CN107957367B - Construction method of traditional Chinese medicine material element fingerprint and application of traditional Chinese medicine material element fingerprint in identification of producing areas of traditional Chinese medicine materials - Google Patents
Construction method of traditional Chinese medicine material element fingerprint and application of traditional Chinese medicine material element fingerprint in identification of producing areas of traditional Chinese medicine materials Download PDFInfo
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Abstract
The invention discloses a construction method of a traditional Chinese medicine material element fingerprint spectrum and application thereof in identifying the producing area of a traditional Chinese medicine material. The construction method comprises the steps of collecting and crushing traditional Chinese medicine samples in different producing areas, digesting and digesting the traditional Chinese medicines by using a microwave digestion instrument, measuring the element content in the traditional Chinese medicine samples by using an inductively coupled plasma mass spectrometry, and converting element composition into a traditional Chinese medicine element fingerprint spectrum with the abscissa representing the element type and the ordinate representing the element content by using a method of converting data into graphs. The construction method of the invention converts the element composition of the traditional Chinese medicinal materials into the element fingerprint map for the first time, is used for identifying the origin of the traditional Chinese medicinal materials, can more intuitively reflect the element difference information, improves the accuracy of origin identification, has the advantages of accuracy, convenience and quickness, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of analysis and test, and particularly relates to a method for constructing a traditional Chinese medicine element fingerprint spectrum and a traditional Chinese medicine producing area identification method based on the traditional Chinese medicine element fingerprint spectrum.
Background
The traditional Chinese medicine is a treasure of Chinese nationality, wherein the traditional Chinese medicine is an important component of Chinese medicine. The traditional Chinese medicinal materials in different producing areas may have differences in quality, drug effect and main component content, so that some illegal merchants sell traditional Chinese medicinal materials of counterfeit high-quality producing areas due to the drive of interests. The identification of the origin of the traditional Chinese medicinal materials has positive significance for protecting the rights and interests of consumers and producers and standardizing the market of the traditional Chinese medicinal materials.
The Chinese medicinal materials can absorb elements from soil and growth environment thereof in the growth process, so that the content and the variety of the elements of the Chinese medicinal materials in different production areas are different after the Chinese medicinal materials are harvested, and the enrichment degree of the elements in the Chinese medicinal materials is related to the elements in the growth soil. Therefore, the origin and the production area of the traditional Chinese medicinal materials can be identified by using the elements in the traditional Chinese medicinal materials.
At present, most of analysis technologies for tracing the origin of a place based on elements in food are combined with multivariate statistical methods, and an effective index is screened out by mainly measuring several or more elements and then utilizing mathematical statistical methods such as variance analysis, cluster analysis, discriminant analysis and the like to establish a discriminant model. The element fingerprint technology method is applied to the identification of the origin of food and is researched more, but most of the methods have the problems of few analysis element types, difference of effective identification index elements and the like, and cannot truly reflect the element information of the food. The chromatographic fingerprint can reflect the comprehensive condition of multiple indexes integrally and is widely applied to the aspects of quality control, authenticity identification and the like of traditional Chinese medicines, but the chromatographic fingerprint is only limited to organic component analysis, and the establishment of the element fingerprint for tracing the origin of the traditional Chinese medicines has not been reported at home and abroad.
Disclosure of Invention
The invention aims to: the method solves the problems that the traditional Chinese medicinal materials in the traditional Chinese medicinal material market have serious counterfeit origin place traditional Chinese medicinal materials and are difficult to identify, and provides a new method for constructing the element fingerprint of the traditional Chinese medicinal materials and a method for identifying the origin place of the traditional Chinese medicinal materials based on the element fingerprint of the traditional Chinese medicinal materials.
In order to achieve the purpose, the invention provides a method for constructing traditional Chinese medicine element fingerprints, which is characterized in that traditional Chinese medicine samples in different producing areas are collected and crushed, then a microwave digestion instrument is used for digesting and digesting the traditional Chinese medicines, an inductively coupled plasma mass spectrum is used for measuring the element content in the traditional Chinese medicine samples, and the element composition is converted into the traditional Chinese medicine element fingerprints with the abscissa representing the element type and the ordinate representing the element content by a method of converting data into graphs.
