CN115283668A - 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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- CN115283668A CN115283668A CN202210854204.6A CN202210854204A CN115283668A CN 115283668 A CN115283668 A CN 115283668A CN 202210854204 A CN202210854204 A CN 202210854204A CN 115283668 A CN115283668 A CN 115283668A
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- methimazole
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- 239000002131 composite material Substances 0.000 title claims abstract description 148
- -1 Tin disulfide-gold Chemical compound 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 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 57
- 239000010931 gold Substances 0.000 claims abstract description 56
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a tin disulfide-gold composite material, and a preparation method and application thereof. The tin disulfide-gold composite material comprises a tin disulfide nanosheet and gold nanoparticles growing on the surface of the tin disulfide nanosheet, and the preparation method comprises the following steps: and mixing the tin disulfide nanosheet, the gold precursor and the solvent, 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 reducing agent, has the effects of high sensitivity, good reproducibility, good stability, simple operation and the like when being applied to detection and analysis, and has high practical application value.
Description
Technical Field
The invention relates to the technical field of detection and analysis, and particularly relates to a tin disulfide-gold composite material and a preparation method and application thereof.
Background
Methimazole (Thiamazole), an imidazole antithyroid drug, acts by inhibiting endoperoxidase in the thyroid, thereby hindering the synthesis of thyroxine (T4) and triiodothyronine (T3). At present, animal experiments show that methimazole can inhibit B lymphocytes from synthesizing antibodies, reduce the level of thyroid stimulating antibodies in blood circulation and restore the function of inhibitory T cells to normal. However, methimazole itself is also a carcinogen, so the research for detecting methimazole is of great significance.
Crystal violet, an excellent stain, is commonly used for nuclear staining and has a wide range of applications in cytology, histology, bacteriology, and the like. 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 technique that can use spectral fingerprints to identify and detect trace molecules, and is therefore widely used in the fields of food safety, environmental analysis, biomedicine, and the like. Coinage metals (gold, silver, copper, etc.) exhibit good performance in SERS applications due to their unique electromagnetic field enhancement effects. However, the uniformity and stability of the free metal particles are poor, which is not favorable for SERS quantitative analysis. However, the preparation of the existing material for preparing the surface-enhanced raman spectroscopy is often complex in process, high in cost and uncontrollable, so that the problem of obtaining a composite material which can be used for trace detection, accurate detection and rapid analysis is still a problem.
Therefore, there is a need to develop a material and method for detecting methimazole and crystal violet rapidly, accurately and sensitively.
Disclosure of Invention
In order to solve the technical problems of slow detection, high detection limit, poor accuracy and low sensitivity in the detection of methimazole and crystal violet in the prior art, the invention aims 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.
The invention also aims to provide application 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, the composition of which comprises a tin disulfide nanosheet and gold nanoparticles grown on the surface of the tin disulfide nanosheet.
Specifically, the tin disulfide-gold composite material is directly modified on the surface of the tin disulfide nanosheet through the spheroidal gold nanoparticles, and the gold nanoparticles can more firmly grow on the surface of the tin disulfide nanosheet through the action of Au-S bonds.
Preferably, the sheet diameter of the tin disulfide nanosheet is 2 to 10 μm.
Preferably, the gold nanoparticles are spheroidal particles with a particle size of 10nm to 300nm.
Further preferably, the gold nanoparticles are spheroidal particles with a particle size of 100nm to 150nm.
In a second aspect, the present invention provides a method for preparing the tin disulfide-gold composite material of the first aspect, comprising the following steps: and mixing the tin disulfide nanosheet, the gold precursor and the solvent, and carrying out ultrasonic-assisted reduction to obtain the tin disulfide-gold composite material.
Specifically, in the preparation method of the tin disulfide-gold composite material, a reducing agent is not used, and the tin disulfide-gold composite material can be obtained only by ultrasonic-assisted reduction at the temperature of 20-35 ℃. The reason why the invention can obtain the tin disulfide-gold composite material only by means of ultrasonic-assisted reaction is that: the surface of the tin disulfide nanosheet is provided with sulfur element which can form Au-S bond with gold element, and under the premise of ultrasonic assistance and easy hydrolysis of chloroauric acid, the gold nanoparticles with metal valence state can directly grow on the surface of the tin disulfide nanosheet without adding a reducing agent.
Preferably, the mass ratio of the tin disulfide nanosheet to the gold precursor is 20.
More preferably, the mass ratio of the tin disulfide nanosheet to the gold precursor is 1.4-1:4.
Preferably, the gold precursor is selected from one or more of gold trichloride, chloroauric acid trihydrate, sodium chloroaurate, potassium chloroaurate and ammonium chloroaurate.
Further preferably, the gold precursor is selected from one or more of chloroauric acid trihydrate, sodium chloroaurate, potassium chloroaurate and ammonium chloroaurate.
Still further 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 nanosheet to the solvent is 1.
