CN108760716B - Surface-enhanced Raman spectrum wet tissue and preparation method and application thereof - Google Patents
Surface-enhanced Raman spectrum wet tissue and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a surface-enhanced Raman spectrum wet tissue, which comprises the steps of covering dendritic gold nanoparticles on the surface of a paper substrate subjected to cleaning treatment by a physical deposition method, immersing the substrate loaded with the dendritic gold nanoparticles into a humectant, and taking out the substrate to obtain the surface-enhanced Raman spectrum wet tissue. Also discloses a surface-enhanced Raman spectrum wet tissue and application thereof in trace residue detection. The surface-enhanced Raman spectrum wet tissue can not only finish the detection of dye molecules with particularly strong Raman signals such as rhodamine 6G and the like in field detection, but also be applied to chemical or biological probe molecules, and the probe molecules can comprise molecules with less strong Raman signals such as pesticide residues, stimulants, environmental pollutants, illegal additive molecules and the like.
Description
Technical Field
The invention belongs to the technical field of sensitive detection and analysis, and particularly relates to a surface-enhanced Raman spectrum wet tissue and a preparation method and application thereof.
Background
The Surface Enhanced Raman Spectroscopy (SERS) technology is an important microanalysis detection means, simple and clear spectral information can be obtained only by enhancing target molecules or groups in an extremely complex system, and an enhancement factor can be increased to 1014-1015This enables single molecule detection.
As is well known, the SERS technology requires a substrate matched with the SERS technology, and micro-detection is one of the most important applications of the SERS technology, which requires that the substrate must satisfy the following conditions: firstly, the sampling is simple and convenient and the operation is easy; second, the reproducibility and stability are good; thirdly, the detection sensitivity is high; fourthly, the preparation is simple, the carrying is convenient, the cost performance is high, and the product can survive the examination of the market.
Although the preparation method of the SERS substrate directly made of the carbon material, the noble metal nano material and the oxide material is simple and convenient, and the sensitivity is high, the disadvantages that the sampling is complicated, the stability is poor, and the SERS substrate cannot be directly applied to field detection cannot be overcome. For decades, many great developments are made around the preparation work of SERS substrates by various chemical methods and physical methods, at present, most of the SERS substrates used in laboratories use silicon wafers, glass sheets or porous alumina as supports, and precious metal nanostructures are dripped or modified on the supports, however, the support materials are expensive, the preparation process is complicated, and short plates with poor reproducibility and sensitivity and limited application range of the traditional SERS substrates cannot be made up for.
The sensitive detection capability of the SERS substrate is mainly based on the enhanced local electromagnetic field formed by the local surface plasmon resonance characteristic of the noble metal nanoparticles. So far, in order to further enhance the SERS signal intensity, a large number of noble metal nanoparticles with unique morphology, such as nano-dimers, nano-cubes, nano-stars, nano-sea urchins, etc., have been developed to obtain higher local electromagnetic field intensity. However, the noble metal has the defects of poor dispersibility and difficult adsorption, and although the noble metal has high chemical activity, the nano materials with special shapes are easy to deform, and further lose SERS activity. The dendritic gold nanoparticles are not easily adsorbed on a silicon wafer, a glass sheet or porous alumina as a support although the dendritic gold nanoparticles have high chemical activity.
Disclosure of Invention
The surface-enhanced Raman spectrum wet tissue disclosed by the invention greatly improves the reproducibility and stability of an SERS detection signal and improves the detection effect of SERS, is a high-sensitivity surface-enhanced Raman spectrum wet tissue, and can be applied to detection of trace residues such as pesticide residues, pollutants, illegal additives and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: the first aspect of the invention provides a preparation method of a surface-enhanced Raman spectrum wet tissue, wherein dendritic gold nanoparticles are covered on the surface of a paper substrate subjected to cleaning treatment by a physical deposition method, and the paper substrate loaded with the dendritic gold nanoparticles is immersed into a humectant and taken out to obtain the surface-enhanced Raman spectrum wet tissue. The wet-tissue-type SERS substrate has the characteristics of light weight, thinness, low cost, simple preparation process, large storage capacity, strong adsorption and enrichment capacity, capability of batch production and the like, and is hopeful to become the best choice for SERS detection.