Specifically, the construction method of the fingerprint of the traditional Chinese medicine elements comprises the following steps:
(1) taking traditional Chinese medicinal materials of a target producing area and traditional Chinese medicinal materials of a producing area to be identified as traditional Chinese medicinal material samples, wherein the quantity of the traditional Chinese medicinal materials of the target producing area is more than 10;
(2) adding nitric acid into a traditional Chinese medicine sample, standing for reacting for 0.5h, then adding hydrogen peroxide, and digesting by using a microwave digestion instrument, wherein the method comprises the following steps: firstly, the temperature is 120 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 30 atm; ② the temperature is 150 ℃, the temperature is kept for 3min, and the upper limit of the pressure is 35 atm; ③ the temperature is 180 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 35 atm; fourthly, keeping the temperature at 210 ℃ for 15min, and keeping the upper limit of the pressure at 40 atm;
(3) the inductively coupled plasma mass spectrometry is used for respectively measuring the traditional Chinese medicine samples: the output power of the high-frequency generator is 1.55kW, the plasma gas is 15.0L/min, the auxiliary gas is 0.8L/min, the carrier gas is 0.8L/min, the compensation gas is 0.35L/min, the collision gas is helium, 4.3mL/min, the sampling depth is 10mm, automatic sample introduction is performed, the solution lifting rate is 0.4rps, the solution lifting time is 30s, the solution stabilizing rate is 0.1rps, the solution stabilizing time is 30s, an internal standard element is introduced on line through a T-shaped three-way pipe, and the atomizer: MicroMist; temperature of the atomization chamber: 2 ℃; the plasma gas, the auxiliary gas, the carrier gas and the compensation gas are all argon gas;
(4) converting the element data determined in the step (3) into an element fingerprint by a data-to-graph method: firstly, sorting elements according to the atomic number, then reducing the element content of more than 8000mg/kg by 10000 times, reducing the element content of 1000-8000 mg/kg by 1000 times, and reducing the element content of 20-1000 mg/kg by 10 times, then drawing a relation curve representing the element type and the content size, and connecting the curves by smooth lines to respectively obtain the traditional Chinese medicine element fingerprint of a target place of production and the traditional Chinese medicine element fingerprint of a place of production to be identified.
As a preferable technical scheme of the construction method of the fingerprint of the elements of the Chinese medicinal materials, the elements comprise 49 types: li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Ba, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hg, Tl, Pb, Bi.
As a preferable technical scheme of the construction method of the element fingerprint of the traditional Chinese medicine, in the step (4), when the element content is too low, a local amplification graph is adopted for representing the relation curve.
In order to achieve the purpose of the invention, the invention also provides a traditional Chinese medicine material element fingerprint spectrum which is constructed by the construction method of the traditional Chinese medicine material element fingerprint spectrum.
The fingerprint of the Chinese medicinal material element can be used for identifying the producing area of the Chinese medicinal material.
In order to achieve the above object of the present invention, the present invention further provides a method for identifying the origin of a Chinese medicinal material based on the fingerprint of the element of the Chinese medicinal material, which comprises the following steps:
(a) taking the average value of the element contents in at least ten traditional Chinese medicine samples of the target producing area as the standard content of the elements, and constructing a traditional Chinese medicine element standard fingerprint spectrum of the target producing area;
(b) constructing a traditional Chinese medicine element fingerprint spectrum of the traditional Chinese medicine of a target producing area;
(c) constructing a traditional Chinese medicine element fingerprint spectrum of a producing area to be identified;
(d) using SPSS software, adopting distance analysis in correlation analysis, and calculating the similarity between the traditional Chinese medicine element fingerprint spectrum of the traditional Chinese medicine material in the target origin place obtained in the step (b) and the traditional Chinese medicine element standard fingerprint spectrum of the target origin place obtained in the step (a) according to an included angle cosine formula to obtain the similarity range of the element standard fingerprint spectrum of the target origin place;
(e) using SPSS software, adopting distance analysis in correlation analysis, calculating the similarity between the traditional Chinese medicine element fingerprint spectrum of the origin to be identified obtained in the step (c) and the traditional Chinese medicine element standard fingerprint spectrum of the target origin obtained in the step (a) according to an included angle cosine formula, and if the obtained similarity is larger than the lowest value of the similarity range obtained in the step (d), judging the traditional Chinese medicine of the origin to be identified as the traditional Chinese medicine of the target origin; and (d) if the obtained similarity is less than the lowest value of the similarity range obtained in the step (d), judging that the traditional Chinese medicinal material of the origin to be identified is not the traditional Chinese medicinal material of the target origin.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the construction method of the invention converts the element composition of the traditional Chinese medicinal materials into the element fingerprint map for the first time, is used for identifying the origin of the traditional Chinese medicinal materials, can more intuitively reflect the element difference information, improves the accuracy of origin identification, has the advantages of accuracy, convenience and quickness, and has good application prospect.
