Method for identifying plant soot and common carbon adulterants thereof

Abstract

The invention discloses a method for identifying plant soot and common carbon counterfeit species thereof, which comprises a scanning electron microscope method, a Raman spectrum Raman method, a Fourier transform infrared spectroscopy (FTIR) method, an X-ray energy spectrum XPS method, a specific surface area test BET method and data analysis, can be used as a rapid qualitative identification method for traditional Chinese medicine plant soot and common carbon counterfeit species thereof, and has the advantages of high accuracy and good reproducibility.

Description

Technical Field

[0001] The present invention relates to a method for identifying medicinal materials, and specifically, to a method for identifying carbonized white frost and its common carbonaceous adulterants. Background Art

[0002] Carbonized white frost, also known as soot from the stove chimney, soot in the stove chimney, and soot from the cooking pot, etc., is the soot adhering to the stove chimney or chimney after weeds are burned. When collecting, it needs to be gently scraped off and the impurities are sifted out. "Compendium of Materia Medica" describes carbonized white frost as "this is the soot in the stove forehead and the smoke furnace. Its quality is light, so it is called frost". The traditional medicinal materials obtained by fire processing have a history of thousands of years in our country and can be traced back to "Prescriptions for Fifty-two Diseases" (recorded: "To stop bleeding, burn hair and apply it to the wound"), and are often used in diseases such as sores, blood syndromes, and arthralgia syndromes. Up to now, the theory of "carbonized medicine for hemostasis" has also been guiding clinical practice in traditional Chinese medicine, and many scientific research workers have actively carried out relevant research on the connotation of its hemostatic mechanism to provide guidance for clinical application. Carbonized white frost has a pungent and astringent taste and a warm nature, and can stop bleeding, promote blood circulation to remove stasis, and detoxify, and is applicable to hematemesis, hemoptysis, gingival bleeding, metrorrhagia and leukorrhagia, and oral ulcers. "Illustrated Classic of Materia Medica" mentions that carbonized white frost "mainly promotes digestion and relieves food stagnation, and it is often used in current food-digesting medicines"; "Compendium of Materia Medica" mentions that it "stops various types of bleeding above and below, and metrorrhagia and leukorrhagia in women... all kinds of sores in the throat and mouth"; "Yqiu's Explanation of Materia Medica" records that it "astringes nutrient qi to stop bleeding, clears heat and eliminates stasis... postpartum hemorrhage and various types of bleeding"; "Compendium of Medical Sciences" records that it "purges the heart and reduces fire, removes excessive heat, stops excessive bleeding, and reduces qi to eliminate food stagnation and promote phlegm movement". In addition, carbon-based drugs are also a current research hotspot, involving antibacterial, anti-inflammatory, and drug delivery.

[0003] Currently, carbonized white frost lacks an effective quality evaluation standard. The quality specification standards for carbonized white frost in each region are relatively rough, only making relevant descriptions of appearance traits and texture, etc., and failing to reflect effective quality control methods. Currently, there is no research on the quality control technology related to carbonized white frost, and there is a lack of a quality control method for carbonized white frost. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for identifying carbonized white frost and its common carbonaceous adulterants, which method has high accuracy and good reproducibility and can effectively identify carbonized white frost and its common carbonaceous adulterants.

[0005] To solve the above technical problems, the technical solution adopted by the present invention is:

[0006] A method for identifying Herba Artemisiae Argyi Carbonisata and its common carbonaceous adulterants is the scanning electron microscopy method, including the steps: The genuine Herba Artemisiae Argyi Carbonisata is self-collected and purchased, and the common carbonaceous adulterants are activated carbon or plant carbon samples made from peach wood, chestnut tree, and bamboo. An appropriate amount of the prepared genuine Herba Artemisiae Argyi Carbonisata or its common carbonaceous adulterant samples are placed in a carbon coater for carbon film coating treatment. The thickness of the coated film is about 10 nm. After the treatment is completed, the samples are taken out and fixed on the sample stage. Then, two silver conductive tapes are pasted between the front of the sample and the sample stage to form a conductive path to prevent the samples from being charged during the subsequent observation process. After the samples are installed, the sample stage is placed in the chamber, the chamber door is closed and evacuated. After the vacuum is completed, the electron beam is turned on, and the distance between the sample stage and the lens barrel is adjusted to achieve focusing. At this time, the samples present secondary electron SE images. For the samples, select an appropriate acceleration voltage, find the part to be observed at a low magnification in the Field view mode, appropriately scale the magnification MAG and focus WD, and perform stigmator STG processing to obtain a clear image. After all the parameter settings are completed, switch to the CL constant current mode, and adjust the brightness and contrast to the optimal state, and then take pictures and save the images. By observing the high-resolution images provided by the scanning electron microscopy SEM, the microstructure of the source carbon particles is carefully observed at a unified magnification of 3000 times. The surface of the genuine Herba Artemisiae Argyi Carbonisata particles is relatively rough, the particle sizes are different, presenting a loose porous structure formed by the aggregation of numerous tiny particles, and there are certain gaps between the particles, forming a relatively fluffy shape. The activated carbon particles of the carbonaceous adulterants present irregular sheet-like, fibrous, and needle-like morphological structures. The particles are stacked on top of each other, and there are some holes distributed on the surface, uneven, indicating a higher surface area and a more ordered pore arrangement; the peach wood carbon of the carbonaceous adulterants contains fibrous and sheet-like structures, intertwined and arranged; the chestnut tree carbon samples of the carbonaceous adulterants show sheet-like and layered structures, stacked on top of each other, and arranged relatively closely; the bamboo carbon samples of the carbonaceous adulterants have clearer surface characteristics of the particles, sharp edges, and show a fine structure.

