A graphdiyne / gold nanocomposite material, its preparation method and application

Abstract

This invention proposes a graphyne / gold nanocomposite material, its preparation method, and its application. The graphyne / gold nanocomposite material comprises graphyne and gold nanoparticles loaded on its surface. Graphyne can enrich the gold nanoparticles, and the gold nanoparticles loaded on the graphyne can generate a localized surface plasmon resonance effect, thereby providing a SERS signal response. The substrate of this invention exhibits good SERS signal response to dyes and plant toxins, and the substrate enhancement effect is stable and highly reproducible, ensuring the accuracy and reliability of the detection results. This invention also proposes the application of the above-mentioned graphyne / gold nanocomposite material as a surface-enhanced Raman scattering substrate for detecting isoxazole / tryptamine toxins in mushrooms. This enables rapid detection of psilocybin and amatoxins in complex matrices of fungal samples; it can be used for rapid screening of highly poisonous mushrooms and their products in food safety, showing significant application prospects.

Description

Technical Field

[0001] This invention belongs to the field of enhanced Raman spectroscopy materials technology, specifically relating to a graphdiyne / gold nanocomposite material, its preparation method, and its application. Background Technology

[0002] Mushroom poisoning is a global food safety issue. The highly poisonous Amanita mushroom contains amatoxins (α-amanitin, β-amanitin), which can cause acute liver failure with a mortality rate exceeding 20%. Traditional detection methods primarily rely on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS / MS), but this method requires expensive equipment, specialized operators, and complex sample pretreatment procedures, making it difficult to meet the needs of rapid on-site screening. In recent years, SERS technology has shown promise in the rapid detection of mushroom toxins due to its advantages of specific molecular fingerprints, ultra-high sensitivity, and portability.

[0003] Surface-enhanced Raman scattering (SERS) technology, due to its high sensitivity, shows great potential in trace substance analysis, environmental monitoring, and biomedical diagnostics. The SERS enhancement effect mainly originates from the localized surface plasmon resonance (LSPR) effect generated by noble metal nanostructures. However, traditional SERS technology still faces core challenges in practical applications: mushroom toxins are mostly nonpolar and low-affinity molecules, and these molecules have low enrichment efficiency near metal active sites, resulting in weak SERS signals and poor reproducibility. Conventional colloidal substrates also suffer from insufficient SERS signal stability and a lengthy target capture process. Therefore, there is an urgent need to develop a novel surface-enhanced Raman scattering substrate for mushroom toxins. Summary of the Invention

[0004] To overcome the problems existing in the prior art, one objective of this invention is to provide a graphdiene / gold nanocomposite material. A second objective is to provide a method for preparing the aforementioned graphdiene / gold nanocomposite material. A third objective is to provide applications of the aforementioned graphdiene / gold nanocomposite material. A fourth objective is to provide a method for detecting tryptamine toxins in mushrooms. A fifth objective is to provide a method for detecting isoxazole toxins in mushrooms.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of the present invention provides a graphyne / gold nanocomposite material, comprising graphyne (GDY); the surface of the graphyne is loaded with gold nanoparticles (AuNPs); the morphology of the graphyne is selected from powder, bulk, sponge, gel or film.

[0006] Preferably, the gold nanoparticles have a particle size of 10~40 nm.

[0007] More preferably, the gold nanoparticles have a particle size of 15~30 nm.

[0008] Preferably, the graphyne has a multi-layered block structure.

[0009] More preferably, the multi-layered block structure is formed by the stacking of large-scale thin blocks.

[0010] More preferably, the method for preparing graphynylene includes the following steps: using hexynylbenzene as a precursor, a coupling reaction is carried out on the surface of a copper sheet under catalysis to prepare graphynylene.

[0011] Preferably, the graphyne and gold nanoparticles are combined through π-π interactions / electrostatic interactions.

[0012] The second aspect of the present invention provides a method for preparing the graphyne / gold nanocomposite material described in the first aspect, comprising the following steps: reacting graphyne, a gold source and a reducing agent in a solvent to obtain the graphyne / gold nanocomposite material.

[0013] Preferably, the reducing agent includes at least one of ascorbic acid and sodium citrate.

[0014] Preferably, the gold source includes tetrachloroauric acid.

[0015] Preferably, the reaction temperature is 90~100℃.

[0016] Preferably, the reaction time is 30 to 120 minutes.

[0017] More preferably, the reaction time is 50-80 min.

[0018] Preferably, the mass ratio of the gold source to graphylene is (1~10):1.

