CN113640398A - Method for constructing gypsum standard decoction characteristic map - Google Patents
Method for constructing gypsum standard decoction characteristic map Download PDFInfo
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- CN113640398A CN113640398A CN202110706336.XA CN202110706336A CN113640398A CN 113640398 A CN113640398 A CN 113640398A CN 202110706336 A CN202110706336 A CN 202110706336A CN 113640398 A CN113640398 A CN 113640398A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention relates to a construction method of a characteristic map of a gypsum standard decoction, which comprises the following steps: providing a reference solution, preparing a test solution, detecting the test solution and the reference solution by adopting ion chromatography, introducing a chromatogram obtained by detecting the reference solution and a chromatogram obtained by detecting the test solution into a traditional Chinese medicine chromatogram fingerprint similarity evaluation system, and formulating a characteristic spectrum of a gypsum standard decoction; the reference substance solution is a solution obtained by dissolving a reference substance in a solvent, wherein the reference substance comprises sodium ions, potassium ions and magnesium ions; the preparation of the test solution comprises: extracting the gypsum standard decoction by using an extraction solvent, and collecting an extracting solution to obtain a test sample solution, wherein the extraction solvent is a methane sulfonic acid solution. The invention builds the characteristic map of the gypsum standard decoction for the first time. In the characteristic map, the relative retention time of each characteristic peak is stable, and the overall difference of the relative peak area is obvious compared with that of other mineral drug species, so that the specificity is presented.
Description
Technical Field
The invention relates to the technical field of traditional Chinese medicine detection, in particular to a method for constructing a gypsum standard decoction characteristic map.
Background
Gypsum, which is hydrous calcium sulfate (CaSO)4·2H2O) are named fine stone, fine marble (Bian Lu), Gypsum Fibrosum (supplement to the Yi Yan Yi of the materia Medica), Mirabilitum Crystallina (compendium), and white tiger (pharmacy definition). Gypsum belongs to monoclinic mineral, is usually produced in sedimentary rocks formed in salt lakes and inland lakes of gulf, is a fibrous aggregate, is in the form of long blocks, slabs or irregular blocks, is white, grey white or light yellow, is semitransparent, heavy, soft, has silk-like luster in a longitudinal section, and has light smell and taste.
Gypsum has the following pharmacological actions: (1) the antipyretic effect is as follows: in recent years, the single-ingredient gypsum and the white tiger decoction have certain antipyretic effect on experimental heat-causing rabbits. Natural gypsum is decocted at a ratio of 1: 1, 4mL is taken from the rectum of a rabbit, the antipyretic effect is realized on cow milk and rabbits with vaccine fever, but the antipyretic effect is not realized on pure gypsum. Studies show that gypsum can inhibit the body temperature regulation center which is over excited during fever, has strong and quick antipyretic effect, but is not lasting. (2) Quenching thirst: it can be used for treating animal thirst caused by drinking water prohibited, fever caused by endotoxin, dehydration caused by diuretic or dehydration caused by hypertonic saline, and radiant heat, and has thirst quenching effect. (3) Enhancing the phagocytic action: the gypsum Hanks liquid of 1: 1 can enhance the capability of rabbit alveolar macrophages cultured in vitro to phagocytose staphylococcus albus and colloidal gold, and can promote the maturation of phagocytes. The above-mentioned effects of gypsum may be closely related to the calcium ions contained therein. The BAIHU decoction has effects of enhancing phagocytosis rate and phagocytosis index of mouse abdominal cavity macrophage, promoting function of white blood cell phagocytosis Staphylococcus aureus in vitro, enhancing lymphocyte transformation rate, and promoting mouse antibody generation and serum lysozyme content. The phagocytosis promoting effect of Gypsum Fibrosum and BAIHU decoction may be one of the pharmacological bases for treating infectious diseases. (4) Tranquilizing and antispasmodic effects: when gypsum is taken orally, a part of gypsum is changed into soluble calcium salt to be absorbed under the action of gastric acid, so that the blood calcium concentration is increased, the excitability of muscles is inhibited, and certain sedative and spasmolytic effects are achieved. (5) The antiviral effect is as follows: gypsum has a certain antiviral effect, and metal ions in gypsum can be the effective antiviral components of gypsum. (6) Other functions are as follows: research shows that the gypsum has synergistic effect on the blood sugar reducing efficacy of the ginseng and the rhizoma anemarrhenae. The 2.5% gypsum supernatant is used to replace water and is freely drunk by rats for 1 month, the calcium content in organs such as pituitary gland, adrenal gland, submandibular gland, prostate gland, pancreas, testis, etc. is reduced, and the calcium content in spleen and thymus is increased. Gypsum Fibrosum extract can stimulate isolated Bufo siccus and rabbit heart at small dose, and inhibit at large dose. For isolated small intestine and uterus of rabbit, the amplitude is increased when using small amount of gypsum supernatant, and the tensity is reduced and the amplitude is reduced when using large amount of gypsum supernatant. Gypsum supernatant inhibited the transport of intestinal contents in mice. Gypsum Fibrosum also has effects in reducing permeability of blood vessel, shortening blood coagulation time, and promoting urination.
Traditionally, the gypsum fingerprint is mainly constructed by X-ray diffraction analysis, the X-ray diffractometer is high in price, and the X-ray diffraction analysis is mainly performed on unit cells of mineral drugs, but not on elements in the unit cells, so that the constructed fingerprint can only be applied to the most main part, and other special parts (such as inorganic elements) are ignored.
At present, there is still an urgent need to develop an accurate and reliable detection means for gypsum decoction.
Disclosure of Invention
Based on the background technology, the invention aims to provide a method for constructing a gypsum standard decoction characteristic map. By the method, the trace element characteristic spectrum of the gypsum standard decoction containing the sodium ion characteristic peak, the potassium ion characteristic peak and the magnesium ion characteristic peak is successfully constructed for the first time.
The above object of the present invention can be achieved by the following technical solutions:
a construction method of a characteristic spectrum of a gypsum standard decoction comprises the following steps:
providing a reference solution, preparing a test solution, detecting the reference solution by adopting ion chromatography, detecting the test solution by adopting ion chromatography, introducing a chromatogram obtained by detecting the reference solution and a chromatogram obtained by detecting the test solution into a traditional Chinese medicine chromatogram fingerprint similarity evaluation system, and formulating a characteristic spectrum of a gypsum standard decoction;
the reference substance solution is obtained by dissolving a reference substance in a solvent, wherein the reference substance comprises sodium ions, potassium ions and magnesium ions;
the preparation of the test solution comprises the following steps: extracting the gypsum standard decoction by using an extraction solvent, and collecting an extracting solution to obtain a test sample solution; the extraction solvent is methane sulfonic acid solution.
In one embodiment, the mass percentage of the methanesulfonic acid in the extraction solvent is 0.5% to 0.8%.
In one embodiment, the mass percentage of the methanesulfonic acid in the extraction solvent is 0.5% to 0.65%.
In one embodiment, the leacheate used for detection is a methane sulfonic acid solution, and the concentration of methane sulfonic acid in the leacheate is 19 mmol/L-21 mmol/L.
In one embodiment, the flow rate of the eluent used for the assay is 0.75mL/min to 0.9 mL/min.
In one embodiment, the column temperature used for the detection is 28 ℃ to 32 ℃.
In one embodiment, the detected conditions include: the protective column is IonPac CG12A, the inner diameter of the protective column is 4mm, the column length is 50mm, and the particle size of the filler is 8 μm; the analytical column is IonPac CS12A, the inner diameter of the analytical column is 4mm, the column length is 250mm, and the particle size of the filler is 8 μm; the suppressor is CSRS 4 mm; the temperature of the detection pool is 32-36 ℃; the inhibiting current is 45 mA-49 mA; the sensitivity of the detector is 4.5 muS/cm-5.5 muS/cm; the sample amount is 4.5-5.5 mul.
In one embodiment, the amount of the extraction solvent used per 0.1g of gypsum standard decoction is 15mL to 25 mL.
In one embodiment, the solvent is water.