[0007] The method for identifying Herba Artemisiae Argyi Carbonisata and its common carbonaceous adulterants also includes the Raman spectroscopy method, steps: Place an appropriate amount of Herba Artemisiae Argyi Carbonisata or its common carbonaceous adulterant samples in the middle of a glass slide, press with another glass slide to form a pressed tablet. Set the excitation wavelength of the UHTS300S_VIS spectrometer: 532.219 nm; laser power: 0.997 mW; laser power in the optical fiber: 1.211 mW; grating: G2: 600 g / mm; BLZ: 500.00 nm; central wavelength: 598.957 nm; spectral center: 2093.566 cm -1, configure the readout mode of the DV401_BVF camera: single track 1 - 20; vertical shift speed: 16.25; horizontal shift speed: 0.033 MHz; preamplifier gain: 1.00; cycle time: 5.09667 s; sensor temperature: -59 °C, set the number of accumulations to 1, the integration time to 5 s, set the objective magnification to 50.0 times, start the Raman spectrometer, and perform tests according to the set parameters. After Raman spectroscopy tests, all samples showed characteristic peaks of carbon. The results of self - collected and purchased carbon black from burned plant wick were similar, with relatively low signal intensity and relatively flat curves, indicating similar structures between the two. The signal peaks of activated carbon and chestnut charcoal samples were similar, and the signal intensities of bamboo charcoal and peach charcoal were the strongest. Especially, the intensity of the bamboo charcoal sample was significantly higher than that of other samples, especially with obvious peaks near 1600 cm -1 There is an obvious peak, namely the G peak.

[0008] The identification method of the above - mentioned carbon black from burned plant wick and its common carbon - based adulterants also includes the Fourier transform infrared spectroscopy (FTIR) method. Steps: The test samples are prepared using the tablet - pressing method. An appropriate amount of the sample is thoroughly mixed with potassium bromide in a ratio of 1:200 and ground until uniform. Then, the mixture is pressed into a thin film using a tablet press. Set the spectral scanning range to 4000 - 400 cm -1 , set the number of scanned frames to 16 frames, and the resolution to 4 / cm -1 , each sample is measured 3 times repeatedly. FTIR can detect the vibration modes of chemical bonds and is thus used to analyze the functional groups and chemical bonds in the sample. The infrared spectra of self - collected and purchased carbon black from burned plant wick samples have a high degree of similarity. The spectral peaks of bamboo - charcoal - sourced samples are relatively more, its chemical structure is more complex, containing more functional groups, and the C = C peak in the activated - carbon sample is relatively obvious.

[0009] The identification method of the soot and its common carbonaceous adulterants also includes the X-ray photoelectron spectroscopy (XPS) method. The steps are as follows: Use an X-ray photoelectron spectrometer to test the sample. The excitation source is the monochromatized Al-Kα light source. The power is 200 W during the analysis process. The XPS peaks are calibrated using the C1s peak at 284.8 eV. XPS is used to analyze the elemental composition of the surface of each sample. Three elements are detected in all appropriate samples: carbon, oxygen, and a small amount of nitrogen. The peak at 284.8 eV corresponds to alkyl-type carbon. The peaks at 286.1 - 286.5 eV correspond to alcohol and / or ether groups. The peaks at 288.6 - 289.1 eV correspond to carboxylic acid and ester groups. It is found that each sample consists of a C-C peak, namely peak 1, and a peak with a smaller peak area, namely peak 2 C-OH and / or C-O-C and O-C=O, namely peak 3. C-C represents that the material has more pure carbon structures. O-C=O indicates that there are more carbonyl or carboxyl groups on the material surface, meaning more functional groups or a higher degree of oxidation. C-OH indicates that the material has more hydroxyl groups and is more hydrophilic. The self-collected soot sample has the highest percentage of C-C and lower contents of C-OH and O-C=O. The samples from peach charcoal, chestnut charcoal, and bamboo charcoal have higher contents of C-OH. The sample of activated carbon has the highest content of O-C=O.

[0010] The identification method of the soot and its common carbonaceous adulterants also includes the Brunauer-Emmett-Teller (BET) method for specific surface area measurement. The steps are as follows: Place an appropriate amount of the sample at 125 °C and dry it for 8 hours. Weigh the mass of the sample and the sample tube. After loading the sample into the sample tube, place it in the degassing station and degas it at 100 °C for 1 h. After degassing, weigh the total mass of the sample tube and calculate the mass of the degassed sample. Load the sample tube into the instrument, add liquid nitrogen to the Dewar, set the bath temperature to 77.3 K, and the isotherm type to linear for testing. BET can provide the pore structure and surface properties of the material, and relevant information such as specific surface area and pore size distribution can be calculated. The adsorption isotherm shows the adsorption amounts of different samples at different relative pressures. The self-collected and purchased samples have lower adsorption amounts at low pressures. Activated carbon starts to adsorb significantly at low pressures. The pore sizes of all samples are in the range of 2 - 50 nm. The pore size distribution of activated carbon is concentrated in a smaller pore size range. The pore size distributions of the self-collected and purchased soot are wider, covering a variety of different pore sizes, and the internal structure is more complex. The specific surface area and micropore characteristics of the samples from peach charcoal, chestnut charcoal, and bamboo charcoal are between those of the self-collected samples and activated carbon, and the pore sizes are similar to those of activated carbon. The specific surface area of activated carbon is 1217.085 m² / g, the micropore volume is 0.382 cm³ / g, and the micropore area is 852.470 m² / g, which is much higher than other sample materials, while the average pore size is smaller among the samples. Activated carbon has more micropore structures and more adsorption sites. The specific surface area, micropore volume, and micropore area of the self-collected and purchased samples are smaller, and the average pore size is larger, mainly composed of mesopores.

