring the gold nanoparticles to a liquid-liquid interface, and forming a gold nanoparticle self-assembly film through self-assembly; and transferring the gold nano self-assembly film onto a transparent substrate to obtain the surface enhanced Raman scattering substrate. Through the mode, the gold nanoparticles can be densely and orderly arranged in a liquid-liquid interface in a self-assembly mode, and the gold nanoparticle self-assembly film is transferred to the surface-enhanced Raman scattering substrate formed on the transparent substrate, so that the method can be used for rapid in-situ real-time detection of illegal additive molecules (such as malachite green, rhodamine B and the like) in a liquid-phase system, and is high in detection sensitivity and good in reproducibility.

Description

Surface-enhanced Raman scattering substrate, preparation method thereof and in-situ rapid detection method
Technical Field
The invention relates to the technical field of detection, in particular to a surface-enhanced Raman scattering substrate, a preparation method thereof and an in-situ rapid detection method.
Background
Illegal additives mostly refer to illegal additives in food. Generally, substances which do not belong to new resource foods which are not conventionally considered as food raw materials, which do not belong to approved new resource foods, which do not belong to dual-purpose of medicine and food or which are published as substances for general food management, which are not listed as food additives in various countries and which are allowed to be used by other laws and regulations are illegal additives; such as sudan red, basic orange, etc. The liquid phase system mostly refers to the liquid phase environment of beverage, drinking water, aquaculture water, river and lake water, etc. The existing detection methods for illegal additives in a liquid phase system comprise a high performance liquid chromatography, a high performance liquid chromatography-tandem mass spectrometry, a gas chromatography-tandem mass spectrometry, a solid phase extraction-high performance liquid chromatography, an ultraviolet spectrophotometry, an enzyme-linked immunosorbent assay and the like. Although the traditional detection method has high detection precision and good repeatability, the existing detection method has the disadvantages of complex pretreatment process, long time for instrument analysis and high detection cost, and is not suitable for field detection. Therefore, it is crucial to develop a simple, fast and effective in-situ detection method for illegal additives in liquid phase systems.
The Surface-Enhanced Raman Scattering (SERS) effect refers to that when laser with a proper frequency irradiates the Surface of a noble metal nanoparticle, plasma resonance on the Surface of the noble metal nanoparticle is excited to cause electromagnetic field enhancement, and when a molecule to be detected is placed in the Enhanced electromagnetic field, a Raman Scattering signal of the molecule to be detected is Enhanced by millions or even more times, so that the method is a nondestructive, label-free, high-sensitivity and near-field effect analysis and detection means, and is widely applied to the fields of biology, chemistry, environment and the like. As a molecular spectrum fingerprint identification method, compared with other traditional detection methods, SERS has the advantages of rapidness, simple and convenient operation, no need of sample pretreatment or simple sample pretreatment and the like, and is a real-time nondestructive detection technology with high sensitivity and high space-time resolution.
Experiments and theoretical researches show that the SERS technology can obtain a high-sensitivity signal on a low-concentration substance to be detected, and the premise condition for obtaining a high-quality Raman signal is that the enhancement performance of the SERS active substrate and the enhancement effect of the SERS substrate are determined by factors such as the material and the appearance of the SERS substrate. The conventional SERS substrate is generally prepared by preparing a gold nanoparticle solution, then dropping the gold nanoparticle solution on a substrate, and then drying the gold nanoparticle solution to form a gold nanoparticle aggregate on the substrate. In the method, the gold nanoparticle aggregate is arranged in a manner of directly absorbing the solution to be dropped on the substrate and then drying, and the arrangement of the gold nanoparticles is disordered, so that the detection stability and the signal reproducibility are poor when the formed SERS substrate is used for detecting an object to be detected. Therefore, it is important to develop a SERS substrate with excellent performance for realizing in-situ rapid detection of illegal additive molecules in liquid phase.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the surface-enhanced Raman scattering substrate prepared by the preparation method can be used for in-situ rapid detection of illegal additive molecules in a liquid phase system, and has high sensitivity and good reproducibility.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a method for preparing a surface-enhanced raman scattering substrate is provided, which comprises the following steps:
s1, preparing a gold nanoparticle self-assembly film: adding a solvent into the gold nanoparticle solution, and standing for layering; the solvent is immiscible with the gold nanoparticle solution and floats above the gold nanoparticle solution; injecting an alcohol solution into the gold nanoparticle solution, transferring the gold nanoparticles in the gold nanoparticle solution to an interface between the gold nanoparticle solution and the solvent, and forming a gold nanoparticle self-assembly film through self-assembly;
s2, arranging at least one layer of the gold nanoparticle self-assembly film on a transparent substrate to obtain the surface-enhanced Raman scattering substrate.