In one embodiment, the concentration of sodium ions is 0.8 μ g/mL to 1.2 μ g/mL.
In one embodiment, the concentration of the magnesium ions is 0.8 to 1.2. mu.g/mL.
In one embodiment, the concentration of potassium ions is 0.8 μ g/mL to 1.2 μ g/mL.
In one embodiment, the extraction mode is oscillation extraction.
In one embodiment, the extract is collected by filtration.
In one embodiment, the characteristic map of the gypsum standard decoction comprises 3 characteristic peaks, wherein the peak 1 is Na+Peak, Peak 2 is K+Peak, Peak 3 is Mg2+Peak, peak 3 (Mg)2+) The peak corresponding to the reference substance is a reference peak S, the relative retention time of each remaining characteristic peak is within +/-10% of the corresponding specified value, and the specified values of the relative retention time of each characteristic peak are respectively as follows: peak 1 was 0.48 and Peak 2 was 0.66.
The application of the characteristic spectrum of the gypsum standard decoction in detecting the mineral medicine decoction is characterized in that the characteristic spectrum of the gypsum standard decoction is obtained by the construction method. In one embodiment, the mineral decoction is a mirabilite standard decoction, an oyster standard decoction or a talc standard decoction.
The mineral medicine decoction usually contains sodium ions, potassium ions and magnesium ions, the contents of the metal ions are totally and obviously different among the decoctions of different types of mineral medicines, and the identification of the decoctions of the mineral medicines is realized by detecting the contents of the sodium ions, the potassium ions and the magnesium ions in the decoctions of the mineral medicines and comparing the contents with the contents of the sodium ions, the potassium ions and the magnesium ions reflected by the characteristic maps.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts ion chromatography to construct the characteristic map of the gypsum standard decoction for the first time, and the characteristic map is a trace element characteristic map containing a sodium ion characteristic peak, a potassium ion characteristic peak and a magnesium ion characteristic peak.
According to the invention, the proper types of extraction solvents are adopted to realize effective extraction of sodium ions, potassium ions and magnesium ions in the gypsum standard decoction, and the characteristic spectrum of metal ions in the gypsum standard decoction is constructed by further matching with proper ion chromatography detection conditions.
In the characteristic map, the relative retention time of each characteristic peak is stable, and the relative peak area is obviously different from the whole decoction of other mineral medicine varieties (such as mirabilite and the like), so that the specificity is presented. Therefore, the characteristic map constructed by the invention can not only realize accurate, reliable detection and effective identification of sodium ions, potassium ions and magnesium ions in gypsum standard decoction and be convenient for ensuring the uniformity and stability of the quality of the medicament, but also can be used for comparison with other kinds of decoction of mineral medicaments, such as: the mirabilite decoction, the oyster decoction and the talc standard decoction are distinguished, so that the purpose of qualitative identification is achieved.
Drawings
FIG. 1 is a characteristic chromatogram of a standard decoction of gypsum (flow rate of elution is 0.8 mL/min);
FIG. 2 is a characteristic chromatogram of a standard decoction of Gypsum Fibrosum (flow rate of eluate is 1.0 mL/min);
FIG. 3 is a characteristic chromatogram of a standard decoction of Gypsum Fibrosum (flow rate of eluate is 1.2 mL/min);
FIG. 4 is a characteristic chromatogram of a standard decoction of gypsum (18mmol/L methanesulfonic acid solution);
FIG. 5 is a characteristic chromatogram of a standard decoction of Gypsum Fibrosum (20mmol/L methanesulfonic acid solution);
FIG. 6 is a standard decoction chromatogram of Gypsum Fibrosum (22mmol/L methanesulfonic acid solution);
FIG. 7 is a characteristic chromatogram of standard decoction of Gypsum Fibrosum (28 deg.C, 30 deg.C, 32 deg.C);
FIG. 8 shows the species of the extracted acids (0.1% hydrochloric acid solution, 0.1% sulfuric acid solution, 0.1% methanesulfonic acid solution) and "%" is a mass percentage;
FIG. 9 shows the results of examining the types of acids extracted from the standard decoction of Gypsum Fibrosum (0.1% hydrochloric acid solution, 0.1% sulfuric acid solution, 0.1% methanesulfonic acid solution), where "%" is the mass percentage;
FIG. 10 shows the concentration of the extracted acid (0.26%, 0.34%, 0.44%, 0.54%, 0.64%, 0.80%, 1.00%), "%" is in mass%;
FIG. 11 shows the results of examining the concentrations of extracted acids (0.26%, 0.34%, 0.44%, 0.54%, 0.64%, 0.80%, 1.00%) in the standard decoction profile of Gypsum Fibrosum, wherein "%" is in percentage by mass;
FIG. 12 is a volume of extracted acid (10mL, 20mL, 30mL) study;
FIG. 13 shows the results of examining the amount of acid extracted from the standard decoction of Gypsum Fibrosum (10mL, 20mL, 30 mL);
FIG. 14 is an overlay of characteristic spectra of standard decoction of 23 batches of gypsum;
FIG. 15 shows peak identification of characteristic spectrum of standard decoction of Gypsum Fibrosum;
FIG. 16 is a study of gypsum standard decoction feature map specialization;
FIG. 17 is a chromatogram obtained by examining the durability of a characteristic spectrum of a standard decoction of Gypsum Fibrosum at different column temperatures;
FIG. 18 is a graph of durability difference chromatogram from flow rate investigation of a standard decoction of Gypsum Fibrosum;
FIG. 19 is a chromatogram for examining chromatographic columns with different durability of a gypsum standard decoction feature map;
FIG. 20 is a chromatogram for examining the concentrations of leacheate with different durability according to the characteristic spectrum of gypsum standard decoction;
FIG. 21 is a characteristic spectrum of Natrii sulfas standard decoction;
FIG. 22 is a characteristic spectrum of a standard decoction of Concha Ostreae;
FIG. 23 is a standard decoction profile of Talcum.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described in more detail below. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments or examples set forth herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of two or more of the associated listed items, including any and all combinations of two or more of the associated listed items, or all of the associated listed items.
The application of ion chromatography to determine the content of inorganic elements is more, and the method can be applied to detection of heavy metals in the environment and detection of inorganic elements in the industry. For example: the patent literature discloses a method for detecting the content of trace metal ions in high-purity thiourea by ion chromatography, which applies ion chromatography to detect sodium, ammonium, potassium, magnesium and calcium cations and belongs to quantitative detection. Currently, the application of ion chromatography to gypsum is also relatively rare and is mainly applied to the detection of industrial gypsum, for example: ion chromatography is adopted to determine the content of calcium sulfate in the desulfurized gypsum powder [ J ]. physicochemical examination (chemical division), 2014,50(01):89-92) and ion chromatography is adopted to study the desulfurized gypsum and determine the content of calcium sulfate in the desulfurized gypsum powder; xudan Hua, Meiyi Fei, etc. (Xudan Hua, Meiyi Fei, Liu Shihua, ion chromatography for simultaneous determination of fluorine and chlorine [ J ] in gypsum and gypsum products, Chinese building materials science 2014,23(01):1-2) by ion chromatography for simultaneous determination of fluorine and chlorine in gypsum and gypsum products. So far, no ion chromatography technology is introduced into the research on mineral medical gypsum, particularly the ion chromatography is applied to the research on establishing the gypsum or gypsum standard decoction characteristic map, so that the establishment of the gypsum standard decoction characteristic map by using the ion chromatography is a technical blank in the current research. However, ion chromatography has not been applied to gypsum standard decoction characteristic map construction.
Based on the above, the extraction solvent of a proper type is adopted in the invention to realize effective extraction of sodium ions, potassium ions and magnesium ions in the gypsum standard decoction, and a characteristic spectrum of metal ions in the gypsum standard decoction is constructed by further matching with a proper ion chromatography detection condition.