[0011] The identification method of the soot and its common carbonaceous adulterants also includes data analysis. By using the mineral automatic analysis system TIMA, TESCAN Integrated Mineral Analyzer to view the SEM-related data, using LabSpec5 for basic data processing, conducting a preliminary analysis of the original data, performing peak fitting of the Raman spectrum through Origin 2024b, the process is as follows: analysis → peak value and baseline → peak value analysis → peak fitting → median → blank subtraction → peak addition → fitting degree adjustment → completion, and the peak area, peak height of the fitting data and the percentage of the peak area of the fitting data can be obtained. The FTIR spectrum is also corrected and smoothed for the baseline through Origin2024b, and XPS uses Avantage 6.8 for background subtraction and curve fitting.

[0012] After analysis by different methods, it is found that the soot has special physical and chemical properties. SEM shows that the surfaces of the self-collected and purchased soot particles are relatively rough, showing a loose and porous structure. This may be because the formation of the soot is due to the accumulation of soot generated by plant combustion on the chimney and the bottom of the pot. During this process, repeated high-temperature combustion and cooling may have led to the porosity and rough surface of the particles. The XPS analysis results further reveal that the soot has a high C-C percentage, which can indirectly indicate that repeated combustion has a significant impact on the proportion of oxides in the soot. The Raman spectra of the self-collected and purchased soot indicate a high degree of crystal defects and a relatively disordered structure, while the crystal structures of other samples are more perfect and have fewer defects, which highly coincides with the results observed by SEM. The FTIR spectra of the self-collected and purchased soot show that they have similar molecular skeletons and functional groups, further confirming the similarity of the self-collected and purchased soot in physical and chemical properties. The BET results show that the self-collected and purchased soot has a small specific surface area and is mainly composed of mesopores, but at relatively high relative pressures, it can adsorb more gas or liquid through the capillary condensation mechanism, which may be closely related to the exertion of its medicinal efficacy.

[0013] Through a variety of analysis means, the present invention reveals the differences in the physical and chemical properties between the soot and its common carbonaceous adulterated products, provides a scientific basis for the quality control and clinical application of the soot, and helps to promote the modernization of the quality control standard of the soot and its application and development in modern medicine. Future research can further explore the clinical efficacy and pharmacological mechanism of the soot, continuously enrich its theoretical basis, and provide support for the scientific nature of the clinical application of the soot. Description of the Drawings

[0014] Figure 1 Details of the sample scanning electron microscope (a - e self-collected; f - j purchased; k - m activated carbon; n - p peach charcoal; q - s chestnut charcoal; t - v bamboo charcoal);

[0015] Figure 2 Raman superposition spectra of various samples;

[0016] Figure 3 Raman spectrum peak fitting of different samples (A) Self - collected; (B) Purchased; (C) Activated carbon; (D) Peach wood charcoal; (E) Chestnut tree charcoal; (F) Bamboo charcoal;

[0017] Figure 4 Fourier transform infrared spectra of different samples; Z: Self - collected soot from straw; G: Purchased soot from straw; H: Activated carbon; T: Peach wood charcoal; L: Chestnut tree charcoal; Z*: Bamboo charcoal;

[0018] Figure 5 C1s spectra and fitting curves of various samples (A) Self - collected; (B) Purchased; (C) Activated carbon; (D) Peach wood; (E) Chestnut tree; (F) Bamboo;

[0019] Figure 6 Nitrogen adsorption - desorption isotherms and pore size distribution maps of various samples. (A) Self - collected; (B) Purchased; (C) Activated carbon; (D) Peach wood; (E) Chestnut tree; (F) Bamboo. Detailed implementation manners

[0020] The present invention will be further described below in conjunction with the detailed implementation manners. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content recorded in the present invention, those skilled in the art can make various changes or modifications to the present invention, but these equivalent forms also fall within the scope defined by the appended claims of this application.

[0021] Example 1:

[0022] 1 Instruments and materials

[0023] 1.1 Instruments

[0024] Mira3 scanning electron microscope (TESCAN, Czech Republic); CL probe (TESCAN, Czech Republic); WITec alpha300R confocal Raman spectrometer (WITec, Germany) equipped with UHTS300 high - sensitivity spectrometer (WITec, Germany), iDus 401CCD camera (Andor Technology, Belfast), ZEISS EC Epiplan infinity - corrected plan - achromatic objective lens (ZEISS, Germany); Nicolet is5 Fourier transform infrared spectrometer; ESCALB 250 and ESCALAB250Xi photoelectron spectrometers (Thermo Fisher Scientific, USA); Autosorb - iQ automatic specific surface area and pore size distribution analyzer (Taconn, USA).

[0025] 1.2 Materials

[0026] Five batches of self - collected Palvis Fumi Carebonisatus, numbered as: Z1 (Bengbu, Anhui), Z2 (Bengbu, Anhui), Z3 (Weifang, Shandong), Z4 (Bengbu, Anhui), Z5 (Bengbu, Anhui); Five batches of Palvis Fumi Carebonisatus samples purchased from Bozhou Chinese Herbal Medicine Professional Market, identified as traditional Chinese medicine Palvis Fumi Carebonisatus by Professor Liu Xunhong of Nanjing University of Chinese Medicine, numbered as: G1 (Sanyitang, Bozhou, Anhui, S20230415), G2 (Huarongtang, Bozhou, Anhui, H20230415), G3 (Ruyintang, Bozhou, Anhui, R20230416), G4 (Tiancetang, Bozhou, Anhui, T20230417), G5 (Qianwengtang, Bozhou, Anhui, Q20230417); Three batches of activated carbon, numbered as: H1 (Liyang Zhuxi Activated Carbon Co., Ltd., 20240321), H2 (Liyang Zhuxi Activated Carbon Co., Ltd., 20240412), H3 (Liyang Zhuxi Activated Carbon Co., Ltd., 20240418). In addition, common and different - textured plants on the current market, such as Prunus persica (L.) Batsch (T1, T2, T3), Castanea mollissima Blume (L1, L2, L3), and Bambusoideae (Z*1, Z*2, Z*3), were selected to make corresponding plant charcoal samples. All samples passed through the 6 - mesh sieve (100 - mesh) of the pharmacopoeia.

