Keel authenticity identification method based on energy dispersion type X-ray fluorescence spectrometry

Abstract

The invention belongs to the technical field of traditional Chinese medicine identification, and provides an energy dispersion type X-ray fluorescence spectrometry-based dragon bone authenticity identification method, which comprises the following steps of: detecting a dragon bone sample to be detected by adopting an energy dispersion X-ray spectrometer, and calculating element composition and content in the detected sample by adopting a standard-sample-free basic parameter method; taking the occurrence characteristics of the U element as fingerprint characteristics for identifying the authenticity of the keel, if the EDX does not detect the U element, preliminarily judging that the to-be-detected keel sample is a counterfeit product, and if the U element is detected, preliminarily judging that the to-be-detected keel sample is a genuine product; and the determination result is further supported by combining the SrO content. The identification method disclosed by the invention is simple and convenient to operate, efficient and accurate, realizes nondestructive detection, and is particularly suitable for identifying precious medicinal materials.

Description

Technical Field

[0001] This invention belongs to the field of traditional Chinese medicine identification technology, specifically relating to a method for identifying the authenticity of dragon bone based on energy dispersive X-ray fluorescence spectroscopy. Background Technology

[0002] Dragon bone is a traditional mineral-based Chinese medicinal material, derived from the fossilized bones or tusks of ancient mammals such as three-toed horses, rhinoceroses, deer, cattle, and elephants. It possesses calming, sedative, and astringent properties, and is primarily used for palpitations, insomnia, and slow-healing sores. Due to the unique origin of dragon bone, there are currently no definitive substitutes. The circulation of dragon bone is decreasing, while market demand has been rising in recent years, leading to a corresponding increase in the price of genuine products. Dragon bone products come in various specifications, and the market is currently flooded with counterfeit products, such as modern bones processed to resemble dragon bone in surface features and shape, shaped using lime, or dragon bone fragments or powder mixed with loess and then bound together with adhesives.

[0003] The main methods for identifying dragon bone are morphological identification, microscopic identification, simple chemical identification, X-ray diffraction, and infrared spectroscopy. These methods have the following drawbacks: (1) strong subjectivity: morphological identification relies on experience and is easily affected by human factors; (2) destructive testing: chemical analysis requires grinding or dissolving the sample, which cannot preserve the original medicinal material; (3) low efficiency: existing technologies such as X-ray diffraction require complex pretreatment of the sample before testing, which cannot achieve rapid testing in large batches.

[0004] The increasing difficulty in identifying genuine and counterfeit dragon bones and evaluating their quality not only causes problems for enterprises but also affects the safety and efficacy of clinical medication. Therefore, there is an urgent need to find a new method for identifying dragon bones that is simple, efficient, and non-destructive. Summary of the Invention

[0005] The purpose of this invention is to provide a method for identifying the authenticity of keel based on energy dispersive X-ray fluorescence spectroscopy, in order to solve the problems of low efficiency, strong subjectivity, and high destructiveness in existing keel identification methods.

[0006] To achieve the above objectives, the specific technical solution of this invention is as follows: a method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy, which uses an energy-dispersive X-ray spectrometer (EDX) to detect the keel sample to be tested, and uses the standard-free basic parameter method (FP) to calculate the elemental composition and content in the sample; the presence characteristics of element U are used as fingerprint characteristics for identifying the authenticity of keel. If element U is not detected by EDX, the keel sample to be tested is preliminarily determined to be counterfeit; if element U is detected, the keel sample to be tested is preliminarily determined to be genuine.

[0007] The present invention is further configured such that the identification method also includes the detection of Sr element. If U element is detected in the keel sample to be tested, and the content of SrO is ≥0.19%, it further supports that the keel sample to be tested is genuine. If U element is not detected in the keel sample to be tested, and SrO <0.16%, it further supports that the keel sample is counterfeit.

[0008] The present invention is further configured such that the identification method also includes the detection of auxiliary elements, including Ba, Y, As, I, Pb, Nd and Ce; if at least two auxiliary elements are detected simultaneously in the keel sample to be tested, it further supports the determination of authenticity.

[0009] The present invention is further configured such that the EDX uses an Rh target X-ray tube and the element detection range is Al-U.

[0010] The present invention is further configured such that if the EDX does not detect the U element, that is, the U element content in the keel sample to be tested does not reach the detection limit, the U3O8 content is <0.001%.

[0011] The present invention is further configured such that the keel sample to be tested generally does not require sample treatment, and impurities such as mud adhering to the surface of special samples can be scraped off.

[0012] Compared with the prior art, the present invention has the following beneficial effects:

[0013] (1) High accuracy: This invention innovatively uses U element as fingerprint feature element, and the verification group accuracy reaches 100%, which is significantly better than traditional identification methods; (2) Non-destructive testing: The integrity of the sample is well maintained, which is especially suitable for the identification needs of precious medicinal materials; (3) High efficiency and speed: The detection time is short, which greatly improves the detection efficiency and is suitable for screening large batches of samples; (4) Simple operation: The detection method of this invention does not require complex pretreatment of the sample to be tested, which reduces the technical requirements for operators; (5) Good reproducibility: The detection results are stable and reliable, and are less affected by human factors; (6) Strong scalability: This method can be extended to the identification of other fossil medicinal materials (such as dragon teeth, stone swallows, etc.), providing technical support for the establishment of a standardized identification system for fossil medicinal materials. Attached Figure Description

[0014] Figure 1 This represents the percentage of each element in the entire sample.