Preferably, the ultrasonic-assisted reduction is carried out under the conditions that the ultrasonic frequency is 35 kHz-45 kHz and the ultrasonic power is 400W-500W.
Further preferably, the ultrasonic-assisted reduction is carried out under the conditions that the ultrasonic frequency is 40kHz and the ultrasonic power is 450W.
Preferably, the temperature of the ultrasonic-assisted reduction is 20 ℃ to 35 ℃.
Further preferably, the temperature of the ultrasonic-assisted reduction is 25 ℃ to 30 ℃.
Preferably, the time of the ultrasonic-assisted reduction is 30min to 90min.
Further preferably, the time of the ultrasonic-assisted reduction is 40min to 80min.
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 nanosheet comprises the following steps: dissolving tin tetrachloride and cysteine in water, and carrying out hydrothermal reaction to obtain the tin disulfide nanosheet.
Preferably, the mass ratio of the stannic chloride to the cysteine is 1.5-1:1.
Preferably, the temperature of the hydrothermal reaction is 180-220 ℃.
Preferably, the time of the hydrothermal reaction is 15-24 h.
Preferably, the preparation method of the tin disulfide nanosheet further comprises the steps of centrifuging, washing the precipitate, and vacuum drying.
Preferably, the temperature of the vacuum drying is 40-80 ℃.
Preferably, the vacuum drying is performed under the condition that the vacuum degree is 0.1MPa to 1 MPa.
Preferably, the preparation method of the tin disulfide-gold composite material comprises the following steps:
1) Mixing the tin disulfide nanosheets with a solvent to prepare a tin disulfide nanosheet dispersion;
2) Dissolving the gold precursor in a solvent to prepare Jin Qianqu body fluid;
3) Mixing the tin disulfide nanosheet dispersion liquid obtained in the step 1) and the Jin Qianqu body fluid obtained 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 of step 1) is 0.5g/L to 4g/L.
Preferably, the concentration of the Jin Qianqu body fluid in the step 2) is 5 g/L-40 g/L.
Further preferably, the concentration of the Jin Qianqu body fluid in the step 2) is 10 g/L-25 g/L.
In a fourth aspect, the invention provides an application of the tin disulfide-gold composite material in the first aspect in detection of methimazole.
Preferably, the application is specifically: application of a tin disulfide-gold composite material in detecting content of methimazole in a serum sample.
In a fifth aspect, the invention provides a method for detecting methimazole, comprising the steps of:
1) Mixing methimazole with different concentrations and the tin disulfide-gold composite material in the first aspect respectively, measuring a Raman spectrogram of the mixture, and constructing a standard curve;
2) Mixing the tin disulfide-gold composite material and the solution to be detected, and then measuring a Raman spectrogram of the mixture;
3) Selecting 1365cm -1 And (3) calculating the content of methimazole in the sample to be detected according to the standard curve in the step 1).
Preferably, the mixing time in step 1) is 8min to 12min.
Further preferably, the mixing time in step 1) is 10min to 12min.
Preferably, the determination in step 1) and step 2) is carried out using a 785nm laser as a light source.
Preferably, the determination in step 1) and step 2) is a measurement of the Raman shift between 1000 and 1800cm -1 Raman spectrum of (a).
In a sixth aspect, the invention provides the use of the tin disulfide-gold composite material of the first aspect for detecting crystal violet.
The beneficial effects of the invention are: the tin disulfide-gold composite material has the advantages of controllable size of gold nanoparticles, simple preparation method and no need of reducing agent, and has the effects of high sensitivity, good reproducibility, good stability, simple operation and the like when being applied to detection and analysis, thereby having very high practical application value.
The method specifically comprises the following steps:
1) The gold nanoparticles in the tin disulfide-gold composite material directly grow on the surface of the tin disulfide nanosheet, are distributed uniformly, are firmly combined with the gold nanoparticles, 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 protection, no use of reducing agent, controllable gold nanoparticle particle size and good reproducibility;
3) According to the invention, gold nanoparticles are grown on the tin disulfide nanosheet 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 the tin disulfide-gold composite material for the determination of methimazole, and establishes a rapid, high-accuracy, good-repeatability, low-detection-limit and high-universality detection method for methimazole, and the detection limit of the method can be as low as 2.7ng/mL, the adding standard recovery rate is 89.7% -98.1%, and the Relative Standard Deviation (RSDs) is 2.1-8.5%, thereby showing that the detection method has the advantages of high accuracy and strong practicability in the determination of actual samples;
5) The tin disulfide-gold composite material is used as an auxiliary material for Raman spectrum analysis, and can be used for detecting a serum sample or an aqueous solution sample with low methimazole content;
6) The tin disulfide-gold composite material can also be used for detecting and analyzing crystal violet compounds, and can prove that the tin disulfide-gold composite material has wide application range and strong practicability.
Drawings
Figure 1 is an XRD spectrum of the tin disulfide nanoplatelets and the tin disulfide-gold composite of example 1.
Figure 2 is an SEM image of the tin disulfide nanoplatelets of example 1.