The invention provides a method for constructing a characteristic map of a gypsum standard decoction, which comprises the following steps:
providing a reference solution, preparing a test solution, detecting the reference solution by adopting ion chromatography, detecting the test solution by adopting ion chromatography, introducing a chromatogram obtained by detecting the reference solution and a chromatogram obtained by detecting the test solution into a traditional Chinese medicine chromatogram fingerprint similarity evaluation system, and formulating a characteristic spectrum of a gypsum standard decoction;
the reference substance solution is obtained by dissolving a reference substance in a solvent, wherein the reference substance comprises sodium ions, potassium ions and magnesium ions;
the preparation of the test solution comprises the following steps: extracting the gypsum standard decoction by using an extraction solvent, and collecting an extracting solution to obtain a test sample solution; the extraction solvent is methane sulfonic acid solution.
The traditional Chinese medicine chromatogram fingerprint similarity evaluation system is software which is issued by the State pharmacopoeia Committee and can compare the similarity of the chromatogram.
The "extraction solvent" in the present invention is the "extraction acid" mentioned in the specific examples, and the concentration of the extraction acid is expressed by mass percentage unless otherwise specified.
It should be noted that, in the construction method of the present invention, the steps are not limited by the time sequence.
The mass percent of methane sulfonic acid in the extraction solvent can be selected from, including but not limited to, any one of the following concentrations or a range of concentrations between any two of the following concentrations: 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%. In one example, the mass percentage of the methanesulfonic acid in the extraction solvent is 0.5% to 0.8%. Preferably, the mass percentage of the methane sulfonic acid in the extraction solvent is 0.5-0.65%. More preferably, the mass percentage of the methanesulfonic acid in the extraction solvent is 0.5% to 0.55%, for example 0.54%.
In one example, the eluent used for detection is a methanesulfonic acid solution with a methanesulfonic acid concentration of 19mmol/L to 21mmol/L, and the molar concentration of the methanesulfonic acid in the eluent can be selected from, but is not limited to, any one of the following concentrations or a concentration range between any two of the following concentrations: 19mmol/L, 19.5mmol/L, 20mmol/L, 20.5mmol/L, 21 mmol/L.
In one example, the flow rate of the eluent used for the assay is 0.75mL/min to 0.9mL/min, for example, the flow rate of the eluent can be selected from, including but not limited to, any of the following flow rates or a range of flow rates between any two of the following flow rates: 0.75mL/min, 0.8mL/min, 0.85mL/min, 0.9 mL/min.
In one example, the column temperature used for the detection is 28 ℃ to 32 ℃. The column temperature used for the detection may be selected from, including but not limited to, any of the following temperatures, 0.5 ℃ plus or minus any of the following temperatures, or a temperature range between any two temperatures: 28 ℃, 29 ℃, 30 ℃, 31 ℃ and 32 ℃.
In one example, the detected conditions include: the protective column is IonPac CG12A, the inner diameter of the protective column is 4mm, the column length is 50mm, and the particle size of the filler is 8 μm; the analytical column is IonPac CS12A, the inner diameter of the analytical column is 4mm, the column length is 250mm, and the particle size of the filler is 8 μm; the suppressor is CSRS 4 mm; the temperature of the detection pool is 32-36 ℃; the inhibiting current is 45 mA-49 mA; the sensitivity of the detector is 4.5 muS/cm-5.5 muS/cm; the sample amount is 4.5-5.5 mul. The detection cell temperature can be 32 deg.C, 33 deg.C, 34 deg.C, 35 deg.C, 36 deg.C, the suppression current can be 45mA, 46mA, 47mA, 48mA, 49mA, the detector sensitivity can be 4.5 μ S/cm, 5 μ S/cm, 5.5 μ S/cm, and the sample amount can be 4.5 μ l, 5 μ l, 5.5 μ l. It is understood that the detection condition adopted by the present invention may be a recommended condition of the apparatus used, for example, a recommended suppression current of 47 mA.
In one example, the amount of the extraction solvent is 15mL to 25mL per 0.1g of gypsum standard decoction. The amount of the extraction solvent per 0.1g of gypsum standard decoction may be selected from, including but not limited to, any one of the following amounts or a range between any two amounts: 15mL, 17mL, 19mL, 21mL, 23mL, 25 mL.
In one example, the solvent is water. Such as ultrapure water.
In one example, the concentration of the sodium ions is 0.8 to 1.2. mu.g/mL. The concentration of the sodium ions may be selected from, including but not limited to, any one of the following concentrations or a range of concentrations between any two of the following concentrations: 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL, 1.1. mu.g/mL, 1.2. mu.g/mL.
In one example, the concentration of the magnesium ions is 0.8 to 1.2. mu.g/mL. The concentration of the magnesium ions may be selected from, including but not limited to, any one of the following concentrations or a range of concentrations between any two of the following concentrations: 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL, 1.1. mu.g/mL, 1.2. mu.g/mL.
In one example, the potassium ion concentration is 0.8 μ g/mL to 1.2 μ g/mL. The concentration of potassium ions may be selected from, including but not limited to, any one of the following concentrations or a range of concentrations between any two of the following concentrations: 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL, 1.1. mu.g/mL, 1.2. mu.g/mL.
In one example, the extraction mode is oscillation extraction.
In one example, the extract is collected by filtration.
In one example, the construction method comprises the following steps:
providing a reference solution, preparing a test solution, detecting the reference solution by adopting ion chromatography, detecting the test solution by adopting ion chromatography, introducing a chromatogram obtained by detecting the reference solution and a chromatogram obtained by detecting the test solution into a traditional Chinese medicine chromatogram fingerprint similarity evaluation system, and formulating a characteristic spectrum of a gypsum standard decoction;
the reference substance solution is a solution obtained by dissolving a reference substance in a solvent, and the reference substance comprises sodium ions, potassium ions and magnesium ions;
the preparation of the test solution comprises the following steps: extracting the gypsum standard decoction by using an extraction solvent, and collecting an extracting solution to obtain a test sample solution; the extraction solvent is methane sulfonic acid solution;
the mass percent of the methane sulfonic acid in the extraction solvent is 0.5-0.65%;
detecting whether the used leacheate is a methane sulfonic acid solution, wherein the concentration of methane sulfonic acid in the leacheate is 19 mmol/L-21 mmol/L;
detecting the flow rate of the adopted leacheate to be 0.75 mL/min-0.9 mL/min;
the column temperature used for detection is 28-32 ℃.
In one example, the characteristic map of the gypsum standard decoction comprises 3 characteristic peaks, wherein the peak 1 is Na+Peak, Peak 2 is K+Peak, Peak 3 is Mg2+Peak, peak 3 (Mg)2+) The peak corresponding to the reference substance is a reference peak S, the relative retention time of each remaining characteristic peak is within +/-10% of the corresponding specified value, and the specified values of the characteristic peaks are respectively as follows: peak 1 was 0.48 and Peak 2 was 0.66. Due to Na+、K+、Mg2+The control is readily available and it is recommended that each characteristic peak be matched using retention times consistent with its reference.
The invention also provides application of the characteristic spectrum of the gypsum standard decoction in detection of mineral medicine decoction, wherein the characteristic spectrum of the gypsum standard decoction is obtained by the construction method.
In the characteristic spectrum provided by the invention, the relative retention time of each peak is stable, and although the relative peak areas of the peaks in different batches of gypsum standard decoctions are different, the difference is limited in the gypsum standard decoction, and is very obvious compared with the decoctions of other mineral medicines (such as mirabilite, oyster and talc), and the difference of the relative retention areas in the decoctions of different mineral medicines is enough to distinguish the gypsum standard decoction from other mineral medicines.
The mineral medicine is prepared with mineral and rock and other mineral and mineral processing product, and may be also fossil of ancient organism, such as cinnabar, realgar, gypsum, calamine, etc. In particular, the "mineral drug" according to the invention can be selected from the following: mirabilite, oyster and talcum.
The preparation method of the gypsum standard decoction provided by the embodiment of the invention comprises the following steps of: decocting decoction pieces of Gypsum Fibrosum in water, and drying the decoction.
In the decoction process of the embodiment of the present invention, the number of times of decoction is preferably multiple (e.g., 2 times, 3 times, 4 times, etc.), and if the decoction is multiple times, the decoctions obtained by multiple times of decoction may be combined and then dried. Preferably, the number of times of decoction is two.