[0015] Figure 2 Figures a to c show the average content of each element in the whole sample. Figures a to c show the content comparison results of genuine and counterfeit products. Counterfeit products include self-made counterfeit products and externally sourced counterfeit products. Figure d shows the content comparison results of self-made and externally sourced counterfeit products.

[0016] Figure 3 A bar chart showing the SrO content measured in each sample.

[0017] Figure 4 The presence characteristics of U and Sr in the sample. Detailed Implementation

[0018] The present invention will now be described with reference to specific embodiments; however, the scope of protection of the present invention is not limited to the following embodiments. After reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0019] This invention provides a method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy. The method involves using an energy-dispersive X-ray spectrometer (EDX) to detect the keel sample and employing the standard-free basic parameter method (FP) to calculate the elemental composition and content of the sample. The presence of nitrogen (U) is used as a fingerprint-like characteristic for identifying the authenticity of the keel. If U is not detected by EDX, the keel sample is preliminarily determined to be counterfeit; if U is detected, the keel sample is preliminarily determined to be genuine.

[0020] Furthermore, the identification method also includes the detection of Sr element. If U element is detected in the keel sample to be tested, and the content of SrO is ≥0.19%, it further supports that the keel sample to be tested is genuine. If U element is not detected in the keel sample to be tested, and the content of SrO is <0.16%, it further supports that the keel sample is counterfeit.

[0021] Furthermore, the identification method also includes the detection of auxiliary elements, which include Ba, Y, As, I, Pb, Nd and Ce; if at least two auxiliary elements are detected simultaneously in the keel sample to be tested, it further supports the determination of authenticity.

[0022] In the embodiments of the present invention, the EDX uses an Rh target X-ray tube, the element detection range is Al-U, and each element is represented in oxide form.

[0023] In an embodiment of the present invention, U was not detected by EDX, indicating that the U content in the tested keel sample did not reach the detection limit of EDX, and the U3O8 content was <0.001%.

[0024] In embodiments of the present invention, the keel sample to be tested generally does not require sample treatment. For special samples with impurities such as mud on the surface, these can be scraped off.

[0025] The method of the present invention will be further described below with reference to specific embodiments.

[0026] Example 1

[0027] In a specific embodiment of the present invention, the instrument used is: an EDX-LE Plus energy-dispersive X-ray fluorescence analyzer, with an X-ray tube target material of Rh, a high-energy generator with a maximum tube voltage of 50kV, a maximum tube current of 1000μA, and a maximum output of 50W, analyzed under atmospheric conditions, with collimators available in 1 / 3 / 5 / 10mm sizes, and standard equipment including 5 primary filters (6 types including OPEN), PCEDX-Navi analysis software, a testing range of Al-U, and a Shimadzu (Japan) membrane; Mylar membrane (a type of high-molecular polyester film).

[0028] Test samples: Samples were collected from Bozhou Kaishuo Pharmaceutical Co., Ltd., totaling 31 batches. According to Ye Yuqing, an expert from the National Famous Traditional Chinese Medicine Experts Inheritance Studio, samples LG1-LG26 were genuine; samples CLG33-CLG37 were externally acquired counterfeit products; and samples SLG27-SLG32 were self-made counterfeit products. The handling method for self-made counterfeit products is shown in Table 1, and the information of the samples to be tested is shown in Table 2.

[0029] Table 1. Self-made counterfeit products and their handling methods

[0030]

[0031] Table 2 Information on Samples to be Tested

[0032]

[0033] A method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy, specifically including the following steps:

[0034] (1) Sample preparation: Generally, no sample preparation is required. For special samples with impurities such as mud on the surface, they can be scraped off as needed.

[0035] (2) Sample determination: Instrument: EDX-LE Plus; Atmosphere: Atmospheric; Collimator: 3mm; Sample cup: Mylar membrane, working conditions are shown in Table 3 below.

[0036] Table 3. Detection conditions for EDX

[0037]

[0038] During the determination, the sample to be tested is placed flat on a plate covered with a Mylar membrane, placed in the test window, the analysis conditions are selected, the sample name is entered, and the start button is clicked. In this embodiment, the content of each element is calculated and measured using the standard-free basic parameter method. EDX testing was performed on 37 samples, with two sites randomly selected from each sample, for a total of 74 valid test sites.

