CN115283668B - Tin disulfide-gold composite material and preparation method and application thereof - Google Patents
Tin disulfide-gold composite material and preparation method and application thereof Download PDFInfo
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- CN115283668B CN115283668B CN202210854204.6A CN202210854204A CN115283668B CN 115283668 B CN115283668 B CN 115283668B CN 202210854204 A CN202210854204 A CN 202210854204A CN 115283668 B CN115283668 B CN 115283668B
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- methimazole
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- -1 Tin disulfide-gold Chemical compound 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title abstract description 22
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229960002178 thiamazole Drugs 0.000 claims abstract description 75
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 claims abstract description 72
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010931 gold Substances 0.000 claims abstract description 59
- 229910052737 gold Inorganic materials 0.000 claims abstract description 59
- 239000002135 nanosheet Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- 238000001514 detection method Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000001237 Raman spectrum Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000001069 Raman spectroscopy Methods 0.000 claims description 34
- 230000004044 response Effects 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- WPEJSSRSFRWYJB-UHFFFAOYSA-K azanium;tetrachlorogold(1-) Chemical compound [NH4+].[Cl-].[Cl-].[Cl-].[Cl-].[Au+3] WPEJSSRSFRWYJB-UHFFFAOYSA-K 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 229940076131 gold trichloride Drugs 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 description 48
- 239000006185 dispersion Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000004611 spectroscopical analysis Methods 0.000 description 20
- 210000002966 serum Anatomy 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000002064 nanoplatelet Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 8
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 8
- 235000018417 cysteine Nutrition 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
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- 230000001965 increasing effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 3
- XUIIKFGFIJCVMT-GFCCVEGCSA-N D-thyroxine Chemical compound IC1=CC(C[C@@H](N)C(O)=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-GFCCVEGCSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
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- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 210000001744 T-lymphocyte Anatomy 0.000 description 1
- AUYYCJSJGJYCDS-LBPRGKRZSA-N Thyrolar Chemical compound IC1=CC(C[C@H](N)C(O)=O)=CC(I)=C1OC1=CC=C(O)C(I)=C1 AUYYCJSJGJYCDS-LBPRGKRZSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003200 antithyroid agent Substances 0.000 description 1
- 229940043671 antithyroid preparations Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 210000003719 b-lymphocyte Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000017531 blood circulation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 210000003855 cell nucleus Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010905 molecular spectroscopy Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 229940034208 thyroxine Drugs 0.000 description 1
- XUIIKFGFIJCVMT-UHFFFAOYSA-N thyroxine-binding globulin Natural products IC1=CC(CC([NH3+])C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention discloses a tin disulfide-gold composite material, and a preparation method and application thereof. The composition of the tin disulfide-gold composite material comprises tin disulfide nano sheets and gold nano particles growing on the surfaces of the tin disulfide nano sheets, and the preparation method comprises the following steps: mixing tin disulfide nanosheets, gold precursors and solvents, and carrying out ultrasonic-assisted reduction to obtain the tin disulfide-gold composite material. The tin disulfide-gold composite material can be used for rapidly detecting the content of methimazole or crystal violet. The tin disulfide-gold composite material has the advantages of controllable size of gold nanoparticles, simple preparation method and no need of using a reducing agent, and can have the effects of high sensitivity, good reproducibility, good stability, simplicity in operation and the like when being applied to detection analysis, thereby having high practical application value.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to a tin disulfide-gold composite material, a preparation method and application thereof.
Background
Methimazole (Thiamazole), an imidazole antithyroid drug, acts by inhibiting thyroperoxidase, thereby impeding thyroxine (T4) and triiodothyronine (T3) synthesis. At present, animal experiments show that the methimazole can inhibit B lymphocyte from synthesizing antibodies, reduce the level of thyroid stimulating antibodies in blood circulation and restore the function of inhibitory T cells to be normal. However, methimazole itself is also a carcinogen, so the research for detecting methimazole is significant.
Crystal violet is an excellent stain, is commonly used for cell nucleus staining, and has extremely wide application in cytology, histology, bacteriology and other aspects. However, currently, there are few methods for detecting crystal violet, and further development is required.
Surface Enhanced Raman Spectroscopy (SERS) is a nondestructive, rapid and sensitive molecular spectroscopy technology, and can be used for identifying and detecting trace molecules by utilizing spectral fingerprints, so that the method is widely applied to the fields of food safety, environmental analysis, biomedicine and the like. Coin-family metals (gold, silver, copper, etc.) exhibit good performance in SERS applications due to their unique electromagnetic field enhancement effect. However, the uniformity and stability of the free metal particles is poor, which is detrimental to SERS quantitative analysis. However, the preparation process for preparing the surface enhanced raman spectroscopy analysis material is often complex, has high cost and is uncontrollable, so that the aim of obtaining a composite material which can be used for trace detection, accurate detection and rapid analysis is still a difficult problem.
Therefore, there is a need to develop a material and method for rapid, accurate and sensitive detection of methimazole and crystal violet.
Disclosure of Invention
In order to solve the technical problems of slow detection, high detection limit, poor accuracy and low sensitivity in the prior art for detecting methimazole and crystal violet, one of the purposes of the invention is to provide a tin disulfide-gold composite material.
The second purpose of the invention is to provide a preparation method of the tin disulfide-gold composite material.