[0027] 2 Methods

[0028] 2.1 Scanning Electron Microscope (SEM)

[0029] Put an appropriate amount of the prepared sample into the carbon - coating instrument for carbon - film coating treatment, and the film thickness is about 10 nm. After the treatment, take out the sample and fix it on the sample stage. Then, stick two silver conductive tapes between the front of the sample and the sample stage to form a conductive path to prevent the sample from charging during subsequent observation. After the sample is installed, place the sample stage in the chamber, close the chamber door and evacuate. After the vacuum is completed, turn on the electron beam. Adjust the distance between the sample stage and the lens barrel to achieve focusing. At this time, the image presented by the sample is a secondary electron (SE) image. Select an appropriate acceleration voltage for the sample, find the part to be observed at a low magnification in the Field mode, appropriately scale the magnification (MAG) and focus (WD), and perform astigmatism correction (STG) to obtain a clear image. After all parameter settings are completed, switch to the CL (constant current) mode, adjust the brightness and contrast to the best state, and then take pictures and save the images.

[0030] 2.2 Raman Spectroscopy

[0031] Place an appropriate amount of the sample in the middle of a glass slide and press it tightly with another glass slide to form a pressed slice. Set the excitation wavelength of the UHTS300S_VIS spectrometer: 532.219 nm; laser power: 0.997 mW; laser power in the optical fiber: 1.211 mW; grating: G2: 600 g / mm; BLZ: 500.00 nm; central wavelength: 598.957 nm; spectral center: 2093.566 cm -1 Configure the readout mode of the DV401_BVF camera: single track (1 - 20); vertical shift speed: 16.25; horizontal shift speed: 0.033 MHz; preamplifier gain: 1.00; cycle time: 5.09667 s; sensor temperature: -59 °C. Set the number of accumulations to 1 and the integration time to 5 s. Set the objective magnification to 50.0 times. Start the Raman spectrometer and perform tests according to the set parameters.

[0032] 2.3 Fourier Transform Infrared Spectroscopy (FTIR)

[0033] The test sample was prepared using the pressed slice method. An appropriate amount of the sample was thoroughly mixed with potassium bromide at a ratio of 1:200 and ground until homogeneous, and then the mixture was pressed into a thin slice using a tablet press. Set the spectral scanning range to 4000 - 400 cm -1 and set the number of scanning frames to 16 frames and the resolution to 4 / cm -1 and each sample was measured 3 times repeatedly.

[0034] 2.4 X-ray Photoelectron Spectroscopy (XPS)

[0035] The sample was tested using an X-ray photoelectron spectrometer. The excitation source was a monochromatized Al-Kα light source, the power was 200 W during the analysis process, and the XPS peaks were calibrated using the peak of C1s at 284.8 eV.

[0036] 2.5 Specific Surface Area Test (BET)

[0037] Place an appropriate amount of the sample at 125 °C and dry it for 8 hours. Weigh the mass of the sample and the sample tube, and after loading the sample into the sample tube, put it into the degassing station and degas it at 100 °C for 1 h. After degassing, weigh the total mass of the sample tube and calculate the mass of the sample after degassing. Load the sample tube into the instrument, add liquid nitrogen to the Dewar, set the bath temperature to 77.3 K, the isotherm type to linear, and perform the test.

[0038] 2.6 Data Analysis

[0039] View SEM-related data through the Mineral Automatic Analysis System (TIMA, TESCAN Integrated Mineral Analyzer). Use LabSpec 5 for basic data processing and conduct a preliminary analysis of the original data. Perform peak fitting of the Raman spectrum through Origin2024b (Analysis → Peaks and Baseline → Peak Analysis → Peak Fitting → Median → Subtract Background → Add Peak → Adjust Fit → Finish) to obtain the peak area, peak height of the fitting data, and the percentage of the peak area of the fitting data. The FTIR spectrum is also corrected for baseline and smoothed through Origin 2024b. XPS uses Avantage 6.8 for background subtraction and curve fitting.

[0040] 3 Results

[0041] 3.1 Scanning Electron Microscope (SEM)

[0042] By observing the high-resolution images provided by the scanning electron microscope SEM, the microstructure of the source carbon particles was carefully observed at a unified magnification of 3000 times. The surface of the genuine Baicao Frost particles is relatively rough, with different particle sizes, presenting a loose porous structure formed by the aggregation of numerous tiny particles, and there are certain gaps between the particles, forming a relatively fluffy morphology. The carbonaceous adulterated activated carbon particles show irregular sheet-like, fibrous, and needle-like morphological structures, with the particles stacked on top of each other, and there are some holes distributed on the surface, uneven, indicating a higher surface area and a more ordered pore arrangement; the carbonaceous adulterated peach charcoal contains fibrous and sheet-like structures, intertwined and arranged; the carbonaceous adulterated chestnut charcoal sample shows sheet-like and layered structures, stacked on top of each other, and arranged relatively closely; the surface characteristics of the carbonaceous adulterated bamboo charcoal sample particles are clearer, with sharp edges, showing a fine structure.

