Construction method and application of characteristic chromatogram of baoyao decoction pieces and formula granules

Abstract

The application discloses a kind of hundred medicine decoction pieces and the construction method of characteristic chromatogram of its formula granule, comprising: preparation reference solution, the reference solution includes control decoction piece reference solution and gallic acid control reference solution;Take hundred medicine decoction piece or hundred medicine decoction formula granule to prepare test sample solution;Take preset amount of reference solution and test sample solution, inject into liquid chromatograph, the liquid chromatograph is with octadecylsilane bonding silica gel as filler, with methanol as mobile phase A, with phosphoric acid solution as mobile phase B and carries out gradient elution, establishes characteristic chromatogram.The application can provide data basis for hundred medicine decoction piece and its formula granule quality control, effectively guarantee the stability and controllability of hundred medicine decoction piece and its formula granule product quality.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of quality analysis and detection of traditional Chinese medicine, and particularly relates to a construction method and application of characteristic chromatogram of Baiyaojian decoction pieces and formula granules thereof. BACKGROUND

[0002] Baiyaojian is a dry koji block prepared by fermentation of Chinese gall, tea leaves and distiller's grains, which has the effects of clearing heat and reducing phlegm, generating saliva and stopping thirst, and can be used for treating lung heat cough, wind-fire toothache, tongue erosion and chronic dysentery and prolapse of the anus. Baiyaojian is derived from Chinese gall, although complex changes occur during the fermentation process, the chemical composition and pharmacological effects are changed, but the main medicinal substance is Chinese gall. Therefore, Baiyaojian may have the same chemical components as Chinese gall, such as tannins, gallic acid and other substances.

[0003] According to literature retrieval, there are few studies on the characteristic chromatogram of Baiyaojian decoction pieces and formula granules, and most of the research reports focus on the determination of gallic acid content, and only part of the research on the quality standard evaluation of Baiyaojian. One article reports that Baiyaojian uses high performance liquid chromatography (HPLC) to draw the HPLC fingerprint of Baiyaojian, but the method has certain adaptability problems, and it takes a long time and cannot be quickly identified. There is no relevant literature and patent report on the research of Baiyaojian extract. Therefore, it is urgent to provide a more efficient identification and detection method suitable for Baiyaojian extract.

[0004] Moreover, the quality standard of Baiyaojian is not included in the 2020 edition of Chinese Pharmacopoeia, and thin layer identification is mainly used in local standards, lacking of characteristic chromatogram and fingerprint chromatogram research, and there is no perfect qualitative detection method for this product in the current standard. Baiyaojian formula granules are prepared by extraction, concentration, drying and granulation for clinical use. Compared with the decoction pieces, Baiyaojian decoction pieces and formula granules have lost their inherent form, and it is impossible to distinguish them from Chinese gall extract only from the aspects of appearance and properties. SUMMARY

[0005] The technical problem to be solved by the present application is to provide a construction method of characteristic chromatogram of Baiyaojian decoction pieces and formula granules thereof, which has good reproducibility, is accurate and reliable, can provide data basis for large-scale production quality control of Baiyaojian decoction pieces and formula granules, and ensure the stability and controllability of the product quality of Baiyaojian decoction pieces and formula granules.

[0006] In order to solve the above technical problems, the present application provides a construction method of characteristic chromatogram of Baiyaojian decoction pieces and formula granules thereof, comprising the following steps:

[0007] Preparation of reference solution, the reference solution includes control decoction piece reference solution and gallic acid reference solution;

[0008] Take Baiyao Decoction pieces or Baiyao Decoction formula granules to prepare the test solution;

[0009] Take a predetermined amount of reference solution and test solution, inject into the liquid chromatograph, the liquid chromatograph uses octadecylsilane-bonded silica gel as the filler, uses methanol as the mobile phase A, and uses the phosphoric acid solution as the mobile phase B to perform gradient elution, and establishes the characteristic spectrum.

[0010] In an embodiment, the gradient elution is performed according to the following procedure:

[0011] 0-5min, mobile phase A is 2%, mobile phase B is 98%;

[0012] 5min-10min, mobile phase A from 2%→16%, mobile phase B from 98%→84%;

[0013] 10min-20min, mobile phase A from 16%→22%, mobile phase B from 84%→78%;

[0014] 20min-22min, mobile phase A from 22%→90%, mobile phase B from 78%→10%;

[0015] 22min-25min, mobile phase A is 90%, mobile phase B is 10%.

[0016] In an embodiment, the volume concentration of the phosphoric acid solution is 0.05%-0.15%. Preferably, the volume concentration of the phosphoric acid solution is 0.1%.