It is a further object of the present invention to provide the use of the tin disulfide-gold composite material.
The technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a tin disulfide-gold composite material comprising tin disulfide nanoplatelets and gold nanoparticles grown on the surface of the tin disulfide nanoplatelets.
Specifically, the tin disulfide-gold composite material is directly modified on the surface of a tin disulfide nano sheet through spherical gold nano particles, and the gold nano particles can firmly grow on the surface of the tin disulfide nano sheet through the action of Au-S bonds.
Preferably, the sheet diameter of the tin disulfide nano sheet is 2-10 μm.
Preferably, the gold nanoparticles are spheroidal particles with a particle size of 10 nm-300 nm.
Further preferably, the gold nanoparticles are spheroidal particles with a particle size of 100nm to 150nm.
In a second aspect, the invention provides a method for preparing the tin disulfide-gold composite material in the first aspect, which comprises the following steps: mixing tin disulfide nanosheets, gold precursors and solvents, and carrying out ultrasonic-assisted reduction to obtain the tin disulfide-gold composite material.
Specifically, the preparation method of the tin disulfide-gold composite material does not need a reducing agent, and the tin disulfide-gold composite material can be obtained only by ultrasonic-assisted reduction at the temperature of 20-35 ℃. The reason that the tin disulfide-gold composite material can be obtained by the ultrasonic assisted reaction is as follows: the surface of the tin disulfide nanosheet is provided with sulfur elements, the sulfur elements can form Au-S bonds with gold elements, and then gold nanoparticles in a metal valence state can be directly grown on the surface of the tin disulfide nanosheet under the precondition that ultrasound assistance and chloroauric acid are easy to hydrolyze under the condition that a reducing agent is not added.
Preferably, the mass ratio of the tin disulfide nanosheets to the gold precursor is 20:1-1:10.
Further preferably, the mass ratio of the tin disulfide nanosheets to the gold precursor is 1:0.4-1:4.
Preferably, the gold precursor is selected from one or more of gold trichloride, chloroauric acid trihydrate, sodium chloroaurate, potassium chloroaurate, ammonium chloroaurate.
Further preferably, the gold precursor is selected from one or more of chloroauric acid trihydrate, sodium chloroaurate, potassium chloroaurate, ammonium chloroaurate.
Still more preferably, the gold precursor is selected from chloroauric acid trihydrate.
Preferably, the solvent is one or more of water and ethanol.
Further preferably, the solvent is water.
Preferably, the mass ratio of the tin disulfide nano-sheet to the solvent is 1:1800-1:1980.
Preferably, the ultrasonic-assisted reduction is performed under the conditions that the ultrasonic frequency is 35 kHz-45 kHz and the ultrasonic power is 400-500W.
Further preferably, the ultrasound-assisted reduction is performed at an ultrasound frequency of 40kHz and an ultrasound power of 450W.
Preferably, the temperature of the ultrasound-assisted reduction is 20-35 ℃.
Further preferably, the temperature of the ultrasound-assisted reduction is 25 ℃ to 30 ℃.
Preferably, the time of the ultrasonic-assisted reduction is 30-90 min.
Further preferably, the time of the ultrasonic-assisted reduction is 40 min-80 min.
Preferably, the preparation method of the tin disulfide-gold composite material further comprises the steps of solid-liquid separation, washing precipitation and drying.
Preferably, the drying is carried out at a temperature of 25℃to 120 ℃.
Preferably, the preparation method of the tin disulfide nanosheets comprises the following steps: dissolving tin tetrachloride and cysteine in water, and carrying out hydrothermal reaction to obtain the tin disulfide nanosheets.
Preferably, the mass ratio of the stannic chloride to the cysteine is 1:0.5-1:1.
Preferably, the temperature of the hydrothermal reaction is 180 ℃ to 220 ℃.
Preferably, the time of the hydrothermal reaction is 15-24 hours.
Preferably, the preparation method of the tin disulfide nanosheets further comprises the steps of centrifugation, washing precipitation and vacuum drying.
Preferably, the temperature of the vacuum drying is 40-80 ℃.
Preferably, the vacuum drying is performed under a vacuum degree of 0.1MPa to 1 MPa.
Preferably, the preparation method of the tin disulfide-gold composite material comprises the following steps:
1) Mixing tin disulfide nano-sheets and a solvent to prepare tin disulfide nano-sheet dispersion liquid;
2) Dissolving gold precursor in solvent to prepare gold precursor liquid;
3) And (3) mixing the tin disulfide nanosheet dispersion liquid in the step (1) and the gold precursor liquid in the step (2), and carrying out ultrasonic-assisted reduction to obtain the tin disulfide-gold composite material.
Preferably, the concentration of the tin disulfide nanosheet dispersion liquid in the step 1) is 0.5 g/L-4 g/L.
Preferably, the concentration of the gold precursor solution in the step 2) is 5g/L to 40g/L.
Further preferably, the concentration of the gold precursor solution in the step 2) is 10g/L to 25g/L.
In a fourth aspect, the invention provides the use of the tin disulfide-gold composite material of the first aspect for detecting methimazole.
Preferably, the application is specifically: the application of the tin disulfide-gold composite material in detecting the content of methimazole in serum samples.