Preferably, the paper substrate is selected from one of porous ultrathin fiber paper, mask paper or non-woven fabric.
Preferably, the cleaning treatment of the paper substrate comprises the following steps: completely spreading the dry paper substrate in absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, and repeatedly rinsing with double distilled water; then, the paper substrate is completely spread in double distilled water and is taken out after being subjected to ultrasonic treatment for 30 minutes, and the paper substrate is dried in a clean environment.
Preferably, the physical deposition method comprises the following steps: dispersing the dendritic gold nanoparticles into double distilled water to prepare a dendritic metal nano sol material; and (3) putting the paper substrate into a dendritic metal nano sol material to dip the dendritic gold nano particles.
Preferably, the paper substrate loaded with the dendritic gold nanoparticles is completely immersed into 80% glycerol solution to dip the humectant, and the paper substrate is obliquely taken out to obtain the surface-enhanced Raman spectrum wet tissue.
Preferably, the dendritic gold nanoparticles are synthesized by a surfactant method: mixing a surfactant and chloroauric acid to form a dendritic metal nano precursor aqueous solution, then adding an ascorbic acid solution, standing, repeatedly centrifuging, performing ultrasonic treatment, and collecting precipitate to obtain dendritic gold nanoparticles with a monomer structure of 100-2000 nm; wherein the molar ratio of the added surfactant, the chloroauric acid and the ascorbic acid is as follows: 6: 1.6: 5. the dendritic gold nano material with the particle size of 100nm-2000nm prepared according to the proportion is uniform in size and similar in structure, and can grow finer secondary dendrites, so that the dendritic gold nano material has more and better 'hot spot' structures, and the sensitivity of the SERS detection wet tissue is greatly enhanced. The product has good dispersibility, and can be quickly and effectively soaked and adsorbed by the substrate, thereby remarkably improving the reproducibility of SERS detection.
Preferably, the surfactant is prepared by laboratory, and the preparation steps are as follows: the mass ratio of the dihalogenated substance of long-chain alkane to the 1-methyl pyrrole is 1: 2, adding the mixture into an excessive acetone solution, and stirring for 30 minutes in a dark place; and refluxing and condensing for 48 hours at 70 ℃ under the protection of nitrogen atmosphere to obtain the surfactant.
Preferably, the dihalide of the long-chain alkane is selected from one of 1, 10-dibromodecane, 1, 8-dibromooctane and 1, 12-dibromododecane.
In another aspect, the invention provides a surface-enhanced raman spectroscopy wet tissue prepared by the preparation method of any one of the above-mentioned components.
The third aspect of the invention provides application of the surface-enhanced Raman spectrum wet tissue in trace residue detection.
The invention has the beneficial effects that:
(1) the surface-enhanced Raman spectrum wet tissue can not only finish the detection of dye molecules with particularly strong Raman signals such as rhodamine 6G and the like in field detection, but also be applied to chemical or biological probe molecules, and the probe molecules can comprise molecules with less strong Raman signals such as pesticide residues, stimulants, environmental pollutants, illegal additive molecules and the like.
(2) The wet tissue type SERS substrate simplifies sampling, enables the sample collection of SERS detection to be carried out from a laboratory to a supermarket, a field and an accident scene, and greatly expands the application range of the SERS technology.
(3) According to the invention, fiber paper, mask paper and non-woven fabric are preferably selected for cleaning treatment, and as the surface of the paper is very rough and has a large number of micro-nano structures and fold structures, and the surfaces of the micro-nano structures contain abundant hydroxyl groups, the gold nanoparticles can be fixed on the surface of the paper by physical adsorption or formation of surface hydrogen bond acting force.
