CN114324159A - Cleaning and reassembling method for surface enhanced Raman spectrum substrate - Google Patents
Cleaning and reassembling method for surface enhanced Raman spectrum substrate Download PDFInfo
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- CN114324159A CN114324159A CN202111601997.2A CN202111601997A CN114324159A CN 114324159 A CN114324159 A CN 114324159A CN 202111601997 A CN202111601997 A CN 202111601997A CN 114324159 A CN114324159 A CN 114324159A
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- 239000000758 substrate Substances 0.000 title claims abstract description 112
- 238000000479 surface-enhanced Raman spectrum Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004140 cleaning Methods 0.000 title claims abstract description 21
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000003795 desorption Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- OJIYIVCMRYCWSE-UHFFFAOYSA-M Domiphen bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCOC1=CC=CC=C1 OJIYIVCMRYCWSE-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 36
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 22
- 239000013078 crystal Substances 0.000 description 17
- 238000001069 Raman spectroscopy Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
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- MEPOPDXPZMVZCW-UHFFFAOYSA-M [Br-].C(CCCCCCCCCCC)CC[N+](OC1=CC=CC=C1)(C)C Chemical compound [Br-].C(CCCCCCCCCCC)CC[N+](OC1=CC=CC=C1)(C)C MEPOPDXPZMVZCW-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Abstract
The invention discloses a method for cleaning and reassembling a surface enhanced Raman spectrum substrate, which comprises the following steps: s1, soaking the used surface-enhanced Raman spectrum substrate in desorption liquid; then taking out the substrate, and rinsing with water to obtain an intermediate substrate; and S2, placing the intermediate substrate into an aqueous solution A, reacting, taking out the substrate and drying, wherein the solute of the aqueous solution A is one of a mixture of a reducing agent and a quaternary ammonium compound and a mixture of the reducing agent, the quaternary ammonium compound and a surfactant. The method can clean and reassemble the used surface-enhanced Raman spectrum substrate, thereby realizing recycling, has simple and convenient operation and lower cost, and overcomes the defect that the detection function of the surface-enhanced Raman spectrum substrate is lost by dripping the substance to be detected.
Description
Technical Field
The invention relates to the technical field of surface-enhanced Raman spectroscopy, in particular to a method for cleaning and reassembling a surface-enhanced Raman spectroscopy substrate.
Background
The surface enhanced raman spectroscopy has extremely high surface detection sensitivity and selectivity, is an important tool for researching interfaces, and is widely applied to various fields such as electrochemical adsorption, biomedicine, environmental science, material science, geological science and the like, particularly the rapid development of nanotechnology in recent years, and the surface enhanced raman Scattering Effect (SERS) detection is more widely applied to the aspects of quantitative detection and trace substance analysis.
The precondition for generating the surface enhanced raman scattering effect is that the substrate must have nanometer-scale roughness or particles with the particle size of tens to hundreds of nanometers are prepared, so that the establishment of a proper nano structure is the key for generating the SERS effect. A good SERS substrate should have the condition (1) that it has higher sensitivity; (2) signals at different positions on the surface of the substrate are uniform; (3) the stability and the reproducibility are good; (4) a clean substrate. At present, metals with strong enhancement effect are mainly B group metals such as Au, Ag, Cu and the like, and the nano structure of the metal can generate huge enhancement effect.
Studies have shown that the greatest enhancement is obtained with the first layer of molecules adsorbed on the metal surface. Although SERS has a long-range enhancing effect, the enhancing effect is often exponentially reduced with the increase of the distance, and is related to the surface morphology and physical properties of metals and the effects of adsorbed molecules and metals, so that dropping a substance to be detected can cause the SERS substrate to lose the detection effect. At present, SERS substrates prepared from B group metals such as Au, Ag, Cu and the like are commonly used, the preparation process of the SERS substrates is complex, the consumed time is long, the preparation cost is high, the SERS substrates are only used for one time, and irreversible damage can be caused to the environment. Therefore, the research on the clean and re-assembly of the SERS substrate has important significance for the cyclic utilization of the SERS substrate.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for cleaning and reassembling a surface enhanced Raman spectrum substrate, the method can clean and reassemble the used surface enhanced Raman spectrum substrate so as to realize cyclic utilization, the method is simple and convenient to operate and low in cost, and the defect that the detection function of the surface enhanced Raman spectrum substrate is lost due to the dropwise addition of a substance to be detected is overcome.