[0043] Specific process observation and reason analysis: By observing the high-resolution images provided by the SEM, the microstructure of the source carbon particles was carefully observed at a unified magnification of 3000 times ( Figure 1 ). It is worth noting that the surface of the Baicao Frost particles is relatively rough, with different particle sizes, presenting a loose porous structure formed by the aggregation of numerous tiny particles, and there are certain gaps between the particles, forming a relatively fluffy morphology ( Figure 1 a - e). In contrast, the particles of the purchased Baicao Frost are roughly the same as the self-collected samples, and most particles also show a rough surface ( Figure 1 f - j); the activated carbon particles show irregular sheet-like, fibrous, and needle-like morphological structures, with the particles stacked on top of each other, and there are some holes distributed on the surface, uneven, indicating a higher surface area and a more ordered pore arrangement ( Figure 1 k - m); the peach charcoal contains fibrous and sheet-like structures, intertwined and arranged (Figure 1 (n - p); Chestnut charcoal samples showed flaky and layered structures, stacked on top of each other and arranged relatively closely Figure 1 (q - s); The surface characteristics of bamboo charcoal sample particles were clearer, with sharp edges, showing a fine structure Figure 1 (t - v). Figure 1 SEM details of samples (a - e self - collected; f - j purchased; k - m activated carbon; n - p peach charcoal; q - s chestnut charcoal; t - v bamboo charcoal)

[0044] 3.2 Raman spectroscopy

[0045] Place an appropriate amount of soot or its common carbon - based adulterated samples in the middle of a glass slide, press it with another glass slide to form a pressed tablet. Set the excitation wavelength of the UHTS300S_VIS spectrometer: 532.219 nm; laser power: 0.997 mW; laser power in the optical fiber: 1.211 mW; grating: G2:600 g / mm; BLZ: 500.00 nm; central wavelength: 598.957 nm; spectral center: 2093.566 cm -1 , configure the readout mode of the DV401_BVF camera: single - track 1 - 20; vertical shift speed: 16.25; horizontal shift speed: 0.033 MHz; pre - amplifier gain: 1.00; cycle time: 5.09667 s; sensor temperature: - 59 °C. Set the accumulation times to 1 and the integration time to 5 s. Set the objective magnification to 50.0 times. Start the Raman spectrometer and perform tests according to the set parameters. After Raman spectroscopy tests, all samples showed characteristic peaks of carbon. The results of self - collected and purchased soot were similar, with relatively low signal intensity and a relatively flat curve, indicating similar structures between the two. The signal peaks of activated carbon and chestnut charcoal samples were similar, probably because the physical properties of the plant raw materials used to prepare activated carbon were similar to those of chestnut trees. The signal intensity of bamboo charcoal and peach charcoal was the strongest, especially the signal intensity of bamboo charcoal samples was significantly higher than that of other samples, especially with obvious peaks near 1600 cm -1 .

[0046] Specific process observation and reason analysis: After Raman spectroscopy tests, all samples showed characteristic peaks of carbon, but there were some differences( Figure 2 ). The results of self - collected and purchased soot were similar, with relatively low signal intensity and a relatively flat curve, indicating similar structures between the two. The signal peaks of activated carbon and chestnut charcoal samples were similar, probably because the physical properties of the plant raw materials used to prepare activated carbon were similar to those of chestnut trees. The signal intensity of bamboo charcoal and peach charcoal was the strongest, especially the signal intensity of bamboo charcoal samples was significantly higher than that of other samples, especially with obvious peaks near 1600 cm -1 .

[0047] The D peak is generated by the stretching vibrations of carbon-carbon (C-C) bonds and carbon-carbon double bonds (C=C), and it is related to the local defects and disorder of the material; the G peak is the in-plane stretching vibration of sp2 hybridized carbon atoms in carbon materials, indicating the existence of a highly ordered graphene layered structure in the material. The intensity ratio of the D peak to the G peak (I(D) / I(G)) is an important parameter for the crystal defects or disorder degree of carbon atoms in the material, reflecting the crystal quality and structural integrity of the material. When the ratio is higher, it indicates a higher degree of crystal defects or disorder of carbon atoms in the material; when the ratio is lower, it indicates a more perfect crystal structure and fewer defects in the material. In comparison, the I(D) / I(G) ratio of the self-collected sample is 0.91, indicating that the carbon material of this sample has a relatively high degree of disorder or crystal defects; the I(D) / I(G) ratios of the purchased sample and chestnut charcoal are close to that of the self-collected sample, also showing a high degree of disorder; the I(D) / I(G) ratios of the samples from activated carbon, peach charcoal, and bamboo charcoal are relatively low, indicating that these samples have a better crystal structure and a lower defect density (Table 1). This method can effectively distinguish carbon black from carbon samples from other sources.

[0048] Fitting the Raman spectral peaks of the samples ( Figure 3 and Table 2), the self-collected and purchased samples show certain similarities in the peak area ratio, but the high absolute peak area of activated carbon indicates more active sites. The area ratio of peak 1 to peak 2 of peach charcoal is the highest, indicating that it contains more aromatic structures, which may endow it with higher thermal stability and mechanical strength. The ratio of the bamboo-derived sample is the lowest, showing a higher content of carbonyl compounds.

[0049] Table 1 Intensity ratios of characteristic Raman spectral peaks of different samples

[0050]

[0051] Table 2 Fitting data of Raman spectral peaks of different samples

[0052]

[0053] 3.3 Fourier transform infrared spectroscopy (FTIR)

[0054] FTIR can detect the vibration modes of chemical bonds and is thus used to analyze the functional groups and chemical bonds in the sample. The infrared spectra of the self-collected and purchased carbon black samples have a high degree of similarity. The bamboo charcoal-derived sample has relatively more spectral peaks, its chemical structure is more complex, and it contains more functional groups. The C=C peak in the activated carbon sample is relatively obvious.

