Constructing method of ion chromatography characteristic chromatograms of mother-of-pearl medicinal material, processed product and preparation of mother-of-pearl medicinal material

Abstract

The invention provides an ion chromatography detection method for nacre mother of pearl. According to the ion chromatography detection method, anions and cations in the nacre mother of pearl are detected by adopting an ion chromatography method. According to the method, single-variety research is performed on the concha margaritiferallsta formula granules and the calcined concha margaritiferallsta formula granules by adopting an ion chromatography only water adding mode, the calcined concha margaritiferallsta is scientifically identified, the method has the characteristics of comprehensive detection and simple operation, and the concha margaritiferallsta formula granules and the calcined concha margaritiferallsta formula granules can be effectively identified; and uniform and stable quality of the concha margaritifera formula granules and the calcined concha margaritifera formula granules can be ensured. The invention is suitable for mother-of-pearl medicinal materials, decoction pieces, calcined mother-of-pearl decoction pieces, mother-of-pearl standard decoction, calcined mother-of-pearl standard decoction and formula granules thereof.

Description

Technical Field

[0001] The present invention relates to an ion chromatography detection method for mother-of-pearl and a method for constructing an ion chromatography characteristic spectrum of mother-of-pearl medicinal materials, processed products and formulated granules. Background Art

[0002] Mother of pearl is the shell of the clams Hyriopsis cumingii (Lea), Cristariapicata (Leeach), or Pteria martensii (Dunker). It primarily contains calcium carbonate (CaCO3). It has a salty flavor and a cold nature. It enters the liver and heart meridians. It has the effects of calming the liver and suppressing yang, calming the mind and relieving convulsions, and improving eyesight and removing cataracts. It is mainly used clinically to treat headaches, dizziness, palpitations, insomnia, red eyes, cataracts, and blurred vision. Li Guiping [1] The content of amino acids in different varieties of mother-of-pearl was determined and analyzed. Zhu used o-phthalaldehyde and β-mercaptoethanol as derivatization reagents, pre-column derivatization, ODS (C18) column separation, pH 5.6 acetate buffer, methanol binary gradient elution, fluorescence detection, and separated and determined the content of 8 amino acids in mother-of-pearl within 32 minutes. Law used acetic acid decalcification method to extract soluble protein from the mother-of-pearl of Pinctada martensii, and found that its main component was protein aggregates. Amino acid analysis showed that this protein was rich in glycine, aspartic acid, alanine, glutamic acid, and leucine. Wang Haibo et al. established HPLC characteristic profiles for mother-of-pearl medicinal materials from different origins and selected Agilent ZORBAX SB-C 18 Chromatographic column (4.6 mm × 250 mm, 5 μm), column temperature 30 °C, wavelength 254 nm, flow rate 0.5 mL min -1 , using acetonitrile-0.1% phosphoric acid aqueous solution (gradient elution). The results showed that this method can be used for quality control of pearl mother-of-pearl medicinal materials. Qiao Yihan et al. used SAS and SPSS statistical software to perform cluster analysis and principal component analysis to establish an amino acid HPLC fingerprint of the pearl layer powder of pearl mother-of-pearl and determine the amino acid content. They used a Venusi1-AA amino acid analysis column (4.6mm×250mm, 5μm), a column temperature of 28°C, an injection volume of 10μl, a wavelength of 254nm, and a flow rate of 0.9mL·min. -1 , with sodium acetate aqueous solution at pH 6.5 as mobile phase A, and 80% acetonitrile aqueous solution as mobile phase B. Currently, the quality research on mother-of-pearl mainly focuses on the detection of amino acids and proteins contained therein, in order to reflect the medicinal effects of mother-of-pearl through the detection of these indicators.

[0003] However, the authenticity identification of mother-of-pearl is still a technical difficulty. The appearance of counterfeits is highly similar to that of the authentic ones, and there is a lack of standardized detection methods. For example, counterfeits such as Tianjin Li Mussels and Dorsal Horn Toothless Mussels belong to the same family of mussels as the authentic Triangular Hyriopsis and Pleated Crown Mussels. They are similar in appearance, color, and texture. After processing, they are all irregular flakes with a pearly luster on the surface, which is very easy to confuse. Shell powder pressed products or coated imitations are even more difficult to identify. The surface can be artificially manufactured with a "nacre texture" and even have the illusion of "peeling off layers". The pharmacopoeia only describes the source, properties, and microscopic characteristics of mother-of-pearl, and does not specify quantitative indicators (such as the thickness of the nacre layer and the threshold value of calcium carbonate content), resulting in no clear basis for laboratory testing. Traditional identification relies on experience, such as "looking at the luster, touching the texture, and smelling the odor", which is highly subjective and difficult for ordinary consumers or grassroots pharmacists to master. There are literature reports on the use of atomic absorption spectrophotometry and ion chromatography to determine calcium content (Xu Yan, et al., Determination of calcium in Qingkailing injection and mother-of-pearl hydrolyzate and preliminary study on its form, Chinese Patent Medicine, February 2003). This literature only discloses the ratio of bound calcium to free calcium in mother-of-pearl hydrolyzate.

[0004] The publicly available calcined mother-of-pearl formula granules, standard number: SCYPBZ(PFKL)-2025007 (trial), measure the content of calcined mother-of-pearl only in terms of calcium carbonate content (each 1g should contain 140mg to 450mg of calcium carbonate (CaCO3)). Evaluating the quality of calcined mother-of-pearl based solely on calcium carbonate content cannot reflect the impact of the processing process on the efficacy of the drug, cannot achieve the purpose of quality control, and cannot realize the identification of mother-of-pearl and its processed products. Currently, there is no ion chromatography method for quality testing of mother-of-pearl. Summary of the Invention

[0005] The present invention provides a method for detecting nacre by ion chromatography and a method for constructing an ion chromatography characteristic spectrum of nacre medicinal materials, processed products and formulated granules.

[0006] The present invention provides an ion chromatography detection method for mother-of-pearl, which uses ion chromatography to detect anions and cations in mother-of-pearl, wherein the chromatographic conditions for detecting anions are:

[0007] The styrene-divinylbenzene organic polymer was used as the filler (IonPac AS11 anion analysis column, column length: 250 mm, inner diameter: 4 mm, particle size: 9 μm; IonPac AG11-HC anion guard column, column length: 50 mm, inner diameter: 4 mm, particle size: 9 μm); the detector was a conductivity detector; the detection method was suppressed conductivity detection; 16 mmol / L potassium hydroxide solution was used as the eluent; the flow rate was 0.8-1.2 ml / min; the column temperature was 25-35°C; the theoretical plate number was calculated based on Cl - Peak calculation should be no less than 3000;

[0008] The chromatographic conditions for cations are:

[0009] Styrene-divinylbenzene organic polymer was used as filler (IonPac CS12A cation analysis column, column length: 250 mm, inner diameter: 4 mm, particle size: 8 μm; IonPac CG12A cation guard column, column length: 50 mm, inner diameter: 4 mm, particle size: 8 μm, or a column with equivalent performance); the detector was a conductivity detector; the detection method was suppressed conductivity detection; 20 mmol / L methanesulfonic acid solution was used as eluent; the flow rate was 0.8-1.2 ml / min; the column temperature was 25-35°C; the number of theoretical plates was calculated based on K + Peak count should be no less than 3000.