Drawings
FIG. 1 is the standard fingerprint of the elements of the American ginseng from Jilin produced in example 1.
FIG. 2 is the fingerprint of the elements of American ginseng produced in Canada, obtained in example 2.
FIG. 3 is the fingerprint of the American ginseng obtained in example 3.
FIG. 4 is the fingerprint of the element of the Jilin produced American ginseng A obtained in example 4.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and the parameters, proportions and the like of the embodiments may be suitably selected without materially affecting the results.
Example 1
(1) Constructing traditional Chinese medicine material element fingerprint
a. 10 representative samples of American ginseng from Jilin were collected.
b. Microwave digestion and digestion of traditional Chinese medicinal materials: accurately weighing 0.5g of uniformly crushed traditional Chinese medicine samples, placing the samples in a microwave digestion tank, adding 5mL of nitric acid, standing for reaction for 0.5h, then adding 1mL of hydrogen peroxide, covering the digestion tank, placing the tank in a microwave digestion instrument for digestion, after digestion is finished, driving yellow smoke out on an electric heating plate, using ultrapure water to perform constant volume to 25mL, and simultaneously performing a flow blank experiment; wherein, the microwave digestion condition is divided into the following 4 stages: firstly, the temperature is 120 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 30 atm; ② the temperature is 150 ℃, the temperature is kept for 3min, and the upper limit of the pressure is 35 atm; ③ the temperature is 180 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 35 atm; fourthly, the temperature is 210 ℃, the temperature is kept for 15min, and the upper limit of the pressure is 40 atm.
c. The 49 elements tested by inductively coupled plasma mass spectrometry (ICP-MS) refer to: li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Ba, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hg, Tl, Pb, Bi.
Preparing a proper standard solution according to the content of the elements.
Standard solution: the method is characterized in that the method is characterized by comprising the following steps of preparing standard solution (1000ug/ml, national steel material testing center) of single elements of Sc, Hg, Se, P, Rb, Cs and Mo; ca. K, Mg and Na multi-element standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Ni, Pb, Sb, Sn, Sr, Ti, Tl, V, Zn multielement standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); la, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y multi-element standard solutions (100ug/ml, national analysis and test center for nonferrous metals and electronic materials) are respectively treated with 2 percent of HNO3Diluting step by step.
Internal standard solution: ge single element standard solution (1000ug/ml, national analysis and test center for nonferrous metals and electronic materials); rh, In and Re single element standard solutions (1000ug/ml, national center for testing iron and steel materials) were mixed and diluted.
The test conditions of inductively coupled plasma mass spectrometry (ICP-MS) refer to: the output power of the high-frequency generator is 1.55kW, the plasma gas (argon) is 15.0L/min, the auxiliary gas (argon) is 0.8L/min, the carrier gas (argon) is 0.8L/min, the compensation gas (argon) is 0.35L/min, the collision gas is helium, 4.3mL/min (He mode), the sampling depth is 10mm, automatic sampling is performed, the solution lifting rate is 0.4rps, the solution lifting time is 30s, the solution stabilizing rate is 0.1rps, the solution stabilizing time is 30s, the internal standard element is introduced on line through a T-shaped three-way pipe, and the atomizer: MicroMist; temperature of the atomization chamber: 2 ℃.
d. Converting element data into an element fingerprint spectrum in a mode of converting data into graphs, and the specific process comprises the following steps: firstly, sorting elements according to the size of atomic number; reducing the element (K) with the element content of more than 8000Mg/kg by 10000 times, reducing the element (Mg, P, Ca) with the element content of 1000-8000 Mg/kg by 1000 times, and reducing the element (Na, Al, Mn, Fe, Ba, Sr) with the element content of 20-1000 Mg/kg by 10 times; drawing a relation curve of the type of the element and the content of the element by using Excel software, wherein the curves are connected by adopting smooth lines; fourthly, elements with too low content are shown by adopting a local magnification graph.