(4) The dendritic gold nanoparticles are synthesized by adopting a surfactant method, and the material has abundant 'hot spot' structures, and is dendritic and pointed, so that the sensitivity of SERS detection can be greatly enhanced, and the detection limit is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a physical representation of a SERS wet wipe prepared according to the experimental procedure described in the summary of the invention;
FIG. 2 is a transmission electron microscope image of the supported nano-sized dendritic metal monomer in the wet wipe;
FIG. 3 is a absorption spectrogram obtained by using the wet tissue to collect a rhodamine 6G sample for SERS detection;
FIG. 4 is a diagram of the result of the reproducibility detection of the rhodamine 6G sample collected by the wet wipe of the invention;
FIG. 5 is a graph showing an absorption spectrum obtained by SERS detection of fipronil samples collected by using the wet tissue of the present invention;
FIG. 6 shows an absorption spectrum obtained by SERS detection of bisphenol A samples collected by the wet tissue of the present invention;
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the preparation work of the SERS substrate has been developed, but there still exist important practical problems of poor reproducibility, poor stability, difficult substrate preparation, tedious sampling, difficult storage, and the like. In view of this, the wet-tissue-type SERS substrate is light, thin, low in cost, simple in preparation process, large in storage capacity, strong in adsorption and enrichment capacity, and capable of being mass-produced, and is hopeful to become the best choice for SERS detection.
A preparation method of a surface-enhanced Raman spectrum wet tissue comprises the steps of covering dendritic gold nanoparticles on the surface of a paper substrate subjected to cleaning treatment through a physical deposition method, immersing the substrate loaded with the dendritic gold nanoparticles into a humectant, and taking out the substrate to obtain the surface-enhanced Raman spectrum wet tissue.
The paper substrate is selected because the surface of the paper is very rough, and a large number of micro-nano structures and fold structures exist, and the surfaces of the micro-nano structures contain abundant hydroxyl groups, so that the gold nanoparticles can be fixed on the surface of the paper through physical adsorption or surface hydrogen bond acting force.
The dendritic gold nanoparticles are selected as the adsorption object because the dendritic gold nanoparticles have the property of uniform and easily-dispersed colloid, and the dendritic structures are easy to adsorb and not easy to fall off from the substrate material, so that the dendritic fractal structures have huge application space in the aspect of SERS detection because of the characteristics of more complex crystal structures, large specific surface, high activity, sharp edge structures and the like in numerous nano structures with different appearances. The dendritic gold nanoparticles have abundant 'hot spot' structures, and the dendritic and pointed structural characteristics can greatly enhance the sensitivity of SERS detection and reduce the detection limit.
Compared with the existing SERS substrate preparation technology, the preparation method of the surface-enhanced Raman spectrum wet tissue disclosed by the invention has the advantages of low cost, high sensitivity and repeatability, good stability, strong adsorption and enrichment capacities, simple and convenient preparation process, convenience in carrying and capability of batch production. And the disadvantages that the application range of the traditional and laboratory SERS substrates is limited, and the traditional and laboratory SERS substrates cannot be directly applied to field sampling and detection are overcome.
The paper substrate is selected from one of porous ultrathin fiber paper, mask paper or non-woven fabric. Porous ultrathin fiber paper, mask paper and non-woven fabric are selected, the surface of the paper is very rough, and a large number of micro-nano structures and fold structures are arranged on the surface of the paper, and the surfaces of the micro-nano structures contain abundant hydroxyl groups, so that the gold nanoparticles can be fixed on the surface of the paper through physical adsorption or surface hydrogen bond acting force.
Cleaning and processing the substrate: completely spreading the dry paper substrate in absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, and repeatedly rinsing with double distilled water; then, the paper substrate is completely spread in double distilled water and is taken out after being subjected to ultrasonic treatment for 30 minutes, and the paper substrate is dried in a clean environment.
The pretreatment of the paper substrate can effectively clean the surface of the wet tissue, and can effectively prevent other impurities attached to the wet tissue from influencing the detection of the substance to be detected.
Preferably, the physical deposition method comprises the following steps: dispersing the dendritic gold nanoparticles into double distilled water to prepare a dendritic metal nano sol material; the substrate is put into a dendritic metal nano sol material to be dipped with dendritic gold nano particles. The preparation method is simple and convenient to operate.