[0019] The third aspect of this invention provides for the application of the graphdiyne / gold nanocomposite material described in the first aspect in any of the following aspects: a) Surface-enhanced Raman scattering substrate; b) Prepare a Raman spectroscopy detection system for detecting dye molecules; c) Raman spectroscopy detection of dye molecules; d) Prepare a Raman spectroscopy detection system for detecting plant toxins; e) Raman spectroscopy detection of plant toxins.

[0020] Preferably, the dye molecule includes at least one of malachite green, MB, crystal violet, rhodamine B, methyl green, and methyl violet.

[0021] Preferably, the plant toxin is a mushroom toxin.

[0022] More preferably, the types of mushroom toxins include cyclic peptides, isoxazoles, hydrazines, bipyridines, tryptamines, ergots, and choline derivatives.

[0023] More preferably, the tryptamine-type mushroom toxins include at least one of psilocybin, dephosphorylated psilocybin, and bufotoxin.

[0024] More preferably, the isoxazole-type mushroom toxins include at least one of muscarinic acid and amatoxins.

[0025] A fourth aspect of the present invention provides a method for detecting tryptamine toxins in mushrooms, comprising the following steps: S1. Plot the standard Raman spectrum curve of tryptamine toxins; S2. Extract the fungal sample with alcohol and collect the extract; dry the extract into a crude extract and redissolve it in a solution with pH 6 to obtain the test sample solution; mix the test solution with a dispersion of graphyne / gold nanocomposite material and incubate; perform Raman spectroscopy on the incubated mixture and calculate the concentration of tryptamine toxins in the test sample solution according to the standard curve.

[0026] Preferably, the tryptamine toxin is psilocybin.

[0027] Preferably, the Raman spectroscopy detection is performed when the Raman spectrum is located at 1552 cm⁻¹. -1 The intensity of the characteristic peak signal at that location.

[0028] Preferably, the specific method of step S1 includes: mixing standard solutions of tryptamine toxins of different concentrations with a dispersion of graphyne / gold nanocomposite material and incubating them; performing Raman spectroscopy on the incubated mixture and plotting a standard curve of tryptamine toxins based on the concentration and characteristic peak signal intensity.

[0029] Preferably, the linear range for the detection of tryptamine toxins is 1.0~500.0 μg / L.

[0030] Preferably, the incubation time is 10-30 minutes.

[0031] The fifth aspect of this invention provides a method for detecting isoxazole toxins in mushrooms, comprising the following steps: S1. Plot the standard Raman spectrum curves of isoxazole toxins; S2. Extract the fungal sample with alcohol and collect the extract; dry the extract into a crude extract and redissolve it in a solution with pH 6 to obtain the test sample solution; mix the test solution with a dispersion of graphyne / gold nanocomposite material and incubate; perform Raman spectroscopy on the incubated mixture and calculate the concentration of isoxazole toxins in the test sample solution according to the standard curve.

[0032] Preferably, the isoxazole toxin is amatoxins.

[0033] Preferably, the Raman spectroscopy detection is performed when the Raman spectrum is located at 944 cm⁻¹. -1 The intensity of the characteristic peak signal at that location.

[0034] Preferably, the specific method of step S1 includes: mixing isoxazole toxin standard solutions of different concentrations with a dispersion of graphyne / gold nanocomposite material and incubating them; performing Raman spectroscopy on the incubated mixture and plotting a standard curve of isoxazole toxin based on the concentration and characteristic peak signal intensity.

[0035] Preferably, the linear range for the detection of isoxazole toxins is 5.0~500.0 μg / L.

[0036] Preferably, the incubation time is 5-20 minutes.

[0037] The beneficial effects of this invention are: This invention proposes a graphdiyne / gold nanocomposite material, wherein gold nanoparticles are loaded on the surface of the graphdiyne; wherein, graphdiyne, as a novel carbon material with high specific surface area, has sp and sp... 2 The two-dimensional planar structure composed of hybrid carbon atoms can enrich gold nanoparticles through π-π interactions / electrostatic interactions. Furthermore, the multi-layered bulk structure of graphyne, with its flake-like edges, facilitates the formation of active sites and the loading of metal atoms, accelerating the exposure and increase in the number of active sites. Gold nanoparticles loaded on graphyne can generate a localized surface plasmon resonance effect, thereby providing a SERS signal response. The substrate of this invention achieves a dual-functional effect of "enrichment + enhancement," exhibiting good SERS signal responses to dyes and plant toxins, with high sensitivity, high stability, and good batch-to-batch reproducibility. The substrate enhancement effect is stable and highly reproducible, ensuring the accuracy and reliability of the detection results.