In step S1, the gold nanoparticle solution is typically a gold nanoparticle aqueous solution; the particle size of the gold nanoparticles in the gold nanoparticle solution is generally 10-150 nm. The solvent is typically an oil phase solvent; according to some embodiments of the present invention, the solvent is an alkane organic solvent, and specifically, at least one of hexane and heptane can be used. The solvent is added into the gold nanoparticle solution to generate oil-water stratification, the oil phase solvent floats above the gold nanoparticle solution, and the alcohol solution is added to reduce the surface charge of the gold nanoparticles and lower the oil-water interface, so that the gold nanoparticles can ascend and transfer to the oil-water interface, and the self-assembled monolayer film of the gold nanoparticles is formed through self-assembly. Among them, ethanol solution is usually used as the alcohol solution.
In step S1, the gold nanoparticle solution may be prepared by reacting a gold salt solution with a reducing agent. According to some embodiments of the invention, the gold nanoparticle solution is prepared by a preparation method comprising the steps of:
a. boiling the reducing agent solution, adding a gold salt solution, and then carrying out thermal reflux treatment to obtain a gold nanoparticle seed solution;
b. and adding a gold salt solution into the gold nanoparticle seed solution, and heating to prepare the gold nanoparticle solution.
The gold nanoparticles in the gold nanoparticle solution prepared by the method have uniform size, and can be used for preparing a surface enhanced Raman scattering substrate, so that the sensitivity, stability and reproducibility of the surface enhanced Raman scattering substrate can be further improved.
According to some embodiments of the invention, in step a, the reducing agent solution is selected from a citrate solution; in the step a and/or the step b, the gold salt solution is at least one selected from chloroauric acid solution and sodium chloroaurate solution. The concentration of the reducing agent solution is generally 2-2.5 mM (i.e. mmol/L); the concentration of the gold salt solution is generally 20 to 30 mM. In addition, in the step a, the time of the thermal reflux treatment is generally 10 to 20 min.
According to some embodiments of the invention, step b comprises in particular the steps of:
① adding a gold salt solution into the gold nanoparticle seed solution, and then carrying out heating treatment;
② repeating step ① at least once to obtain gold nanoparticle solution;
or ③ adding reducing agent solution into the gold nanometer particle solution obtained in step ② to obtain a second round of gold nanometer particle seed solution, then preparing gold nanometer particle solution containing gold nanometer particles with required particle size according to step ① or steps ① and ②, by the above method or further repeating step ③, preparing gold nanometer particle solution according to the particle size requirement of the required gold nanometer particles.
In the step ①, the concentration of the gold salt solution is generally 20-30 mM, the time of the heating treatment is generally 20-30 min, and the concentration of the reducing agent solution in the step ③ is generally 50-70 mM.
In step S1, the volume ratio of the gold nanoparticle solution, the alkane organic solvent, and the ethanol solution may be 5:5: 2.