[0010] Preferably, in the chromatographic conditions, the flow rate is 0.8 ml per minute and the column temperature is 35°C.

[0011] It includes the following steps:

[0012] a. Pre-treatment of the test sample: prepare anionic and cationic test sample solutions separately;

[0013] b. Detect according to the above chromatographic conditions to obtain anion chromatogram and cation chromatogram respectively.

[0014] Wherein, the preparation method of the anion test solution described in step a is:

[0015] Take 0.1g of the sample to be tested, place it in a 100ml-1000ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat (power 600W, frequency 40kHz) for 30-60 minutes. Let it cool, dilute it with water to the scale, shake it well, filter it, and take the filtrate as the test solution;

[0016] The method for preparing the cationic test solution is:

[0017] Take 0.1g of the sample to be tested and place it in a 100-1000ml polyethylene volumetric flask. Add an appropriate amount of 0.1%-0.3% methanesulfonic acid solution to completely dissolve it, dilute it to the scale, shake well, filter, and take the filtrate as the test solution.

[0018] Preferably, the preparation method of the anion test solution described in step a is:

[0019] In the preparation method of the anion test solution, the sample to be tested is placed in a 100 ml polyethylene volumetric flask and ultrasonically treated for 30 minutes;

[0020] In the preparation method of the cationic test solution, the sample to be tested is placed in a 1000ml polyethylene volumetric flask; the concentration of the methanesulfonic acid solution is 0.1%.

[0021] The anion chromatogram contains at least three characteristic peaks, peak 1 is chloride ion, peak 3 is sulfate ion, the relative retention time is: peak 2: 1.16, peak 3: 2.65, and the relative retention time fluctuates by 10%; the relative peak areas of mother-of-pearl are: peak 1: 0.01, peak 3: 0.20, and the relative peak areas of calcined mother-of-pearl are: peak 1: 0.01, peak 3: 1.68, and the relative peak areas fluctuate by 10%.

[0022] The cation chromatogram contains at least four characteristic peaks, and the relative retention times are: peak 1: 0.74, peak 3: 1.61, peak 4: 1.95, and the relative retention time fluctuates by 10%; the relative peak areas of mother-of-pearl are: peak 1: 16.18, peak 3: 2.74, peak 4: 258.01, and the relative peak areas of calcined mother-of-pearl are: peak 1: 74.65, peak 3: 0.97, peak 4: 335.16, and the relative peak areas fluctuate by 10%; wherein, peak 1 is sodium ion, peak 2 is potassium ion, peak 3 is magnesium ion, and peak 4 is calcium ion.

[0023] Wherein, the nacre is native nacre or calcined nacre.

[0024] The present invention also provides a method for constructing an ion chromatographic characteristic spectrum of mother-of-pearl medicinal materials, processed products, and formula granules, which adopts the ion chromatography detection method of mother-of-pearl to construct the ion chromatographic characteristic spectrum of mother-of-pearl medicinal materials, processed products, and formula granules; wherein the anion chromatogram contains at least three characteristic peaks, peak 1 is chloride ion, peak 3 is sulfate ion, the relative retention time is: peak 2: 1.16, peak 3: 2.65, and the relative retention time fluctuates by 10%; the relative peak areas of mother-of-pearl are: peak 1: 0.01, peak 3: 0.20, and the relative peak areas of calcined mother-of-pearl are: peak 1: 0.01, peak 3: 1.68, and the relative peak areas fluctuate by 10%.

[0025] The cation chromatogram contains at least four characteristic peaks, and the relative retention times are: peak 1: 0.74, peak 3: 1.61, peak 4: 1.95, and the relative retention time fluctuates by 10%; the relative peak areas of mother-of-pearl are: peak 1: 16.18, peak 3: 2.74, peak 4: 258.01, and the relative peak areas of calcined mother-of-pearl are: peak 1: 74.65, peak 3: 0.97, peak 4: 335.16, and the relative peak areas fluctuate by 10%; wherein, peak 1 is sodium ion, peak 2 is potassium ion, peak 3 is magnesium ion, and peak 4 is calcium ion.

[0026] The present invention provides a method for identifying nacre or fumed nacre. The method for constructing an ion chromatographic characteristic spectrum is used to construct an ion chromatographic characteristic spectrum for identifying nacre or fumed nacre. If the relative retention times and relative peak areas of anions and cations are both within the numerical range of the spectrum, the nacre is identified as nacre or fumed nacre. When the nacre of the present invention is detected using ion chromatography (IC), the main difficulties lie in two aspects: sample pretreatment and matrix interference.

[0027] 1. Complex sample pretreatment

[0028] Mineral matrix is ​​difficult to dissolve: the main component of mother of pearl is calcium carbonate (CaCO3), which needs to be dissolved by acid (such as hydrochloric acid), but it will introduce high concentrations of Cl- and Ca 2+ Plasma interferes with subsequent ion separation.

[0029] Many organic interferences: For example, the formula granules often contain Chinese herbal extracts (such as sugars, organic acids, saponins, etc.), which will raise the baseline and mask low-content ion signals, requiring solid phase extraction (SPE) or dilution treatment.

[0030] Calcium ion inhibitory effect: Ca 2+ Too high a concentration may cause the ion exchange column to be overloaded, affecting the weakly retained ions (such as Na + , K + ) separation.

[0031] 2. Difficulty in optimizing chromatographic conditions

[0032] High background conductivity: Ca 2+ Mg 2+ Isocations can generate high background signals in suppressive ICs, reducing detection sensitivity.

[0033] Gradient elution limitation: If you need to detect multivalent cations (such as Ca 2+ Mg 2+ ) and monovalent ions (such as Na + , K + ), gradient elution can easily lead to baseline drift, and the eluent concentration needs to be carefully optimized.

[0034] Column life problem: High salt samples may shorten the life of ion exchange columns and require pre-column or online dilution.

[0035] 3. Technical pitfalls in practical applications

[0036] Matrix effect: Even after pretreatment, residual organic matter may inhibit the response of target ions (such as F-, Cl-), resulting in low results.

[0037] High requirements for method validation: the linear range (calcium carbonate content spans a wide range, 140-450 mg / g), recovery rate (Ca after acid dissolution) and the like need to be verified.2+ complete release) and durability (fluctuations in mother-of-pearl composition between batches).