Figure 3 is an SEM image of the tin disulfide-gold composite of example 1.
Figure 4 is a particle size distribution plot of gold nanoparticles on a tin disulfide-gold composite in example 1.
Figure 5 is an SEM image of the tin disulfide-gold composite of example 2.
Figure 6 is a particle size distribution plot of gold nanoparticles on a tin disulfide-gold composite in example 2.
Figure 7 is an SEM image of the tin disulfide-gold composite of example 3.
Figure 8 is a graph of the particle size distribution of gold nanoparticles on the tin disulfide-gold composite in example 3.
Figure 9 is an SEM image of the tin disulfide-gold composite of example 4.
Figure 10 is a particle size distribution plot of gold nanoparticles on a tin disulfide-gold composite in example 4.
Figure 11 is an SEM image of the tin disulfide-gold composite of example 5.
Figure 12 is a graph of the particle size distribution of gold nanoparticles on a tin disulfide-gold composite in example 5.
Figure 13 is an SEM image of the tin disulfide-gold composite of example 6.
Figure 14 is a graph of the particle size distribution of gold nanoparticles on the tin disulfide-gold composite in example 6.
FIG. 15 is a Raman spectrum of the tin disulfide-gold composite material and the aqueous solution of methimazole of example 1 under different mixing time conditions.
Figure 16 is a graph of the results of the mixing of the tin disulfide-gold composite and the aqueous methimazole solution of example 1 measured at different mixing times for 1365cm -1 Histogram of the raman characteristic peak intensity at (a).
FIG. 17 is a Raman spectrum of the tin disulfide-gold composite material of examples 1 to 6 for detecting a methimazole aqueous solution having a concentration of 0.5 mg/L.
FIG. 18 is a Raman spectrum obtained by measuring different concentrations of methimazole aqueous solutions with the tin disulfide-gold composite material in example 1.
FIG. 19 is a standard curve of the tin disulfide-gold composite material of example 1 measured in different concentrations of methimazole in water.
FIG. 20 is a Raman spectrum of the tin disulfide-gold composite material prepared in the same batch for detecting the methimazole aqueous solution.
Fig. 21 is a raman spectrum of the tin disulfide-gold composite material prepared in different batches for detecting methimazole aqueous solution.
FIG. 22 is a Raman spectrum of the tin disulfide-gold composite of example 1 used to detect methimazole-containing serum-1.
FIG. 23 is a Raman spectrum of the tin disulfide-gold composite material 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.
Figure 25 is a raman spectrum of the tin disulfide-gold composite of example 1 used to detect methimazole-containing serum-4.
FIG. 26 is a Raman spectrum of the tin disulfide-gold composite material of examples 1 to 6 for detecting crystal violet substance.
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 the mixture into a reaction kettle, reacting for 18h at 200 ℃, centrifuging the product at 4000rpm for 3min, washing for three times, and drying in vacuum to obtain the tin disulfide nanosheet;
2) Dispersing the tin disulfide nanosheets obtained in the step 1) into water to obtain 2.0g/L of tin disulfide dispersion liquid;
3) Mixing 1.0mL of 2.0g/L tin disulfide dispersion liquid with 160 mu L of 20g/L chloroauric acid trihydrate aqueous solution, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of frequency of 40kHz, power of 450W and temperature of about 25-30 ℃ to obtain reacted liquid;
4) Centrifuging the liquid reacted in the step 3) for 3min under the condition that the rotating speed is 4000rpm, washing and precipitating for 3 times by using water, 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 the mixture into a reaction kettle, reacting for 18h at 200 ℃, centrifuging the product at 4000rpm for 3min, washing for three times, and drying in vacuum to obtain the tin disulfide nanosheet;
2) Dispersing the tin disulfide nanosheets obtained in the step 1) into water to obtain 2.0g/L of tin disulfide dispersion liquid;
3) Mixing 1.0mL of 2.0g/L tin disulfide dispersion liquid with 40 mu L of 20g/L chloroauric acid trihydrate aqueous solution, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of frequency of 40kHz, power of 450W and temperature of about 25-30 ℃ to obtain reacted liquid;
4) Centrifuging the liquid reacted in the step 3) for 3min under the condition that the rotating speed is 4000rpm, washing and precipitating for 3 times by using water, 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 the mixture into a reaction kettle, reacting for 18 hours at 200 ℃, centrifuging the product for 3min at 4000rpm, washing for three times, and drying in vacuum to obtain a tin disulfide nanosheet;
2) Dispersing the tin disulfide nanosheets obtained in the step 1) into water to obtain 2.0g/L of tin disulfide dispersion liquid;
3) Mixing 1.0mL of 2.0g/L tin disulfide dispersion liquid with 80 mu L of 20g/L chloroauric acid trihydrate aqueous solution, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of the frequency of 40kHz, the power of 450W and the temperature of about 25-30 ℃ to obtain reacted liquid;