[0038] This invention also proposes the application of the aforementioned graphdiene / gold nanocomposite material as a surface-enhanced Raman scattering substrate for the detection of isoxazole / tryptamine toxins in mushrooms. Specifically, the substrate of this invention exhibits high sensitivity for the detection of psilocybin and amatoxins, with limits of detection (LODs) reaching 0.35 μg / L and 1.3 μg / L, respectively, and wide linear ranges of 1.0-500.0 μg / L and 5.0-500.0 μg / L, respectively. The substrate of this invention demonstrates good selectivity and anti-interference properties in the detection of psilocybin and amatoxins, enabling rapid detection of psilocybin and amatoxin content in complex matrices of fungal samples. It can be used for rapid screening of highly poisonous mushrooms and their products in food safety applications, showing significant application potential. Attached Figure Description

[0039] Figure 1 This is a schematic diagram illustrating the experimental principle of GDY@AuNPs substrate preparation according to the present invention.

[0040] Figure 2 The images show the Raman spectral characterization (A), infrared spectral characterization (B), X-ray photoelectron spectroscopy (CD), and transmission electron microscopy (EF) of the GDY@AuNPs substrate of this invention.

[0041] Figure 3 This study investigates the time stability of the GDY@AuNPs substrate with psilocybin (A) and amatoxins (B) of this invention.

[0042] Figure 4 The SERS signal tests designed for different dyes on the GDY@AuNPs substrate of this invention are as follows: SERS spectra of malachite green standard solution at different concentrations (A); SERS spectra of methylene blue standard solution (B); SERS spectra of crystal violet standard solution (C); SERS spectra of rhodamine B standard solution (D); SERS spectra of methyl green standard solution (E); and SERS spectra of methyl violet standard solution (F).

[0043] Figure 5 The SERS signal enhancement factors of the dyes on the GDY@AuNPs substrate of this invention were calculated as follows: Malachite Green (A), Methylene Blue (B), Crystal Violet (C), Rhodamine B (D), Methyl Green (E), and Methyl Violet (F).

[0044] Figure 6 SERS spectra (A) of psilocybin standard solutions at different concentrations (1.0, 5.0, 10.0, 50.0, 100.0, 500.0 μg / L) and their corresponding standard curves and linear equations (B).

[0045] Figure 7 The results of the detection spectrum of psilocybin in mushroom samples by the GDY@AuNPs substrate of the present invention are shown in the following images: red onion Boletus sample (A), yellow onion Boletus sample (B), and purple onion Boletus sample (C).

[0046] Figure 8 SERS spectra (A) of muscarine standard solutions of different concentrations (5.0, 10.0, 50.0, 100.0, 500.0) and their corresponding standard curves and linear equations (B).

[0047] Figure 9 The results of the detection of amatoxins in mushroom samples using the GDY@AuNPs substrate are shown in the following spectra: red onion Boletus sample (A), yellow onion Boletus sample (B), and purple onion Boletus sample (C). Detailed Implementation

[0048] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials used in the following embodiments can be obtained from conventional commercial channels or prepared and isolated through simple synthesis; unless otherwise specified, the processes employed are conventional processes in the art.

[0049] Example 1 This embodiment provides a graphdiyne / gold nanocomposite material (GDY@AuNPs), which is prepared by electrostatic adsorption of GDY and AuNPs. The preparation process is described below. Figure 1 The specific preparation steps are as follows: Preparation of S1 and GDY: GDY was synthesized in situ on a copper substrate via a cross-coupling reaction (e.g. Figure 1 Desilication of Graphynylene monomer hexa[(trimethylsilyl)ethynyl)]benzene: Graphynylene monomer was dissolved in tetrahydrofuran under an ice-water bath and argon atmosphere. Tetrabutylammonium fluoride was added under light-protected conditions to initiate the desilication reaction. The reaction was quenched with ethyl acetate and washed with saturated sodium chloride solution. The upper organic phase was separated, dehydrated, filtered, and rotary evaporated to obtain hexaethynylbenzene. Hexaethynylbenzene cross-coupling reaction: Copper foil and 50 mL of pyridine were simultaneously added to a flask and heated to 110 °C under an argon atmosphere. Hexaethynylbenzene was dissolved in 50 mL of pyridine and slowly added to the flask through a constant-pressure separatory funnel, and reacted at 110 °C for 36 h. Product separation and purification: GDY grown on the copper sheet was ultrasonically exfoliated, and the product was washed successively with acetone and hot N,N-dimethylethylenediamine by centrifugation. Subsequently, the product was soaked in hydrochloric acid and sodium hydroxide solution for 3 h, washed with ultrapure water until the supernatant was neutral, and then dried in a vacuum drying oven at 60 °C for 24 h to obtain a black solid powder.