In a fifth aspect, the present invention provides a method for detecting methimazole, comprising the steps of:
1) Respectively mixing methimazole with different concentrations and the tin disulfide-gold composite material of the first aspect, measuring a Raman spectrum of the mixture, and constructing a standard curve;
2) Mixing the tin disulfide-gold composite material of the first aspect with a solution to be tested, and measuring a Raman spectrum of the mixed material;
3) Selecting 1365cm -1 And (3) calculating the methimazole content in the sample to be detected according to the Raman response intensity value and the standard curve in the step (1).
Preferably, the mixing time in the step 1) is 8-12 min.
Further preferably, the mixing time in step 1) is 10min to 12min.
Preferably, the measurements in step 1) and step 2) use a 785nm laser as the light source.
Preferably, the assays in step 1) and step 2) are tested for ramanThe displacement is 1000-1800 cm -1 Is a raman spectrum of (c).
In a sixth aspect, the present invention provides the use of a tin disulfide-gold composite according to the first aspect for detecting crystal violet.
The beneficial effects of the invention are as follows: the tin disulfide-gold composite material has the advantages of controllable size of gold nanoparticles, simple preparation method and no need of using a reducing agent, and can have the effects of high sensitivity, good reproducibility, good stability, simplicity in operation and the like when being applied to detection analysis, thereby having high practical application value.
The method comprises the following steps:
1) The gold nanoparticles in the tin disulfide-gold composite material are directly grown on the surface of the tin disulfide nanosheets, are uniformly distributed, are firmly combined, and are suitable for being used as a material for increasing Raman signals in Raman detection;
2) The tin disulfide-gold composite material is directly prepared by a room-temperature ultrasonic-assisted reduction method, and the preparation method has the advantages of rapidness, simplicity, environmental friendliness, no use of reducing agent, controllable gold nanoparticle particle size and good reproducibility;
3) According to the invention, gold nanoparticles are grown on tin disulfide nanosheets in situ by an ultrasonic assistance method, so that the coagulation of the gold nanoparticles can be effectively reduced, a large number of electromagnetic hot spots capable of enhancing Raman signals are generated, and the prepared tin disulfide-gold composite material is used for detecting the content of methimazole in water or serum, and has good sensitivity and reproducibility;
4) The invention also uses tin disulfide-gold composite material for measuring methimazole, and establishes a rapid, high-accuracy, good-repeatability, low-detection limit and high-universality methimazole detection method, the detection limit of the method can be as low as 2.7ng/mL, the standard adding recovery rate is 89.7% -98.1%, and the Relative Standard Deviation (RSDs) is 2.1% -8.5%, thereby indicating that the detection method has the advantages of high accuracy and strong practicability in actual sample measurement;
5) The tin disulfide-gold composite material can be used as an auxiliary material for Raman spectrum analysis, and can be used for detecting a serum sample or an aqueous solution sample with lower methimazole content;
6) The tin disulfide-gold composite material can also be used for detecting and analyzing crystal violet compounds, and can be used for indicating that the tin disulfide-gold composite material has wide application range and strong practicability.
Drawings
Fig. 1 is an XRD spectrum of the tin disulfide nanoplatelets and tin disulfide-gold composite in example 1.
Fig. 2 is an SEM image of tin disulfide nanoplatelets of example 1.
Fig. 3 is an SEM image of the tin disulfide-gold composite of example 1.
FIG. 4 is a graph showing the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 1.
Fig. 5 is an SEM image of the tin disulfide-gold composite in example 2.
FIG. 6 is a graph showing the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 2.
Fig. 7 is an SEM image of the tin disulfide-gold composite in example 3.
FIG. 8 is a graph showing the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 3.
Fig. 9 is an SEM image of the tin disulfide-gold composite in example 4.
FIG. 10 is a graph showing the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 4.
Fig. 11 is an SEM image of the tin disulfide-gold composite in example 5.
FIG. 12 is a graph showing the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 5.
Fig. 13 is an SEM image of the tin disulfide-gold composite in example 6.
FIG. 14 is a graph showing the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 6.
Fig. 15 is a raman spectrum of the tin disulfide-gold composite and the aqueous methimazole solution of example 1 measured under different stirring and mixing time conditions.
FIG. 16 is a graph showing measurements of 1365cm for the tin disulfide-gold composite and the aqueous methimazole solution of example 1 under different stirring and mixing time conditions -1 A histogram of raman characteristic peak intensities at.
FIG. 17 is a Raman spectrum of the tin disulfide-gold composite material of examples 1 to 6 for detecting an aqueous methimazole solution at a concentration of 0.5 mg/L.
Fig. 18 is a raman spectrum obtained by measuring various concentrations of methimazole in water solution with the tin disulfide-gold composite material in example 1.
Fig. 19 is a graph of the standard curve of tin disulfide-gold composite in example 1 measured under different concentration of methimazole aqueous solutions.
FIG. 20 is a Raman spectrum of a tin disulfide-gold composite prepared in the same batch for detecting an aqueous solution of methimazole.
FIG. 21 is a Raman spectrum of tin disulfide-gold composites prepared in different batches for detecting aqueous methimazole solutions.
FIG. 22 is a Raman spectrum of the tin disulfide-gold composite of example 1 for detecting methimazole-containing serum-1.