Furthermore, in the first decoction process, the water amount is 7-9 times of that of the gypsum decoction pieces, the gypsum decoction pieces are soaked for 25-35 min before decoction, and the decoction is heated and boiled by strong fire (the power is 450-550W) and then kept slightly boiled by slow fire (the power is 180-220W) for 40-50 min. After the decoction is finished, filtering with a screen (200 meshes) to obtain a filtrate (decoction), and cooling the filtrate with cold water. In the step, the water adding amount can be 7 times, 7.5 times, 8 times, 8.5 times and 9 times of the gypsum decoction pieces, the time for soaking the gypsum decoction pieces before decoction can be 25min, 30min and 35min, the corresponding power of strong fire can be 450W, 470W, 490W, 500W, 520W and 550W, the corresponding power of slow fire can be 180W, 200W, 210W and 220W, and the time for keeping the micro-boiling can be controlled at 40min, 45min and 50 min.
Furthermore, in the second decoction process, the water amount is 5-6.5 times of that of the gypsum decoction pieces, and the decoction is carried out by heating with strong fire (the power is 450-550W) to boil and then keeping the slight boiling with slow fire (the power is 180-220W) for 25-35 min. After the decoction is finished, filtering with a screen (200 meshes) to obtain a filtrate (decoction), and cooling the filtrate with cold water. In the step, the water adding amount can be 5 times, 5.5 times, 6 times and 6.5 times of that of gypsum decoction pieces, the corresponding power of strong fire can be 450W, 470W, 490W, 500W, 520W and 550W, the corresponding power of slow fire can be 180W, 200W, 210W and 220W, and the micro-boiling duration can be controlled to be 25min, 30min and 35 min.
It is understood that the decoction may be first concentrated (including but not limited to, concentration under reduced pressure) to obtain a fluid extract and then dried, including but not limited to, vacuum freeze-drying.
Example 1 establishment of a method for analyzing a characteristic Pattern
1. Instruments, reagents and reagents
1.1 Instrument: ion chromatograph (Dionex ICS-6000, semmer feishell science ltd); cation suppressors (CSRS 3004 mm, seimer feishel technologies ltd); IonPac CG12A protective column (4X 50mm, 8 μm); IonPac CS12A analytical column (4X 250mm, 8 μm); one-ten-thousandth analytical balance (ME204E, mettler-toledo); ultrapure water systems (Milli-Q Direct, Merck, Inc.).
1.2 reagent: hydrochloric acid (guangzhou chemical reagent factory, premium grade purity); sulfuric acid (guangzhou chemical reagent factory, premium grade purity); methanesulfonic acid (MSA, alatin reagent (shanghai) ltd., 99.5%); the water was ultrapure water (self-made in the laboratory).
1.3 reagent: sodium component analysis standard substance in water (national defense science and technology industry application chemical first-class metering station, concentration: 1000 mug/mL, batch number: GBW (E) 080526); potassium single element solution standard substance (Beijing northern great institute of metrological technology, concentration: 1000. mu.g/mL, lot number: GBW (E) 083296); magnesium single element solution standard substance (Beijing northern great industry measurement and technology research institute, concentration: 1000. mu.g/mL, lot number: GBW (E) 083298); the lot number information for the 23 gypsum standard decoctions is shown in Table 1 below.
TABLE 1, 23 batch Gypsum medicinal materials and decoction piece information sheet
| Serial number | Medicine lot number | Decoction piece batch number | Producing area |
| 1 | G161022 | GP161022 | No. 9 mine of Lanling town of Lanling county of Linyi city, Shandong province |
| 2 | G161023 | GP161023 | No. 3 mine of Lanling town of Lanling county of Lin-Yi City of Shandong province |
| 3 | G161024 | GP161024 | Shandong provinceZhuang city of jujube |
| 4 | G1901008 | GP1901008 | Yanglin town of Yingcheng county of Xiaogan City of Hubei province |
| 5 | G1901009 | GP1901009 | Yanglin town of Yingcheng county of Xiaogan City of Hubei province |
| 6 | G1901010 | GP1901010 | New river industrial area in city of Yicheng city of Xiaogan city of Hubei province |
| 7 | G1903178 | GP1903178 | Yao mountain town of summer county of fortune city of Shanxi province |
| 8 | G1903179 | GP1903179 | Sizhizhen in Xixia city of Shanxi province |
| 9 | G1903180 | GP1903180 | Shanxi province fortune city summer county temple front town |
| 10 | G1906106 | GP1906106 | Sanlong town of Lingshan county of Guangxi Qinzhou city |
| 11 | G2004040 | GP2004040 | Yongzhou City, Hunan Province |
| 12 | G2005079 | GP2005079 | Guangdong province |
| 13 | G2005080 | GP2005080 | Guangdong province |
| 14 | G2005083 | GP2005083 | Xindu District, Chengdu City, Sichuan Province |
| 15 | G2005084 | GP2005084 | Guangxi Yulin city Yuzhou district |
| 16 | G2005085 | GP2005085 | Lotus pool for urban four-river province |
| 17 | G2005086 | GP2005086 | Lotus pool for urban four-river province |
| 18 | G2005087 | GP2005087 | Guangxi Yulin City |
| 19 | G2005094 | GP2005094 | Heat-releasing district in the city of Bozhou province, Anhui province |
| 20 | G2005095 | GP2005095 | Heat-releasing district in the city of Bozhou province, Anhui province |
| 21 | G2005096 | GP2005096 | Heat-releasing district in the city of Bozhou province, Anhui province |
| 22 | G2005097 | GP2005097 | Heat-releasing district in the city of Bozhou province, Anhui province |
| 23 | G2006002 | GP2006002 | Heat-releasing district in the city of Bozhou province, Anhui province |
The 23 batches of gypsum standard decoction are prepared by taking the gypsum decoction pieces of the batches in the table 1 and processing the gypsum decoction pieces by the following process:
(1) taking 100g of gypsum decoction pieces, adding water for decoction twice:
adding 8 times of water into the first decoction, soaking for 30 minutes, heating with strong fire (power of 500W) to boil, keeping slightly boiling with slow fire (power of 200W) for 45 minutes, filtering with 200-mesh sieve while hot, and rapidly cooling the filtrate with cold water;
adding 6 times of water for the second decoction, boiling with strong fire (power of 500W), maintaining slight boiling with slow fire (power of 200W) for 30min, filtering with 200 mesh sieve, and cooling the filtrate with cold water;
(2) mixing the two filtrates, concentrating under reduced pressure to obtain clear paste with volume of about 100ml, subpackaging into 10ml penicillin bottles with volume of 3ml each, vacuum freeze drying, taking out, and rolling aluminum cap.
2. Preparation of reference solutions
Taking a proper amount of sodium component analysis standard substance, potassium single element solution standard substance and magnesium single element solution standard substance in water, precisely weighing, placing in a 30mL plastic vial, adding ultrapure water to prepare a solution containing Na in 1mL+、K+、Mg 2+1. mu.g each of the solutions.
3. Determination of chromatographic conditions
The chromatographic method of the gypsum standard decoction characteristic spectrum is inspected, and the influence of different flow rates and different leacheate concentrations on the ion chromatogram is inspected.
(1) Determination of optimal flow rate
In the experiment, three flow rates of 0.8ml/min, 1.0ml/min and 1.2ml/min are selected for comparison to determine the optimal flow rate.
Preparing a test solution: grinding appropriate amount of standard decoction of Gypsum Fibrosum (GT1903178), weighing about 0.1g, placing into a 30ml plastic bottle, adding 20ml of 0.54% methanesulfonic acid solution, shaking to dissolve, shaking, and filtering to obtain filtrate.
Chromatographic conditions are as follows: selecting an IonPac CG12A (4X 50mm) protective column, an IonPac CS12A (4X 250mm) analytical column and a CSRS 4mm suppressor; using 20mmol/L methane sulfonic acid solution as leacheate; the flow rates are respectively 0.8ml per minute, 1.0ml per minute and 1.2ml per minute; the column temperature is 30 ℃; the temperature of the detection pool is 35 ℃; the suppression current was 47 mA; the detector sensitivity was 5 mus per cm; the sample amount is 5 mul; the results are shown in FIGS. 1, 2 and 3.