[0050] The product obtained in step (1) of Example 1 was characterized using Raman spectroscopy, infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Figure 2 As shown in A, the Raman spectrum is located at 1350 cm⁻¹. -1 1550 cm -1 The positions correspond to sp on the benzene ring, respectively. 2 The D peak is caused by defects and disorder in the hybrid carbon atom, and the G peak is caused by the stretching vibration of sp hybrid carbon atoms on the benzene ring. Furthermore, -C≡CC≡C- is observed at 2280 cm⁻¹. -1 The presence of a weak Raman signal indicates that GDY was successfully prepared. Figure 2 As shown in B, the IR spectrum of GDY is located at 1772 cm⁻¹. -1 and 1634 cm -1 The absorption at this point can be attributed to C=O and C=C bonds. The IR wavenumber is 2119 cm⁻¹. -1 A weak characteristic peak can be observed at this point, originating from C≡C tensile vibration. The XPS spectrum of GDY shows that its main elemental composition is C and O (…). Figure 2 (C in the middle). Figure 2 The D-value in the image shows the high-resolution C1s XPS spectrum of GDY. The C1s peak is fitted to four sub-peaks, among which the 284.3 eV sub-peak corresponds to the sp-value of the benzene ring. 2 The hybrid carbon-carbon double bond (C=C), the sub-peak at 285.2 eV is attributed to the sp hybrid carbon-carbon triple bond (C≡C), and the sub-peaks at 286.9 eV and 288.5 eV are attributed to CO and C=O, respectively.

[0051] Preparation of S2 and GDY@AuNPs substrates: The GDY@AuNPs substrate preparation process is as follows: Figure 1 As shown in section B: 100 μL of GDY aqueous dispersion (1 mg / mL) was added to 5 mL of 0.01 wt.% HAuCl4 aqueous solution and stirred at room temperature. The solution was then heated to 115 °C and boiled, with 20 μL of sodium citrate solution (1%) added dropwise. After reacting for 1 h, the mixture was cooled to room temperature. The resulting GDY@AuNPs solid was obtained by centrifugation, washed repeatedly with ultrapure water, and finally redispersed in 5 mL of ultrapure water. Figure 2E in the figure is the TEM characterization image of GDY. GDY is composed of large-scale thin block stacking, thus exhibiting a multi-layered block structure. The thin sheet-like structure at the edges is conducive to the formation of active sites and the loading of metal atoms, which accelerates the exposure and increase in number of active sites. Figure 2 F in the figure represents the TEM image of GDY@AuNPs obtained by the one-step reduction method. AuNPs loading was successfully implemented on GDY, while the basic morphology of GDY was maintained.

[0052] Time stability of GDY@AuNPs substrate: To investigate the time stability of the GDY@AuNPs substrate, the concentrations of psilocybin (50.0 μg / L) and amanitamine (500.0 μg / L) were fixed in this example, and the optimal substrate preparation conditions in steps (1) to (3) of Example 1 were selected. Psilocybin and amanitamine were located at 1552 cm⁻¹, respectively. -1 and 944 cm -1 The intensity fluctuation of the characteristic peak at the point of origin is less than 10.0% within 5 weeks, indicating that GDY@AuNPs has good stability within 5 weeks. Figure 3 ).

[0053] SERS performance characterization of GDY@AuNPs substrate The SERS signal enhancement factor of various dyes was calculated. EF (Enhancement Factor) EF Numerical values ​​were used to evaluate the SERS performance of the GDY@AuNPs substrate prepared in Example 1. EF The numerical calculation formula is as follows: (1); Among them, C Raman C represents the concentration of the analyte in a standard Raman spectroscopy experiment. SERS I represents the concentration of the analyte in the SERS experiment. Raman I represents the signal intensity of the characteristic peak of the same analyte measured under ordinary Raman conditions. SERS The signal intensity of the characteristic peak of the target analyte measured under SERS conditions.