[0039] (3) Results Analysis: Qualitative and quantitative analyses of genuine and counterfeit keel samples were performed using the EDX-LE Plus instrument under standard-free basic parameter conditions. The obtained energy spectra were analyzed using the system's built-in software, PCEDX-Navi, to quickly and accurately determine the main constituent elements (Ca, P, K, Cl, S, etc.), trace elements (Fe, Mn, Zn, etc.), rare earth elements (Y, Ce, Nd, etc.), and radioactive element (U), totaling 21 elements. The measured values ​​are expressed in the form of element oxides. The content of each element in the samples is shown in Tables 4 and 5. The percentage of each element in each sample is shown in... Figure 1 Counterfeit products include both self-made counterfeit products and externally sourced counterfeit products.

[0040] Table 4. Elemental (Oxide) Composition of Genuine Keel Bone

[0041]

[0042]

[0043] Table 5. Elemental composition (represented by oxides) of counterfeit products

[0044]

[0045] Combining the EDX detection process with Tables 4 and 5, Figure 1 , Figure 2 The EDX test results shown indicate that genuine keel samples exhibit a U / La line at 13.62 kev, and U is detected in all genuine keel samples, representing a 100% detection rate. In contrast, all counterfeit samples failed to reach the detection limit for U, meaning no U was detected. Therefore, this common difference between genuine and counterfeit products can be used as a fingerprint-like identification feature.

[0046] To further verify the above results, 10 batches of samples were randomly selected from the whole sample to form a verification group. Two sites were randomly selected from each sample for detection. The detection results of U element are shown in Table 6.

[0047] Table 6. Results of Random Sample Validation Tests

[0048]

[0049] In Table 6, "-" indicates that the element is not present or that the element is below the detection limit.

[0050] Table 6 shows that EDX did not detect U in any of the counterfeit keel samples (U3O8 content < 0.001%), while U was detected in all genuine samples. Therefore, based on the detection of U3O8 by EDX, the identification results show that the accuracy rate for identifying counterfeit products is 100%.

[0051] Further analysis of the EDX test results revealed a significant difference in SrO content between genuine and counterfeit keel bones. The SrO content in each sample was as follows: Figure 3 As shown, the average SrO content in genuine dragon bone is 0.392%, which is significantly higher than the 0.070% found in counterfeit products. Figure 3 The difference in SrO content between genuine and counterfeit products is readily apparent; the maximum SrO content (0.15%) in the counterfeit sample group is significantly lower than the minimum SrO content (0.193%) in the genuine sample group. Based on the above analysis results, the occurrence characteristics of U and Sr elements in genuine and counterfeit keel samples were analyzed, and the results are shown below. Figure 4 ,Depend on Figure 4 It is evident that genuine and counterfeit products can be further distinguished based on the content of U and Sr elements. Using characteristic elements as identification indicators can achieve the purpose of identification. Cluster analysis using SPSS software can further separate genuine and counterfeit products in the phylogenetic diagram.

[0052] Furthermore, according to the EDX test results shown above, the number of elements detected in the counterfeit products (SLG27-SLG32, CLG33-CLG37) is far fewer than that in the genuine products. The counterfeit products contained 13 elements: Ca, P, S, Fe, Cl, Sr, K, Mn, Cu, Zn, Ni, Ti, and Si. In contrast, genuine keel samples did not show the presence of Ba, Y, As, I, Pb, Nd, and Ce. Moreover, the element content of the counterfeit products was not significantly different between self-made and externally sourced products. Therefore, Ba, Y, As, I, Pb, Nd, and Ce are used as auxiliary elements to distinguish genuine from counterfeit keel.

[0053] In summary, the technical solution of this invention is the first to utilize EDX technology for non-destructive identification of dragon bones. The characteristic U element content of genuine and counterfeit dragon bones serves as a fingerprint-like feature for distinguishing their authenticity, and the SrO content in the dragon bone sample is used as a further identification feature. Simultaneously, the content of auxiliary elements, including Ba, Y, As, I, Pb, Nd, and Ce, can be included to assist in identification. This method is simple, accurate, and non-destructive, enabling rapid identification of large quantities of dragon bone medicinal materials.

[0054] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings are similarly included within the patent protection scope of the present invention.

Claims

1. A method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy, characterized in that, The keel sample was tested using EDX, and the elemental composition and content in the sample were calculated using the standard-free basic parameter method. The presence of element U was used as a fingerprint feature to identify the authenticity of the keel. If element U was not detected by EDX, the keel sample was preliminarily determined to be counterfeit. If element U was detected, the keel sample was preliminarily determined to be genuine.

2. The method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy according to claim 1, characterized in that, It also includes the detection of Sr. If the keel sample tested contains U and the SrO content is ≥0.19%, it further supports that the keel sample is genuine. If the keel sample tested does not contain U and the SrO content is <0.16%, it further supports that the keel sample is counterfeit.

3. The method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy according to claim 2, characterized in that, It also includes the detection of auxiliary elements, including Ba, Y, As, I, Pb, Nd and Ce. If at least two auxiliary elements are detected in the keel sample to be tested, it further supports the determination of authenticity.

4. The method for identifying the authenticity of keel based on energy-dispersive X-ray fluorescence spectroscopy according to claim 1, characterized in that, The EDX instrument uses an Rh target X-ray tube, and the element detection range is Al-U.

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