[0038] Ion chromatography using only water addition mode is used to study single varieties of mother-of-pearl formula granules and calcined mother-of-pearl formula granules, and scientifically identify calcined mother-of-pearl. This method features comprehensive testing and simple operation, can effectively identify mother-of-pearl formula granules and calcined mother-of-pearl formula granules, and can ensure the uniformity and stability of the quality of the mother-of-pearl formula granules and calcined mother-of-pearl formula granules. The present invention is applicable to mother-of-pearl medicinal materials, decoction pieces, calcined mother-of-pearl decoction pieces, mother-of-pearl standard decoctions, calcined mother-of-pearl standard decoctions, and their formula granules. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Reference characteristic spectrum (peak 1 (S): Cl - Peak 3: SO4 2- ; Among them, chromatographic column: Dionex IonPacTM AS11-HC, 4*250mm, 9μm; guard column: Dionex IonPacTM AG11-HC, 4*50mm, 9μm);

[0040] Figure 2 Reference characteristic spectrum (peak 1: Na + Peak 2 (S): K + Peak 3: Mg 2+ Peak 4: Ca 2+ ; Among them, chromatographic column: DionexIonPac TM CS12A, 4 mm × 250 mm, 8 μm; guard column: Dionex IonPac TM CG12A, 4 mm × 50 mm, 8 μm);

[0041] Figure 3 : Control characteristic spectrum (peak 1 (S): Cl - Peak 3: SO4 2- ; Among them, chromatographic column: Dionex IonPacTMAS11-HC, 4*250mm, 9μm; guard column: Dionex IonPacTM AG11-HC, 4*50mm, 9μm);

[0042] Figure 4 Reference characteristic spectrum (peak 1: Na + Peak 2 (S): K + Peak 3: Mg 2+ Peak 4: Ca 2+ , where column: Dionex IonPac TMCS12A, 4 mm × 250 mm, 8 μm; guard column: Dionex IonPac TM CG12A, 4 mm × 50 mm, 8 μm);

[0043] Figure 5 Reference characteristic spectrum (peak 1 (S): Cl - Peak 3: SO4 2- ; Among them, chromatographic column: Dionex IonPacTM AS11-HC, 4*250mm, 9μm; guard column: Dionex IonPacTM AG11-HC, 4*50mm, 9μm);

[0044] Figure 6 Reference characteristic spectrum (peak 1: Na + Peak 2 (S): K + Peak 3: Mg 2+ Peak 4: Ca 2+ ; Among them, chromatographic column: DionexIonPac TM CS12A, 4 mm × 250 mm, 8 μm; guard column: Dionex IonPac TM CG12A, 4 mm × 50 mm, 8 μm);

[0045] Figure 7 Column temperature investigation;

[0046] Figure 8 Flow rate investigation;

[0047] Figure 9 Investigation of solvent addition amount;

[0048] Figure 10 Extraction time investigation;

[0049] Figure 11 Chromatographic peak identification;

[0050] Figure 12 Column temperature investigation;

[0051] Figure 13 Flow rate investigation;

[0052] Figure 14 Investigation of solvent addition amount;

[0053] Figure 15 Acid concentration investigation;

[0054] Figure 16 Chromatographic peak identification (Note: from bottom to top: blank, sodium ion, potassium ion, magnesium ion, calcium ion, calcined mother-of-pearl standard decoction);

[0055] Figure 17Mother of pearl formula particle characteristics-KL01;

[0056] Figure 18 Mother of pearl formula particle characteristics-KL02;

[0057] Figure 19 Mother of pearl formula particle characteristics-KL03;

[0058] Figure 20 Characteristics of calcined mother-of-pearl formula particles-DKL01;

[0059] Figure 21 Characteristics of calcined mother-of-pearl formula particles-DKL02;

[0060] Figure 22 Characteristics of calcined mother-of-pearl formula particles-DKL03;

[0061] Figure 23 Mother of pearl formula particle characteristics-KL01;

[0062] Figure 24 Mother of pearl formula particle characteristics-KL02;

[0063] Figure 25 Characteristics of mother-of-pearl hemp formula particles-KL03;

[0064] Figure 26 Characteristics of calcined mother-of-pearl formula particles-DKL01;

[0065] Figure 27 Characteristics of calcined mother-of-pearl formula particles-DKL02;

[0066] Figure 28 Characteristics of calcined mother-of-pearl formula particles-DKL03. DETAILED DESCRIPTION

[0067] Example 1 Ion chromatography detection of the pearl mother-of-pearl and calcined pearl mother-of-pearl formula particles of the present invention

[0068] The chromatographic conditions and system suitability test used a styrene-divinylbenzene organic polymer as the filler (IonPac AS11 anion analysis column, column length 250 mm, inner diameter 4 mm, particle size 9 μm; and an IonPac AG11-HC anion guard column, column length 50 mm, inner diameter 4 mm, particle size 9 μm, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 16 mmol / L potassium hydroxide solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. The theoretical plate number is calculated based on Cl - Peak count should be no less than 3000.

[0069] Preparation of Reference Solution: Place 0.1 g of mother-of-pearl reference medicinal material in a 100 ml polyethylene volumetric flask, add an appropriate amount of water, and sonicate (600 W, 40 kHz) for 30 minutes. Allow to cool, dilute to volume with water, shake well, and filter. The filtrate is used as the reference medicinal material solution. Separately, accurately weigh an appropriate amount of chloride ion and add water to a solution containing 5 μg per 1 ml. This is used as the reference substance solution.

[0070] Preparation of test solution: Take an appropriate amount of the product, grind it into powder, take about 0.1 g, place it in a 100 ml polyethylene volumetric flask, add an appropriate amount of water, and ultrasonically treat it (power 600 W, frequency 40 kHz) for 30 minutes. Let it cool, dilute it to the scale with water, shake it well, filter it, and take the filtrate as the test solution.

[0071] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0072] The test sample chromatogram should show three characteristic peaks, and the retention time should correspond to the three characteristic peaks in the reference material chromatogram. Peak 1 should correspond to the retention time of the corresponding reference material peak. The peak corresponding to the chloride ion reference material peak is the S peak. The relative retention time of each characteristic peak and the S peak is calculated. The relative retention time should be within ±10% of the specified value. The specified values ​​are: 1.16 (peak 2), 2.66 (peak 3) (see Figure 1 ).

[0073] The content of cation was determined by ion chromatography (General Chapter 0513 of the Chinese Pharmacopoeia 2020 Edition).

[0074] Chromatographic conditions and system suitability tests were conducted using a styrene-divinylbenzene organic polymer as the filler (IonPac CS12A cation analysis column, 250 mm length, 4 mm inner diameter, 8 μm particle size; and an IonPac CG12A cation guard column, 50 mm length, 4 mm inner diameter, 8 μm particle size, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 20 mmol / L methanesulfonic acid solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. Theoretical plates were calculated based on K. + Peak count should be no less than 3000.