Comparing 3 chromatograms with different flow rates, and finding that when the selected flow rate is 1.0ml/min or 1.2ml/min, the peak information is complete, the peak separation degree is good, but the peak inversion occurs; when 0.8ml/min is selected as the flow rate, the peak information is complete, the peak separation degree is good, and no peak inversion occurs, so 0.8ml/min is selected as the flow rate of the leaching solution.
(2) Investigation of leacheate
In the experiment, 3 kinds of eluents with the concentrations of 18mmol/L methane sulfonic acid solution, 20mmol/L methane sulfonic acid solution and 22mmol/L methane sulfonic acid solution are selected for comparison, and the eluents with the proper concentrations are determined.
The preparation of the test solution is described in section "(1) determination of optimum flow rate" above.
Chromatographic conditions are as follows: selecting an IonPac CG12A (4X 50mm, 8 μm) protective column, an IonPac CS12A (4X 250mm, 8 μm) analytical column and a CSRS 4mm suppressor; respectively taking 18mmol/L methane sulfonic acid solution, 20mmol/L methane sulfonic acid solution and 22mmol/L methane sulfonic acid solution as leacheate; the flow rate was 0.8ml per minute; the column temperature is 30 ℃; the temperature of the detection pool is 35 ℃; the suppression current was 47 mA; the detector sensitivity was 5 mus per cm; the sample amount is 5 mul; the results are shown in FIGS. 4,5 and 6.
By comparing chromatograms of 3 kinds of leacheate with different concentrations, it can be found that when 18mmol/L, 20mmol/L and 22mmol/L methane sulfonic acid solutions are selected as the leacheate, the separation degree effect of each characteristic peak is consistent and the base line is relatively stable, but when the concentration of the leacheate is 18mmol/L, the elution time is relatively long; when the concentration of the leacheate is 22mmol/L, the peak emergence time of each characteristic peak is earlier, and each characteristic peak is compact, so that the concentration of the leacheate is determined to be 20mmol/L for saving analysis time and analysis results.
(3) Investigation of column temperature
In the experiment, 3 different column temperatures of 28 ℃, 30 ℃ and 32 ℃ are selected for comparison, and the proper chromatographic column temperature is determined.
The preparation of the test solution is described in section "(1) determination of optimum flow rate" above.
Chromatographic conditions are as follows: selecting an IonPac CG12A (4X 50mm, 8 μm) protective column, an IonPac CS12A (4X 250mm, 8 μm) analytical column and a CSRS 4mm suppressor; using 20mmol/L methane sulfonic acid solution as leacheate; the flow rate was 0.8ml per minute; the column temperatures were 28 deg.C, 30 deg.C, and 32 deg.C, respectively; the temperature of the detection pool is 35 ℃; the suppression current was 47 mA; the detector sensitivity was 5 mus per cm; the sample amount is 5 mul; the results are shown in FIG. 7.
Comparing 3 chromatograms with different column temperatures can find that the base lines of the 3 chromatograms with different column temperatures are stable and the separation degree is good, and each characteristic peak response is higher at the column temperature of 30 ℃, so that 30 ℃ is selected as the optimal column temperature.
(4) Determination of chromatographic conditions
Selecting an IonPac CG12A (4X 50mm, 8 μm) protective column, an IonPac CS12A (4X 250mm, 8 μm) analytical column and a CSRS 4mm suppressor; using 20mmol/L methane sulfonic acid solution as leacheate; the flow rate was 0.8ml per minute; the column temperature is 30 ℃; the temperature of the detection pool is 35 ℃; the suppression current was 47 mA; the detector sensitivity was 5 mus per cm; the amount of sample was 5. mu.l.
4. Examination of pretreatment method of test solution
A sample pretreatment method of a gypsum standard decoction characteristic spectrum is considered, and the types, concentration and dosage of extracted acid are mainly considered.
(1) Investigation of extracted acid species
The experiment inspects the influence of different types of extracted acid on the characteristic spectrum of the gypsum standard decoction, selects 0.1 percent (w/w) hydrochloric acid solution, 0.1 percent (w/w) sulfuric acid solution and 0.1 percent (w/w) methane sulfonic acid solution as extraction solvents, and observes 3 trace ion peaks Na+、K+、Mg2+Peak type and separation effect of the peak, and calculating the total peak area/sample weighing amount of 3 characteristic peaks to compare the influence of different acid species on the characteristic spectrum of the gypsum standard decoction, and selecting the optimal extracted acid species by taking the obtained large total peak area/sample weighing amount as the standard.
Taking a proper amount of gypsum standard decoction (GT1903180), grinding, taking about 0.1g, precisely weighing, paralleling 3 groups, placing 2 parts of each group into a 30ml plastic bottle, respectively and precisely adding 0.1% (w/w) hydrochloric acid solution, 0.1% (w/w) sulfuric acid solution and 20ml of 0.1% (w/w) methane sulfonic acid solution, fully shaking to dissolve, shaking uniformly, filtering, taking subsequent filtrate, injecting into an ion chromatograph, injecting according to chromatographic conditions determined under the item of ' determination of chromatographic conditions ' 3 ', carrying out sample injection analysis, recording peak areas of characteristic peaks, and calculating ' total peak area/sample weighing ', wherein the results are shown in Table 2, figure 8 and figure 9.
TABLE 2 survey result table of acid extraction from gypsum standard decoction feature map
The results show that different acid types are adopted as extraction solvents, the characteristic maps have obvious difference, 0.1% (w/w) of methane sulfonic acid is used as the extraction solvent, and the total peak area/sample weighing amount is larger than that of other two acids, so that methane sulfonic acid is selected as the extraction acid type.
(2) Examination of the concentration of extracted acid
The experiment inspects the influence of different extracted acid concentrations on the gypsum standard decoction characteristic diagram, selects 0.26% (w/w) methane sulfonic acid solution, 0.34% (w/w) methane sulfonic acid solution, 0.44% (w/w) methane sulfonic acid solution, 0.54% (w/w) methane sulfonic acid solution, 0.64% (w/w) methane sulfonic acid solution, 0.80% (w/w) methane sulfonic acid solution and 1.00% (w/w) methane sulfonic acid solution as extraction solvents, and observes 3 trace ion peaks Na+、K+、Mg2+Peak type and separation effect of the peak, and calculating the total peak area/sample weighing amount of 3 characteristic peaks to compare the influence of different acid concentrations on the characteristic spectrum of the gypsum standard decoction, and selecting the optimal extracted acid concentration.
Taking a proper amount of gypsum standard decoction (GT1906106), grinding, taking about 0.1g, precisely weighing, paralleling 7 groups, placing 2 parts of each group into a 30ml plastic bottle, precisely adding 0.26% (w/w) methane sulfonic acid solution, 0.34% (w/w) methane sulfonic acid solution, 0.44% (w/w) methane sulfonic acid solution, 0.54% (w/w) methane sulfonic acid solution, 0.64% (w/w) methane sulfonic acid solution, 0.80% (w/w) methane sulfonic acid solution, 20ml of 1.00% (w/w) methane sulfonic acid solution, weighing, fully shaking to dissolve, shaking up, filtering, taking subsequent filtrate, sampling and analyzing according to the chromatographic conditions determined under the item 'determination of 3. chromatographic conditions', recording the peak area of each characteristic peak, and calculating the 'total peak area/sample amount', and the result is shown in Table 3, figure 10 and figure 11.
TABLE 3 survey result table of acid concentration extracted from standard decoction of Gypsum Fibrosum
The results show that different concentrations of methane sulfonic acid are used as extraction solvents, the characteristic maps have obvious difference, 0.54% (w/w) methane sulfonic acid is used as the extraction solvent, and the 'total peak area/sample weighing amount' is the largest, so that 0.54% (w/w) methane sulfonic acid solution is selected as the optimal concentration of the extraction acid.