Preferably, the substrate loaded with the dendritic gold nanoparticles is completely immersed into an 80% glycerol solution to dip the humectant, and the substrate is taken out in an inclined manner to obtain the surface-enhanced Raman spectrum wet tissue.
Preferably, the dendritic gold nanoparticles are synthesized by a surfactant method: mixing a surfactant and chloroauric acid to form a dendritic metal nano precursor aqueous solution, then adding an ascorbic acid solution, standing, repeatedly centrifuging, performing ultrasonic treatment, and collecting precipitate to obtain dendritic gold nanoparticles with a monomer structure of 100-2000 nm; wherein the molar ratio of the added surfactant, the chloroauric acid and the ascorbic acid is as follows: 6: 1.6: 5.
the gold nanoparticles are synthesized by adopting a surfactant method, the surfactant method is simple and convenient to prepare and low in risk, and compared with methods such as an electrochemical deposition method and a metal replacement method, the surfactant method can effectively reduce the agglomeration of the product, effectively disperses the product, and can be quickly and effectively soaked and adsorbed by the substrate, so that the repeatability of SERS detection is effectively improved.
The prepared dendritic gold nano material with the particle size of 100nm-2000nm is uniform in size and similar in structure, and can grow finer secondary dendrites, so that the dendritic gold nano material has more and better hot spot structures, and the sensitivity of SERS detection wet tissue is greatly enhanced. The product has good dispersibility, and can be quickly and effectively soaked and adsorbed by the substrate, thereby remarkably improving the reproducibility of SERS detection.
Preferably, the surfactant is prepared by laboratory, and the preparation steps are as follows: the mass ratio of the dihalogenated substance of long-chain alkane to the 1-methyl pyrrole is 1: 2, adding the mixture into an excessive acetone solution, and stirring for 30 minutes in a dark place; and refluxing and condensing for 48 hours at 70 ℃ under the protection of nitrogen atmosphere to obtain the surfactant.
The reason for selecting the dihalogenated product of the long-chain alkane to prepare the surfactant is that the long-chain alkane surfactant has a regulating and controlling effect on the formation of the gold nano-branched structure.
Preferably, the dihalide of the long-chain alkane is selected from one of 1, 10-dibromodecane, 1, 8-dibromooctane and 1, 12-dibromododecane.
A surface enhanced Raman spectroscopy wet wipe prepared according to the preparation method of any one of the preceding claims.
An application of a surface-enhanced Raman spectrum wet tissue in trace residue detection. The surface-enhanced Raman spectrum wet tissue can not only finish detection of dye molecules with particularly strong Raman signals such as rhodamine 6G and the like in field detection, but also be applied to chemical or biological probe molecules, wherein the probe molecules can comprise molecules with less strong Raman signals such as pesticide residues, stimulants, environmental pollutants, illegal additive molecules and the like.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
All reagents used in the examples are commercially available from manufacturers and lots as follows:
1, 10-dibromodecane: purchased from Shanghai Michelin Biochemical technology, Inc., lot number: c10097715;
methyl pyrrolidine: purchased from Shanghai Michelin Biochemical technology, Inc., lot number: c10099940;
gold chloride acid: purchased from national pharmaceutical group chemical agents limited, lot number: 20170313, respectively;
ascorbic acid purchased from national pharmaceutical group chemical agents limited, lot number: 20170524, respectively;
glycerol: purchased from national pharmaceutical group chemical agents limited, lot number: 20170909, respectively;
rhodamine 6G: purchased from shanghai alatin biochemical science and technology, inc, lot number: 200708074, respectively;
fipronil: purchased from shanghai alatin biochemical science and technology, inc, lot number: g1727032;
bisphenol A was purchased from Bailingwei science and technology, Inc. under batch No. L H60M 21.