The invention provides a method for cleaning and reassembling a surface enhanced Raman spectrum substrate, which comprises the following steps:
s1, soaking the used surface-enhanced Raman spectrum substrate in desorption liquid; then taking out the substrate, and rinsing with water to obtain an intermediate substrate;
and S2, placing the intermediate substrate into an aqueous solution A, reacting, taking out the substrate and drying, wherein the solute of the aqueous solution A is one of a mixture of a reducing agent and a quaternary ammonium compound and a mixture of the reducing agent, the quaternary ammonium compound and a surfactant.
Preferably, in S1, the desorption solution consists of concentrated hydrochloric acid, concentrated nitric acid and water.
Preferably, the volume ratio of the concentrated hydrochloric acid to the concentrated nitric acid to the water is 2.8-3.2:0.9-1.1: 5-50.
Preferably, in S1, the soaking time is 1-20S.
Preferably, in S1, the temperature of the water is 30-40 ℃.
Preferably, in S1, the rinsing time is 10-30S.
Preferably, in S2, the reducing agent is at least one of sodium borohydride and lithium aluminum hydride.
In S2, the quaternary ammonium compound is at least one of dodecyltrimethylammonium bromide, dodecyldimethylbenzylammonium bromide, dodecylbenzylquaternary ammonium salt, dialkyl quaternary ammonium salt, alkylpyridinium quaternary ammonium salt, and (2-hydroxyethyl) trimethylammonium hydroxide.
The dodecyl trimethyl ammonium bromide, the dodecyl dimethyl phenoxyethyl ammonium bromide, the dodecyl dimethyl benzyl ammonium bromide, the dodecyl benzyl quaternary ammonium salt, the dialkyl quaternary ammonium salt, the alkyl pyridine quaternary ammonium salt and the like are not only quaternary ammonium compounds, but also surfactants and have dispersibility, so that when the dodecyl trimethyl ammonium bromide, the dodecyl dimethyl phenoxyethyl ammonium bromide, the dodecyl dimethyl benzyl ammonium bromide, the dialkyl quaternary ammonium salt, the alkyl pyridine quaternary ammonium salt and the like are used as quaternary ammonium compounds, the surfactants can not be added any more, and the surfactants can also be added.
Preferably, in S2, the surfactant is an alkylbenzene sulfonate, an alkyl sulfonate salt, an alkyl sulfonate, an alkyl sulfate、Alkyl sulfonic acetamide, dodecyl trimethyl ammonium bromide, dodecyl dimethyl phenoxy ethyl ammonium bromide, dodecyl dimethyl benzylAt least one of ammonium bromide, dodecyl benzyl quaternary ammonium salt, dialkyl quaternary ammonium salt and alkyl pyridine quaternary ammonium salt.
The alkylbenzene sulfonate may be sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, etc.
Preferably, in S2, the molar ratio of the quaternary ammonium compound to the reducing agent is 100:2.5 to 3.5.
Preferably, in S2, when the solute of the aqueous solution A is a mixture of a reducing agent and a quaternary ammonium compound, the concentration of the quaternary ammonium compound is 0.09-0.11 mol/L.
Preferably, in S2, when the solute of the aqueous solution a is a mixture of a reducing agent, a quaternary ammonium compound and a surfactant, the molar ratio of the quaternary ammonium compound to the surfactant is 1: 0.5-0.7.
Preferably, in S2, when the solute of the aqueous solution a is a mixture of a reducing agent, a quaternary ammonium compound and a surfactant, the concentration of the quaternary ammonium compound is 0.06 to 0.07 mol/L.
Preferably, in S2, the reaction temperature is 25-30 ℃.
Preferably, in S2, the reaction time is 15-30 min.