According to some embodiments of the invention, in step S2, the transparent substrate is a flexible transparent substrate. The surface-enhanced Raman scattering substrate is prepared by adopting the flexible transparent substrate, and when the surface-enhanced Raman scattering substrate is further applied to illegal additive molecules, the wrapping shape of the surface-enhanced Raman scattering substrate can be flexibly changed according to the shape of an object to be detected, so that the gold nanoparticle self-assembly film on the surface-enhanced Raman scattering substrate is in full contact with the object to be detected for detection, and the detection flexibility and sensitivity are improved.
The transparent substrate may be at least one of Polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA) and polyethylene terephthalate (PET). The flexible material is adopted, the substrate is light in weight, when the substrate is used for preparing the surface enhanced Raman scattering substrate and further used for detecting illegal additive molecules in a liquid phase system, one side of the gold-containing nano-particle self-assembly film on the surface enhanced Raman scattering substrate faces downwards and is attached and contacted with the surface of a solution to be detected for detection, and the substrate can suspend on the surface of the solution to be detected due to the fact that the density of the substrate is smaller than that of the solution to be detected, real-time in-situ detection can be achieved, an object to be detected does not need to be damaged or is not required to be extracted and then dripped on the substrate.
According to some embodiments of the present invention, at least one layer of the gold nanoparticle self-assembly thin film is disposed on the transparent substrate in step S2 by using LB technology (i.e., Langmuir-Blodgett transfer technology). The number of layers of the gold nanoparticle self-assembly film can be specifically 2, 3, 4, 5 and the like; preferably 2 layers.
In a second aspect of the present invention, there is provided a surface-enhanced raman scattering substrate prepared by any one of the methods for preparing a surface-enhanced raman scattering substrate according to the first aspect of the present invention.
The third aspect of the invention provides an in-situ rapid detection method for illegal additive molecules in a liquid phase system, which specifically comprises the following steps: one side of the gold-containing nano particle self-assembly film on the surface enhanced Raman scattering substrate of the second aspect of the invention is attached and contacted with the surface of the solution to be detected, and then a Raman spectrometer is adopted for detection. The illegal additive molecule comprises at least one of malachite green, rhodamine B, Sudan red and basic orange; liquid phase systems include, but are not limited to, beverages, drinking water, aquaculture water, river and lake water.
According to the detection method, by adopting the surface enhanced Raman scattering substrate of the second aspect of the invention, one side of the gold-containing nano-particle self-assembly film on the surface enhanced Raman scattering substrate is downward in an inverted mode and is in contact with the surface of the solution to be detected for detection, the operation is simple and convenient, the in-situ rapid detection of illegal additive molecules in a liquid phase system can be realized, and the object to be detected does not need to be damaged or extracted and then dropped on the surface enhanced Raman scattering substrate; and the detection sensitivity is high, and the stability and the reproducibility are good.
The Raman scattering signal of the solution to be detected is detected by adopting the Raman spectrometer, specifically, laser is injected from one side, deviating from the gold nanoparticle self-assembly film, of the surface enhanced Raman scattering substrate, the focusing depth is adjusted to enable the laser to be focused on the gold nanoparticle self-assembly film, then in-situ SERS detection of illegal additive molecules in a liquid phase system is carried out, an SERS graph is obtained, and qualitative analysis can be carried out according to characteristic peaks. Wherein, the wavelength of the laser used for Raman spectrum detection is generally 532nm, 633nm or 785nm, and the scanning range is 200-2000 cm-1。
Generally, the enhancement effect on the SERS signal is better when the number of layers of the gold nanoparticle self-assembled thin film on the surface-enhanced raman scattering substrate is larger, but since the surface-enhanced raman scattering substrate is detected in an inverted manner in the above detection method, if the number of layers of the gold nanoparticle self-assembled thin film is too large, the transmittance of the laser and the SERS signal is reduced. Experience shows that the detection method adopts the surface enhanced Raman scattering substrate containing two layers of gold nanoparticle self-assembly films to carry out detection, so that the SERS signal can be enhanced maximally while the transmittance is ensured.