4) Centrifuging the liquid reacted in the step 3) for 3min under the condition that the rotating speed is 4000rpm, washing and precipitating for 3 times by using water, 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 the mixture into a reaction kettle, reacting for 18h at 200 ℃, centrifuging the product at 4000rpm for 3min, washing for three times, and drying in vacuum to obtain the tin disulfide nanosheet;
2) Dispersing the tin disulfide nanosheets obtained in the step 1) into water to obtain 2.0g/L of tin disulfide dispersion liquid;
3) Mixing 1.0mL of 2.0g/L tin disulfide dispersion liquid with 240 mu L of 20g/L chloroauric acid trihydrate aqueous solution, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions that the frequency is 40kHz, the power is 450W and the temperature is about 25-30 ℃ to obtain liquid after reaction;
4) Centrifuging the liquid reacted in the step 3) for 3min under the condition that the rotating speed is 4000rpm, washing and precipitating for 3 times by using water, 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 the mixture into a reaction kettle, reacting for 18h at 200 ℃, centrifuging the product at 4000rpm for 3min, washing for three times, and drying in vacuum to obtain the tin disulfide nanosheet;
2) Dispersing the tin disulfide nanosheets obtained in the step 1) into water to obtain 2.0g/L of tin disulfide dispersion liquid;
3) Mixing 1.0mL of 2.0g/L tin disulfide dispersion liquid with 320 mu L of 20g/L chloroauric acid trihydrate aqueous solution, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of frequency of 40kHz, power of 450W and temperature of about 25-30 ℃ to obtain reacted liquid;
4) Centrifuging the liquid reacted in the step 3) for 3min under the condition that the rotating speed is 4000rpm, washing and precipitating for 3 times by using water, 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 the mixture into a reaction kettle, reacting for 18h at 200 ℃, centrifuging the product at 4000rpm for 3min, washing for three times, and drying in vacuum to obtain the tin disulfide nanosheet;
2) Dispersing the tin disulfide nanosheets obtained in the step 1) into water to obtain 2.0g/L of tin disulfide dispersion liquid;
3) Mixing 1.0mL of 2.0g/L tin disulfide dispersion liquid with 400 mu L of 20g/L chloroauric acid trihydrate aqueous solution, adding water to dilute the mixture to 4.0mL, and carrying out ultrasonic assisted reaction for 60min under the conditions of frequency of 40kHz, power of 450W and temperature of about 25-30 ℃ to obtain reacted liquid;
4) Centrifuging the liquid reacted in the step 3) for 3min under the condition that the rotating speed is 4000rpm, washing and precipitating for 3 times by using water, and drying at 60 ℃ to obtain the tin disulfide-gold composite material.
The vacuum drying in examples 1 to 6 was carried out under a vacuum degree of 0.1MPa to 1 MPa.
Characterization of materials
1) XRD patterns of the tin disulfide nanoplatelets and the tin disulfide-gold composite in example 1 are shown in fig. 1.
As can be seen from fig. 1: the characteristic peaks of the tin disulfide nanosheet in example 1 at 15.0 °, 28.2 °, 30.3 °, 32.1 °, 41.9 °, 49.9 ° and 52.5 ° correspond to the standard card PDF #23-0677, and belong to SnS 2 Characteristic peaks of the phase. Compared with the tin disulfide nanosheet, the tin disulfide-gold composite material not only contains SnS 2 The characteristic peaks of the phase, moreover containing the characteristic peaks at 38.2 °, 44.4 °, 64.6 °, 77.5 °, 81.7 °, which correspond to the gold standard card JCPDS #04-0784, attributed to the gold phase, make it possible to verify that the tin disulfide-gold composite material of example 1 consists of gold and tin disulfide.
It should be noted that, since the tin disulfide nanosheets in examples 2 to 6 were the same as in example 1, and the reaction principle for producing the tin disulfide-gold composite material was the same as in example 1, it can be said that the tin disulfide nanosheets and the tin disulfide-gold composite material in examples 2 to 6 had the same phase as in example 1.
2) The Scanning Electron Microscope (SEM) image of the tin disulfide nanoplatelets of example 1 is shown in fig. 2. SEM image of the tin disulfide-gold composite in example 1 is shown in fig. 3. The particle size distribution plot of the gold nanoparticles on the tin disulfide-gold composite 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 is composed of a tin disulfide nanosheet and gold nanoparticles growing on the tin disulfide nanosheet, and the gold nanoparticles are distributed on the tin disulfide nanosheet more uniformly in the embodiment 1, 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 nanoparticles distributed densely. Meanwhile, the sheet diameter of the tin disulfide nanosheet in example 1 is 2 to 5 μm, the particle diameter of the gold nanoparticles is 20 to 200nm, the distribution is mainly 100 to 150nm, and the average particle diameter of the particle diameter distribution of the gold nanoparticles is as follows: 124 +/-11 nm.