Example 1
(1) Putting the dried white fiber paper into absolute ethyl alcohol to be completely spread, carrying out ultrasonic treatment for 30 minutes, and repeatedly rinsing with double distilled water; then, completely spreading the fiber paper in double distilled water, performing ultrasonic treatment for 30 minutes, taking out, and drying in a clean environment;
(2) adding 9 parts of 0.1 mol/L surfactant aqueous solution into 100 parts of double distilled water, stirring uniformly, adding 1 part of 0.24 mol/L chloroauric acid aqueous solution, mixing uniformly to form a yellow precursor, adding 7.5 parts of 0.1 mol/L ascorbic acid aqueous solution into the precursor, quickly changing the solution from the previous yellow color to blue-gray color, standing for 24 hours to cure and stabilize the dendritic structure, centrifuging for 15 minutes at 8000 rpm, pouring out the supernatant, adding a proper amount of double distilled water, performing ultrasonic washing to remove the supernatant, repeating the operation three times to obtain dendritic gold nanoparticles with a monomer structure of 100nm-2000nm, wherein the specific synthetic method of the related surfactant comprises the steps of adding 1, 10-dibromodecane and 1-methylpyrrole into excess acetone solution according to the mass ratio of 1: 2, stirring for 30 minutes in a dark place, and performing reflux condensation for 48 hours at 70 ℃ under the protection of nitrogen to obtain the surfactant;
(3) dispersing the gold nanoparticles in the step (2) into double distilled water to prepare a metal nano sol material;
(4) putting the dry fiber paper prepared in the step (1) into the metal nano sol material prepared in the step (3) to soak and dip gold nano particles;
(5) and (3) completely immersing the fiber paper initially loaded with the gold nanoparticles obtained in the step (4) into an 80% glycerol solution to dip the humectant, taking out the fiber paper in an inclined mode after a moment to obtain the surface-enhanced Raman spectrum wet tissue, completely spreading the surface-enhanced Raman spectrum wet tissue on clean and dry fiber paper, and sealing and storing the fiber paper in a self-sealing bag.
The prepared surface-enhanced Raman spectrum wet tissue is loaded with dendritic gold nanoparticles with a high hot spot structure, is sealed and stored after being moisturized by a humectant, and the finished product is shown in figure 1, and figure 2 is a transmission electron microscope image of dendritic gold nanoparticles included in the wet tissue. And (4) repeatedly wiping the surfaces of the apples sprayed with the rhodamine 6G by using wet tissues respectively to finish sampling. And repeatedly wiping the surfaces of the apples sprayed with the rhodamine 6G by 20 pieces of wet tissues to finish sampling of the rhodamine 6G sample in the repeated detection experiment. The wet piece of cloth after will accomplishing the sample carries out SERS respectively and detects, and the SERS condition is laser wavelength: 638 nm; integration time: 3 seconds; integration times: 2 times.
Rhodamine 6G, also known as rose bengal 6G, is a laser dye, a fluorescent dye, widely used for detecting mitochondrial membrane potential, and also commonly used for apoptosis detection. As can be seen from the graph 3, the wet tissue can simply, conveniently and effectively sample the rhodamine sample on the surface of the apple, the rhodamine 6G sample collected by the wet tissue is detected by using the SERS technology, and an extremely obvious SERS spectrum absorption peak of the rhodamine 6G is obtained, which indicates that the sampling mode is effective.
In order to verify the reproducibility of the wet tissue, 20 times of repeated operations are carried out on a rhodamine 6G sample, a reproducibility spectrogram for testing the wet tissue sampling by using rhodamine 6G as a probe molecule is shown in figure 4, the spectral line shows good repeatability, and the repeatability of the wet tissue is proved to be credible, so that the wet tissue has great application potential and good reproducibility in the aspects of rhodamine detection and sampling.