Preferably, in S2, the drying temperature is 25 to 30 ℃, and the relative humidity at the time of drying is 70 to 80%.
The water is ultrapure water.
Has the advantages that:
firstly, desorbing and cleaning an object to be detected adsorbed on a surface-enhanced Raman spectrum substrate, then separating the surface-enhanced Raman spectrum substrate from a desorption treatment environment before the surface-enhanced Raman spectrum substrate is damaged, and finally reassembling a protective layer on the treated surface-enhanced Raman spectrum substrate by using a protective agent;
the desorption solution is a mixed solution of concentrated hydrochloric acid, concentrated nitric acid and water, has strong oxidizing property, can desorb most of substances to be detected, and does not destroy the detection performance of the surface enhanced Raman spectrum substrate by selecting proper soaking desorption time, so that the surface enhanced Raman spectrum substrate can be desorbed circularly, and the front detection and the back detection are not interfered;
in the environment of resisting oxidation and preventing agglomeration, the quaternary ammonium compound is used for reaction, and the protective layer is reassembled on the surface of the surface-enhanced Raman spectrum substrate, so that the detection performance of the surface-enhanced Raman spectrum substrate cannot be interfered, the surface uniformity of the substrate can be improved, the attenuation degree of the surface-enhanced Raman spectrum effect before and after the surface-enhanced Raman spectrum substrate is treated can be effectively reduced, and the detection performance of the substrate before and after cleaning treatment can be ensured; the addition of the surfactant can prevent agglomeration and promote the formation of a protective layer; the quaternary ammonium compound and the surfactant of proper types are selected, so that the surface uniformity of the substrate can be further improved, and the attenuation degree of the surface enhanced Raman spectrum effect before and after the surface enhanced Raman spectrum substrate is treated can be further reduced; the method is simple to operate, can realize the recycling of the surface enhanced Raman spectrum substrate, and overcomes the defect that the traditional surface enhanced Raman spectrum substrate can only be used once.
Drawings
Fig. 1 is a photograph of a gold nanorod substrate after detection of crystal violet before and after reassembly in example 1, wherein a is before reassembly and b is after reassembly.
FIG. 2 is a Raman spectrum of crystal violet detection using a gold nanorod substrate before and after reassembly in example 1, wherein a is before reassembly and b is after reassembly.
Fig. 3 is a photograph of the gold nanorod substrate after ice toxicity detection before and after reassembly in example 2, wherein a is before reassembly and b is after reassembly.
FIG. 4 is a Raman spectrum of ice toxicity detection using a gold nanorod substrate before and after reassembly in example 2, wherein a is before reassembly and b is after reassembly.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A method for cleaning and reassembling a surface enhanced Raman spectrum substrate comprises the following steps:
s1, preparing a gold nanorod substrate, and dripping 2 mu L of 10-7The mol/L crystal violet solution is dried and then is carried outSERS detection, wherein each substrate is detected for 5 times, and a Raman spectrogram is recorded;
putting 3mL of concentrated hydrochloric acid, 1mL of concentrated nitric acid and 5mL of water in a beaker, and uniformly mixing to obtain desorption solution; placing the gold nanorod substrate dropwise added with the crystal violet solution for use in desorption solution for soaking for 10s, then quickly taking out the substrate, placing the substrate in ultrapure water of 25 ℃ for rinsing for 30s, and then airing in an oven of 25 ℃ to obtain an intermediate substrate;
s2, uniformly mixing 100mL of dodecyl dimethyl phenoxy ethyl ammonium bromide aqueous solution with the concentration of 0.1mol/L, 60mL of sodium dodecyl benzene sulfonate aqueous solution with the concentration of 0.1mol/L and 3mL of sodium borohydride aqueous solution with the concentration of 0.1mol/L, adding the mixture into an intermediate substrate, standing and reacting for 30min at 28 ℃, taking out, placing in a constant temperature and humidity box with the temperature of 25 ℃ and the relative humidity of 70%, and airing to obtain a recombined surface enhanced Raman spectrum substrate;
taking the surface enhanced Raman spectroscopy substrate which is reassembled, and dripping 2 mu L of 10-7Carrying out SERS detection on the crystal violet solution in mol/L after air drying, detecting each substrate for 5 times, and recording a Raman spectrogram; and compared with the Raman spectrogram measured on the gold nanorod substrate before recombination in S1, and the result is shown in a figure 1-2.