SEM images of the tin disulfide-gold composite material and the particle size distribution of the gold nanoparticles on the tin disulfide-gold composite material in example 2 are shown in fig. 5 and 6, respectively. SEM images of the tin disulfide-gold composite material and the particle size distribution of the gold nanoparticles on the tin disulfide-gold composite material in example 3 are shown in fig. 7 and fig. 8, respectively. The SEM image of the tin disulfide-gold composite material and the particle size distribution of the gold nanoparticles on the tin disulfide-gold composite material in example 4 are shown in fig. 9 and 10, respectively. The SEM image of the tin disulfide-gold composite material and the particle size distribution of the gold nanoparticles on the tin disulfide-gold composite material in example 5 are shown in fig. 11 and 12, respectively. The SEM image of the tin disulfide-gold composite material in example 6 and the particle size distribution diagram of the gold nanoparticles on the tin disulfide-gold composite material 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 produced tin disulfide-gold composite materials composed of tin disulfide nanosheets and gold nanoparticles grown on the tin disulfide nanosheets.
The conditions of the gold nanoparticles grown on the surface of the tin disulfide nanosheets in examples 1 to 6 are shown in table 1.
Table 1 cases of gold nanoparticles grown on the surface of tin disulfide nanosheets in examples 1 to 6
Note: the description of the "distribution" in the topographical features in table 1 refers specifically to the distribution of gold nanoparticles on the tin disulfide nanoplatelets.
As can be seen from fig. 5 to 14 and table 1: the main difference between the embodiments 2 to 6 lies in the difference between the particle size of the gold nanoparticles and the distribution thereof on the tin disulfide nanosheet, specifically: with the increase of the amount of chloroauric acid trihydrate, the particle size of the gold nanoparticles on the tin disulfide nanosheet gradually increased, and it is evident from examples 5 to 6 that the gold nanoparticles on the surface of the tin disulfide-gold composite material had stacked. The particle diameters of the gold nanoparticles in examples 2 to 5 were mainly distributed in the range of 25nm to 350nm.
Application example 1
A method for detecting methimazole, comprising the steps of:
1) Mixing 40 μ L of the tin disulfide-gold composite dispersion of example 1 (solvent is water) and 0.5mg/L of methimazole aqueous solution according to a volume ratio of 1:2, stirring, sucking 40 μ L of the mixed liquid drop on a silicon wafer at mixing time of 2min, 4min, 6min, 8min, 10min, 12min, respectively, drying immediately, and measuring Raman shift of 900cm under the condition of using excitation wavelength of 785nm -1 ～1800cm -1 The Surface-Enhanced Raman Scattering (SERS) response value is set to be measured in parallel for 5 times, and then the mean value of SERS response is plotted into a Raman spectrogram (see fig. 15), so as to obtain the most suitable mixing time (10 min to 12min, namely the mixing time when the strongest characteristic peak signal in the Raman spectrogram of fig. 16 is relatively stable);
2) Preparing methimazole standard solutions (the solvent is water) with the concentrations of 0, 5 mu g/L, 10 mu g/L, 50 mu g/L, 100 mu g/L, 250 mu g/L, 500 mu g/L, 750 mu g/L and 1000 mu g/L, and preparing the tin disulfide-gold composite material of the example 1 into 2mg/L tin disulfide-gold composite material dispersion liquid by using water;
3) Respectively taking 80 mu L of the methimazole standard solutions with different concentrations in the step 2), respectively mixing with 40 mu L of 2mg/L of the tin disulfide-gold composite material dispersion liquid of the embodiment 1, dripping the mixture on a silicon wafer, drying and measuring SERS response signal values, carrying out parallel measurement for 5 times, drawing a spectrogram according to the SERS response mean value, and calculating 1365cm of the spectrogram -1 A standard curve between the raman response intensity value at (a) and the methimazole concentration;
4) Mixing 40 mu L of 2mg/mL tin disulfide-gold composite material dispersion liquid (solvent is water) of example 1 with a sample to be detected (mixing time is more than 10 min) to prepare liquid, dripping the liquid on a silicon wafer, drying and measuring SERS response, carrying out parallel measurement for 5 times, drawing a spectrogram according to the SERS response mean value, and calculating 1365cm of the spectrogram -1 And (4) calculating the content of methimazole in the sample to be detected according to 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 sampled under different stirring and mixing time conditions (2 min, 4min, 6min, 8min, 10min, 12 min) to obtain corresponding raman spectra (corresponding to step 1 in application example 1), as shown in fig. 15. The tin disulfide-gold composite material and the methimazole aqueous solution in example 1 were measured for 1365cm under different sample preparation time conditions -1 A histogram of the raman characteristic peak intensity (corresponding to step 1 in application example 1) as 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 -1 The signal peak of (a) is the strongest, so it can be used as a characteristic peak to carry out the basis for quantitative analysis of methimazole. The Raman spectrum is at 1365cm with increasing time of mixing of the tin disulfide-gold composite and methimazole in the liquid -1 The intensity of the characteristic peak at the position is 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 overall response signal peak of the Raman spectrumIs the strongest, and shows that the Raman enhancement effect of the tin disulfide-gold composite material is more obvious. The raman spectrum when the mixing time of the tin disulfide-gold composite material and methimazole was 10min and 12min was slightly reduced in response intensity compared to the raman spectrum when the mixing time was 8min, but from fig. 16, it can be seen that the two sets of raman spectra at the 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 reliability.