(2) Identification of producing area of traditional Chinese medicinal materials based on element fingerprint
Taking the average value of the element content in 10 American ginseng samples produced in Jilin as the standard content of the element, constructing an element standard fingerprint of American ginseng produced in Jilin according to the construction method of the traditional Chinese medicine element fingerprint (see figure 1), using SPSS software to perform distance analysis in correlation analysis, and calculating the similarity of the element standard fingerprint and the element standard fingerprint of American ginseng produced in Jilin according to an included angle cosine formula (see table 1), wherein the similarity range of the element standard fingerprint of American ginseng produced in Jilin is 0.9368-0.9928.
TABLE 1 similarity of American ginseng samples from Jilin to their mean values
Example 2 identification of the origin of American ginseng produced in Canada
(1) Constructing traditional Chinese medicine mineral element fingerprint
a. Collecting American ginseng samples produced in Canada.
b. Microwave digestion and digestion of traditional Chinese medicinal materials: accurately weighing 0.5g of uniformly crushed traditional Chinese medicine samples, placing the samples in a microwave digestion tank, adding 5mL of nitric acid, standing for reaction for 0.5h, then adding 1mL of hydrogen peroxide, covering the digestion tank, placing the tank in a microwave digestion instrument for digestion, after digestion is finished, driving yellow smoke out on an electric heating plate, using ultrapure water to perform constant volume to 25mL, and simultaneously performing a flow blank experiment; wherein, the microwave digestion condition is divided into the following 4 stages: firstly, the temperature is 120 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 30 atm; ② the temperature is 150 ℃, the temperature is kept for 3min, and the upper limit of the pressure is 35 atm; ③ the temperature is 180 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 35 atm; fourthly, the temperature is 210 ℃, the temperature is kept for 15min, and the upper limit of the pressure is 40 atm.
c. The 49 elements tested by inductively coupled plasma mass spectrometry (ICP-MS) refer to: li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Ba, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hg, Tl, Pb, Bi.
Preparing a proper standard solution according to the content of the elements.
Standard solution: the method is characterized in that the method is characterized by comprising the following steps of preparing standard solution (1000ug/ml, national steel material testing center) of single elements of Sc, Hg, Se, P, Rb, Cs and Mo; ca. K, Mg and Na multi-element standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Ni, Pb, Sb, Sn, Sr, Ti, Tl, V, Zn multielement standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); la, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y multi-element standard solutions (100ug/ml, national analysis and test center for nonferrous metals and electronic materials) are respectively treated with 2 percent of HNO3Diluting step by step.
Internal standard solution: ge single element standard solution (1000ug/ml, national analysis and test center for nonferrous metals and electronic materials); rh, In and Re single element standard solutions (1000ug/ml, national center for testing iron and steel materials) were mixed and diluted.
The test conditions of inductively coupled plasma mass spectrometry (ICP-MS) refer to: the output power of the high-frequency generator is 1.55kW, the plasma gas (argon) is 15.0L/min, the auxiliary gas (argon) is 0.8L/min, the carrier gas (argon) is 0.8L/min, the compensation gas (argon) is 0.35L/min, the collision gas is helium, 4.3mL/min (He mode), the sampling depth is 10mm, automatic sampling is performed, the solution lifting rate is 0.4rps, the solution lifting time is 30s, the solution stabilizing rate is 0.1rps, the solution stabilizing time is 30s, the internal standard element is introduced on line through a T-shaped three-way pipe, and the atomizer: MicroMist; temperature of the atomization chamber: 2 ℃.
d. The method converts element data into an element fingerprint map (see fig. 2) by converting the data into a graph, and comprises the following specific processes: firstly, sorting elements according to the size of atomic number; reducing the element (K) with the element content of more than 8000Mg/kg by 10000 times, reducing the element (Mg, P, Ca) with the element content of 1000-8000 Mg/kg by 1000 times, and reducing the element (Na, Al, Mn, Fe, Ba, Sr) with the element content of 20-1000 Mg/kg by 10 times; drawing a relation curve of the type of the element and the content of the element by using Excel software, wherein the curves are connected by adopting smooth lines; fourthly, elements with too low content are shown by adopting a local magnification graph.