[0075] Preparation of Reference Solution: 0.1 g of mother-of-pearl reference medicinal material was placed in a 1000 ml polyethylene volumetric flask. An appropriate amount of 0.1% methanesulfonic acid solution was added to completely dissolve the solution. The solution was diluted to volume, shaken, and filtered. The filtrate was used as the reference medicinal material solution. Separately, an appropriate amount of potassium ion was accurately weighed and added to water to a solution containing 5 μg per 1 ml. This was used as the reference material solution.

[0076] Preparation of test solution: Take an appropriate amount of this product, grind it into powder, take about 0.1g, place it in a 100ml polyethylene volumetric flask, add an appropriate amount of 0.1% methanesulfonic acid solution to dissolve it completely, and dilute to the scale, shake well, filter, and take the filtrate as the test solution.

[0077] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0078] The test sample chromatogram should show 4 characteristic peaks, and the retention time should correspond to the 4 characteristic peaks in the reference material chromatogram. Peak 2 should correspond to the retention time of the corresponding reference material peak. The peak corresponding to the potassium ion reference material peak is the S peak. The relative retention time of each characteristic peak and the S peak is calculated. The relative retention time should be within ±10% of the specified value. The specified values ​​are: 0.74 (peak 1), 1.63 (peak 3), 1.97 (peak 4) (see Figure 2 ).

[0079] Example 2 Mother-of-pearl medicinal materials and decoction pieces, calcined mother-of-pearl decoction pieces

[0080] The chromatographic conditions and system suitability test used a styrene-divinylbenzene organic polymer as the filler (IonPac AS11 anion analysis column, column length 250 mm, inner diameter 4 mm, particle size 9 μm; and an IonPac AG11-HC anion guard column, column length 50 mm, inner diameter 4 mm, particle size 9 μm, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 16 mmol / L potassium hydroxide solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. The theoretical plate number is calculated based on Cl - Peak count should be no less than 3000.

[0081] Preparation of Reference Solution: Place 0.1 g of mother-of-pearl reference medicinal material in a 100 ml polyethylene volumetric flask, add an appropriate amount of water, and sonicate (600 W, 40 kHz) for 30 minutes. Allow to cool, dilute to volume with water, shake well, and filter. The filtrate is used as the reference medicinal material solution. Separately, accurately weigh an appropriate amount of chloride ion and add water to a solution containing 5 μg per 1 ml. This is used as the reference substance solution.

[0082] Preparation of test solution: Take 0.1 g of fine powder of this product, place it in a 100 ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat (power 600 W, frequency 40 kHz) for 30 minutes. Let cool, dilute with water to the scale, shake well, filter, and take the filtrate as the test solution.

[0083] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0084] The test sample chromatogram should show three characteristic peaks, and the retention time should correspond to the three characteristic peaks in the reference material chromatogram. Peak 1 should correspond to the retention time of the corresponding reference material peak. The peak corresponding to the chloride ion reference material peak is the S peak. The relative retention time of each characteristic peak and the S peak is calculated. The relative retention time should be within ±10% of the specified value. The specified values ​​are: 1.16 (peak 2), 2.66 (peak 3) (see Figure 3 ).

[0085] The content of cation was determined by ion chromatography (General Chapter 0513 of the Chinese Pharmacopoeia 2020 Edition).

[0086] Chromatographic conditions and system suitability tests were conducted using a styrene-divinylbenzene organic polymer as the filler (IonPac CS12A cation analysis column, 250 mm length, 4 mm inner diameter, 8 μm particle size; and an IonPac CG12A cation guard column, 50 mm length, 4 mm inner diameter, 8 μm particle size, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 20 mmol / L methanesulfonic acid solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. Theoretical plates were calculated based on K. + Peak count should be no less than 3000.

[0087] Preparation of Reference Solution: 0.1 g of mother-of-pearl reference medicinal material was placed in a 1000 ml polyethylene volumetric flask. An appropriate amount of 0.1% methanesulfonic acid solution was added to completely dissolve the solution. The solution was diluted to volume, shaken, and filtered. The filtrate was used as the reference medicinal material solution. Separately, an appropriate amount of potassium ion was accurately weighed and added to water to a solution containing 5 μg per 1 ml. This was used as the reference material solution.

[0088] Preparation of test solution: Take 0.1 g of fine powder of this product and place it in a 1000 ml polyethylene volumetric flask. Add an appropriate amount of 0.1% methanesulfonic acid solution to dissolve it completely, and dilute to the scale. Shake well, filter, and take the filtrate as the test solution.

[0089] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0090] The test sample chromatogram should show 4 characteristic peaks, and the retention time should correspond to the 4 characteristic peaks in the reference material chromatogram. Peak 2 should correspond to the retention time of the corresponding reference material peak. The peak corresponding to the potassium ion reference material peak is the S peak. The relative retention time of each characteristic peak and the S peak is calculated. The relative retention time should be within ±10% of the specified value. The specified values ​​are: 0.74 (peak 1), 1.63 (peak 3), 1.97 (peak 4) (see Figure 4 ).

[0091] Example 3 Pearl mother standard decoction, calcined pearl mother standard decoction

[0092] Chromatographic conditions and system suitability tests were conducted using a styrene-divinylbenzene organic polymer as the filler (IonPac AS11 anion analysis column, 250 mm length, 4 mm inner diameter, 9 μm particle size; and an IonPac AG11-HC anion guard column, 50 mm length, 4 mm inner diameter, 9 μm particle size, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 16 mmol / L potassium hydroxide solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. The theoretical plate number is calculated based on Cl - Peak count should be no less than 3000.

[0093] Preparation of Reference Solution: Place 0.1 g of mother-of-pearl reference medicinal material in a 100 ml polyethylene volumetric flask, add an appropriate amount of water, and sonicate (600 W, 40 kHz) for 30 minutes. Allow to cool, dilute to volume with water, shake well, and filter. The filtrate is used as the reference medicinal material solution. Separately, accurately weigh an appropriate amount of chloride ion and add water to a solution containing 5 μg per 1 ml. This is used as the reference substance solution.

[0094] Preparation of test solution: Take 0.1 g of this product, place it in a 100 ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat (power 600 W, frequency 40 kHz) for 30 minutes. Let cool, dilute with water to the scale, shake well, filter, and take the filtrate as the test solution.

[0095] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0096] The test sample chromatogram should show three characteristic peaks, and the retention time should correspond to the three characteristic peaks in the reference material chromatogram. Peak 1 should correspond to the retention time of the corresponding reference material peak. The peak corresponding to the chloride ion reference material peak is the S peak. The relative retention time of each characteristic peak and the S peak is calculated. The relative retention time should be within ±10% of the specified value. The specified values ​​are: 1.16 (peak 2), 2.66 (peak 3) (see Figure 5 ).