Fig. 1 is a photograph of a gold nanorod substrate after detection of crystal violet before and after reassembly in example 1, wherein a is before reassembly and b is after reassembly.
FIG. 2 is a Raman spectrum of crystal violet detection using a gold nanorod substrate before and after reassembly in example 1, wherein a is before reassembly and b is after reassembly.
As can be seen from fig. 1 and 2: in the Raman spectrum before reassembly, at 720cm-1、915cm-1、937cm-1、1170cm-1、1584cm-1、1617cm-1A characteristic peak of the crystal violet solution appears, which shows that the gold nanorod substrate has good detection performance; in the Raman spectrogram after the recombination, the characteristic peak of the crystal violet solution is the same as that before the recombination, and the intensity of the characteristic peak is almost the same as that before the recombination (see Table 1), thereby showing that the detection performance of the recombined gold nanorod substrate obtained by adopting the method of the invention is not damagedBad, the detection performance is good, can reuse.
TABLE 1 Strength results of Crystal Violet characteristic peaks before and after reassembly
| Number of |
1 st time | 2 nd time | 3 rd time | 4 th time | 5 th time | Average |
| Before reassembly | 4550 | 4620 | 4580 | 4650 | 4290 | 4538 |
| After being reassembled | 4890 | 4750 | 3990 | 4200 | 4170 | 4400 |
Example 2
A method for cleaning and reassembling a surface enhanced Raman spectrum substrate comprises the following steps:
s1, preparing a gold nanorod substrate, dripping 2 mu L of 10ng/mg of glacial toxic solution, carrying out SERS detection, detecting each substrate for 5 times, and recording a Raman spectrogram;
putting 3mL of concentrated hydrochloric acid, 1mL of concentrated nitric acid and 5mL of water in a beaker, and uniformly mixing to obtain desorption solution; placing the gold nanorod substrate dropwise added with the crystal violet solution for use in desorption solution for soaking for 10s, then quickly taking out the substrate, placing the substrate in ultrapure water of 25 ℃ for rinsing for 30s, and then airing in an oven of 25 ℃ to obtain an intermediate substrate;
s2, uniformly mixing 100mL of dodecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.1mol/L and 3mL of sodium borohydride aqueous solution with the concentration of 0.1mol/L, adding the mixture into an intermediate substrate, standing and reacting for 30min at 28 ℃, taking out the intermediate substrate, placing the intermediate substrate in a constant-temperature constant-humidity box with the temperature of 25 ℃ and the relative humidity of 70%, and airing to obtain a recombined surface-enhanced Raman spectrum substrate;
taking a surface-enhanced Raman spectrum substrate which is re-assembled, dropwise adding 2 mu L of 10ng/mg glacial toxic solution, carrying out SERS detection, detecting each substrate for 5 times, and recording a Raman spectrogram; and compared with the Raman spectrogram measured on the gold nanorod substrate before recombination in S1, and the result is shown in FIGS. 3-4.
Fig. 3 is a photograph of the gold nanorod substrate after ice toxicity detection before and after reassembly in example 2, wherein a is before reassembly and b is after reassembly.
FIG. 4 is a Raman spectrum of ice toxicity detection using a gold nanorod substrate before and after reassembly in example 2, wherein a is before reassembly and b is after reassembly.
As can be seen in fig. 3 and 4: in Raman spectrograms before and after the re-assembly, characteristic peaks of the ice toxicity are the same, and the intensity difference of the characteristic peaks is almost the same (see Table 2), so that the detection performance of the re-assembled gold nanorod substrate obtained by the method is not damaged, the detection performance is good, and the re-assembled gold nanorod substrate can be repeatedly used.