(2) Identification of producing area of traditional Chinese medicinal materials based on element fingerprint
And (3) using SPSS software to perform distance analysis in correlation analysis, calculating the similarity between the American ginseng element fingerprint produced in Canada and the American ginseng element standard fingerprint produced in Jilin to be 0.7951 according to an included angle cosine formula, and judging the American ginseng produced in non-Jilin to be consistent with the actual condition if the similarity is lower than a similarity threshold value 0.9368 of the American ginseng element standard fingerprint produced in Jilin.
Example 3 identification of the origin of American ginseng
(1) Constructing traditional Chinese medicine mineral element fingerprint
a. American ginseng samples were collected.
b. Microwave digestion and digestion of traditional Chinese medicinal materials: accurately weighing 0.5g of uniformly crushed traditional Chinese medicine samples, placing the samples in a microwave digestion tank, adding 5mL of nitric acid, standing for reaction for 0.5h, then adding 1mL of hydrogen peroxide, covering the digestion tank, placing the tank in a microwave digestion instrument for digestion, after digestion is finished, driving yellow smoke out on an electric heating plate, using ultrapure water to perform constant volume to 25mL, and simultaneously performing a flow blank experiment; wherein, the microwave digestion condition is divided into the following 4 stages: firstly, the temperature is 120 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 30 atm; ② the temperature is 150 ℃, the temperature is kept for 3min, and the upper limit of the pressure is 35 atm; ③ the temperature is 180 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 35 atm; fourthly, the temperature is 210 ℃, the temperature is kept for 15min, and the upper limit of the pressure is 40 atm.
c. The 49 elements tested by inductively coupled plasma mass spectrometry (ICP-MS) refer to: li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Ba, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hg, Tl, Pb, Bi.
Preparing a proper standard solution according to the content of the elements.
Standard solution: the method is characterized in that the method is characterized by comprising the following steps of preparing standard solution (1000ug/ml, national steel material testing center) of single elements of Sc, Hg, Se, P, Rb, Cs and Mo; ca. K, Mg and Na multi-element standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Ni, Pb, Sb, Sn, Sr, Ti, Tl, V, Zn multielement standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); la, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y multi-element standard solutions (100ug/ml, national analysis and test center for nonferrous metals and electronic materials) are respectively treated with 2 percent of HNO3Diluting step by step.
Internal standard solution: ge single element standard solution (1000ug/ml, national analysis and test center for nonferrous metals and electronic materials); rh, In and Re single element standard solutions (1000ug/ml, national center for testing iron and steel materials) were mixed and diluted.
The test conditions of inductively coupled plasma mass spectrometry (ICP-MS) refer to: the output power of the high-frequency generator is 1.55kW, the plasma gas (argon) is 15.0L/min, the auxiliary gas (argon) is 0.8L/min, the carrier gas (argon) is 0.8L/min, the compensation gas (argon) is 0.35L/min, the collision gas is helium, 4.3mL/min (He mode), the sampling depth is 10mm, automatic sampling is performed, the solution lifting rate is 0.4rps, the solution lifting time is 30s, the solution stabilizing rate is 0.1rps, the solution stabilizing time is 30s, the internal standard element is introduced on line through a T-shaped three-way pipe, and the atomizer: MicroMist; temperature of the atomization chamber: 2 ℃.
d. The method converts element data into an element fingerprint map (see fig. 3) by converting the data into a graph, and comprises the following specific processes: firstly, sorting elements according to the size of atomic number; reducing the element (K) with the element content of more than 8000Mg/kg by 10000 times, reducing the element (Mg, P, Ca) with the element content of 1000-8000 Mg/kg by 1000 times, and reducing the element (Na, Al, Mn, Fe, Ba, Sr) with the element content of 20-1000 Mg/kg by 10 times; drawing a relation curve of the type of the element and the content of the element by using Excel software, wherein the curves are connected by adopting smooth lines; fourthly, elements with too low content are shown by adopting a local magnification graph.
(2) Identification of producing area of traditional Chinese medicinal materials based on element fingerprint
And (3) using SPSS software to perform distance analysis in correlation analysis, calculating the similarity of the American ginseng element fingerprint and the Jilin American ginseng element standard fingerprint to be 0.8156 according to an included angle cosine formula, wherein the similarity is lower than a similarity threshold value 0.9368 of the Jilin American ginseng element standard fingerprint, and judging that the American ginseng is not the Jilin American ginseng and is consistent with the actual situation.