[0097] The content of cation was determined by ion chromatography (General Chapter 0513 of the Chinese Pharmacopoeia 2020 Edition).

[0098] Chromatographic conditions and system suitability tests were conducted using a styrene-divinylbenzene organic polymer as the filler (IonPac CS12A cation analysis column, 250 mm length, 4 mm inner diameter, 8 μm particle size; IonPac CG12A cation guard column, 50 mm length, 4 mm inner diameter, 8 μm particle size, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 20 mmol / L methanesulfonic acid solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. Theoretical plates were calculated based on K. + Peak count should be no less than 3000.

[0099] Preparation of Reference Solution: 0.1 g of mother-of-pearl reference medicinal material was placed in a 1000 ml polyethylene volumetric flask. An appropriate amount of 0.1% methanesulfonic acid solution was added to completely dissolve the solution. The solution was diluted to volume, shaken, and filtered. The filtrate was used as the reference medicinal material solution. Separately, an appropriate amount of potassium ion was accurately weighed and added to water to a solution containing 5 μg per 1 ml. This was used as the reference material solution.

[0100] Preparation of test solution: Take 0.1 g of this product and place it in a 1000 ml polyethylene volumetric flask. Add an appropriate amount of 0.1% methanesulfonic acid solution to completely dissolve it, and dilute to the scale. Shake well, filter, and take the filtrate as the test solution.

[0101] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0102] The test sample chromatogram should show 4 characteristic peaks, and the retention time should correspond to the 4 characteristic peaks in the chromatogram of the reference medicinal material. Peak 2 should correspond to the retention time of the corresponding reference material peak, and the peak corresponding to the potassium ion reference is the S peak. The relative retention time of each characteristic peak and the S peak should be calculated. The relative retention time should be within the range of ±10% of the specified value, which is 0.74 (peak 1), 1.63 (peak 3), 1.97 (peak 4) (see Figure 6 ).

[0103] Example 4 Ion Chromatography Detection Condition Screening Test of the Present Invention

[0104] 1. Anion method

[0105] 1.1 Chromatographic conditions

[0106] The column was filled with styrene-divinylbenzene organic polymer (IonPac AS11 anion analysis column, 250 mm length, 4 mm inner diameter, 9 μm particle size; IonPac AG11-HC anion guard column, 50 mm length, 4 mm inner diameter, 9 μm particle size, or a column of equivalent performance); the detector was a conductivity detector; the detection method was suppressed conductivity detection; the eluent was 16 mmol / L potassium hydroxide solution; the flow rate was 0.8 ml / min; and the column temperature was 35°C. The theoretical plate number was calculated based on Cl - Peak count should be no less than 3000.

[0107] 1.2 Preparation of reference solution

[0108] Place 0.1g of mother-of-pearl control medicinal material in a 100ml polyethylene volumetric flask, add an appropriate amount of water, and sonicate (power 600W, frequency 40kHz) for 30 minutes. Let cool, dilute to the mark with water, shake well, filter, and use the filtrate as the control medicinal material reference solution. Separately, accurately weigh an appropriate amount of chloride ion and add water to a solution containing 5μg per 1ml. This will serve as the reference substance solution.

[0109] 1.3 Preparation of test solution

[0110] Take 0.1 g of this product, place it in a 100 ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat (power 600 W, frequency 40 kHz) for 30 minutes. Let it cool, dilute it to the scale with water, shake it well, filter it, and take the filtrate as the test solution.

[0111] 1.4 Determination method

[0112] Accurately pipette 25 μl of reference solution and test solution respectively, inject them into ion chromatograph and measure to obtain the result.

[0113] 1.5. Chromatographic conditions and system suitability investigation

[0114] 1.5.1 Column temperature investigation

[0115] Based on the experimental conditions proposed above, the column temperatures of 25℃, 30℃ and 35℃ were investigated respectively. Figure 7 , Table 1-2.

[0116] Table 1 Column temperature investigation-relative retention time

[0117]

[0118] Table 2 Column temperature investigation-relative peak area

[0119]

[0120] The results showed that when the column temperature was 35℃, the chromatogram peak shape was more symmetrical, the separation was better, and the peaks were more complete. Therefore, the column temperature was determined to be 35℃.

[0121] 1.5.2 Flow rate investigation

[0122] Based on the experimental conditions proposed above, the flow rates of 0.8ml / min, 1.0ml / min and 1.2ml / min were investigated respectively. Figure 8 , Table 3-4.

[0123] Table 3 Flow rate investigation-relative retention time

[0124]

[0125] Table 4 Flow rate investigation-relative peak area

[0126]

[0127] The results showed that when the flow rate was 0.8 ml / min, the chromatogram peak shape was better and the separation was moderate. Therefore, the flow rate was determined to be 0.8 ml / min.

[0128] 1.6 Preparation of test solution

[0129] 1.6.1 Investigation of solvent addition amount

[0130] Take 0.1g of this product and place it in 100ml, 500ml and 1000ml polyethylene volumetric flasks respectively, add appropriate amount of water, and ultrasonically treat (power 600W, frequency 40kHz) for 30 minutes, let cool, dilute with water to the scale, shake well, filter, and take the filtrate to obtain. Figure 9 .

[0131] The results showed that when the amount of solvent added was 100 ml, the peak shape of the characteristic chromatographic peak was better. Therefore, the amount of solvent added for the test sample was determined to be 100 ml.

[0132] 1.6.2 Extraction time investigation

[0133] Take 0.1g of this product, place it in a 100ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat it (power 600W, frequency 40kHz) for 30 minutes, 45 minutes, and 60 minutes respectively. Let it cool, dilute it with water to the scale, shake it well, filter it, and take the filtrate to obtain it. Figure 10 .

[0134] The results showed that the peak shapes of the characteristic chromatographic peaks were not much different when the ultrasonic treatment lasted for 30 minutes, 45 minutes and 60 minutes, so the extraction time for the test sample was selected as 30 minutes.

[0135] 1.7. Characteristic spectrum anion method determination

[0136] Determined by ion chromatography (General Chapter 0513 of the Chinese Pharmacopoeia 2020 Edition).

[0137] The chromatographic conditions and system suitability test used a styrene-divinylbenzene organic polymer as the filler (IonPac AS11 anion analysis column, column length 250 mm, inner diameter 4 mm, particle size 9 μm; and an IonPac AG11-HC anion guard column, column length 50 mm, inner diameter 4 mm, particle size 9 μm, or a column of equivalent performance); a conductivity detector; suppressed conductivity detection; a 16 mmol / L potassium hydroxide solution as the eluent; a flow rate of 0.8 ml / min; and a column temperature of 35°C. The theoretical plate number is calculated based on Cl - Peak count should be no less than 3000.