FIG. 23 is a Raman spectrum of the tin disulfide-gold composite of example 1 for detecting methimazole-containing serum-2.
FIG. 24 is a Raman spectrum of the tin disulfide-gold composite of example 1 for detecting methimazole-containing serum-3.
FIG. 25 is a Raman spectrum of the tin disulfide-gold composite of example 1 used for detecting methimazole-containing serum-4.
FIG. 26 is a Raman spectrum of tin disulfide-gold composite materials used for detecting crystal violet substances in examples 1 to 6.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A tin disulfide-gold composite material and a preparation method thereof comprise the following steps:
1) Dissolving 500mg of stannic chloride and 400mg of cysteine in 80mL of deionized water, transferring into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product at 4000rpm for 3 minutes, washing for three times, and vacuum drying to obtain tin disulfide nanosheets;
2) Dispersing the tin disulfide nanosheets in the step 1) into water to prepare 2.0g/L tin disulfide dispersion liquid;
3) Mixing 1.0mL of a tin disulfide dispersion liquid with 160 mu L of a 20g/L aqueous solution of chloroauric acid trihydrate, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of 40kHz, 450W of power and about 25-30 ℃ to obtain a reacted liquid;
4) Centrifuging the liquid after the reaction in the step 3) for 3min at the rotating speed of 4000rpm, washing the precipitate with water for 3 times, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
Example 2
A tin disulfide-gold composite material and a preparation method thereof comprise the following steps:
1) Dissolving 500mg of stannic chloride and 400mg of cysteine in 80mL of deionized water, transferring into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product at 4000rpm for 3 minutes, washing for three times, and vacuum drying to obtain tin disulfide nanosheets;
2) Dispersing the tin disulfide nanosheets in the step 1) into water to prepare 2.0g/L tin disulfide dispersion liquid;
3) Mixing 1.0mL of a tin disulfide dispersion liquid with 40 mu L of a 20g/L aqueous solution of chloroauric acid trihydrate, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of 40kHz, 450W of power and about 25-30 ℃ to obtain a reacted liquid;
4) Centrifuging the liquid after the reaction in the step 3) for 3min at the rotating speed of 4000rpm, washing the precipitate with water for 3 times, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
Example 3
A tin disulfide-gold composite material and a preparation method thereof comprise the following steps:
1) Dissolving 500mg of stannic chloride and 400mg of cysteine in 80mL of deionized water, transferring into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product at 4000rpm for 3 minutes, washing for three times, and vacuum drying to obtain tin disulfide nanosheets;
2) Dispersing the tin disulfide nanosheets in the step 1) into water to prepare 2.0g/L tin disulfide dispersion liquid;
3) Mixing 1.0mL of a tin disulfide dispersion liquid with 80 mu L of a 20g/L aqueous solution of chloroauric acid trihydrate, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of 40kHz, 450W of power and about 25-30 ℃ to obtain a reacted liquid;
4) Centrifuging the liquid after the reaction in the step 3) for 3min at the rotating speed of 4000rpm, washing the precipitate with water for 3 times, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
Example 4
A tin disulfide-gold composite material and a preparation method thereof comprise the following steps:
1) Dissolving 500mg of stannic chloride and 400mg of cysteine in 80mL of deionized water, transferring into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product at 4000rpm for 3 minutes, washing for three times, and vacuum drying to obtain tin disulfide nanosheets;
2) Dispersing the tin disulfide nanosheets in the step 1) into water to prepare 2.0g/L tin disulfide dispersion liquid;
3) Mixing 1.0mL of a tin disulfide dispersion liquid with 240 mu L of a 20g/L aqueous solution of chloroauric acid trihydrate, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of 40kHz, 450W of power and about 25-30 ℃ to obtain a reacted liquid;
4) Centrifuging the liquid after the reaction in the step 3) for 3min at the rotating speed of 4000rpm, washing the precipitate with water for 3 times, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
Example 5
A tin disulfide-gold composite material and a preparation method thereof comprise the following steps:
1) Dissolving 500mg of stannic chloride and 400mg of cysteine in 80mL of deionized water, transferring into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product at 4000rpm for 3 minutes, washing for three times, and vacuum drying to obtain tin disulfide nanosheets;
2) Dispersing the tin disulfide nanosheets in the step 1) into water to prepare 2.0g/L tin disulfide dispersion liquid;
3) Mixing 1.0mL of a tin disulfide dispersion liquid with 320 mu L of a 20g/L aqueous solution of chloroauric acid trihydrate, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of 40kHz, 450W of power and about 25-30 ℃ to obtain a reacted liquid;
4) Centrifuging the liquid after the reaction in the step 3) for 3min at the rotating speed of 4000rpm, washing the precipitate with water for 3 times, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
Example 6
A tin disulfide-gold composite material and a preparation method thereof comprise the following steps:
1) Dissolving 500mg of stannic chloride and 400mg of cysteine in 80mL of deionized water, transferring into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product at 4000rpm for 3 minutes, washing for three times, and vacuum drying to obtain tin disulfide nanosheets;
2) Dispersing the tin disulfide nanosheets in the step 1) into water to prepare 2.0g/L tin disulfide dispersion liquid;
3) Mixing 1.0mL of a tin disulfide dispersion liquid with 400 mu L of a 20g/L aqueous solution of chloroauric acid trihydrate, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of 40kHz, 450W of power and about 25-30 ℃ to obtain a reacted liquid;
4) Centrifuging the liquid after the reaction in the step 3) for 3min at the rotating speed of 4000rpm, washing the precipitate with water for 3 times, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
The vacuum drying in examples 1 to 6 was performed at a vacuum degree of 0.1MPa to 1 MPa.