In addition, as can be seen from fig. 15 and 16, the content of methimazole in the sample to be detected with a low concentration can be accurately and efficiently detected within about 10min by using the tin disulfide-gold composite material of the present invention.
It should be noted that the subsequent performance tests (fig. 17 to 26) are performed on the basis of fully mixing the tin disulfide-gold composite material and methimazole, that is, other raman spectrograms are measured by setting the stirring and mixing time of the sample to be measured and the tin disulfide-gold composite material to 10min to 12min for sample preparation.
2) After 40 μ L of the tin disulfide-gold composite dispersion (solvent is water) in 2mg/mL of examples 1 to 6 and 0.5mg/L of methimazole aqueous solution were mixed, the mixture was dropped on a silicon wafer, and a corresponding Raman spectrum was obtained by drying and measurement, as shown in FIG. 17. The blank in FIG. 17 is the Raman spectrum measured after drying of the wafer by dropping only the aqueous solution containing mercaptoimidazole.
As can be seen from fig. 17: the Raman spectra of examples 1-6 at the same concentration were measured at a Raman shift of 1365cm -1 All possess a strong signal peak. In comparison with examples 2 and 3, 1365cm is included in respect of examples 1, 4, 5 and 6 -1 The raman response signal peak intensity is relatively strong.
3) The raman spectrum obtained by using the tin disulfide-gold composite material in example 1 to detect different concentrations of methimazole standard solutions (corresponding to step 2 in application example 1) is shown in fig. 18. The intensity of the raman response signal peak at this position and the corresponding methimazole concentration are mathematically processed to obtain a standard curve graph of the tin disulfide-gold composite material of example 1 under different methimazole standard solution concentrations, as shown in fig. 19.
As can be seen from fig. 18 and 19: with the increase of the methimazole concentration, the concentration is 1365cm -1 The signal peak at (a) is gradually increased. The concentration C of the methimazole aqueous solution and the corresponding sample to be tested are positioned at 1365cm -1 The intensity I of the Raman signal peak is in a linear relation, and the relation of the intensity I and the Raman signal peak satisfies the following relation: i =272.0+10.27C 2 ＝0.9968。
4) And (3) repeatability test: 80 mu L of 0.5mg/L methimazole and 40 mu L of 2mg/L of the tin disulfide-gold composite dispersion liquid (the solvent is water) of the example 1 are mixed, the mixture is dripped on a silicon wafer, 27 random point SERS response values are tested after drying (785 nm laser is used as a light source, the integration time is 5 s), and a Raman spectrum of the same batch of tin disulfide-gold composite material for detecting methimazole is obtained, and is shown in figure 20.
In addition, 11 batches of tin disulfide-gold composite materials were prepared according to the method of example 1, under similar test conditions (using 785nm laser as light source and 5s integration time), and raman spectra of different batches of tin disulfide-gold composite materials for detecting methimazole were obtained, as shown in fig. 21.
As can be seen from fig. 20 and 21: the reproducibility of the Raman spectrogram of the tin disulfide-gold composite material prepared in the same batch and different batches is good, so that the Raman shift of the tin disulfide-gold composite material can be shown to be 1365cm -1 。
Application example 2
A method for detecting the content of methimazole in serum, comprising the steps of:
1) Respectively taking 40 mu L of serum sample-1, serum sample-2, serum sample-3 and serum sample-4 as samples to be detected, diluting the samples by one time with water (namely adding water to fix the volume to 80 mu L), uniformly mixing the samples with 40 mu L of tin disulfide-gold composite material, dropping 40 mu L of the mixture on a silicon wafer for drying, measuring an SERS response value by adopting 785nm laser as a light source, and drawing the mean value of the SERS response value into a Raman spectrogram (shown in figures 22-25);
2) Locating at 1365cm in Raman spectrum -1 The intensity of the characteristic peak (see table 2) is calculated by referring to the standard curve in application example 1 to obtain the concentration value of methimazole in clinical samples (i.e. the concentration of methimazole in the sample to be tested is calculated by referring to I =272.0+ 10.27C). The detection limit is the concentration at signal-to-noise ratio (S/N) 3:1. When the noise N =100, the detection limit was calculated to be 2.7 μ g/L by substituting the 3-fold signal-to-noise ratio into the curve.