TABLE 2 Strength results of characteristic peaks of Ice toxicity before and after reassembly
| Number of |
1 st time | 2 nd time | 3 rd time | 4 th time | 5 th time | Average |
| Before reassembly | 5160 | 5560 | 5090 | 4890 | 4900 | 5120 |
| After being reassembled | 3570 | 3890 | 3990 | 4270 | 4080 | 3960 |
Example 3
A method for cleaning and reassembling a surface enhanced Raman spectrum substrate comprises the following steps:
s1, preparing a gold nanorod substrate, and dripping 2 mu L of 10-7Drying the crystal violet solution in the air, performing SERS detection for 5 times on each substrate, and recording a Raman spectrogram at 720cm for 5 times-1、915cm-1、937cm-1、1170cm-1、1584cm-1、1617cm-1The characteristic peak of the crystal violet solution appears, which indicates that the substrate has good detection performance;
putting 3mL of concentrated hydrochloric acid, 1mL of concentrated nitric acid and 50mL of water in a beaker, and uniformly mixing to obtain desorption solution; placing the gold nanorod substrate dropwise added with the crystal violet solution for use in a desorption solution for soaking for 20s, then quickly taking out the substrate, placing the substrate into ultrapure water at 40 ℃ for rinsing for 10s, and then airing in an oven at 25 ℃ to obtain an intermediate substrate;
s2, uniformly mixing 100mL of dodecyl dimethyl benzyl ammonium bromide aqueous solution with the concentration of 0.1mol/L, 70mL of sodium dodecyl sulfate aqueous solution with the concentration of 0.1mol/L and 3.5mL of aluminum lithium hydride aqueous solution with the concentration of 0.1mol/L, adding the mixture into an intermediate substrate, standing and reacting for 15min at 30 ℃, taking out, placing in a constant temperature and humidity box with the temperature of 30 ℃ and the relative humidity of 80%, and airing to obtain a recombined surface enhanced Raman spectrum substrate;
taking the surface enhanced Raman spectroscopy substrate which is reassembled, and dripping 2 mu L of 10-7And (2) carrying out SERS detection on the solution of mol/L crystal violet after airing, detecting each substrate for 5 times, recording a Raman spectrogram, and finding that the characteristic peaks of the crystal violet before and after the recombination are the same and the intensity difference of the characteristic peaks is almost the same (see table 3), thereby showing that the detection performance of the recombined gold nanorod substrate obtained by adopting the method is not damaged, the detection performance is good, and the recombined gold nanorod substrate can be repeatedly used.
TABLE 3 Strength results of characteristic peaks of crystal violet before and after reassembly
| Number of |
1 st time | 2 nd time | 3 rd time | 4 th time | 5 th time | Average |
| Before reassembly | 6540 | 6490 | 5830 | 6110 | 7490 | 5680 |
| After being reassembled | 7510 | 6580 | 6620 | 5930 | 7100 | 6640 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for cleaning and reassembling a surface enhanced Raman spectrum substrate is characterized by comprising the following steps:
s1, soaking the used surface-enhanced Raman spectrum substrate in desorption liquid; then taking out the substrate, and rinsing with water to obtain an intermediate substrate;
and S2, placing the intermediate substrate into an aqueous solution A, reacting, taking out the substrate and drying, wherein the solute of the aqueous solution A is one of a mixture of a reducing agent and a quaternary ammonium compound and a mixture of the reducing agent, the quaternary ammonium compound and a surfactant.
2. The method for cleaning and reassembling the surface-enhanced Raman spectrum substrate according to claim 1, wherein in S1, the desorption solution is composed of concentrated hydrochloric acid, concentrated nitric acid and water.
3. The method for cleaning and reassembling the surface-enhanced Raman spectrum substrate according to claim 2, wherein a volume ratio of concentrated hydrochloric acid to concentrated nitric acid to water is 2.8-3.2:0.9-1.1: 5-50.
4. The method for cleaning and reassembling a surface-enhanced raman spectroscopy substrate according to any one of claims 1 to 3, wherein the soaking time is 1 to 20S in S1.