Characterization of materials
1) XRD patterns of the tin disulfide nanoplatelets and tin disulfide-gold composites in example 1 are shown in fig. 1.
As can be seen from fig. 1: the characteristic peaks of tin disulfide nanosheets in example 1 at 15.0 °, 28.2 °, 30.3 °, 32.1 °, 41.9 ° 49.9 °, 52.5 ° correspond to standard card pdf#23-0677, and belong to SnS 2 Characteristic peaks of the phases. Compared with tin disulfide nano-sheet, the tin disulfide-gold composite material not only contains SnS 2 Characteristic peaks of the phases, which correspond to gold standard card JCPDS #04-0784 and which are attributed to the gold phase, and which contain characteristic peaks at 38.2 °, 44.4 °, 64.6 °, 77.5 °, 81.7 °, confirm that the tin disulfide-gold composite material in example 1 is composed of gold and tin disulfide.
Since the tin disulfide nanoplatelets in examples 2 to 6 and example 1 and the reaction principle for preparing the tin disulfide-gold composite material are the same as in example 1, it can be explained that the tin disulfide nanoplatelets and the tin disulfide-gold composite material in examples 2 to 6 have the same phases as in example 1.
2) Scanning electron microscope (Scanning Electron Microscope, SEM) images of tin disulfide nanoplatelets in example 1 are shown in fig. 2. SEM images of tin disulfide-gold composites in example 1 are shown in fig. 3. The particle size distribution of gold nanoparticles on tin disulfide-gold composites in example 1 is shown in fig. 4.
As can be seen from fig. 2 to 4: the tin disulfide-gold composite material prepared under the reaction condition of the embodiment 1 consists of tin disulfide nano sheets and gold nano particles growing on the tin disulfide nano sheets, and the gold nano particles in the embodiment 1 are uniformly distributed on the tin disulfide nano sheets, so that the uniformity of SERS signals on the composite material can be effectively improved, and the detection sensitivity of the composite material can be effectively improved by the gold nano particles which are densely distributed. Meanwhile, the tin disulfide nanosheets in example 1 have a sheet diameter of 2 μm to 5 μm, while the gold nanoparticles have a particle diameter of 20nm to 200nm, and are mainly distributed at 100nm to 150nm, and the gold nanoparticles have a particle diameter distribution having an average particle diameter of: 124.+ -. 11nm.
SEM images of the tin disulfide-gold composite and particle size distribution diagrams of gold nanoparticles on the tin disulfide-gold composite in example 2 are shown in fig. 5 and 6, respectively. SEM images of the tin disulfide-gold composite and particle size distribution diagrams of gold nanoparticles on the tin disulfide-gold composite in example 3 are shown in fig. 7 and 8, respectively. SEM images of the tin disulfide-gold composite and particle size distribution diagrams of gold nanoparticles on the tin disulfide-gold composite in example 4 are shown in fig. 9 and 10, respectively. SEM images of the tin disulfide-gold composite and particle size distribution diagrams of gold nanoparticles on the tin disulfide-gold composite in example 5 are shown in fig. 11 and 12, respectively. SEM images of the tin disulfide-gold composite and particle size distribution diagrams of gold nanoparticles on the tin disulfide-gold composite in example 6 are shown in fig. 13 and 14, respectively.
As can be seen from fig. 5 to 14: under similar reaction conditions, examples 2 to 6 all were able to produce tin disulfide-gold composites composed of tin disulfide nanoplatelets and gold nanoparticles grown on the tin disulfide nanoplatelets.
The gold nanoparticles grown on the surface of tin disulfide nanoplatelets in examples 1 to 6 are shown in table 1.
TABLE 1 cases of gold nanoparticles grown on the surface of tin disulfide nanoplatelets in examples 1 to 6
Note that: the description of the "distribution" in the topographical features in table 1 refers specifically to the distribution of gold nanoparticles on tin disulfide nanoplatelets.
As can be seen from fig. 5 to 14 and table 1: examples 2 to 6 are mainly different in particle size of gold nanoparticles and distribution thereof on tin disulfide nanoplatelets, and specifically are: with the increase of the amount of chloroauric acid trihydrate, the particle size of the gold nanoparticles on the tin disulfide nanosheets gradually increases, and the phenomenon that the gold nanoparticles on the surface of the tin disulfide-gold composite material are stacked can be obviously seen in examples 5 to 6. The gold nanoparticles in examples 2 to 5 have a particle diameter mainly distributed in the range of 25nm to 350nm.