The beneficial technical effects of the invention are as follows: the invention provides a surface-enhanced Raman scattering substrate, a preparation method thereof and an in-situ rapid detection method, wherein the preparation method comprises the steps of adding a solvent into a gold nanoparticle solution, standing and layering; the solvent is immiscible with the gold nanoparticle solution and floats above the gold nanoparticle solution to form a layering phenomenon with a liquid-liquid interface; then injecting the alcohol solution into the gold nanoparticle solution, transferring the gold nanoparticles in the gold nanoparticle solution to a liquid-liquid interface, and further forming a compact gold nanoparticle self-assembly film through self-assembly; and transferring the gold nano self-assembly film onto a transparent substrate to prepare the surface enhanced Raman scattering substrate. From above, a dense and ordered gold nanoparticle arrangement can be formed on a liquid-liquid interface in a self-assembly mode, a gold nanoparticle self-assembly film is transferred to a surface enhanced raman scattering substrate formed on a transparent substrate, the surface enhanced raman scattering substrate can be used for detecting illegal additive molecules (including malachite green, rhodamine B, sudan red, basic orange and the like), once the illegal additive molecules enter gaps among the gold nanoparticles on the gold nanoparticle self-assembly film in the detection process (the gap width is usually less than 10nm and is called as a 'hot spot'), raman scattering signals (namely SERS signals) of the illegal additive molecules are strongly enhanced, and the sensitivity is high; and the compact and regular arrangement of the gold nanoparticles on the gold nanoparticle self-assembly film can ensure that the detected SERS signal has high uniformity and good stability and reproducibility. In addition, one side of the gold-containing nanoparticle self-assembly film on the surface enhanced Raman scattering substrate faces downwards and is in contact with the surface of the solution to be detected in an inverted mode, rapid in-situ real-time detection of illegal additive molecules in a liquid phase system is carried out, the object to be detected does not need to be damaged or extracted and then the object to be detected is dripped on the surface enhanced Raman scattering substrate for detection, and the operation is simple and convenient.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below.
FIG. 1 is a TEM photograph of gold nanoparticles in a gold nanoparticle solution prepared in step S2 of example 1;
FIG. 2 is a SEM photograph of the self-assembled gold nanoparticle thin film obtained in step S3 of example 1;
FIG. 3 is a scanning electron microscope photograph of the gold nanoparticle aggregate prepared in step S3 of comparative example 1;
FIG. 4 is a SERS detection spectrum of Malachite green molecules in lake water at different concentrations using the surface enhanced Raman scattering substrate of example 1;
FIG. 5 is a drawing of a lake water 10 using the surface enhanced Raman Scattering substrate of example 1-6A spectrogram of M malachite green molecule SERS detection reproducibility;
FIG. 6 is a graph of the surface enhanced Raman Scattering substrate of comparative example 1 applied to 10 in lake water-6And (3) a spectrogram of the reproducibility of the M malachite green molecule SERS detection.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A surface-enhanced Raman scattering substrate is prepared by the following steps:
s1, boiling 150mL of 2.2mM sodium citrate solution, quickly adding 1mL of 25mM chloroauric acid solution, and stopping heating after thermal reflux is carried out for 10min to obtain a gold nanoparticle seed solution;
s2, preparing a gold nanoparticle solution; the method specifically comprises the following steps:
① adding 1mL of a chloroauric acid solution with a concentration of 25mM into the gold nanoparticle seed solution obtained in step S1, and heating for 30 min;
②, repeating the step ① twice to finish the first round of growth of the gold nanoparticles to obtain a gold nanoparticle solution containing gold nanoparticles with the particle size of 15-28 nm;
③ taking 55mL of the gold nanoparticle solution prepared in the first round, adding 53mL of ultrapure water and 2mL of sodium citrate solution with the concentration of 60mM, and taking the solution as a gold nanoparticle seed solution for the second round to grow;
④ adding 1mL of chloroauric acid solution with the concentration of 25mM into the gold nanoparticle seed solution prepared in the step ③, and heating for 30 min;
⑤, repeating step ④ twice to finish the growth of the gold nanoparticles in the second round and obtain a gold nanoparticle solution in the second round;
⑥ taking 55mL of the second round of gold nanoparticle solution prepared in step ⑤, adding 53mL of ultrapure water and 2mL of sodium citrate solution with the concentration of 60mM, and taking the solution as a third round of grown gold nanoparticle seed solution;
⑦ adding 1mL of chloroauric acid solution with concentration of 25mM into the gold nanoparticle seed solution prepared in step ⑥, and heating for 30 min;
⑧ repeating step ⑦ twice to complete the growth of the third round of gold nanoparticles and obtain a third round of gold nanoparticle solution.