Example 4 identification of the origin of American Ginseng A from Jilin
(1) Constructing traditional Chinese medicine mineral element fingerprint
a. Collecting American ginseng A sample produced by Jilin.
b. Microwave digestion and digestion of traditional Chinese medicinal materials: accurately weighing 0.5g of uniformly crushed traditional Chinese medicine samples, placing the samples in a microwave digestion tank, adding 5mL of nitric acid, standing for reaction for 0.5h, then adding 1mL of hydrogen peroxide, covering the digestion tank, placing the tank in a microwave digestion instrument for digestion, after digestion is finished, driving yellow smoke out on an electric heating plate, using ultrapure water to perform constant volume to 25mL, and simultaneously performing a flow blank experiment; wherein, the microwave digestion condition is divided into the following 4 stages: firstly, the temperature is 120 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 30 atm; ② the temperature is 150 ℃, the temperature is kept for 3min, and the upper limit of the pressure is 35 atm; ③ the temperature is 180 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 35 atm; fourthly, the temperature is 210 ℃, the temperature is kept for 15min, and the upper limit of the pressure is 40 atm.
c. The 49 elements tested by inductively coupled plasma mass spectrometry (ICP-MS) refer to: li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Ba, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hg, Tl, Pb, Bi.
Preparing a proper standard solution according to the content of the elements.
Standard solution: the method is characterized in that the method is characterized by comprising the following steps of preparing standard solution (1000ug/ml, national steel material testing center) of single elements of Sc, Hg, Se, P, Rb, Cs and Mo; ca. K, Mg and Na multi-element standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Ni, Pb, Sb, Sn, Sr, Ti, Tl, V, Zn multielement standard solution (100ug/ml, national analysis and test center for nonferrous metals and electronic materials); la, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y multi-element standard solutions (100ug/ml, national analysis and test center for nonferrous metals and electronic materials) are respectively treated with 2 percent of HNO3Diluting step by step.
Internal standard solution: ge single element standard solution (1000ug/ml, national analysis and test center for nonferrous metals and electronic materials); rh, In and Re single element standard solutions (1000ug/ml, national center for testing iron and steel materials) were mixed and diluted.
The test conditions of inductively coupled plasma mass spectrometry (ICP-MS) refer to: the output power of the high-frequency generator is 1.55kW, the plasma gas (argon) is 15.0L/min, the auxiliary gas (argon) is 0.8L/min, the carrier gas (argon) is 0.8L/min, the compensation gas (argon) is 0.35L/min, the collision gas is helium, 4.3mL/min (He mode), the sampling depth is 10mm, automatic sampling is performed, the solution lifting rate is 0.4rps, the solution lifting time is 30s, the solution stabilizing rate is 0.1rps, the solution stabilizing time is 30s, the internal standard element is introduced on line through a T-shaped three-way pipe, and the atomizer: MicroMist; temperature of the atomization chamber: 2 ℃.
d. The method converts element data into an element fingerprint map (see fig. 4) by converting the data into a graph, and comprises the following specific processes: firstly, sorting elements according to the size of atomic number; reducing the element (K) with the element content of more than 8000Mg/kg by 10000 times, reducing the element (Mg, P, Ca) with the element content of 1000-8000 Mg/kg by 1000 times, and reducing the element (Na, Al, Mn, Fe, Ba, Sr) with the element content of 20-1000 Mg/kg by 10 times; drawing a relation curve of the type of the element and the content of the element by using Excel software, wherein the curves are connected by adopting smooth lines; fourthly, elements with too low content are shown by adopting a local magnification graph.