5. The method for cleaning and reassembling a surface-enhanced Raman spectroscopy substrate according to any one of claims 1 to 4, wherein in S1, the temperature of water is 25 to 40 ℃; preferably, in S1, the rinsing time is 10-30S.
6. The method for cleaning and reassembling a surface-enhanced Raman spectrum substrate according to any one of claims 1 to 5, wherein in S2, the reducing agent is at least one of sodium borohydride and lithium aluminum hydride; preferably, in S2, the quaternary ammonium compound is dodecyltrimethylammonium bromide, dodecyldimethylbenzylammonium bromideAt least one of ammonium, dodecyl benzyl quaternary ammonium salt, dialkyl quaternary ammonium salt, alkyl pyridine quaternary ammonium salt and (2-hydroxyethyl) trimethyl ammonium hydroxide; preferably, in S2, the surfactant is an alkylbenzene sulfonate, an alkyl sulfonate salt, an alkyl sulfonate, an alkyl sulfate、At least one of alkyl sulfonic acetamide, dodecyl trimethyl ammonium bromide, dodecyl dimethyl phenoxyethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, dodecyl benzyl quaternary ammonium salt, dialkyl quaternary ammonium salt and alkyl pyridine quaternary ammonium salt.
7. The method for cleaning and reassembling a surface enhanced raman spectroscopy substrate according to any one of claims 1 to 6, wherein in S2, the molar ratio of the quaternary ammonium compound to the reducing agent is 100:2.5 to 3.5; preferably, in S2, when the solute of the aqueous solution A is a mixture of a reducing agent and a quaternary ammonium compound, the concentration of the quaternary ammonium compound is 0.09-0.11 mol/L; preferably, in S2, when the solute of the aqueous solution a is a mixture of a reducing agent, a quaternary ammonium compound and a surfactant, the molar ratio of the quaternary ammonium compound to the surfactant is 1: 0.5-0.7; preferably, in S2, when the solute of the aqueous solution a is a mixture of a reducing agent, a quaternary ammonium compound and a surfactant, the concentration of the quaternary ammonium compound is 0.06 to 0.07 mol/L.
8. The method for cleaning and reassembling a surface-enhanced raman spectroscopy substrate according to any one of claims 1 to 7, wherein the reaction temperature is 25 to 30 ℃ in S2.
9. The method for cleaning and reassembling a surface-enhanced raman spectroscopy substrate according to any one of claims 1 to 8, wherein the reaction time is 15 to 30min in S2.
10. The method for cleaning and reassembling a surface-enhanced raman spectroscopy substrate according to any one of claims 1 to 9, wherein the drying temperature is 25 to 30 ℃ and the relative humidity at the time of drying is 70 to 80% in S2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111601997.2A CN114324159B (en) | 2021-12-24 | 2021-12-24 | Clean recombination assembly method of surface enhanced Raman spectrum substrate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090257056A1 (en) * | 2007-04-24 | 2009-10-15 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Surface enhanced raman detection on metalized nanostructured polymer films |
| CN104359893A (en) * | 2014-11-19 | 2015-02-18 | 吉林大学 | Thermal-structured recombinant preparation method of SERS (surface-enhanced Raman scattering) substrate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090257056A1 (en) * | 2007-04-24 | 2009-10-15 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Surface enhanced raman detection on metalized nanostructured polymer films |
| CN104359893A (en) * | 2014-11-19 | 2015-02-18 | 吉林大学 | Thermal-structured recombinant preparation method of SERS (surface-enhanced Raman scattering) substrate |
Non-Patent Citations (4)
| Title |
|---|
| HANG ZHAO等: "A silver self‐assembled monolayer‐decorated polydimethylsiloxane flexible substrate for in situ SERS detection of low‐abundance molecules" * |
| MING YANG LV等: "Low-cost Au nanoparticle-decorated cicada wing as sensitive andrecyclable substrates for surface enhanced Raman scattering" * |
| 傅小奇;章国林;: "可循环使用表面增强拉曼散射基底研究进展" * |
| 杜永均: "可重复使用、长寿命的三维阵列SERS基底研究及光谱分析" * |
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