[0054] In this experiment, malachite green, MB, crystal violet, rhodamine B, methyl green, and methyl violet dye standards were sequentially diluted with ultrapure water to gradients of 0.01, 0.10, 1.0, 100.0, and 1000.0 μg / L. These dye gradient solutions were then sequentially mixed with the GDY@AuNPs substrate dispersion prepared in Experiment 1 at a 1:1 volume ratio. After incubation for 10 min, 20.0 μL of the mixture was dropped onto a silicon wafer, and SERS measurements were performed under 785 nm laser irradiation. Figure 4As shown in A, the concentration of the malachite green standard solution is as low as 0.010 μg / L, and it is located at 1618 cm⁻¹. -1 The characteristic peaks can still be observed on the GDY@AuNPs substrate, indicating the presence of SERS signals for malachite green. EF Values ​​as high as 1.23 × 10 8 ( Figure 5 A in the example. Figure 4 As shown in B, the concentration of the MB standard solution is as low as 0.10 μg / L, located at 1620 cm⁻¹. -1 The characteristic peaks can still be observed at this location, indicating the SERS signal of the GDY@AuNPs substrate against the MB. EF The value reached 6.09 × 10 7 ( Figure 5 (B) in the example. Figure 4 As shown in C, when the concentration of the crystal violet standard solution is as low as 1.0 μg / L, it can be observed to be located at 1170 cm⁻¹. -1 Characteristic peaks, SERS signal of crystal violet on GDY@AuNPs substrate. EF The value is 1.95 × 10 6 ( Figure 5 (C in the text). For example, Figure 4 As shown in D, when the concentration of Rhodamine B standard solution reaches 10.0 μg / L, it is located at 1510 cm⁻¹. -1 The characteristic peaks can still be observed in the SERS signal of Rhodamine B on the GDY@AuNPs substrate. EF The value is 1.78 × 10 6 ( Figure 5 (D in the example). Figure 4 As shown in E, when the concentration of the methyl green standard solution is as low as 0.10 μg / L, it is located at 1620 cm⁻¹. -1 The characteristic peaks can still be observed on the GDY@AuNPs substrate for the SERS signal of methyl green. EF The value is 1.14 × 10 6 ( Figure 5 (E in the text). For example, Figure 4 As shown in F, when the concentration of the methyl violet standard solution is as low as 1.0 μg / L, it is located at 1620 cm⁻¹. -1 The characteristic peaks can still be observed on the GDY@AuNPs substrate for the SERS signal of methyl violet. EF The value is 4.08 × 10 5 ( Figure 5 (F in the text). In this experimental characterization, the SERS performance of GDY@AuNPs prepared in Experiment Characterization 1 was evaluated, and the SERS performance of this substrate for the various dyes mentioned above was calculated. EF The value can reach 10 5 ~10 8This indicates that the substrate has good SERS performance.

[0055] Application Example 1 This invention provides an application example of a method for detecting the psilocybin content in mushrooms, comprising the following steps: (1) The psilocybin standard was successively diluted with ultrapure water (pH=6) to concentrations of 1.0, 5.0, 10.0, 50.0, 100.0, and 500.0 μg / L. The above gradient solutions were then mixed sequentially with the GDY@AuNPs substrate dispersion prepared in Example 1 at a volume ratio of 1:1. After standing and incubating for 20 min, 20.0 μL of the mixture was dropped onto a silicon wafer, and SERS was measured under 785 nm laser irradiation. Figure 6 (A in the figure). Based on the relationship between the concentration of the target analyte and the SERS intensity, the corresponding linear equation was obtained, and the results are shown in the figure. Figure 6 (B in the standard curve). According to the standard curve, the substrate showed good linearity for psilocybin in the range of 1.0-500.0 μg / L, with a LOD of 0.35 μg / L (σ / s, n=11).

[0056] (2) Accurately weigh 2.0 g of uniform fungal sample and place it in a 15 mL centrifuge tube. Use methanol as the extraction solvent, with a solvent-to-sample ratio of 1:3 (mL / g). The extraction process is performed with ultrasonic assistance for 30 min, and the residual biomass is extracted four times. Filter the extract and obtain crude extract by rotary evaporation at 35 °C. Redissolve the crude extract in 5 mL of ultrapure water (pH=6) and filter using a 0.22 μm filter membrane. Mix the filtered extract with the GDY@AuNPs substrate dispersion prepared in Example 1 at a volume ratio of 1:1, incubate for 20 min, and drop the mixture (20.0 μL) onto a silicon wafer. Perform SERS determination under 785 nm laser irradiation. Figure 7 AC in the middle.