Determination of recovery and relative standard deviation
The determination method comprises the following steps:
1) Sampling: respectively taking 40 mu L of serum sample-1, serum sample-2, serum sample-3 and serum sample-4 as samples to be detected;
2) And (3) adding and calculating: respectively mixing a sample (i.e. a test sample) to be tested with 40 mu L of 100 mu g/L methimazole standard solution and 200 mu g/L methimazole standard solution, then uniformly mixing with 40 mu L of 2.0mg/mL tin disulfide-gold composite material dispersion (the solvent is water) (the mixing time is 10-12 min), dripping on a silicon wafer for drying, and then adopting a 785nm laser as a light source to collect the mixture for 5s, wherein the Raman shift is measured to be 1365cm under the high-power (about 100 mW) condition -1 Calculating the corresponding recovery rate and Relative Standard Deviation (RSD), and calculating the following formula:
recovery = (spiked sample measurement-sample measurement) ÷ spiked amount × 100%;
relative standard deviation = [ (single measurement value-average value) ÷ average value ] × 100%.
The tin disulfide-gold composite material of example 1 was used to measure methimazole content in serum, and the results of the above test are shown in table 2.
TABLE 2 test results of methimazole content in different samples to be tested
Note: n in Table 2 represents the number of detections, and the standard solution concentration of methimazole in the labeling process in the table represents the amount of labeling.
The tin disulfide-gold composite material of example 1 was used to detect the raman spectrum of methimazole-containing serum-1, as shown in fig. 22. The raman spectrum of the tin disulfide-gold composite material of example 1 for detecting serum-2 containing methimazole is shown in fig. 23. The tin disulfide-gold composite material of example 1 was used to detect the raman spectrum of methimazole-containing serum-3, as shown in fig. 24. The tin disulfide-gold composite of example 1 was used to detect a raman spectrum of methimazole-containing serum-4, as shown at 25. The results of the tin disulfide-gold composite in example 1, used to test different methimazole-containing sera, are 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 content of the methimazole in a serum sample-1, a serum sample-2, a serum sample-3 and a serum sample-4 can be respectively detected to be 113.2 mu g/L, 89.1 mu g/L, 86.5 mu g/L and 89.8 mu g/L. Meanwhile, the recovery rate of the detection method in the 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 high accuracy.
Application example 3
A method for detecting crystal violet which differs from a method for detecting methimazole in that: selecting Raman shift 1173cm in Raman spectrum -1 As a basis for a standard curve and detection analysis, comprising the steps of:
1) Measuring the time for uniformly mixing the sample to be measured and the tin disulfide-gold composite material and obtaining an accurate Raman spectrogram;
2) Preparing crystal violet solutions (the solvent is water) with different concentrations, and preparing the tin disulfide-gold composite material into tin disulfide-gold composite material dispersion liquid by using water;
3) Respectively taking 40 mu L of the crystal violet solutions with different concentrations in the step 2), respectively mixing with the tin disulfide-gold composite material dispersion liquid, dripping on a silicon wafer, drying, measuring SERS response signal values, performing parallel measurement for 5 times, drawing a spectrogram according to the SERS response mean value, and calculating 1173cm of the spectrogram -1 A standard curve between the raman response intensity value at (a) and the crystal violet concentration;
4) Mixing the tin disulfide-gold composite material dispersion (water as solvent) and the sample to be detected (the mixing time is longer than the time in the step 1) to prepare liquid, dripping the liquid on a silicon wafer, drying and measuring SERS response, carrying out parallel measurement for 5 times, drawing a spectrogram according to the SERS response mean value, and calculating 1173cm of the spectrogram -1 And (4) calculating the content of the crystal violet in the sample to be detected according to the standard curve of the step 3).
Application example 4
A method of detecting crystal violet, comprising the steps of:
the same mass (40. Mu.L of 2 mg/mL) of the tin disulfide-gold composite dispersion of examples 1-6 (solvent water) and 0.1mg/L of crystal violet solution were mixed and stirred at a volume ratio of 1:2 for 10min, 40. Mu.L of the mixture was dropped onto a silicon wafer, immediately dried and measured for Raman shift of 900cm using an excitation wavelength of 785nm, a collection time of 5s, and high power (about 100 mW) -1 ～1800cm -1 And setting parallel determination for 5 times, and then drawing the mean value of SERS response into a Raman spectrogram.
The raman spectra obtained for the detection of crystal violet species and the raman spectra obtained by dropping only the crystal violet aqueous solution on the silicon wafer (i.e., blank control) for the tin disulfide-gold composite materials of examples 1 to 6 are shown in fig. 26.
As can be seen from fig. 26: compared with the raman spectrum of the blank control, the tin disulfide-gold composite material in the embodiments 1 to 6 shows the raman enhancement effect after being mixed with the sample to be tested containing the crystal, and the raman shift is 1173cm -1 The maximum signal value of the Raman response can be used as a characteristic response peak,and detecting the content of the crystal violet in the sample by adopting a detection method and a detection principle similar to those for detecting the methimazole.