S3, adding 5mL of the gold nanoparticle solution prepared in the step S2 into a serum bottle, adding 5mL of hexane into the serum bottle, and suspending the hexane above the gold nanoparticle solution after the hexane is added to form a layering phenomenon with a liquid-liquid interface; then slowly injecting 2mL of ethanol solution into the gold nanoparticle solution, transferring the gold nanoparticles in the gold nanoparticle solution to a liquid-liquid interface, and forming a gold nanoparticle self-assembly film through self-assembly;
and S4, transferring the gold nanoparticle film self-assembly film prepared in the step S3 to a flexible transparent PDMS substrate by adopting an LB technology to form a PDMS-supported gold nanoparticle self-assembly monolayer film, and thus obtaining the surface enhanced Raman scattering substrate.
Example 2
A surface-enhanced Raman scattering substrate is prepared by the following steps:
s1, boiling 150mL of 2mM sodium citrate solution, quickly adding 1mL of 20mM chloroauric acid solution, and stopping heating after thermal reflux for 15min to obtain a gold nanoparticle seed solution;
s2, preparing a gold nanoparticle solution; the method specifically comprises the following steps:
① adding 1mL of 20mM chloroauric acid solution into the gold nanoparticle seed solution obtained in step S1, and heating for 30 min;
②, repeating step ① twice to finish the growth of the gold nanoparticles in the first round and obtain a gold nanoparticle solution in the first round;
③ taking 55mL of the first round of gold nanoparticle solution prepared in step ②, adding 53mL of ultrapure water and 2mL of 50mM sodium citrate solution, and using the solution as a second round of growing gold nanoparticle seed solution;
④ adding 1mL of chloroauric acid solution with the concentration of 25mM into the gold nanoparticle seed solution prepared in the step ③, and heating for 30 min;
⑤, repeating step ④ twice to finish the growth of the gold nanoparticles in the second round and obtain a gold nanoparticle solution in the second round;
⑥ taking 60mL of the second round of gold nanoparticle solution prepared in step ⑤, adding 53mL of ultrapure water and 2mL of sodium citrate solution with the concentration of 60mM, and taking the solution as a third round of grown gold nanoparticle seed solution;
⑦ adding 1mL of chloroauric acid solution with concentration of 25mM into the gold nanoparticle seed solution prepared in step ⑥, and heating for 30 min;
⑧ repeating step ⑦ twice to complete the growth of the third round of gold nanoparticles and obtain a third round of gold nanoparticle solution.
S3, adding 5mL of the gold nanoparticle solution prepared in the step S2 into a serum bottle, adding 5mL of hexane into the serum bottle, and suspending the hexane above the gold nanoparticle solution after the hexane is added to form a layering phenomenon with a liquid-liquid interface; then slowly injecting 2mL of ethanol solution into the gold nanoparticle solution, transferring the gold nanoparticles in the gold nanoparticle solution to a liquid-liquid interface, and forming a gold nanoparticle self-assembly film through self-assembly; preparing 3 gold nanoparticle self-assembly films by adopting the method;
and S4, sequentially transferring the 3 pieces of gold nanoparticle self-assembly thin films prepared in the step S3 to the same flexible transparent PMMA substrate by adopting an LB technology, and laminating to form a PMMA-supported gold nanoparticle self-assembly three-layer film to obtain the surface enhanced Raman scattering substrate.