[0138] Preparation of Reference Solution: Place 0.1 g of mother-of-pearl reference medicinal material in a 100 ml polyethylene volumetric flask, add an appropriate amount of water, and sonicate (600 W, 40 kHz) for 30 minutes. Allow to cool, dilute to volume with water, shake well, and filter. The filtrate is used as the reference medicinal material solution. Separately, accurately weigh an appropriate amount of chloride ion and add water to a solution containing 5 μg per 1 ml. This is used as the reference substance solution.

[0139] Preparation of test solution: Take 0.1 g of this product, place it in a 100 ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat (power 600 W, frequency 40 kHz) for 30 minutes. Let cool, dilute with water to the scale, shake well, filter, and take the filtrate as the test solution.

[0140] Determination method: Accurately aspirate 25μl of reference solution and test solution respectively, inject them into ion chromatograph, and determine the result.

[0141] 1.8 Methodological Review

[0142] 1.8.1 Chromatographic peak identification

[0143] Preparation of test solution: According to the experimental conditions proposed above, prepare the test solution of calcined mother-of-pearl standard decoction.

[0144] Preparation of reference solution: Take 0.1g of mother-of-pearl reference medicinal material and place it in a 100ml polyethylene volumetric flask. Add an appropriate amount of water and sonicate (power 600W, frequency 40kHz) for 30 minutes. Let cool, dilute to the mark with water, shake well, filter, and use the filtrate as the reference medicinal material solution. Separately, take an appropriate amount of chloride ion in water, accurately weigh it, and add water to make a solution containing 5μg per 1ml. Take an appropriate amount of sulfate solution standard substance in water, accurately weigh it, and add water to make a solution containing 5μg per 1ml. This will serve as the reference substance solution.

[0145] Preparation of negative control solution: According to the experimental conditions proposed above, prepare a negative control solution lacking the mother-of-pearl standard decoction. Figure 11 .

[0146] The results showed that peak 1 was chloride ion and peak 3 was sulfate ion. In the following methodological investigation, the three characteristic peaks in the sample were investigated.

[0147] 1.8.2 Precision test

[0148] Prepare the test solution using 0.1 g of the standard decoction of calcined mother-of-pearl. Repeat the test by injecting 25 μl six times according to the proposed experimental method. Calculate the retention time and peak area of ​​each characteristic peak. (See Table 5-6.)

[0149] Table 5 Precision investigation-retention time

[0150]

[0151] Table 6 Precision Investigation-Peak Area

[0152]

[0153] The results showed that the RSD of the retention time of each characteristic peak was 0.04%-0.11%, and the RSD of the peak area was 0.37%-9.04%. This method has good precision.

[0154] 1.8.3 Repeatability Study

[0155] Six portions of the standard decoction of calcined mother-of-pearl were prepared and assayed according to the proposed experimental method. See Tables 7-8.

[0156] Table 7 Repeatability study - relative retention time

[0157]

[0158] Table 8 Repeatability study - relative peak area

[0159]

[0160] The results showed that the RSD of the relative retention time of each characteristic peak was 0.00%, and the RSD of the relative peak area was 0.00%-0.42%. This method has good repeatability.

[0161] 1.8.4 Intermediate precision study

[0162] 1.8.4.1 Inspection by different personnel and time

[0163] Based on the experimental conditions proposed above, different individuals (A and B) weighed two portions of the standard decoction of calcined mother-of-pearl at different times (T1 and T2) to prepare test samples for determination. See Tables 9-10.

[0164] Table 9 Personnel and time inspection-relative retention time

[0165]

[0166] Table 10 Personnel and time investigation-relative peak area

[0167]

[0168]

[0169] The results showed that the intermediate precision of this method was good.

[0170] 1.8.5 Durability Assessment

[0171] 1.8.5.1 Stability test

[0172] Based on the experimental conditions proposed above, take the same test solution and measure it at 0h, 2h, 4h, 8h, 16h, and 32h respectively. See Table 11-12.

[0173] Table 11 Stability Study-Retention Time

[0174]

[0175] Table 12 Stability Study-Peak Area

[0176]

[0177] The results showed that the RSDs of the characteristic peak retention times were between 0.13% and 1.85%, and the sample solution was stable within 32 hours.

[0178] In summary, the RSDs of the relative retention times of the characteristic peaks met the requirements in all the above investigations, and this method is good.

[0179] 2. Cationic method

[0180] 2.1 Chromatographic conditions and system suitability test

[0181] The column was filled with styrene-divinylbenzene organic polymer (IonPac CS12A cation analysis column, 250 mm length, 4 mm inner diameter, 8 μm particle size; IonPac CG12A cation guard column, 50 mm length, 4 mm inner diameter, 8 μm particle size, or a column of equivalent performance); the detector was a conductivity detector; the detection method was suppressed conductivity detection; the eluent was 20 mmol / L methanesulfonic acid solution; the flow rate was 0.8 ml / min; and the column temperature was 35°C. The number of theoretical plates was calculated based on K. + Peak count should be no less than 3000.

[0182] 2.2 Preparation of reference solution

[0183] Take 0.1g of mother-of-pearl as a control medicinal material and place it in a 1000ml polyethylene volumetric flask. Add an appropriate amount of 0.1% methanesulfonic acid solution to completely dissolve it. Dilute to the mark, shake well, filter, and use the filtrate as the control medicinal material reference solution. Separately, take an appropriate amount of potassium ion, accurately weigh it, and add water to make a solution containing 5μg per 1ml. This will be used as the control reference solution.

[0184] 2.3 Preparation of test solution

[0185] Take 0.1g of this product and place it in a 1000ml polyethylene volumetric flask. Add an appropriate amount of 0.1% methanesulfonic acid solution to dissolve it completely, dilute it to the scale, shake well, filter, and take the filtrate as the test solution.

[0186] 2.4 Assay

[0187] Accurately pipette 25 μl of reference solution and test solution respectively, inject them into ion chromatograph and measure to obtain the result.

[0188] 2.5 Chromatographic conditions and system suitability test

[0189] 2.5.1 Column temperature investigation

[0190] Based on the experimental conditions proposed above, the column temperatures of 25℃, 30℃ and 35℃ were investigated respectively. Figure 12 , Tables 13-14.

[0191] Table 13 Column temperature investigation-relative retention time

[0192]

[0193] Table 14 Column temperature investigation-relative peak area

[0194]

[0195] The results showed that when the column temperature was 35℃, the chromatogram peak shape was more symmetrical, the separation was better, and the peaks were more complete. Therefore, the column temperature was determined to be 35℃.

[0196] 2.5.2 Flow rate investigation

[0197] Based on the experimental conditions proposed above, the flow rates of 0.8ml / min, 1.0ml / min and 1.2ml / min were investigated respectively. Figure 13 , Table 15-16.