Application example 1
A method of detecting methimazole comprising the steps of:
1) Mixing 40 μL of tin disulfide-gold composite dispersion liquid (water as solvent) of example 1 and 0.5mg/L of methimazole water solution according to a volume ratio of 1:2, stirring, respectively sucking 40 μL of mixed liquid drops on a silicon wafer at mixing time of 2min, 4min, 6min, 8min, 10min and 12min, immediately drying, and measuring Raman shift of 900cm under the condition of using excitation wavelength of 785nm -1 ～1800cm -1 Surface Enhanced Raman (SERS) response values of (Surface-Enhanced Raman Scattering, abbreviated as SERS), and parallel measurement is set for 5 times, and then the average value of the SERS response is plotted into a raman spectrum (see fig. 15), so as to obtain the most suitable mixing time (10 min-12 min, i.e., the mixing time in which the strongest characteristic peak signal in the raman spectrum of fig. 16 is relatively stable);
2) The methimazole standard solutions (solvent is water) with the concentration of 0, 5 mug/L, 10 mug/L, 50 mug/L, 100 mug/L, 250 mug/L, 500 mug/L, 750 mug/L and 1000 mug/L are prepared, and the tin disulfide-gold composite material of the example 1 is prepared into a 2mg/L tin disulfide-gold composite material dispersion liquid by using water;
3) Mixing 80 μL of methimazole standard solutions with different concentrations in the step 2) with 40 μL of 2mg/L of the tin disulfide-gold composite material dispersion liquid of the example 1, dripping the mixture on a silicon wafer, drying, measuring signal values of SERS response, measuring for 5 times in parallel, drawing a spectrogram according to an average value of the SERS response, and calculating 1365cm of the obtained solution -1 A standard curve between the raman response intensity value and the methimazole concentration;
4) Mixing 40 μL 2mg/mL tin disulfide-gold composite dispersion liquid (water as solvent) of example 1 with a sample to be tested (mixing time is longer than 10 min) to obtain a liquid, dripping the liquid on a silicon wafer, drying, measuring SERS response, performing parallel measurement for 5 times, drawing a spectrogram according to the mean value of the SERS response, and calculating 1365cm of the spectrogram -1 And (3) calculating the methimazole content in the sample to be detected according to the Raman response intensity value of the sample and the standard curve of the step (3).
Construction of method for detecting methimazole
1) The tin disulfide-gold composite material and methimazole in example 1 were placed in water, and the corresponding raman spectra (corresponding to step 1 in application example 1) were measured by sampling under different stirring and mixing conditions (2 min, 4min, 6min, 8min, 10min, 12 min) as shown in fig. 15. The tin disulfide-gold composite material and the methimazole aqueous solution in example 1 were measured under conditions of different sample preparation times with respect to 1365cm -1 A histogram of raman characteristic peak intensities (corresponding to step 1 in application example 1) is shown in fig. 16.
As can be seen from fig. 15 and 16: at a Raman shift of 900cm -1 ～1800cm -1 Is located at 1365cm on the Raman spectrum of (C) -1 The signal peak of (2) is the strongest, so that it can be used as the basis for quantitative analysis of methimazole. With increasing time of mixing the tin disulfide-gold composite and methimazole in the liquid, a position of 1365cm in the raman spectrum was found -1 The intensity of the characteristic peak at the position is firstly enhanced and then weakened, and finally the characteristic peak tends to be stable.
Meanwhile, when the mixing time of the tin disulfide-gold composite material and the methimazole is 8min, the corresponding response signal peak of the whole Raman spectrum is strongest, which shows that the Raman enhancement effect of the tin disulfide-gold composite material is obvious. The raman spectra when the mixing time of tin disulfide-gold composite and methimazole was 10min and 12min showed slightly weaker response intensity than the raman spectra when the mixing time was 8min, but from fig. 16, it can be seen that the two sets of raman spectra with mixing time of 10min and 12min were located at 1365cm -1 The response intensity of the signal peak is relatively close, which indicates that when the mixing time of the tin disulfide-gold composite material and the methimazole in the liquid is 10min or more than 10min, the concentration of the methimazole in the liquid to be measured is relatively stable and uniform, and the measured result has certain credibility.
In addition, as can be seen from fig. 15 and 16, the tin disulfide-gold composite material of the present invention can accurately and efficiently detect the methimazole content in the sample to be measured having a low concentration within about 10 minutes.
It should be noted that, the subsequent performance tests (fig. 17 to 26) are all performed on the basis of fully mixing the tin disulfide-gold composite material and methimazole, that is, other raman spectra are all obtained by preparing samples by setting the mixing time of the sample to be tested and the tin disulfide-gold composite material to 10min to 12min.
2) After 40. Mu.L of 2mg/mL of the tin disulfide-gold composite dispersion (the solvent is water) and 0.5mg/L of the methimazole aqueous solution in examples 1 to 6 were respectively mixed, the mixture was respectively dropped onto a silicon wafer, and the corresponding Raman spectra were obtained by drying and measurement, as shown in FIG. 17. The blank in fig. 17 is a raman spectrum measured after the silicon wafer is dried with a water solution containing only mercaptoimidazole.
As can be seen from fig. 17: the raman spectra measured at the same concentration in examples 1 to 6 had a raman shift of 1365cm compared to the raman spectrum of the blank group -1 All have a strong signal peak. As compared with example 2 and example 3, the dimensions of example 1, example 4, example 5 and example 6 were set at 1365cm -1 The raman response signal peak intensity at this point is relatively strong.