[0017] In an embodiment, the predetermined amount of the reference solution and the test solution is 0.5μL-1.5μL;

[0018] The liquid chromatograph uses octadecylsilane-bonded silica gel as the filler, the column length is 100mm, the inner diameter is 2.1mm, the particle size is 1.6μm-1.8μm, and the column temperature is 24℃-26℃;

[0019] When performing gradient elution, the flow rate of the mobile phase is 0.24mL / min-0.26mL / min;

[0020] The ultraviolet detection wavelength of the liquid chromatograph is 260nm-280nm.

[0021] In an embodiment, the test solution is prepared by the following method:

[0022] Take Baiyaojian decoction pieces or Baiyaojian formula granules, grind them through 45-55 mesh screen, then take 0.1-0.3 g and mix them with 50-70% methanol, the methanol added is 95-105 mL, after ultrasonic treatment for 25-35 min, cool, shake, filter, take the filtrate, prepare the test sample solution.

[0023] In one embodiment, the gallic acid reference solution is prepared as follows:

[0024] Take gallic acid reference substance, add 40-60% methanol to prepare a gallic acid reference solution containing 0.1 mg gallic acid per 1 mL;

[0025] The control decoction piece reference solution is prepared as follows:

[0026] Take 0.1-0.3 g of Baiyaojian control decoction pieces, add 45-55 mL water, heat and reflux for 25-35 min, then filter, evaporate the filtrate to dryness, mix the residue with 40-60% methanol, the methanol added is 95-105 mL, after ultrasonic treatment for 25-35 min, cool, shake, filter, take the filtrate, prepare the control decoction piece reference solution.

[0027] In one embodiment, the characteristic pattern of the Baiyaojian decoction pieces or Baiyaojian formula granules includes 8 common peaks, wherein peak 1 corresponds to gallic acid.

[0028] In one embodiment, the characteristic pattern of the Baiyaojian decoction pieces or Baiyaojian formula granules takes peak 1 as the reference peak S, and the relative retention time of peak 2, peak 3, peak 4, peak 5, peak 6, peak 7, and peak 8 to S peak is as follows: peak 2 is 3.28, peak 3 is 3.52, peak 4 is 3.61, peak 5 is 3.78, peak 6 is 3.97, peak 7 is 5.59, and peak 8 is 5.84, and the error range of the specified value is ±15%.

[0029] Correspondingly, the application also provides a characteristic pattern of Baiyaojian decoction pieces and formula granules thereof, which is obtained by the above-mentioned method for constructing the characteristic pattern of Baiyaojian decoction pieces and formula granules thereof.

[0030] And, the application of the characteristic pattern of Baiyaojian decoction pieces and formula granules thereof in (1) or (2):

[0031] (1) the authenticity identification and ingredient detection of Baiyaojian decoction pieces and formula granules thereof;

[0032] (2) the differentiation of Baiyaojian decoction pieces and formula granules thereof from Chinese gall medicinal materials.

[0033] The present application has the following beneficial effects:

[0034] The present application, by the construction method of the characteristic map, takes gallnut decoction control decoction piece and gallic acid control product as reference, combines with suitable chromatographic conditions, compares the UPLC characteristic map of gallnut medicinal material before and after fermentation, and effectively identifies gallnut decoction extract.

[0035] In the process of constructing the UPLC characteristic map of gallnut decoction formula granules, the characteristic map of gallnut medicinal material before and after fermentation is introduced for comparison and analysis under suitable chromatographic conditions when constructing the UPLC characteristic map of gallnut decoction formula granules, the water-soluble component characteristic components before and after fermentation of gallnut are researched, and the water-soluble component chromatographic peak is well separated, the characteristic map information is rich, the chromatographic peak shape is good, and the method is fast, simple and efficient, the result is objective, precise and reliable. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is the chromatographic peak identification chart of gallnut decoction in the present application;

[0037] Figure 2 is the UPLC characteristic map of gallnut decoction formula granules in the present application;

[0038] Figure 3 is the local enlarged view of the UPLC characteristic map of gallnut decoction formula granules in the present application;

[0039] Figure 4 is the control characteristic map of gallnut decoction formula granules in the present application;

[0040] Figure 5 is the local enlarged view of the control characteristic map of gallnut decoction formula granules in the present application;

[0041] Figure 6 is the characteristic map comparison chart of gallnut decoction formula granules and gallnut decoction control decoction piece in the present application;

[0042] Figure 7 is the characteristic map comparison chart of gallnut decoction formula granules and gallnut in example 1 of the present application. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings and specific embodiments.