[0198] Table 15 Flow rate investigation-relative retention time

[0199]

[0200] Table 16 Flow rate investigation-relative peak area

[0201]

[0202] The results showed that when the flow rate was 0.8 ml / min, the chromatogram peak shape was better and the separation was moderate. Therefore, the flow rate was determined to be 0.8 ml / min.

[0203] 2.6 Preparation of test solution

[0204] 2.6.1 Investigation of solvent addition amount

[0205] Take 0.1g of this product and place it in 100ml, 500ml and 1000ml polyethylene volumetric flasks respectively, add appropriate amount of 0.1% methanesulfonic acid solution to dissolve it completely, and dilute to the scale, shake well, filter, and take the filtrate to obtain. Figure 14 .

[0206] The results showed that when the amount of solvent added was 1000 ml, the peak shape of the characteristic chromatographic peak was better. Therefore, the amount of solvent added for the test sample was determined to be 1000 ml.

[0207] 2.6.2 Acid concentration investigation

[0208] Take 0.1g of this product and place it in a 1000ml polyethylene volumetric flask. Add appropriate amount of 0%, 0.1%, and 0.3% methanesulfonic acid solution respectively to dissolve it completely, and dilute to the scale. Shake well, filter, and take the filtrate to obtain the product. Figure 15 .

[0209] The results showed that when 0% methanesulfonic acid solution was added, the test sample solution did not dissolve and the chromatographic peak was small. When 0.1% and 0.3% methanesulfonic acid solutions were added respectively, the peak shapes of the characteristic chromatographic peaks were not much different. Therefore, 0.1% methanesulfonic acid solution was selected as the extraction solvent for the test sample.

[0210] 2.7 Methodological Review

[0211] 2.7.1 Chromatographic peak identification

[0212] Preparation of test solution: According to the experimental conditions proposed above, prepare the test solution of calcined mother-of-pearl standard decoction.

[0213] Preparation of Reference Solution: Take 0.1g of mother-of-pearl reference medicinal material and place it in a 1000ml polyethylene volumetric flask. Add an appropriate amount of 0.1% methanesulfonic acid solution to completely dissolve it. Dilute to the mark, shake well, filter, and use the filtrate as the reference medicinal material solution. Separately, take an appropriate amount of sodium ion, accurately weighed, and add water to make a solution containing 5μg per 1ml; take an appropriate amount of potassium ion, accurately weighed, and add water to make a solution containing 5μg per 1ml; take an appropriate amount of magnesium ion, accurately weighed, and add water to make a solution containing 10μg per 1ml; take an appropriate amount of calcium ion, accurately weighed, and add water to make a solution containing 10μg per 1ml; these will serve as the reference substance solution.

[0214] Preparation of negative control solution: According to the experimental conditions proposed above, prepare a negative control solution lacking the mother-of-pearl standard decoction. Figure 16 .

[0215] As can be seen from the figure, there is no interference in the negative test. The results show that peak 1 is sodium ion, peak 2 is potassium ion, peak 3 is magnesium ion, and peak 4 is calcium ion.

[0216] 2.7.2 Precision test

[0217] Prepare the test solution with 0.1 g of the standard decoction of calcined mother-of-pearl. Repeat the test with six 25 μl injections per injection according to the proposed experimental method. Calculate the retention time and peak area of ​​each characteristic peak. (See Tables 17-18.)

[0218] Table 17 Precision Investigation-Retention Time

[0219]

[0220] Table 18 Precision Investigation-Peak Area

[0221]

[0222]

[0223] The results showed that the RSD of the retention time of each characteristic peak was 0.02%-0.04%, and the RSD of the peak area was 0.13%-1.53%. This method has good precision.

[0224] 2.7.3 Repeatability Study

[0225] Six portions of the standard decoction of calcined mother-of-pearl were prepared and assayed according to the proposed experimental method. See Tables 19-20.

[0226] Table 19 Repeatability Study-Relative Retention Time

[0227]

[0228] Table 20 Repeatability study - relative peak area

[0229]

[0230] The results showed that the RSD of the relative retention time of each characteristic peak was 0.00%, and the RSD of the relative peak area was 6.93%-8.17%. This method has good reproducibility.

[0231] 2.7.4 Intermediate precision study

[0232] 2.7.4.1 Inspection by different personnel and time

[0233] Based on the experimental conditions proposed above, different individuals (A and B) weighed two portions of the standard decoction of calcined mother-of-pearl at different times (T1 and T2) to prepare test samples for determination. See Tables 21-22.

[0234] Table 21 Personnel and time inspection - relative retention time

[0235]

[0236]

[0237] Table 22 Personnel and time investigation-relative peak area

[0238]

[0239] The results showed that the method had good intermediate precision when the same sample was measured by different personnel at different times.

[0240] 2.7.5 Durability assessment

[0241] 2.7.5.1 Stability test

[0242] Based on the experimental conditions proposed above, take the same test solution and measure it at 0h, 2h, 4h, 8h, 16h, and 26h respectively. See Table 23-24.

[0243] Table 23 Stability Study-Retention Time

[0244]

[0245] Table 24 Stability Study-Peak Area

[0246]

[0247] The results showed that the RSD of the characteristic peak retention time was between 0.06% and 0.17%, and the sample solution was stable within 26 hours.

[0248] In summary, the RSDs of the relative retention times of the characteristic peaks met the requirements in all the above investigations, and this method is good.

[0249] 2.8 Technical Effects

[0250] 2.8.1 Anion Verification of Mother-of-Pearl Formula Particles

[0251] The proposed method was used to determine the characteristic spectra of three batches of samples of this product, and the relative retention time and relative peak area were calculated. Figure 17-19 , Tables 25-26.

[0252] Table 25 Relative retention time of three batches of mother-of-pearl formula particles

[0253]

[0254] Table 26 Relative peak areas of three batches of mother-of-pearl particles

[0255]

[0256] 2.8.2 Anion Verification of Calcined Mother-of-Pearl Formula Particles

[0257] The proposed method was used to determine the characteristic spectra of three batches of samples of this product, and the relative retention time and relative peak area were calculated. Figure 20-22 , Tables 27-28.

[0258] Table 27 Relative retention time of three batches of calcined mother-of-pearl formulation particles

[0259]

[0260] Table 28 Relative peak areas of 3 batches of calcined mother-of-pearl particles

[0261]

[0262] 2.8.3 Cation Verification of Mother-of-Pearl Formula Particles

[0263] Using this method, characteristic spectrum analysis was performed on three batches of samples, and relative retention time and relative peak area ratio were calculated. Figure 23-25 , Tables 29-30.