3) The tin disulfide-gold composite material in example 1 was used for detecting raman spectra (corresponding to step 2 in application example 1) obtained from methimazole standard solutions of different concentrations, as shown in fig. 18. The intensity of the raman response signal peak and the corresponding methimazole concentration at this point were mathematically processed to obtain a standard graph of the tin disulfide-gold composite of example 1 under different concentration methimazole standard solutions, as shown in fig. 19.
As can be seen from fig. 18 and 19: with increasing methimazole concentration, at 1365cm -1 The signal peak at the point is gradually increased. The concentration C of the methimazole aqueous solution and the corresponding sample to be measured are located at 1365cm -1 The intensity I of the Raman signal peak at the position is in a linear relation, and the relation between the intensity I and the intensity I satisfies the following relation: i=272.0+10.27c, r 2 ＝0.9968。
4) Reproducibility test: 80 mu L of 0.5mg/L methimazole and 40 mu L of 2mg/L of the dispersion liquid (water as solvent) of the tin disulfide-gold composite material in the embodiment 1 are mixed and dripped on a silicon wafer, SERS response values of 27 random points (785 nm laser is adopted as a light source, and the integration time is 5 s) are tested after drying, and a Raman spectrum of the same batch of the tin disulfide-gold composite material for detecting the methimazole is obtained, and is shown in figure 20.
In addition, 11 batches of tin disulfide-gold composites were prepared according to the method of example 1, and similar test conditions (785 nm laser was used as the light source, integration time was 5 s) gave raman spectra of different batches of tin disulfide-gold composites for detection of methimazole, as shown in fig. 21.
As can be seen from fig. 20 and 21: the Raman spectrograms of the tin disulfide-gold composite materials prepared in the same batch and different batches have good reproducibility, so that the Raman shift of the tin disulfide-gold composite materials can be 1365cm -1 。
Application example 2
A method for detecting the content of methimazole in serum comprising the steps of:
1) Taking 40 mu L of serum sample-1, serum sample-2, serum sample-3 and serum sample-4 as samples to be measured respectively, diluting by one time with water (namely adding water to a volume of 80 mu L), uniformly mixing with 40 mu L of tin disulfide-gold composite material, taking 40 mu L of the mixture to drop on a silicon wafer, drying, measuring SERS response values under the condition of 785nm laser serving as a light source, and drawing the average value of the SERS response values to obtain Raman spectrograms (shown in figures 22-25);
2) The Raman spectrum is positioned at 1365cm -1 The intensity of the characteristic peak at the point (see table 2), and the concentration value of methimazole in the clinical sample was calculated with reference to the standard curve in application example 1 (i.e., the concentration of methimazole in the sample to be measured was calculated with reference to i=272.0+10.27c). The detection limit is the concentration at a signal to noise ratio (S/N) of 3:1. When noise n=100, the noise ratio was substituted into the curve by 3 times, and the detection limit was calculated to be 2.7 μg/L.
Determination of recovery and relative standard deviation
The method for measuring comprises the following steps:
1) Sampling: taking 40 mu L of serum sample-1, serum sample-2, serum sample-3 and serum sample-4 as samples to be measured;
2) Label addingAnd (3) calculating: mixing a sample to be detected (i.e. a sample) with 40 mu L of 100 mu g/L of methimazole standard solution and 200 mu g/L of methimazole standard solution respectively, then uniformly mixing with 40 mu L of 2.0mg/mL of tin disulfide-gold composite material dispersion liquid (solvent is water) in example 1 (mixing time is 10-12 min), dripping on a silicon wafer for drying, adopting 785nm laser as a light source, collecting time is 5s, and measuring Raman displacement under the condition of high power (about 100 mW) to be 1365cm -1 The SERS response values at these points are calculated, and the corresponding recovery rates and relative standard deviations (Relative Standard Deviation, RSD) are calculated as follows:
recovery = (addition of standard sample measurement value-sample measurement value)/(addition of standard amount x 100%;
relative standard deviation = [ (single measurement-average)/(average ] ×100%).
The tin disulfide-gold composite material in example 1 was used for measuring the methimazole content in serum, and the results of the above-described test are shown in table 2.
TABLE 2 test results of methimazole content in different samples to be tested
Note that: the number of tests indicated by n in table 2, and the concentration of methimazole standard solution in the labeling process in the table indicates the scalar addition.
The tin disulfide-gold composite in example 1 was used for detecting the raman spectrum of serum-1 containing methimazole, as shown in fig. 22. The tin disulfide-gold composite in example 1 was used for detecting the raman spectrum of serum-2 containing methimazole, as shown in fig. 23. The tin disulfide-gold composite in example 1 was used for detecting the raman spectrum of serum-3 containing methimazole, as shown in fig. 24. The tin disulfide-gold composite in example 1 was used to detect the raman spectrum of methimazole-containing serum-4, as shown in 25. The results of the tin disulfide-gold composite in example 1 were used to examine different methimazole-containing sera, as shown in table 2.
As can be seen from fig. 22 to 25 and table 2: by adopting the tin disulfide-gold composite material in the embodiment of the invention to detect the methimazole in serum, the methimazole contents in the serum sample-1, the serum sample-2, the serum sample-3 and the serum sample-4 can be detected to be 113.2 mug/L, 89.1 mug/L, 86.5 mug/L and 89.8 mug/L respectively. Meanwhile, the recovery rate of the detection method in application example 2 is 89.7-98.1%, and the relative standard deviation is 2.1-8.5%, which shows that the detection method has higher accuracy.