[0044] In order to comprehensively reflect the quality information of gallnut decoction decoction piece and its formula granules, and realize comprehensive and effective control of the quality of gallnut decoction decoction piece and its formula granules, the present application provides a construction method of characteristic map of gallnut decoction decoction piece and its formula granules, which will be described in detail as follows:

[0045] 1 Instruments and reagents

[0046] Ultra-high performance liquid chromatograph (ACQUIT UPLC, Waters Corporation), one-thousandth scale (ME204E, Mettler-Toledo Corporation), millionth scale (XP26, Mettler-Toledo Corporation), digital controlled ultrasonic cleaner (KQ500D, Kunshan Ultrasonic Instrument Co., Ltd.), constant temperature water bath (HWS28 type, Shanghai Yiheng Scientific Instrument Co., Ltd.), ultrapure water system (Mili-Q Direct, Merck Co., Ltd.).

[0047] Ethanol (Tianjin Damao Chemical Reagent Co., Ltd.) is analytical grade, methanol (Tianjin Damao Chemical Reagent Co., Ltd.) is analytical grade, methanol (Merck Co., Ltd.) is chromatographic grade, phosphoric acid (Guangzhou Chemical Reagent Factory) is chromatographic grade, water is ultrapure water (laboratory self-made); Baiyaojian control decoction pieces (source: inspected by Guangdong Yifang Pharmaceutical Co., Ltd.); gallic acid (content: 91.5%, China Institute for Drug Control); Baiyaojian formula granules (batch number: G01, G02, G03; source: Guangdong Yifang Pharmaceutical Co., Ltd.).

[0048] 2 Chromatographic conditions and preparation of reference solution and test solution

[0049] 2.1 Chromatographic conditions

[0050] Chromatographic conditions and system suitability test: using octadecylsilane bonded silica gel as the filler, methanol as the mobile phase A, and phosphoric acid solution as the mobile phase B, gradient elution was performed according to the gradient elution table shown in Table 1 to establish the characteristic chromatogram.

[0051] In an embodiment, the volume concentration of the phosphoric acid solution is 0.05%-0.15%. The preset amount of the reference solution and the test solution is 0.5 μL-1.5 μL; the liquid chromatograph uses octadecylsilane bonded silica gel as the filler, the column length is 100 mm, the inner diameter is 2.1 mm, the particle size is 1.6 μm-1.8 μm, and the column temperature is 24°C-26°C; when gradient elution is performed, the flow rate of the mobile phase is 0.24 mL / min-0.26 mL / min; the ultraviolet detection wavelength of the liquid chromatograph is 260 nm-280 nm.

[0052] Preferably, octadecylsilane bonded silica gel (column length 100 mm, inner diameter 2.1 mm, particle size 1.7 μm) is used as the filler of the chromatographic column, methanol is used as the mobile phase A, 0.1% phosphoric acid solution is used as the mobile phase B, gradient elution is performed according to the table 1, the column temperature is 25°C, the flow rate is 0.25 ml per minute, the detection wavelength is 270 nm, and the injection amount is 1 μl.

[0053] Table 1 Gradient elution table

[0054]

[0055] 2.2 Preparation of reference solution

[0056] In one embodiment, the gallic acid reference solution of the control is prepared as follows:

[0057] Take the gallic acid control, add 40%-60% methanol to make a gallic acid control reference solution containing 0.1 mg of gallic acid per 1 mL;

[0058] The control decoction reference solution is prepared as follows:

[0059] Take 0.1 g-0.3 g of the Baiyaojian control decoction, add 45-55 mL of water, heat and reflux for 25-35 min, then filter, evaporate the filtrate to dryness, mix the residue with 40%-60% methanol, the amount of methanol added is 95-105 mL, ultrasonic treatment for 25-35 min, cool, shake well, filter, take the filtrate, and prepare the control decoction reference solution.

[0060] Preferably, the gallic acid reference solution of the control is prepared as follows: take the gallic acid control, add 50% methanol to make a gallic acid control reference solution containing 0.1 mg of gallic acid per 1 mL;

[0061] The control decoction reference solution is prepared as follows:

[0062] Take 0.2 g of the Baiyaojian control decoction, place it in a conical flask with a stopper, add 50 mL of water, heat and reflux for 30 min, filter, evaporate the filtrate to dryness, add 100 mL of 50% methanol to the residue, ultrasonic treatment for 30 min, cool, shake well, filter, take the filtrate, and prepare the control decoction reference solution. The power of ultrasonic treatment is 300 W and the frequency is 40 kHz.