(2) Identification of producing area of traditional Chinese medicinal materials based on element fingerprint
And (3) using SPSS software to perform distance analysis in correlation analysis, calculating the similarity of the element fingerprint of American ginseng in Jilin with the standard fingerprint of the element of American ginseng in Jilin to be 0.9976 according to an included angle cosine formula, wherein the similarity is higher than a similarity threshold value 0.9368 of the standard fingerprint of the element of American ginseng in Jilin, and judging that American ginseng in Jilin is produced and is consistent with the actual situation.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (2)
1. A method for identifying American ginseng produced in Jilin based on an American ginseng element fingerprint spectrum is characterized by comprising the following steps:
(a) taking the average value of the element contents in at least ten American ginseng samples in the Jilin producing area as the standard content of the elements, and constructing an element standard fingerprint of the American ginseng in the Jilin producing area;
(b) constructing an element fingerprint of American ginseng produced in Jilin;
(c) constructing an element fingerprint of American ginseng of a producing area to be identified;
constructing the fingerprint in the steps (a), (b) and (c), which comprises the following steps;
(1) american ginseng produced in Jilin and American ginseng of a production place to be identified are taken as samples, and the number of the American ginseng of the Jilin production place is more than 10;
(2) crushing an American ginseng sample, adding nitric acid, standing for 0.5h, then adding hydrogen peroxide, and digesting by using a microwave digestion instrument, wherein the digestion is divided into 4 stages: firstly, the temperature is 120 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 30 atm; ② the temperature is 150 ℃, the temperature is kept for 3min, and the upper limit of the pressure is 35 atm; ③ the temperature is 180 ℃, the temperature is kept for 2min, and the upper limit of the pressure is 35 atm; fourthly, keeping the temperature at 210 ℃ for 15min, and keeping the upper limit of the pressure at 40 atm;
(3) respectively measuring American ginseng samples by inductively coupled plasma mass spectrometry: the output power of the high-frequency generator is 1.55kW, the plasma gas is 15.0L/min, the auxiliary gas is 0.8L/min, the carrier gas is 0.8L/min, the compensation gas is 0.35L/min, the collision gas is helium, 4.3mL/min, the sampling depth is 10mm, automatic sample introduction is performed, the solution lifting rate is 0.4rps, the solution lifting time is 30s, the solution stabilizing rate is 0.1rps, the solution stabilizing time is 30s, an internal standard element is introduced on line through a T-shaped three-way pipe, and the atomizer: MicroMist; temperature of the atomization chamber: 2 ℃; the plasma gas, the auxiliary gas, the carrier gas and the compensation gas are all argon gas;
(4) converting the element data determined in the step (3) into an element fingerprint by a data-to-graph method: firstly, sorting elements according to the atomic number, then reducing the element content of more than 8000mg/kg by 10000 times, reducing the element content of 1000-8000 mg/kg by 1000 times, and reducing the element content of 20-1000 mg/kg by 10 times, then drawing a relation curve representing the element type and the content size, wherein the curves are connected by smooth lines, and respectively obtaining an element standard fingerprint of American ginseng in Jilin producing areas, an element fingerprint of American ginseng in Jilin producing areas and an element fingerprint of American ginseng in to-be-identified producing areas;
the elements include 49: li, Be, B, Na, Mg, Al, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Ba, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hg, Tl, Pb, Bi;
thus, an element standard fingerprint of the American ginseng of the Jilin producing area, an element fingerprint of the American ginseng of the Jilin producing area and an element fingerprint of the American ginseng of the producing area to be identified are constructed;
(d) using SPSS software, adopting distance analysis in correlation analysis, and calculating the similarity between the element fingerprint of the American ginseng produced in Jilin produced in the step (b) and the element standard fingerprint of the American ginseng produced in Jilin produced in the step (a) according to an included angle cosine formula to obtain the similarity range of the element standard fingerprint of the American ginseng produced in Jilin;
(e) using SPSS software, adopting distance analysis in correlation analysis, calculating the similarity between the element fingerprint of the American ginseng of the origin to be identified obtained in the step (c) and the element standard fingerprint of the American ginseng of the Jilin origin obtained in the step (a) according to an included angle cosine formula, and if the obtained similarity is greater than the lowest value 0.9368 of the similarity range obtained in the step (d), judging that the American ginseng of the origin to be identified is the American ginseng of the Jilin; and (d) if the obtained similarity is less than the lowest value 0.9368 of the similarity range obtained in the step (d), judging that the American ginseng of the origin to be identified is not the American ginseng produced by Jilin.
2. The method of claim 1, wherein in step (4), when the content of the element is too low, the relationship curve is plotted using a local magnification.
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Address after: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee after: Institute of testing and analysis, Guangdong Academy of Sciences (Guangzhou analysis and testing center, China) Address before: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee before: GUANGDONG INSTITUTE OF ANALYSIS (CHINA NATIONAL ANALYTICAL CENTER, GUANGZHOU) |