[0055] Specific process observation and reason analysis: FTIR can detect the vibration modes of chemical bonds and is thus used to analyze the functional groups and chemical bonds in the sample. Figure 4 For 4000 - 400 cm-1 The main peaks within the range are marked. The broad peak (Peak 1) near 3300 cm -1 is generated by the stretching vibration (v(O-H)) of the hydroxyl (-OH) group in the sample. The peak (Peak 2) appearing near 3000 cm -1 is an absorption peak (ν(C-H)) caused by the stretching vibration of C-H in saturated or unsaturated carbon in the sample. The peak (Peak 3) near 1700 cm -1 is the result of the stretching vibration of the carbon-oxygen double bond (C=O) in the hydroxyl group, commonly found in compounds containing C=O double bonds such as ketones, aldehydes, and carboxylic acids (ν(C=O)). The absorption peak (νring) generated by the vibration of the carbon skeleton appears at the position of Peak 4, and the wavenumber here is 1600 cm -1 or so. The peak (Peak 5) near 1430 cm -1 can be attributed to the vibration of the carbon-carbon double bond (C=C). The peak 6 near the wavenumber 1100 cm -1 is an absorption peak (ν(C-C)) generated by the stretching vibration of the C-C bond. The peak (Peak 7) appearing near 900 cm -1 is caused by the bending vibration of the C-H group (δ(C-H)). The infrared spectra of self-collected and purchased soot samples have a high similarity, indicating that they have similar molecular skeletons or functional group arrangements. The spectral peaks of the bamboo charcoal source samples are relatively more, its chemical structure is more complex, and it contains more functional groups. The C=C peak in the activated carbon sample is more obvious, and there are more C=C double bonds in this sample. Soot samples from other sources can be accurately distinguished from soot by the differences in FTIR spectra.

[0056] 3.4 X-ray Photoelectron Spectroscopy (XPS)

[0057] Three elements are detected in all samples: carbon, oxygen, and a small amount of nitrogen. The peak at 284.8 eV corresponds to alkyl-type carbon, the peaks at 286.1 - 286.5 eV correspond to alcohol and / or ether groups, and the peaks at 288.6 - 289.1 eV correspond to carboxylic acid and ester groups. It is found that each sample consists of a C-C peak, namely Peak 1, and a peak with a smaller peak area, namely Peak 2 C-OH and / or C-O-C and O-C=O, namely Peak 3. C-C represents that the material has a more pure carbon structure, O-C=O indicates that there are more carbonyl or carboxyl groups on the material surface, meaning more functional groups or a higher degree of oxidation, and C-OH indicates that the material has more hydroxyl groups and is more hydrophilic. The self-collected soot sample has the highest C-C percentage, and the contents of C-OH and O-C=O are lower. The contents of C-OH in the samples from peach charcoal, chestnut charcoal, and bamboo charcoal sources are higher, and the content of O-C=O in the activated carbon sample is the highest.

[0058] Specific process observation and reason analysis: XPS is used to analyze the elemental composition of the surface of each sample. Three elements are detected in all samples: carbon, oxygen, and a small amount of nitrogen. According to previous research results, the peak at 284.8 eV corresponds to alkyl-type carbon, the peak at 286.1 - 286.5 eV corresponds to alcohol and / or ether groups, and the peak at 288.6 - 289.1 eV corresponds to carboxylic acid and ester groups. Through a refined analysis of the carbon spectra of each sample ( Figure 5 ), it is found that each sample consists of a C-C peak (peak 1), a peak with a smaller peak area (peak 2) (C-OH and / or C-O-C), and O-C=O (peak 3). C-C represents that the material has more pure carbon structures, O-C=O indicates that there are more carbonyl or carboxyl groups on the material surface, meaning more functional groups or a higher degree of oxidation, and C-OH indicates that the material has more hydroxyl groups and is more hydrophilic. The self-collected soot sample has the highest percentage of C-C, indicating that it has more pure carbon structures and is closer to graphite materials. The low contents of C-OH and O-C=O in it also indicate its lower degree of oxidation (Table 3). The samples from peach charcoal, chestnut charcoal, and bamboo charcoal have higher contents of C-OH, probably due to their higher cellulose and lignin contents. The sample of activated carbon has the highest content of O-C=O, which may be related to the oxidation treatment process involved in its preparation.

[0059] Table 3 Chemical structure analysis of the C 1s fine spectrum

[0060]

[0061] 3.5 Specific surface area test (BET)

[0062] BET can provide information on the pore structure and surface properties of materials, and relevant information such as specific surface area and pore size distribution can be calculated. The adsorption isotherm shows the adsorption amounts of different samples at different relative pressures. The self-collected and purchased samples have lower adsorption amounts at low pressures, while activated carbon starts to adsorb significantly at low pressures. The pore sizes of all samples are in the range of 2 - 50 nm. The pore size distribution of activated carbon is concentrated in a smaller pore size range, and the pore size distributions of the self-collected and purchased soot are wider, covering a variety of different pore sizes, with a more complex internal structure. The specific surface areas and micropore characteristics of the samples from peach charcoal, chestnut charcoal, and bamboo charcoal are between those of the self-collected samples and activated carbon, and their pore sizes are similar to those of activated carbon. The specific surface area of activated carbon is 1217.085 m2 / g, the micropore volume is 0.382 cm3 / g, and the micropore area is 852.470 m2 / g, which are much higher than those of other sample materials, while the average pore size is smaller among the samples. Activated carbon has more micropore structures and more adsorption sites. The specific surface areas, micropore volumes, and micropore areas of the self-collected and purchased samples are smaller, and the average pore sizes are larger, mainly consisting of mesopores.

[0063] Specific process observation and reason analysis: BET can provide the pore structure and surface properties of materials, and relevant information such as specific surface area and pore size distribution can be calculated. The adsorption isotherm ( Figure 6 ) shows the adsorption amounts of different samples at different relative pressures. When the relative pressure is at a relatively high level, all isotherms rise sharply, indicating that the adsorption amount of the samples increases significantly under high pressure, but there are differences in the initial adsorption amount among different materials. The adsorption amounts of self - collected and purchased samples are lower at low pressure, while activated carbon starts to adsorb significantly at low pressure. The pore sizes of all samples are in the range of 2 - 50 nm. The pore size distribution of activated carbon is concentrated in a smaller pore size range, while the pore size distributions of self - collected and purchased soot from straw burning are wider, covering a variety of different pore sizes, and the internal structure is more complex. The specific surface areas and micropore characteristics of samples from peach charcoal, chestnut charcoal, and bamboo charcoal are between those of self - collected samples and activated carbon, and their pore sizes are similar to those of activated carbon. The specific surface area of activated carbon is 1217.085 m2 / g, the micropore volume is 0.382 cm3 / g, and the micropore area is 852.470 m2 / g, which are much higher than those of other materials, and the average pore size is smaller among the samples, indicating that activated carbon has more micropore structures, more adsorption sites, and excellent adsorption performance (Table 4). The specific surface areas, micropore volumes, and micropore areas of self - collected and purchased samples are smaller, and the average pore sizes are larger, indicating that the samples are mainly composed of mesopores and can adsorb more gas or liquid through the capillary condensation mechanism at relatively high relative pressures.