[0264] Table 29 Relative retention time of three batches of mother-of-pearl formula particles

[0265]

[0266]

[0267] Table 30 Relative peak areas of 3 batches of mother-of-pearl particles

[0268]

[0269] 2.8.4 Cation Verification of Calcined Mother-of-Pearl Formula Particles

[0270] Using this method, characteristic spectrum analysis was performed on three batches of samples, and relative retention time and relative peak area ratio were calculated. Figures 26-28 , Tables 31-32.

[0271] Table 31 Relative retention time of three batches of calcined mother-of-pearl formulation particles

[0272]

[0273] Table 32 Relative peak areas of 3 batches of calcined mother-of-pearl particles

[0274]

Claims

1. An ion chromatography detection method for mother-of-pearl, characterized by: It uses ion chromatography to detect anions and cations in mother-of-pearl, and the chromatographic conditions for detecting anions are: The styrene-divinylbenzene organic polymer was used as the filler (IonPac AS11 anion analysis column, column length: 250 mm, inner diameter: 4 mm, particle size: 9 μm; IonPac AG11-HC anion guard column, column length: 50 mm, inner diameter: 4 mm, particle size: 9 μm); the detector was a conductivity detector; the detection method was suppressed conductivity detection; 16 mmol / L potassium hydroxide solution was used as the eluent; the flow rate was 0.8-1.2 ml / min; the column temperature was 25-35°C; the theoretical plate number was calculated based on Cl - Peak calculation should be no less than 3000; The chromatographic conditions for cations are: Styrene-divinylbenzene organic polymer was used as filler (IonPac CS12A cation analysis column, column length: 250 mm, inner diameter: 4 mm, particle size: 8 μm; IonPac CG12A cation guard column, column length: 50 mm, inner diameter: 4 mm, particle size: 8 μm, or a column with equivalent performance); the detector was a conductivity detector; the detection method was suppressed conductivity detection; 20 mmol / L methanesulfonic acid solution was used as eluent; the flow rate was 0.8-1.2 ml / min; the column temperature was 25-35°C; the number of theoretical plates was calculated based on K + Peak count should be no less than 3000.

2. The ion chromatography detection method for mother-of-pearl according to claim 1, characterized in that: The chromatographic conditions were: a flow rate of 0.8 ml per minute; and a column temperature of 35°C.

3. The ion chromatography detection method for mother-of-pearl according to claim 1, characterized in that: It includes the following steps: a. Pre-treatment of the test sample: prepare anionic and cationic test sample solutions separately; b. Detect according to the chromatographic conditions of claim 1 to obtain anion chromatograms and cation chromatograms, respectively.

4. The ion chromatography detection method for mother-of-pearl according to claim 3, characterized in that: The preparation method of the anion test solution described in step a is: Take 0.1g of the sample to be tested, place it in a 100ml-1000ml polyethylene volumetric flask, add appropriate amount of water, and ultrasonically treat (power 600W, frequency 40kHz) for 30-60 minutes. Let it cool, dilute it with water to the scale, shake it well, filter it, and take the filtrate as the test solution; The method for preparing the cationic test solution is: Take 0.1g of the sample to be tested and place it in a 100-1000ml polyethylene volumetric flask. Add an appropriate amount of 0.1%-0.3% methanesulfonic acid solution to completely dissolve it, dilute it to the scale, shake well, filter, and take the filtrate as the test solution.

5. The ion chromatography detection method for mother-of-pearl according to claim 4, characterized in that: The preparation method of the anion test solution described in step a is: In the preparation method of the anion test solution, the sample to be tested is placed in a 100 ml polyethylene volumetric flask and ultrasonically treated for 30 minutes; In the preparation method of the cationic test solution, the sample to be tested is placed in a 1000ml polyethylene volumetric flask; the concentration of the methanesulfonic acid solution is 0.1%.

6. The ion chromatography detection method for mother-of-pearl according to any one of claims 1 to 5, characterized in that: The anion chromatogram contains at least three characteristic peaks, peak 1 is chloride ion, peak 3 is sulfate ion, the relative retention times are: peak 2: 1.16, peak 3: 2.65, and the relative retention times fluctuate by 10%; the relative peak areas of mother-of-pearl are: peak 1: 0.01, peak 3: 0.20, and the relative peak areas of calcined mother-of-pearl are: peak 1: 0.01, peak 3: 1.68, and the relative peak areas fluctuate by 10%; The cation chromatogram contains at least four characteristic peaks, and the relative retention times are: peak 1: 0.74, peak 3: The relative peak areas of mother-of-pearl are: Peak 1: 16.18, Peak 3: 2.74, Peak 4: 258.01, and the relative peak areas of calcined mother-of-pearl are: Peak 1: 74.65, Peak 3: 0.97, Peak 4: 335.16, and the relative peak areas fluctuate by 10%; among them, Peak 1 is sodium ion, Peak 2 is potassium ion, Peak 3 is magnesium ion, and Peak 4 is calcium ion.

7. The ion chromatography detection method for mother-of-pearl according to any one of claims 1 to 5, characterized in that: The nacre is native nacre or calcined nacre.

8. A method for constructing an ion chromatographic characteristic spectrum of mother-of-pearl medicinal materials, processed products, and formulated granules, characterized by: The invention uses the ion chromatography detection method of mother-of-pearl as described in any one of claims 1 to 7 to construct an ion chromatogram characteristic spectrum of mother-of-pearl medicinal materials, processed products, and formula granules; wherein the anion chromatogram contains at least three characteristic peaks, peak 1 is chloride ion, peak 3 is sulfate ion, and the relative retention times are: peak 2: 1.16, peak 3: 2.65, with a relative retention time fluctuation of 10%; the relative peak areas of mother-of-pearl are: peak 1: 0.01, peak 3: 0.20, and the relative peak areas of calcined mother-of-pearl are: peak 1: 0.01, peak 3: 1.68, with a relative peak area fluctuation of 10%; The cation chromatogram contains at least four characteristic peaks, and the relative retention times are: peak 1: 0.74, peak 3: 1.61, peak 4: 1.95, and the relative retention time fluctuates by 10%; the relative peak areas of mother-of-pearl are: peak 1: 16.18, peak 3: 2.74, peak 4: 258.01, and the relative peak areas of calcined mother-of-pearl are: peak 1: 74.65, peak 3: 0.97, peak 4: 335.16, and the relative peak areas fluctuate by 10%; wherein, peak 1 is sodium ion, peak 2 is potassium ion, peak 3 is magnesium ion, and peak 4 is calcium ion.

9. A method for identifying mother-of-pearl or calcined mother-of-pearl, characterized by: The ion chromatographic characteristic spectrum constructed by the method for constructing the ion chromatographic characteristic spectrum according to claim 8 is used to identify mother-of-pearl or calcined mother-of-pearl. If the relative retention time and relative peak area of ​​anions and cations are both within the numerical range of the spectrum, it is determined to be mother-of-pearl or calcined mother-of-pearl.

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