Application example 3
A method for detecting crystal violet, which is different from a method for detecting methimazole in that: selecting a Raman shift of 1173cm in the Raman spectrum -1 As a basis for standard curves and detection analysis, comprising the steps of:
1) Measuring the time when the sample to be measured is uniformly mixed with the tin disulfide-gold composite material and an accurate Raman spectrum can be obtained;
2) Preparing crystal violet solutions (water is used as a solvent) with different concentrations, and preparing tin disulfide-gold composite material into tin disulfide-gold composite material dispersion liquid by using water;
3) Taking 40 mu L of each crystal violet solution with different concentrations in the step 2), respectively mixing with tin disulfide-gold composite material dispersion liquid, dripping on a silicon wafer, drying, measuring signal values of SERS response, measuring for 5 times in parallel, drawing a spectrogram according to the mean value of the SERS response, and calculating 1173cm of the solution -1 A standard curve between the raman response intensity value and the crystal violet concentration;
4) Mixing tin disulfide-gold composite material dispersion liquid (solvent is water) with a sample to be tested (the mixing time is longer than that of the step 1) to prepare liquid, dripping the liquid on a silicon wafer, drying, measuring SERS response, measuring for 5 times in parallel, drawing a spectrogram according to the mean value of the SERS response, and calculating 1173cm of the spectrogram -1 And (3) calculating the crystal violet content in the sample to be detected according to the Raman response intensity value of the sample and the standard curve of the step (3).
Application example 4
A method for detecting crystal violet, comprising the steps of:
tin disulfide-gold composite dispersion solutions (solvent is water) of examples 1 to 6 of the same mass (40 mu L of 2 mg/mL) and 0.1mg/L crystal violet aqueous solution were mixed and stirred for 10min according to a volume ratio of 1:2, 40 mu L of the mixed liquid droplets were sucked onto a silicon wafer, immediately dried and Raman shift was measured to be 900cm under the conditions of using an excitation wavelength of 785nm, a collection time of 5s and high power (about 100 mW) -1 ～1800cm -1 And set up to 5 replicates, and then map the mean of the SERS response into a raman spectrum.
The raman spectra for the tin disulfide-gold composite materials used in the above examples 1 to 6 for detecting crystal violet substances and the raman spectra measured by dropping only crystal violet aqueous solution onto silicon wafer (i.e., blank control) are shown in fig. 26.
As can be seen from fig. 26: the tin disulfide-gold composites of examples 1-6 showed raman enhancement effects after mixing with the sample to be tested containing crystals, compared to the raman spectrum of the blank, and showed a raman shift of 1173cm -1 The signal value of the Raman response is the largest, and can be used as a characteristic response peak, and the content of crystal violet in the sample is detected by adopting a detection method and a detection principle similar to those for detecting methimazole.
In particular, the raman shift of the strongest characteristic signal peak in the raman spectrum is different for different molecules, and the interaction force (or the intermolecular affinity) between different molecules and the tin disulfide-gold composite material in examples 1 to 6 is different, so that the raman enhancement effect is different for different examples. Meanwhile, the focused point in the raman spectrogram in the specification is the intensity or area of a raman signal peak (namely, the difference between the signal intensities of a base line and a characteristic peak on the same raman spectrogram), and a plurality of raman spectrum data exist in the same spectrogram, so that the original data are subjected to translation processing in the ordinate direction for convenient observation, and the ordinate of the raman spectrogram mainly plays a role of a reference.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (4)
1. The tin disulfide-gold composite material is characterized by comprising tin disulfide nano sheets and gold nano particles growing on the surfaces of the tin disulfide nano sheets; the diameter of the tin disulfide nano sheet is 2-10 mu m; the gold nanoparticles are spheroidal particles with the particle size of 10 nm-300 nm;
the tin disulfide-gold composite material is prepared by the following method, which comprises the following steps:
mixing tin disulfide nanosheets, gold precursors and solvents, and carrying out ultrasonic-assisted reduction to obtain a tin disulfide-gold composite material;
wherein the mass ratio of the tin disulfide nanosheets to the gold precursor is 20:1-1:10;
the ultrasonic auxiliary reduction is carried out under the conditions that the ultrasonic frequency is 35 kHz-45 kHz and the ultrasonic power is 400W-500W;
the temperature of the ultrasonic-assisted reduction is 20-35 ℃;
the gold precursor is selected from one or more of gold trichloride, chloroauric acid trihydrate, sodium chloroaurate, potassium chloroaurate and ammonium chloroaurate; the solvent is one or more of water and ethanol.
2. The use of the tin disulfide-gold composite material of claim 1 in the detection of methimazole.
3. The method for detecting methimazole is characterized by comprising the following steps of:
1) Respectively mixing methimazole with different concentrations and the tin disulfide-gold composite material according to claim 1, measuring a Raman spectrum of the mixture, and constructing a standard curve;
2) Mixing the tin disulfide-gold composite material according to claim 1 with a solution to be tested, and measuring a Raman spectrum of the mixture;
3) Selecting 1365cm -1 And (3) calculating the methimazole content in the sample to be detected according to the Raman response intensity value and the standard curve in the step (1).
4. Use of the tin disulfide-gold composite material according to claim 1 for detecting crystal violet.
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