[0064] Table 4 Nitrogen adsorption performance parameters of different materials

[0065]

[0066] 4 Conclusions

[0067] Data analysis: View SEM - related data through the mineral automatic analysis system TIMA, TESCAN Integrated Mineral Analyzer, perform basic data processing using LabSpec 5, conduct preliminary analysis on the original data, perform peak fitting of Raman spectra through Origin 2024b, analyze → peak value and baseline → peak value analysis → peak fitting → median → subtract blank → add peak → adjust fitting degree → complete, and the peak area, peak height of the fitting data and the percentage of the peak area of the fitting data can be obtained. The FTIR spectrum is also corrected and smoothed for the baseline through Origin 2024b, and XPS uses Avantage 6.8 to subtract the background and perform curve fitting.

[0068] After analysis by different methods, it was found that soot has special physical and chemical properties. SEM showed that the surfaces of self - collected and purchased soot particles were relatively rough, showing a loose and porous structure. This may be because the formation of soot is due to the accumulation of soot produced by plant combustion on the chimney and the bottom of the pot. During this process, repeated high - temperature combustion and cooling may have led to the porosity and rough surface of the particles. The XPS analysis results further revealed that soot has a relatively high C - C percentage, which can indirectly indicate that repeated combustion has a significant impact on the proportion of oxides in soot. The Raman spectra of self - collected and purchased soot showed a relatively high degree of crystal defects and a disordered structure, while the crystal structures of other samples were more perfect with fewer defects, which was highly consistent with the results observed by SEM. The FTIR spectra of self - collected and purchased soot showed that they have similar molecular skeletons and functional groups, further confirming the similarity in physical and chemical properties between self - collected and purchased soot. The BET results showed that the specific surface areas of self - collected and purchased soot were relatively small and mainly composed of mesopores, but at relatively high relative pressures, they could adsorb more gas or liquid through the capillary condensation mechanism, which may be closely related to the exertion of its medicinal effects.

[0069] Through a variety of analytical means, the present invention reveals the differences in physical and chemical properties between soot and its common adulterated carbonaceous products, providing a scientific basis for the quality control and clinical application of soot, and contributing to the modernization of the quality control standards of soot and its application and development in modern medicine. Future research can further explore the clinical efficacy and pharmacological mechanisms of soot, continuously enrich its theoretical basis, and provide support for the scientific nature of the clinical application of soot.

[0070] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for identifying Baicao Frost and common charcoal-based counterfeits, characterized in that: It is a scanning electron microscope method, which includes the following steps: the genuine Baicao Frost is self-collected and purchased, and the common carbon-related counterfeits are activated carbon or corresponding plant carbon samples made of peach wood, chestnut tree, and bamboo. A proper amount of the prepared genuine Baicao Frost or its common carbon-related counterfeits are placed in a carbon coating instrument for carbon coating treatment, and the coating thickness is about 10nm. After the treatment is completed, the sample is taken out and fixed on the sample stage, and then two silver conductive tapes are attached between the front of the sample and the sample stage to form a conductive path to prevent the sample from being charged during subsequent observations. After the sample is installed, the sample stage is placed in the cabin, the cabin door is closed and vacuum is drawn, and the electron beam is turned on after the vacuum is completed, and the distance between the sample stage and the lens barrel is adjusted to achieve focusing. At this time, the sample presents a secondary electron SE image, and a suitable acceleration voltage is selected for the sample. The part to be observed is found at a low magnification in the field of view mode Field, the magnification MAG is appropriately zoomed in and WD is focused, and an anti-stigmation STG process is performed to obtain a clear image. After all parameters are set, the cut Switch to CL constant current mode, adjust the brightness and contrast to the best state, then take pictures and save the images. Observe the high-resolution images provided by the scanning electron microscope (SEM), and observe the microstructure of the source carbon particles at a uniform magnification of 3000 times. The surface of the genuine Baicao Frost particles is relatively rough, and the particles are of different sizes, showing a loose porous structure formed by the aggregation of many tiny particles, and there are certain gaps between the particles, forming a relatively fluffy shape. The activated carbon particles of the mixed and counterfeit charcoal show irregular flaky, fibrous and needle-like morphological structures. The particles are stacked on each other, and there are some holes on the surface, which is uneven, indicating a higher surface area and a more ordered arrangement of pores; the mixed and counterfeit peach charcoal contains fibrous and flaky structures, which are intertwined; the mixed and counterfeit chestnut charcoal samples of charcoal show flaky and layered structures, which are stacked on each other and arranged relatively tightly; the surface features of the mixed and counterfeit bamboo charcoal samples of charcoal are clearer, with sharp edges, showing a fine structure.