In particular, the raman shifts of the strongest characteristic signal peaks in the raman spectra of different molecules are different, and the interaction forces (or intermolecular affinities) between the different molecules and the tin disulfide-gold composite materials in examples 1 to 6 are different, so that the raman enhancement effects of the different examples are different. Meanwhile, the concerned point in the raman spectrogram in the drawings in the specification is the intensity (i.e. the signal intensity difference between the baseline and the characteristic peak on the same raman spectrum curve) or the area of the raman signal peak, and a plurality of raman spectrum data exist in the same spectrogram, so that for convenience of observation, the original data is translated in the ordinate direction, and the ordinate mainly plays a role of reference.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A tin disulfide-gold composite material is characterized by comprising a tin disulfide nanosheet and gold nanoparticles growing on the surface of the tin disulfide nanosheet.
2. The tin disulfide-gold composite of claim 1, wherein: the diameter of the tin disulfide nanosheet is 2-10 μm; the gold nanoparticles are spheroidal particles with the particle size of 10 nm-300 nm.
3. A method of preparing a tin disulfide-gold composite as set forth in claim 1 or 2, comprising the steps of: and mixing the tin disulfide nanosheet, the gold precursor and the solvent, and carrying out ultrasonic-assisted reduction to obtain the tin disulfide-gold composite material.
4. The method for preparing a tin disulfide-gold composite material according to claim 3, characterized in that: the mass ratio of the tin disulfide nanosheet to the gold precursor is 20-1.
5. The method for preparing a tin disulfide-gold composite material according to claim 3 or 4, characterized in that: the ultrasonic-assisted reduction is carried out under the conditions that the ultrasonic frequency is 35 kHz-45 kHz and the ultrasonic power is 400W-500W.
6. The method for preparing a tin disulfide-gold composite material according to claim 3 or 4, characterized in that: the temperature of the ultrasonic-assisted reduction is 20-35 ℃.
7. The method for preparing a tin disulfide-gold composite material according to claim 3, characterized in that: 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.
8. Use of a tin disulfide-gold composite according to claim 1 or 2 for detecting methimazole.
9. The detection method of methimazole is characterized by comprising the following steps:
1) Mixing methimazole with different concentrations and the tin disulfide-gold composite material according to claim 1 or 2, respectively, measuring a Raman spectrum thereof, and constructing a standard curve;
2) Measuring a raman spectrum of the tin disulfide-gold composite material according to claim 1 or 2 after mixing with a solution to be measured;
3) Selecting 1365cm -1 And (3) calculating the content of methimazole in the sample to be detected according to the standard curve in the step 1).
10. Use of a tin disulfide-gold composite as set forth in claim 1 or 2 for detecting crystal violet.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009108125A1 (en) * | 2008-02-28 | 2009-09-03 | Agency For Science, Technology And Research | Gold nanoparticles |
| CN104227014A (en) * | 2014-09-18 | 2014-12-24 | 东南大学 | Method for preparing gold nano particle and graphene composite material through fast reduction |
| CN107598150A (en) * | 2017-08-15 | 2018-01-19 | 西北大学 | A kind of nano metal/red phosphorus composite and preparation method thereof |
| CN108448091A (en) * | 2018-03-20 | 2018-08-24 | 济南大学 | A kind of MoO2/SnS2Nanocomposite and preparation method thereof |
| US20180267049A1 (en) * | 2017-03-15 | 2018-09-20 | King Fahd University Of Petroleum And Minerals | Method for detecting methimazole by surface-enhanced raman scattering |
| CN110779789A (en) * | 2019-11-14 | 2020-02-11 | 北京蛋白质组研究中心 | Preparation of hydrophilic group modified two-dimensional magnetic nano material and application of hydrophilic group modified two-dimensional magnetic nano material in large-scale enrichment of glycopeptide |
| CN111871431A (en) * | 2020-08-27 | 2020-11-03 | 东北师范大学 | Tin disulfide/gold composite catalyst and preparation method and application thereof |
-
2022
- 2022-07-14 CN CN202210854204.6A patent/CN115283668B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009108125A1 (en) * | 2008-02-28 | 2009-09-03 | Agency For Science, Technology And Research | Gold nanoparticles |
| CN104227014A (en) * | 2014-09-18 | 2014-12-24 | 东南大学 | Method for preparing gold nano particle and graphene composite material through fast reduction |
| US20180267049A1 (en) * | 2017-03-15 | 2018-09-20 | King Fahd University Of Petroleum And Minerals | Method for detecting methimazole by surface-enhanced raman scattering |
| CN107598150A (en) * | 2017-08-15 | 2018-01-19 | 西北大学 | A kind of nano metal/red phosphorus composite and preparation method thereof |
| CN108448091A (en) * | 2018-03-20 | 2018-08-24 | 济南大学 | A kind of MoO2/SnS2Nanocomposite and preparation method thereof |
| CN110779789A (en) * | 2019-11-14 | 2020-02-11 | 北京蛋白质组研究中心 | Preparation of hydrophilic group modified two-dimensional magnetic nano material and application of hydrophilic group modified two-dimensional magnetic nano material in large-scale enrichment of glycopeptide |
| CN111871431A (en) * | 2020-08-27 | 2020-11-03 | 东北师范大学 | Tin disulfide/gold composite catalyst and preparation method and application thereof |
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