(3) Investigation of amount of extracted acid
The experiment inspects the influence of different amounts of extracted acid on the characteristic spectrum of the gypsum standard decoction, selects 10ml, 20ml and 30ml of 0.54% (w/w) methane sulfonic acid solution as an extraction solvent, and observes 3 trace ion peaks Na+、K+、Mg2 +Peak type and separation effect of the peak, and calculating the total peak area/sample weighing amount of 3 characteristic peaks to compare the influence of different acid dosages on the gypsum standard decoction characteristic spectrum, and selecting the optimal extraction acid dosage.
Taking a proper amount of gypsum standard decoction (GT161022), grinding, taking about 0.1g, precisely weighing, paralleling 3 groups, placing 2 parts of each group into a 30ml plastic bottle, precisely adding 10ml, 20ml and 30ml of 0.54% methane sulfonic acid solution respectively, weighing, fully shaking to dissolve, shaking uniformly, filtering, taking subsequent filtrate, performing sample injection analysis according to chromatographic conditions determined under the item of 'determination of 3-chromatographic conditions', recording peak areas of characteristic peaks, and calculating 'total peak area/weighing amount', wherein the results are shown in Table 4, figure 12 and figure 13.
TABLE 4 survey result table of extracted acid dosage of gypsum standard decoction
The results show that different dosages of methanesulfonic acid are used as extraction solvents, the characteristic maps have obvious differences, 20ml of 0.54% (w/w) methanesulfonic acid is used as the extraction solvent, and the 'total peak area/sample weighing amount' is the largest, so 20ml is selected as the optimal dosage of the extraction acid.
(4) Determination of preparation method of test solution
According to the experimental result, the pretreatment method of the gypsum standard decoction characteristic map sample is determined as follows:
grinding a proper amount of standard decoction of the gypsum, precisely weighing about 0.1g of the standard decoction, placing the ground standard decoction in a 30ml plastic bottle, precisely adding 20ml of 0.54% methane sulfonic acid solution, weighing the weight of the solution, fully shaking to dissolve the solution, shaking uniformly, filtering, and taking a subsequent filtrate to obtain the traditional Chinese medicine.
5. Determination of characteristic peaks
Taking 23 batches of gypsum standard decoction samples, investigating the preparation method of the test solution determined under the item '4. test solution pretreatment method', preparing the test solution, precisely absorbing the test solution respectively, determining the chromatographic conditions according to the item '3. chromatographic condition determination', carrying out sample injection determination, carrying out common peak identification on the characteristic spectra of the 23 batches of gypsum standard decoction by using 'traditional Chinese medicine chromatographic fingerprint similarity evaluation software', selecting a trace ion peak 1 (Na) with known components, good peak type and separation degree, stable content and high content+) Peak 2 (K)+) Peak 3 (Mg)2+) The peak is used as characteristic peak of gypsum standard decoction, and as shown in FIG. 14, Mg with large peak area and easily available as control2+And taking the chromatographic peak as a reference peak S, calculating the relative retention time of each characteristic peak and the S peak, and positioning the characteristic peak by using the relative retention time. See table 5 below.
TABLE 5, 23 relative retention time of characteristic spectrum of standard decoction of Gypsum Fibrosum
TABLE 6 and 23 relative peak areas of characteristic spectra of standard gypsum decoction batches
Peak 3 (Mg)2+) For reference peak S, the RSD value of each characteristic peak of 23 batches of gypsum standard decoction and the relative retention time RSD value of the S peak are in the range of 0.58-0.89%, which indicates that the relative retention time of each characteristic peak is relatively stable. The RSD value of the relative peak area of each characteristic peak and the S peak is in the range of 40.62-59.42%, and the relative peak areas of samples in different batches have larger differences, which indicates that the proportions of chemical components represented by the characteristic peaks of gypsum standard decoction in different batches have larger differences.
6. Identification of characteristic peaks
As can be seen from FIG. 15, Na can be found in the standard decoction profile of Gypsum Fibrosum+、K+、Mg2+Keeping the characteristic peak with consistent retention time, and determining that the peak 1 is Na+Peak 2 is K+Peak 3 is Mg2+。
Example 2 verification of the feature mapping methodology
(1) Specialization inspection
With reference to the detection conditions and the method for preparing the sample solution determined in example 1, a sample solution, a reference solution and a blank solvent (0.54% methanesulfonic acid) were prepared by precisely extracting 5. mu.l each of a gypsum standard decoction (GT161022), and the sample solution and the reference solution were measured by injection into an ion chromatograph. The results are shown in FIG. 16.
TABLE 7 chromatographic peak separation parameter Table
The results show that the test solution has the same chromatographic peak at the retention time corresponding to the chromatogram of the control, and the blank solvent also has Na+、K+The chromatographic peaks, but the peak areas are only 2.54% and 4.42% of the sample respectively, have little influence on the sample measurement, and show that the specificity of the method is good.
(2) Precision survey
Grinding appropriate amount of Gypsum Fibrosum Standard decoction (GT161022), weighing about 0.1g, preparing sample solution according to the method for preparing sample solution determined in example 1, repeatedly injecting sample for 6 times under the chromatographic conditions determined in example 1, and adding Mg2+The peak (peak 3) is a reference peak S, the relative retention time and the relative peak area of each characteristic peak and the S peak are calculated, and the RSD value is calculated, and the experimental results are shown in tables 8 and 9.
TABLE 8 Gypsum Standard decoction feature map precision results table (relative retention time)
| Serial number | Na+ | K+ | Mg2+(S) |
| 1 | 0.564 | 0.766 | 1.000 |
| 2 | 0.564 | 0.766 | 1.000 |
| 3 | 0.563 | 0.765 | 1.000 |
| 4 | 0.564 | 0.765 | 1.000 |
| 5 | 0.564 | 0.766 | 1.000 |
| 6 | 0.564 | 0.766 | 1.000 |
| RSD(％) | 0.08 | 0.06 | 0.00 |
TABLE 9 precision results table of gypsum standard decoction characteristic (relative peak area)
The results show that the same sample solution was continuously injected 6 times with Mg2+The peak is a reference peak S, the relative retention time RSD value of each characteristic peak and the S peak is in the range of 0.06% -0.08%, the relative peak area RSD value is in the range of 1.27% -1.37%, and the RSD values are all less than 3.0%, and the instrument precision is good.
(3) Stability survey
Taking appropriate amount of Gypsum Fibrosum Standard decoction (GT161022), grinding, taking about 0.1g, precisely weighing, preparing sample solution according to sample solution preparation method determined in example 1, and analyzing at 0 hr, 3 hr, 5 hr, 7 hr, 9 hr and 12 hr according to chromatographic conditions determined in example 1, respectively, injecting Mg2+The peak is a reference peak S, the relative retention time and the relative peak area of each characteristic peak and the S peak are calculated, and the RSD value is calculated, and the results are shown in tables 10 and 11.
TABLE 10 stability of Gypsum Fibrosum Standard decoction feature map results Table (relative Retention time)
| Time (h) | Na+ | K+ | Mg2+(S) |
| 0 | 0.481 | 0.667 | 1.000 |
| 3 | 0.481 | 0.667 | 1.000 |
| 5 | 0.482 | 0.667 | 1.000 |
| 7 | 0.481 | 0.668 | 1.000 |
| 9 | 0.481 | 0.667 | 1.000 |
| 12 | 0.480 | 0.667 | 1.000 |
| RSD(％) | 0.08 | 0.06 | 0.00 |
TABLE 11 stability of the characteristic spectra of the Standard decoction of Gypsum (relative peak area)
| Time (h) | Na+ | K+ | Mg2+(S) |
| 0 | 0.795 | 0.427 | 1.000 |
| 3 | 0.793 | 0.427 | 1.000 |
| 5 | 0.802 | 0.433 | 1.000 |
| 7 | 0.766 | 0.395 | 1.000 |
| 9 | 0.771 | 0.399 | 1.000 |
| 12 | 0.792 | 0.409 | 1.000 |
| RSD(％) | 1.83 | 3.89 | 0.00 |
The results show that the same sample solution was injected and analyzed at 0 hr, 3 hr, 5 hr, 7 hr, 9 hr and 12 hr, respectively, and Mg is added2+The peak is a reference peak S, the relative retention time RSD value of each characteristic peak and the S peak is in the range of 0.06% -0.08%, the relative peak area RSD value is in the range of 1.83% -3.89%, and the relative peak area RSD values are all less than 4.0%, and the fact that the relative stability of the test solution is good within 12h is shown.