Example 3
A surface-enhanced Raman scattering substrate is prepared by the following steps:
s1, boiling 150mL of 2.5mM sodium citrate solution, quickly adding 1mL of 30mM chloroauric acid solution, and stopping heating after thermal reflux is carried out for 15min to obtain a gold nanoparticle seed solution;
s2, preparing a gold nanoparticle solution; the method specifically comprises the following steps:
① adding 1mL of chloroauric acid solution with the concentration of 30mM into the gold nanoparticle seed solution obtained in the step S1, and heating for 30 min;
②, repeating step ① twice to finish the growth of the gold nanoparticles in the first round and obtain a gold nanoparticle solution in the first round;
③ taking 60mL of the first round of gold nanoparticle solution prepared in step ②, adding 53mL of ultrapure water and 2mL of 50mM sodium citrate solution, and using the solution as a second round of growing gold nanoparticle seed solution;
④ adding 1mL of chloroauric acid solution with the concentration of 30mM into the gold nanoparticle seed solution prepared in the step ③, and heating for 30 min;
⑤, repeating step ④ twice to finish the second round of growth of gold nanoparticles to obtain a gold nanoparticle solution;
s3, adding 5mL of the gold nanoparticle solution prepared in the step S2 into a serum bottle, adding 5mL of hexane into the serum bottle, and suspending the hexane above the gold nanoparticle solution after the hexane is added to form a layering phenomenon with a liquid-liquid interface; then slowly injecting 2mL of ethanol solution into the gold nanoparticle solution, transferring the gold nanoparticles in the gold nanoparticle solution to a liquid-liquid interface, and forming a gold nanoparticle self-assembly film through self-assembly; preparing 2 gold nanoparticle self-assembly films by adopting the method;
and S4, sequentially transferring the 2 gold nanoparticle self-assembly films prepared in the step S3 onto a flexible transparent PET substrate by adopting an LB technology, and stacking to form two PET-supported gold nanoparticle self-assembly film layers to obtain the surface-enhanced Raman scattering substrate.
Comparative example 1
A surface-enhanced Raman scattering substrate is prepared by the following steps:
s1, boiling 150mL of 2.2mM sodium citrate solution, quickly adding 1mL of 25mM chloroauric acid solution, and stopping heating after thermal reflux is carried out for 10min to obtain a gold nanoparticle seed solution;
s2, preparing a gold nanoparticle solution; the method specifically comprises the following steps:
① adding 1mL of a chloroauric acid solution with a concentration of 25mM into the gold nanoparticle seed solution obtained in step S1, and heating for 30 min;
②, repeating the step ① twice to finish the first round of growth of the gold nanoparticles to obtain a gold nanoparticle solution containing gold nanoparticles with the particle size of 15-28 nm;
③ taking 55mL of the gold nanoparticle solution prepared in the first round, adding 53mL of ultrapure water and 2mL of sodium citrate solution with the concentration of 60mM, and taking the solution as a gold nanoparticle seed solution for the second round to grow;
④ adding 1mL of chloroauric acid solution with the concentration of 25mM into the gold nanoparticle seed solution prepared in the step ③, and heating for 30 min;
⑤, repeating step ④ twice to finish the growth of the gold nanoparticles in the second round and obtain a gold nanoparticle solution in the second round;
⑥ taking 55mL of the second round of gold nanoparticle solution prepared in step ⑤, adding 53mL of ultrapure water and 2mL of sodium citrate solution with the concentration of 60mM, and taking the solution as a third round of grown gold nanoparticle seed solution;
⑦ adding 1mL of chloroauric acid solution with concentration of 25mM into the gold nanoparticle seed solution prepared in step ⑥, and heating for 30 min;
⑧ repeating step ⑦ twice to complete the growth of the third round of gold nanoparticles and obtain a third round of gold nanoparticle solution.