2. The method for identifying Baicao Cream and common charcoal-based counterfeits as claimed in claim 1, characterized in that: It also includes Raman spectroscopy, the steps are as follows: place an appropriate amount of Baicao Frost or its common carbon-based counterfeit sample in the middle of a glass slide, press it with another glass slide to form a pressed sheet, set the excitation wavelength of the UHTS300S_VIS spectrometer to 532.219nm; laser power to 0.997mW; laser power in the optical fiber to 1.211mW; Grating: G2: 600g / mm; BLZ: ​​500.00nm; Central wavelength: 598.957nm; Spectral center: 2093.566cm -1 , configure the readout mode of DV401_BVF camera: single track 1-20; vertical shift speed: 16.25; horizontal shift speed: 0.033MHz; preamplifier gain: 1.00; cycle time: 5.09667s; sensor temperature: -59℃, set the cumulative number to 1, the integration time to 5s, set the objective lens magnification to 50.0 times, start the Raman spectrometer, and test according to the set parameters. After Raman spectrum test, the samples all showed the characteristic peaks of carbon. The results of the self-collected and purchased Baicao Shuang were similar, the signal intensity was relatively low, and the curve was relatively flat, indicating that the two had similar structures. The signal peaks of activated carbon and chestnut charcoal samples were similar, and the signal intensities of bamboo charcoal and peach charcoal were the strongest. In particular, the intensity of bamboo charcoal samples was significantly higher than that of other samples, especially at 1600cm -1 There is an obvious peak nearby, namely the G peak.

3. The method for identifying Baicao Cream and common charcoal-based counterfeits as claimed in claim 1, characterized in that: It also includes Fourier transform infrared spectroscopy FTIR method, steps: test an appropriate amount of sample using tableting method to prepare, mix an appropriate amount of sample with potassium bromide at a ratio of 1:200 and grind until uniform, then use a tablet press to press the mixture into thin sheets, set the spectrum scanning range to 4000-400cm -1 , the scanning frame number is set to 16 frames, and the resolution is set to 4 / cm -1 Each sample was measured three times. FTIR can detect the vibration mode of chemical bonds, and then used to analyze the functional groups and chemical bonds in the samples. The infrared spectra of self-collected and purchased Baicao Frost samples have a high degree of similarity. The spectral peaks of bamboo charcoal-derived samples are relatively more, and their chemical structure is more complex, containing more functional groups. The C=C peak in the activated carbon sample is more obvious.

4. The method for identifying Baicao Cream and common charcoal-based counterfeits as claimed in claim 1, characterized in that: It also includes an X-ray energy spectrum XPS method, the steps are: use Xi photoelectron spectrometer to test the sample, the excitation source is Al-Ka light source after monochromatization, the power during the analysis is 200W, the XPS peak is calibrated using the C1s peak at 284.8eV, XPS is used to analyze the elemental composition of the surface of each sample, and three elements are detected in all appropriate samples: carbon, oxygen and a small amount of nitrogen. The peak at 284.8eV corresponds to alkyl carbon, the peak at 286.1-286.5eV corresponds to alcohol and / or ether, and the peak at 288.6-289.1eV corresponds to According to the carboxylic acid and ester groups, it was found that each sample consisted of a CC peak, i.e. peak 1, and a peak with a smaller peak area, i.e. peak 2, C-OH and / or COC and OC=O, i.e. peak 3. CC represents that the material has more pure carbon structure. OC=O indicates that there are more carbonyl or carboxyl groups on the surface of the material, which means more functional groups or a higher degree of oxidation. C-OH indicates that the material has more hydroxyl groups and is more hydrophilic. The self-collected Baicao Frost sample has the highest CC percentage, and the contents of C-OH and OC=O are lower. The contents of C-OH are higher in samples from peach charcoal, chestnut charcoal and bamboo charcoal, and the content of OC=O is the highest in the activated carbon sample.

5. The method for identifying Baicao Cream and common charcoal-based counterfeits as claimed in claim 1, characterized in that: It also includes the BET method for specific surface area test, the steps are as follows: place an appropriate amount of sample at 125°C, dry for 8 hours, weigh the mass of the sample and the sample tube, and put the sample into the sample tube and put it into the degassing station, degas at 100°C for 1 hour, weigh the total mass of the sample tube after degassing, calculate the mass of the sample after degassing, load the sample tube into the instrument, add liquid nitrogen to the Dewar, set the bath temperature to 77.3K, set the isotherm type to linear, and conduct the test. BET can provide the pore structure and surface properties of the material, and can calculate relevant information such as specific surface area and pore size distribution. The adsorption isotherm shows the adsorption amount of different samples under different relative pressures. The adsorption amount of self-collected and purchased samples is lower at low pressure. Activated carbon begins to adsorb significantly at low pressure. The pore size of all samples is 2-50n m, the pore size distribution of activated carbon is concentrated in the smaller pore size range, the pore size distribution of self-collected and purchased Baicao Frost is wider, covering a variety of pore sizes, and the internal structure is more complex. The specific surface area and micropore characteristics of samples from peach charcoal, chestnut charcoal, and bamboo charcoal are between the self-collected samples and activated carbon, and the pore size is similar to that of activated carbon. The specific surface area of ​​activated carbon is 1217.085m2 / g, the micropore volume is 0.382cm3 / g, and the micropore area is 852.470m2 / g, which are much higher than other sample materials, and the average pore size is smaller in the sample. Activated carbon has more microporous structure and more adsorption sites. The specific surface area, micropore volume and micropore area of ​​self-collected and purchased samples are smaller, and the average pore size is larger, which is mainly composed of mesopores.

6. The method for identifying Baicao Cream and common charcoal-based counterfeits as claimed in claim 1, characterized in that: It also includes data analysis, viewing SEM related data through the mineral automatic analysis system TIMA, TESCAN Integrated Mineral Analyzer, using LabSpec 5 for basic data processing, preliminary analysis of the original data, and peak fitting of the Raman spectrum through Origin 2024b, analysis → peak and baseline → peak analysis → peak fitting → median → subtract blank → add peak → adjust fit → complete, you can get the peak area, peak height and percentage of the peak area of ​​the fitting data, the FTIR spectrum is also corrected and smoothed by Origin 2024b, XPS uses Avantage 6.8 for background subtraction and curve fitting.

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