(4) Repeatability survey
Taking about 0.1g of standard decoction of Gypsum Fibrosum (GT161022), precisely weighing, and mixing 6 parts, preparing 6 parts of sample solution according to the method for preparing sample solution determined in example 1, analyzing by feeding sample under the chromatographic conditions determined in example 1, and adding Mg2+The peak is a reference peak S, the relative retention time and the relative peak area of each characteristic peak and the S peak are calculated, and the RSD value is calculated, and the experimental results are shown in tables 12 and 13.
TABLE 12 repeatability results table (relative retention time) of the gypsum standard decoction feature map
TABLE 13 repeatability results table (relative peak area) of the feature map of the standard decoction of Gypsum Fibrosum
| Serial number | Na+ | K+ | Mg2+(S) |
| Repeatability-1 | 1.128 | 0.366 | 1.000 |
| Repeatability-2 | 1.124 | 0.364 | 1.000 |
| Repeatability-3 | 1.127 | 0.365 | 1.000 |
| Repeatability-4 | 1.127 | 0.366 | 1.000 |
| Repeatability-5 | 1.127 | 0.364 | 1.000 |
| Repeatability-6 | 1.125 | 0.370 | 1.000 |
| RSD(％) | 0.13 | 0.58 | 0.00 |
The results show that the same batch of samples was assayed 6 times in duplicate, as Mg2+The peak is a reference peak S, the relative retention time RSD value of each characteristic peak and the S peak is in the range of 0.02-0.03%, and the relative peak area RSD value is in the range of 0.13-0.58%, and is less than 3.0%, so that the method has good repeatability.
(5) Durability examination
Investigation of different column temperatures
Comparing the influence of different column temperatures, namely 28 ℃, 30 ℃ and 32 ℃ on the characteristic spectrum of the gypsum standard decoction.
Collecting about 0.1g of Gypsum Fibrosum Standard decoction (GT161022), weighing, preparing sample solution according to the method for preparing sample solution determined in example 1, performing analysis under the conditions of the same column temperature of 28 deg.C, 30 deg.C and 32 deg.C and the same chromatography conditions as those of example 1, and collecting Mg2+The peak is a reference peak S, the relative retention time and the relative peak area of each characteristic peak and the S peak are calculated, and the RSD value is calculated. The results are shown in tables 14, 15 and 17.
TABLE 14 durability results table for gypsum standard decoction signatures (relative retention time)
| Column temperature (. degree. C.) | Na+ | K+ | Mg2+(S) |
| 28 | 0.483 | 0.676 | 1.000 |
| 30 | 0.482 | 0.668 | 1.000 |
| 32 | 0.480 | 0.659 | 1.000 |
| RSD(％) | 0.31 | 1.33 | 0.00 |
TABLE 15 durability results table for gypsum standard decoction signatures (relative peak area)
| Column temperature (. degree. C.) | Na+ | K+ | Mg2+(S) |
| 28 | 0.796 | 0.408 | 1.000 |
| 30 | 0.776 | 0.403 | 1.000 |
| 32 | 0.761 | 0.405 | 1.000 |
| RSD(％) | 2.26 | 0.65 | 0.00 |
The results show that the relative retention time RSD value of each characteristic peak and the S peak is in the range of 0.31-1.33% and the relative peak area RSD is in the range of 0.65-2.26% at different column temperatures, and show that the change of the column temperature has little influence on the relative retention time and the relative peak area of each characteristic peak when the column temperature is +/-2 ℃.
Investigation of different flow rates
Comparing the influence of different flow rates, namely 0.6ml/min, 0.8ml/min and 1.0ml/min on the gypsum standard decoction characteristic map.
Taking about 0.1g of Gypsum Fibrosum Standard decoction (GT161022), weighing precisely, preparing the sample solution according to the method for preparing the sample solution determined in example 1, except that the flow rates are 0.6ml/min, 0.8ml/min and 1.0ml/min respectively, and determining the rest chromatographic conditions as in example 1Conditions of (1) analysis with Mg2+The peak is a reference peak S, the relative retention time and the relative peak area of each characteristic peak and the S peak are calculated, and the RSD value is calculated. The results are shown in tables 16, 17 and 18.
TABLE 16 durability results table for gypsum standard decoction signatures (relative retention time)
TABLE 17 durability results of gypsum standard decoction signatures (relative peak area)
| Flow rate (ml/min) | Na+ | K+ | Mg2+(S) |
| 0.6 | 0.746 | 0.421 | 1.000 |
| 0.8 | 0.776 | 0.403 | 1.000 |
| 1.0 | 0.779 | 0.429 | 1.000 |
| RSD(％) | 2.37 | 3.26 | 0.00 |
The results show that the relative retention time RSD value of each characteristic peak and the S peak is in the range of 7.16-8.15% and the relative peak area RSD is in the range of 2.37-3.27% under different flow rates, and show that when the flow rate is +/-0.2 ml/min, the change of the flow rate of the leaching solution has a large influence on the relative retention time of each characteristic peak and a small influence on the relative peak area, so that a reference substance is recommended to be adopted for identifying chromatographic peaks. The flow rate of the rinse is tightly controlled.
③ investigation of different chromatographic columns from the same manufacturer
Comparing the chromatographic columns of the same manufacturer with those of different batches for standard decoction Na of gypsum+、K+、Mg2+Influence of the feature profile.
Collecting standard decoction of Gypsum Fibrosum (GT161022), preparing sample solution according to the conditions determined in example 1, respectively using different chromatographic columns of the same manufacturer, performing sample injection analysis under the same conditions as those determined in example 1, and analyzing with Mg2+The peak is a reference peak S, the relative retention time and the relative peak area of each characteristic peak and the S peak are calculated, and the RSD value is calculated. The results are shown in tables 18 and 19 and FIG. 19.
TABLE 18 durability results table for gypsum standard decoction signatures (relative retention time)
TABLE 19 durability results table for gypsum standard decoction signatures (relative peak area)
In tables 18 and 19 above, lines 1 and 2 in run No. 1 are the results of the tests for the two parallel samples, and lines 1 and 2 in run No. 2 are also the results of the tests for the two parallel samples.
The results show that the same manufacturer can measure Na by different chromatographic columns+、K+、Mg2+With Mg2+As a control peak, Na+、K+The relative retention time RSD values are 0.17% and 0.20%, respectively, and the relative peak area RSD values are 1.87% and 5.82%, respectively, which shows that the method has good durability to small variations of different chromatographic columns.
Investigation of different leacheate concentrations
Comparing different leacheate concentrations, wherein the concentration of the methanesulfonic acid is respectively (18mmol/L, pH 1.77) (20mmol/L, pH 1.66) and (22mmol/L, pH 1.66) for gypsum standard decoction Na+、K+、Mg2+Influence of assay.
Collecting standard decoction of Gypsum Fibrosum (GT161022), preparing sample solution according to the conditions determined in example 1, respectively using different leacheate concentrations and other chromatographic conditions identical to the conditions determined in example 1, analyzing by sample injection, and calculating Na+、K+、Mg2+The contents and RSD values, and the experimental results are shown in Table 20, Table 21, and FIG. 20.
TABLE 20 durability results table for gypsum standard decoction signatures (relative retention time)
TABLE 21 durability results table for gypsum standard decoction signatures (relative peak area)
The results show that the eluent methane sulfonic acid concentration is +/-2 mmol/L for Na determination+、K+、Mg2+With Mg2+As a control peak, Na+、K+The relative retention time RSD values were 7.52% and 6.57%, respectively, and the relative peak area RSD values were 0.78% and 4.89%, respectively, indicating that the method is excellent in durability against small fluctuations in the leachant concentration.