S3, sucking the gold nanoparticle solution prepared in the step S2 to drop on a flexible transparent PDMS substrate, and after the gold nanoparticle solution is dried, forming a gold nanoparticle aggregate on the PDMS substrate to obtain the surface enhanced Raman scattering substrate.
The transmission electron microscope is used to observe the gold nanoparticles in the gold nanoparticle solution prepared in step S2 in the method for preparing the surface enhanced raman scattering substrate according to example 1, and the obtained result is shown in fig. 1. As can be seen from fig. 1, the size of the gold nanoparticles in the gold nanoparticle solution prepared by step S2 in example 1 was uniform.
In addition, the self-assembled thin film of gold nanoparticles prepared in step S3 in example 1 and the gold nanoparticle aggregate prepared in step S3 in comparative example 1 were examined using a scanning electron microscope, and the results are shown in fig. 2 and 3. As can be seen from fig. 2, in example 1, the gold nanoparticles in the self-assembled gold nanoparticle thin film formed by self-assembly at the liquid-liquid interface are densely arranged, neat and ordered; as can be seen from fig. 3, in comparative example 1, the gold nanoparticle aggregate is disposed by directly sucking the solution drop on the substrate and then drying, and the arrangement of the gold nanoparticles is disordered.
The surface-enhanced raman scattering substrate of the above embodiments can be used for detection of illegal additive molecules (malachite green, rhodamine B, sudan red, basic orange, etc.), especially in liquid phase systems.
For example, the surface enhanced raman scattering substrate prepared in example 1 can be used to detect different concentrations of malachite green molecules in lake water. The specific configuration of the malachite green molecular concentration is respectively 10-6M (i.e., mol/L), 10-7M、10-8A lake aqueous solution of M, and then detected by the following method: by using the surface-enhanced raman scattering substrate in embodiment 1, one side of the surface-enhanced raman scattering substrate, which contains the gold nanoparticle self-assembled film, faces downward, and is in contact with the surface of the solution to be detected, and then laser is injected from one side of the surface-enhanced raman scattering substrate, which is away from the gold nanoparticle self-assembled film, and the focusing depth is adjusted to focus the laser on the gold nanoparticle self-assembled film, and then in-situ SERS detection of the illegal additive molecules in the liquid phase system is performed. The results of the detection are shown in FIG. 4. As can be seen from FIG. 4, when the surface-enhanced Raman scattering substrate is used for detecting malachite green molecules, the lower limit concentration of detection can reach 10-7M, the detection sensitivity is high. In addition, in the detection process, the substrate can float on the surface of the solution because the density of the substrate is less than that of the solution to be detected, but the gold nanoparticle self-assembly film on the surface of the substrate is immersed in the solution, once part of molecules to be detected in the solution to be detected enter gaps among the gold nanoparticles, Raman scattering signals of the molecules to be detected are obviously enhanced, so that real-time in-situ detection can be realized, the object to be detected does not need to be damaged or is dripped on the substrate after the object to be detected is extracted, and the operation is simple and.