Example 2
(1) Putting the dried facial mask paper into absolute ethyl alcohol to be completely spread, carrying out ultrasonic treatment for 30 minutes, and repeatedly rinsing with double distilled water; then completely spreading the facial mask paper in double distilled water, performing ultrasonic treatment for 30 minutes, taking out, and drying in a clean environment;
(2) adding 9 parts of 0.1 mol/L surfactant aqueous solution into 100 parts of double distilled water, stirring uniformly, adding 1 part of 0.24 mol/L chloroauric acid aqueous solution, mixing uniformly to form a yellow precursor, adding 7.5 parts of 0.1 mol/L ascorbic acid aqueous solution into the precursor, quickly changing the solution from the previous yellow color to blue-gray color, standing for 24 hours to cure and stabilize the dendritic structure, centrifuging for 15 minutes at 8000 rpm, pouring out the supernatant, adding a proper amount of double distilled water, performing ultrasonic washing to remove the supernatant, repeating the operation three times to obtain dendritic gold nanoparticles with a monomer structure of 100nm-2000nm, wherein the specific synthetic method of the related surfactant comprises the steps of adding 1, 8-dibromooctane and 1-methylpyrrole into excess acetone solution according to the mass ratio of 1: 2, stirring for 30 minutes in a dark place, and performing reflux condensation for 48 hours at 70 ℃ under the protection of nitrogen atmosphere to obtain the surfactant;
(3) dispersing the gold nanoparticles in the step (2) into double distilled water to prepare a metal nano sol material;
(4) putting the dry facial mask paper prepared in the step (1) into the metal nano sol material prepared in the step (3) to soak and dip gold nano particles;
(5) and (3) completely immersing the facial mask paper initially loaded with the gold nanoparticles obtained in the step (4) into an 80% glycerol solution to dip the humectant, taking out the facial mask paper in an inclined mode after a moment to obtain the surface enhanced Raman spectrum wet tissue, completely spreading the surface enhanced Raman spectrum wet tissue on clean and dry facial mask paper, and sealing and storing the surface enhanced Raman spectrum wet tissue in a self-sealing bag.
Fipronil is a phenylpyrazole insecticide, which is photolyzed to produce a highly toxic and refractory photolysis product, and is defined by the world health organization as a drug with moderate toxicity to humans. And repeatedly wiping the surface of the egg soaked by the fipronil solution by using a wet tissue to finish sampling. The wet piece of cloth after will accomplishing the sample carries out SERS and detects, and the SERS condition is laser wavelength: 638 nm; integration time: 3 seconds; integration times: 2 times.
As can be seen from the figure 5, the wet tissue can simply, conveniently and effectively complete the sampling of fipronil, the sampled wet tissue is subjected to SERS detection, the spectrum result shows a strong fipronil characteristic absorption peak, the absorption peak intensity is high, the peak separation effect is good, and the embodiment result shows that the sampling mode has a good application prospect in the detection aspect of fipronil residue in eggs.
Example 3
(1) Putting the dried non-woven fabric into absolute ethyl alcohol to be completely spread, carrying out ultrasonic treatment for 30 minutes, and repeatedly rinsing with double distilled water; then, completely spreading the non-woven fabric in double distilled water, performing ultrasonic treatment for 30 minutes, taking out, and drying in a clean environment;
(2) adding 9 parts of 0.1 mol/L surfactant aqueous solution into 100 parts of double distilled water, stirring uniformly, adding 1 part of 0.24 mol/L chloroauric acid aqueous solution, mixing uniformly to form a yellow precursor, adding 7.5 parts of 0.1 mol/L ascorbic acid aqueous solution into the precursor, quickly changing the solution from the previous yellow color to blue-gray color, standing for 24 hours to cure and stabilize the dendritic structure, centrifuging for 15 minutes at 8000 rpm, pouring out the supernatant, adding a proper amount of double distilled water, performing ultrasonic washing to remove the supernatant, repeating the operation three times to obtain dendritic gold nanoparticles with a monomer structure of 100nm-2000nm, wherein the specific synthetic method of the related surfactant comprises the steps of adding 1, 12-dibromododecane and 1-methylpyrrole into excess acetone solution according to the mass ratio of 1: 2, stirring for 30 minutes in a dark place, and performing reflux condensation for 48 hours at 70 ℃ under the protection of nitrogen to obtain the surfactant;
(3) dispersing the gold nanoparticles in the step (2) into double distilled water to prepare a metal nano sol material;
(4) putting the dried non-woven fabric prepared in the step (1) into the metal nano sol material prepared in the step (3) to soak and dip gold nano particles;
(5) and (3) completely immersing the non-woven fabric initially loaded with the gold nanoparticles obtained in the step (4) into an 80% glycerol solution to dip the humectant, taking out the non-woven fabric after being inclined for a moment to obtain the surface enhanced Raman spectrum wet tissue, completely spreading the surface enhanced Raman spectrum wet tissue on clean and dry non-woven fabric, and sealing and storing the non-woven fabric in a self-sealing bag.