[0057] Application Example 2 The present invention provides a method for detecting the content of amanita phalloides in mushrooms, comprising the following steps: (1) The amanita muscarine standard was successively diluted with ultrapure water (pH=6) to concentrations of 5.0, 10.0, 50.0, 100.0, 500.0, and 1000.0 μg / L. The above gradient solutions were then mixed sequentially with the GDY@AuNPs substrate dispersion prepared in Example 1 at a volume ratio of 1:1, incubated for 10 min, and 20.0 μL of the mixture was dropped onto a silicon wafer. SERS measurements were performed under 785 nm laser irradiation. Figure 8 (A in the figure). Based on the relationship between the concentration of the target analyte and the SERS intensity, the corresponding linear equation was obtained, and the results are shown in the figure. Figure 8 (B in the text). According to the standard curve, the GDY@AuNPs exhibited good linearity in the range of 5.0–500.0 μg / L for amauridine, with a LOD of 1.3 μg / L (σ / s, n=11).

[0058] (2) Accurately weigh 0.2 g of uniform fungal sample and place it in a 15 mL centrifuge tube. Add 8 mL of 50% (V / V) methanol-containing 0.5% (V / V) formic acid aqueous solution, vortex mix for 1 min, and sonicate for 10 min. Prepare 10 mL of extract and mix well. Centrifuge and transfer the supernatant to the GDY@AuNPs substrate dispersion prepared in Example 1 at a volume ratio of 1:1. Incubate for 10 min, take 20.0 μL of the mixture, drop it onto a silicon wafer, and perform SERS determination under 785 nm laser irradiation. Figure 9 AC in the middle.

[0059] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A graphdiyne / gold nanocomposite material, characterized in that, The invention includes graphyne; the surface of the graphyne is loaded with gold nanoparticles; the morphology of the graphyne is selected from powder, bulk, sponge, gel or film.

2. The graphdiyne / gold nanocomposite material according to claim 1, characterized in that, The gold nanoparticles have a particle size of 10~40 nm.

3. The graphdiyne / gold nanocomposite material according to claim 1, characterized in that, The graphyne has a multi-layered blocky structure.

4. The method for preparing the graphdiyne / gold nanocomposite material according to any one of claims 1-3, characterized in that, The process includes the following steps: reacting graphyne, a gold source, and a reducing agent in a solvent to obtain the graphyne / gold nanocomposite material.

5. The method for preparing the graphdiyne / gold nanocomposite material according to claim 4, characterized in that, The reducing agent includes at least one of ascorbic acid and sodium citrate; And / or, the gold source includes tetrachloroauric acid.

6. The method for preparing the graphdiyne / gold nanocomposite material according to claim 4, characterized in that, The reaction temperature is 90~100℃.

7. The use of the graphdiyne / gold nanocomposite material according to any one of claims 1-3 in any of the following aspects: a) Surface-enhanced Raman scattering substrate; b) Prepare a Raman spectroscopy detection system for detecting dye molecules; c) Raman spectroscopy detection of dye molecules; d) Prepare a Raman spectroscopy detection system for detecting plant toxins; e) Raman spectroscopy detection of plant toxins.

8. The application according to claim 7, characterized in that, The plant toxin is a mushroom toxin; Preferably, the types of mushroom toxins include cyclic peptides, isoxazoles, hydrazines, bipyridines, tryptamines, ergots, and choline derivatives.

9. A method for detecting tryptamine toxins in mushrooms, characterized in that, Includes the following steps: S1. Plot the standard Raman spectrum curve of tryptamine toxins; S2. Extract the fungal sample with alcohol and collect the extract; dry the extract into a crude extract and redissolve it in a solution with a pH of 6 to obtain the test sample solution; mix the test sample solution with the dispersion of the graphyne / gold nanocomposite material according to any one of claims 1-3 and incubate it; perform Raman spectroscopy on the incubated mixture and calculate the concentration of tryptamine toxins in the test sample solution according to the standard curve.

10. A method for detecting isoxazole toxins in mushrooms, characterized in that, Includes the following steps: S1. Plot the standard Raman spectrum curves of isoxazole toxins; S2. Extract the fungal sample with alcohol and collect the extract; dry the extract into a crude extract and redissolve it in a solution with a pH of 6 to obtain the test sample solution; mix the test sample solution with the dispersion of the graphdiyne / gold nanocomposite material according to any one of claims 1-3 and incubate it; perform Raman spectroscopy on the incubated mixture and calculate the concentration of isoxazole toxins in the test sample solution according to the standard curve.

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