In addition, the surface enhanced Raman scattering substrates prepared in example 1 and comparative example 1 were used for the treatment of 10% in lake water-6SERS detection is carried out on M malachite green molecules to investigate the detection stability and signal reproducibility of the M malachite green molecules to illegal additive molecules in liquid phase, and the obtained results are shown in FIGS. 5 and 6. Wherein, the surface enhanced Raman scattering base of the embodiment 1 of the invention is adoptedBottom to lake water 10-6The relative standard deviation of the reproducibility of SERS detection of M malachite green molecules is 3.2%, and 10% in lake water is subjected to Surface Enhanced Raman Scattering (SERS) by adopting the substrate in comparative example 1-6The relative standard deviation of reproducibility of SERS detection of M malachite green molecules was 40.8%. The results shown in fig. 5 and 6 prove that the gold nanoparticle self-assembled film formed by the liquid-liquid interface self-assembly and LB transfer techniques in example 1 of the present invention as the SERS substrate has better spectral reproducibility and detection stability than the gold nanoparticle aggregate formed by directly dropping the gold particle solution on the substrate in comparative example 1 as the SERS substrate.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A preparation method of a surface enhanced Raman scattering substrate is characterized by comprising the following steps:
s1, preparing a gold nanoparticle self-assembly film: adding a solvent into the gold nanoparticle solution, and standing for layering; the solvent is immiscible with the gold nanoparticle solution and floats above the gold nanoparticle solution; injecting an alcohol solution into the gold nanoparticle solution, transferring the gold nanoparticles in the gold nanoparticle solution to an interface between the gold nanoparticle solution and the solvent, and forming a gold nanoparticle self-assembly film through self-assembly;
s2, arranging at least one layer of the gold nanoparticle self-assembly film on a transparent substrate to obtain the surface-enhanced Raman scattering substrate.
2. The method for preparing a surface-enhanced raman scattering substrate according to claim 1, wherein the solvent is an alkane organic solvent.
3. The method for preparing a surface-enhanced raman scattering substrate according to claim 1, wherein, in step S1, the gold nanoparticle solution is prepared by a preparation method comprising the steps of:
a. boiling the reducing agent solution, adding a gold salt solution, and then carrying out thermal reflux treatment to obtain a gold nanoparticle seed solution;
b. and adding a gold salt solution into the gold nanoparticle seed solution, and heating to obtain the gold nanoparticle solution.
4. The method for preparing a surface-enhanced Raman scattering substrate according to claim 3, wherein in the step a, the reducing agent solution is selected from a citrate solution; in the step a and/or the step b, the gold salt solution is at least one selected from chloroauric acid solution and sodium chloroaurate solution.
5. The method for preparing the surface-enhanced Raman scattering substrate according to claim 3, wherein the step b specifically comprises the following steps:
① adding a gold salt solution into the gold nanoparticle seed solution, and then carrying out heating treatment;
② repeating step ① at least once to obtain gold nanoparticle solution;
or ③ adding reducing agent solution into the gold nanoparticle solution obtained in step ② to obtain a second round of gold nanoparticle seed solution, and preparing gold nanoparticle solution containing gold nanoparticles with required particle size according to step ① or steps ① and ②.
6. The method for preparing a surface-enhanced raman scattering substrate according to claim 1, wherein in step S2, the transparent substrate is a flexible transparent substrate; preferably, the material of the transparent substrate is at least one selected from polydimethylsiloxane, polymethyl methacrylate and polyethylene terephthalate.
7. The method for preparing a surface-enhanced Raman scattering substrate according to any one of claims 1 to 6, wherein at least one layer of the gold nanoparticle self-assembled film is disposed on a transparent substrate by using an LB technique in step S2.
8. The method for preparing a surface-enhanced raman scattering substrate according to claim 7, wherein an LB technique is specifically adopted in step S2, and two layers of the gold nanoparticle self-assembled film are disposed on a transparent substrate.
9. A surface-enhanced raman scattering substrate produced by the method for producing a surface-enhanced raman scattering substrate according to any one of claims 1 to 8.
10. An in-situ rapid detection method for illegal additive molecules in a liquid phase system is characterized by comprising the following steps: attaching and contacting one side of the gold-containing nanoparticle self-assembled film on the surface-enhanced Raman scattering substrate according to claim 9 with the surface of a solution to be detected, and then detecting by using a Raman spectrometer.
CN201911034538.3A 2019-10-29 2019-10-29 Surface-enhanced Raman scattering substrate, preparation method thereof and in-situ rapid detection method Pending CN110790220A (en)

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