Example 3
Referring to example 1, mirabilite, oyster, and talc were prepared into standard decoctions, respectively, and subjected to ion chromatography.
The results of comparing the relative areas of the peaks in the characteristic maps according to fig. 15 (characteristic map of gypsum standard decoction constructed by the present invention), fig. 21 (characteristic map of mirabilite standard decoction), fig. 22 (characteristic map of oyster standard decoction) and fig. 23 (characteristic map of talc standard decoction) show that the Na is detected in the mirabilite standard decoction, the oyster standard decoction and the talc standard decoction, although compared with the gypsum standard decoction+、K+、Mg2+However, there is a significant difference in the amounts that can distinguish them from the gypsum standard decoction.
TABLE 22 and result table of characteristic maps of different varieties of standard decoctions
From the above data, it is shown that in mirabilite standard decoction, Na+The peak area and the relative peak area are obviously higher than those of other standard decoctions and are obviously distinguished from the standard decoction of gypsum; concha Ostreae standard decoction K+、Mg2+Peak is lower than that of standard decoction of Gypsum Fibrosum and its K+The peak relative peak area is also lower than the data of the gypsum standard decoction, and can be obviously distinguished from the gypsum standard decoction; the peak areas and the relative peak areas of the three characteristic peaks in the talc standard decoction are lower than those of the gypsum standard decoction, and can be distinguished from the gypsum standard decoction.
Overall, the invention constructs the characteristic map of the gypsum standard decoction based on the ion chromatographyThe gypsum standard decoction has a characteristic spectrum containing 3 characteristic peaks, wherein peak 1 is Na+Peak, Peak 2 is K+Peak, Peak 3 is Mg2+Peak, peak 3 (Mg)2+) The peak corresponding to the reference substance is a reference peak S, the relative retention time of the other characteristic peaks is within +/-10% of the corresponding specified value, and the specified value of each characteristic peak is as follows: peak 1 was 0.48 and Peak 2 was 0.66, and each characteristic peak was matched with the retention time of its control. Moreover, although there is a difference in the peak relative peak area among different batches of gypsum standard decoction, the difference is limited within the gypsum standard decoction, and is very significant compared with decoction of other mineral drug varieties (such as mirabilite, oyster, talc), and the difference in the relative retention area existing among the different varieties is enough to distinguish the gypsum standard decoction from other mineral drug varieties.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (15)
1. A construction method of a characteristic spectrum of a gypsum standard decoction is characterized by comprising the following steps:
providing a reference solution, preparing a test solution, detecting the reference solution by adopting ion chromatography, detecting the test solution by adopting ion chromatography, introducing a chromatogram obtained by detecting the reference solution and a chromatogram obtained by detecting the test solution into a traditional Chinese medicine chromatogram fingerprint similarity evaluation system, and formulating a characteristic spectrum of a gypsum standard decoction;
the reference substance solution is obtained by dissolving a reference substance in a solvent, wherein the reference substance comprises sodium ions, potassium ions and magnesium ions;
the preparation of the test solution comprises the following steps: extracting the gypsum standard decoction by using an extraction solvent, and collecting an extracting solution to obtain a test sample solution, wherein the extraction solvent is a methane sulfonic acid solution.
2. The method for constructing the characteristic spectrum of the standard gypsum decoction according to claim 1, wherein the mass percent of the methanesulfonic acid in the extraction solvent is 0.5-0.8%.
3. The method for constructing the characteristic spectrum of the standard gypsum decoction according to claim 1, wherein the mass percent of the methanesulfonic acid in the extraction solvent is 0.5-0.65%.
4. The method for constructing the characteristic spectrum of the standard gypsum decoction according to any one of claims 1 to 3, wherein the leacheate used for detection is a methanesulfonic acid solution, and the concentration of the methanesulfonic acid in the leacheate is 19 mmol/L-21 mmol/L.
5. The method for constructing the characteristic spectrum of the standard gypsum decoction according to any one of claims 1 to 3, wherein the flow rate of the leacheate used for detection is 0.75mL/min to 0.9 mL/min.
6. The method for constructing the characteristic spectrum of the standard gypsum decoction according to any one of claims 1 to 3, wherein the column temperature for detection is 28 ℃ to 32 ℃.
7. The method for constructing the characteristic spectrum of the standard gypsum decoction of any one of claims 1 to 3, wherein the detected conditions comprise: the protective column is IonPac CG12A, the inner diameter of the protective column is 4mm, the column length is 50mm, and the particle size of the filler is 8 μm; the analytical column is IonPac CS12A, the inner diameter of the analytical column is 4mm, the column length is 250mm, and the particle size of the filler is 8 μm; the suppressor is CSRS 4 mm; the temperature of the detection pool is 32-36 ℃; the inhibiting current is 45 mA-49 mA; the sensitivity of the detector is 4.5 muS/cm-5.5 muS/cm; the sample amount is 4.5-5.5 mul.
8. The method for constructing the characteristic spectrum of the standard gypsum decoction according to any one of claims 1 to 3, wherein the amount of the extraction solvent used is 15ml to 25ml per 0.1g of the standard gypsum decoction.
9. The method for constructing the characteristic spectrum of the standard gypsum decoction according to any one of claims 1 to 3, wherein the solvent is water.
10. The method for constructing a characteristic spectrum of a gypsum standard decoction according to any one of claims 1 to 3, wherein the concentration of sodium ions is 0.8 to 1.2 μ g/mL, the concentration of magnesium ions is 0.8 to 1.2 μ g/mL, and the concentration of potassium ions is 0.8 to 1.2 μ g/mL.
11. The method for constructing the characteristic spectrum of the standard gypsum decoction according to any one of claims 1 to 3, wherein the standard gypsum decoction is extracted by shaking.
12. The method for constructing the characteristic spectrum of the standard gypsum decoction of any one of claims 1 to 3, wherein the extracting solution is collected by filtration.
13. The method for constructing the characteristic spectrum of the standard gypsum decoction of any one of claims 1 to 3, wherein the characteristic spectrum of the standard gypsum decoction comprises 3 characteristic peaks, and the peak 1 is Na+Peak, Peak 2 is K+Peak, Peak 3 is Mg2+Peak with Mg2+The peak 3 corresponding to the reference substance is a reference peak S, the relative retention time of each remaining characteristic peak is within +/-10% of the corresponding specified value, and the specified values of the characteristic peaks are respectively as follows: peak 1 was 0.48 and Peak 2 was 0.66.
14. Use of a gypsum standard decoction for detecting a mineral medicine decoction, wherein the gypsum standard decoction is obtained by the construction method of any one of claims 1 to 13.
15. The use of claim 14, wherein the mineral decoction is a mirabilite standard decoction, an oyster standard decoction, or a talc standard decoction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102590383A (en) * | 2012-02-13 | 2012-07-18 | 河北中烟工业有限责任公司 | Method for determining content of potassium, sodium, calcium and magnesium in cigarette paper simultaneously |
| CN111537657A (en) * | 2020-06-28 | 2020-08-14 | 黄河三角洲京博化工研究院有限公司 | Method for detecting content of trace metal ions in high-purity thiourea by ion chromatography |
-
2021
- 2021-06-24 CN CN202110706336.XA patent/CN113640398B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102590383A (en) * | 2012-02-13 | 2012-07-18 | 河北中烟工业有限责任公司 | Method for determining content of potassium, sodium, calcium and magnesium in cigarette paper simultaneously |
| CN111537657A (en) * | 2020-06-28 | 2020-08-14 | 黄河三角洲京博化工研究院有限公司 | Method for detecting content of trace metal ions in high-purity thiourea by ion chromatography |
Non-Patent Citations (3)
| Title |
|---|
| 杨春霞 等: "离子色谱法测定土壤中无机阴阳离子含量", 《理化检验(化学分册)》 * |
| 王少明 等: "离子色谱分析的样品前处理方法", 《化学分析计量》 * |
| 纪娟 等: "茂陵石刻表面污染物和可溶盐的分析研究", 《文物保护与考古科学》 * |
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