Bisphenol A is an important organic chemical raw material and is used for manufacturing plastic bottles, inner coatings of food and beverage cans, suction cups for infants and the like, but bisphenol A can also cause endocrine dyscrasia and threaten the health of fetuses and children. Cancer and obesity caused by metabolic disorders are also considered to be associated therewith. And repeatedly wiping the surface of the milk powder tank sprayed with the bisphenol A by using a wet tissue to finish sampling. The wet piece of cloth after will accomplishing the sample carries out SERS and detects, and the SERS condition is laser wavelength: 638 nm; integration time: 3 seconds; integration times: 2 times.
As can be seen from FIG. 6, the wet tissue of the invention can simply, conveniently and effectively complete the sampling of bisphenol A, and the SERS spectrum with the obvious characteristic absorption peak is obtained after the SERS detection is carried out on the wet tissue which completes the sampling, which shows that the sampling mode can also obtain good effect when being applied to the detection of the bisphenol A residue on the milk powder tank.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (6)
1. A preparation method of a surface-enhanced Raman spectrum wet tissue is characterized by comprising the following steps: covering dendritic gold nanoparticles on the surface of the cleaned paper substrate by a physical deposition method, immersing the paper substrate loaded with the dendritic gold nanoparticles into a humectant, and taking out to obtain the surface-enhanced Raman spectrum wet tissue;
the paper substrate is selected from one of porous ultrathin fiber paper, mask paper or non-woven fabric;
cleaning the paper substrate: completely spreading the dry paper substrate in absolute ethyl alcohol, carrying out ultrasonic treatment for 30 minutes, and repeatedly rinsing with double distilled water; then, completely spreading the paper substrate in double distilled water, carrying out ultrasonic treatment for 30 minutes, taking out, and drying in a clean environment;
the physical deposition method comprises the following steps: dispersing the dendritic gold nanoparticles into double distilled water to prepare a dendritic metal nano sol material; soaking the paper substrate in a dendritic metal nano sol material to dip dendritic gold nanoparticles;
and completely immersing the substrate loaded with the dendritic gold nanoparticles into 80% glycerol solution to dip the humectant, and obliquely taking out the substrate to obtain the surface-enhanced Raman spectrum wet tissue.
2. The method of claim 1, wherein: the dendritic gold nanoparticles are synthesized by adopting a surfactant method: mixing a surfactant and chloroauric acid to form a dendritic metal nano precursor aqueous solution, then adding an ascorbic acid solution, standing, repeatedly centrifuging, performing ultrasonic treatment, and collecting precipitate to obtain dendritic gold nanoparticles with a monomer structure of 100-2000 nm; wherein the molar ratio of the added surfactant, the chloroauric acid and the ascorbic acid is as follows: 6: 1.6: 5.
3. the method of claim 2, wherein: the surfactant is prepared by adopting a laboratory, and the preparation steps are as follows: the mass ratio of the dihalogenated substance of long-chain alkane to the 1-methyl pyrrole is 1: 2, adding the mixture into an excessive acetone solution, and stirring for 30 minutes in a dark place; and refluxing and condensing for 48 hours at 70 ℃ under the protection of nitrogen atmosphere to obtain the surfactant.
4. The production method according to claim 3, characterized in that: the dihalide of the long-chain alkane is one of 1, 10-dibromodecane, 1, 8-dibromooctane and 1, 12-dibromododecane.
5. A surface-enhanced Raman spectroscopy wet wipe produced by the production method according to any one of claims 1 to 4.
6. The use of a surface-enhanced Raman spectroscopy wet wipe according to claim 5 for trace residue detection.
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