[0063] 2.3 Preparation of test solution

[0064] In one embodiment, the test solution is prepared as follows:

[0065] Take the Baiyaojian decoction or Baiyaojian formula granules, grind and pass through a 45-55 mesh sieve, then take 0.1 g-0.3 g and mix with 50%-70% methanol, the amount of methanol added is 95-105 mL, ultrasonic treatment for 25-35 min, cool, shake well, filter, take the filtrate, and prepare the test solution.

[0066] Preferably, the Baiyaojian decoction piece test sample solution is prepared as follows: an appropriate amount of powder of the product is finely ground, and about 0.2 g of the powder is accurately weighed and placed in a conical flask with a stopper. 100 ml of 50% methanol is accurately added, the weight is determined, and the mixture is ultrasonically treated (power 300 W, frequency 40 kHz) for 30 minutes. The mixture is allowed to cool, the weight is determined again, the lost weight is made up with 50% methanol, the mixture is shaken and filtered, and the filtrate is collected to obtain the test sample solution.

[0067] The Baiyaojian formula granules test sample solution is prepared as follows: an appropriate amount of powder of the product is finely ground, and about 0.1 g of the powder is accurately weighed and placed in a conical flask with a stopper. 100 ml of 70% methanol is accurately added, the weight is determined, and the mixture is ultrasonically treated (power 300 W, frequency 40 kHz) for 30 minutes. The mixture is allowed to cool, the weight is determined again, the lost weight is made up with 70% methanol, the mixture is shaken and filtered, and the filtrate is collected to obtain the test sample solution.

[0068] 3. Chromatographic determination and establishment of characteristic chromatogram

[0069] 3.1 Determination method

[0070] The formula granule test sample solution prepared according to item 2.3 is accurately taken, and the above-mentioned test sample solution and the reference sample solution of the control decoction piece are determined and analyzed according to the chromatographic conditions in item 2.1. The UPLC characteristic chromatograms of three batches of Baiyaojian formula granules are processed and the common peaks are identified using the "Traditional Chinese Medicine Chromatographic Fingerprint Similarity Evaluation System (2012.0 version)" recommended by the National Pharmacopoeia Committee, and the results are shown in Table Figure 2 . The UPLC control characteristic chromatogram of Baiyaojian formula granules is established, and the results are shown in Table Figure 4 . Eight common peaks with known components, large peak areas, good peak shapes and separation degrees are selected as characteristic peaks of Baiyaojian formula granules. The eight common peaks can correspond to the control decoction piece of Baiyaojian, so the above eight common peaks are selected as the characteristic peaks of the UPLC characteristic chromatogram of Baiyaojian formula granules. The retention time of the peaks is relatively central, and peak 1 is selected as the reference peak S. Peak 1 corresponds to gallic acid. The relative retention times of peaks 2, 3, 4, 5, 6, 7 and 8 to S peak should be within ±15% of the specified value. The specified values are 3.28 (peak 2), 3.52 (peak 3), 3.61 (peak 4), 3.78 (peak 5), 3.97 (peak 6), 5.59 (peak 7) and 5.84 (peak 8).

[0071] Next, the application will be described in conjunction with the examples:

[0072] Example 1

[0073] Determination of Baiyaojian decoction pieces and formula granules and Chinese gall medicinal materials

[0074] Preparation of the test solution of the sumac medicinal material:

[0075] Take about 0.2 g of the powder (pass through a 50-mesh sieve), accurately weigh it, place it in a conical flask with a stopper, accurately add 100 ml of 50% methanol, weigh the weight, ultrasonically treat (power 300 W, frequency 40 kHz) for 30 minutes, take it out, cool it down, re-weigh it, make up the weight loss with 50% methanol, shake it well, filter it, and take the filtrate, which is obtained.

[0076] 3 batches of the Baiyaojian formula granules are prepared according to the preparation of the formula granule test solution under item "2.3". The above-mentioned Baiyaojian formula granule and sumac medicinal material test solution and control medicinal piece reference solution are accurately taken, the chromatographic conditions under item "2.1" are used for determination and analysis. The comparison of the characteristic chromatograms of the Baiyaojian formula granule and the sumac medicinal material is shown in Figure 5 . It can be seen from Figure 5 that the Baiyaojian has 8 characteristic peaks, while the sumac medicinal material has only 7 characteristic peaks, and peak 3 is missing, and the retention times of peaks 7 and 8 of the Baiyaojian are inconsistent with those of peaks 9 and 10 of the sumac medicinal material. That is to say, after comparing the characteristic chromatograms of the Baiyaojian and the sumac, it is found that the Baiyaojian which takes the sumac as the main raw material has added peaks 3, 7 and 8, and has lost peaks 9 and 10 of the sumac. Accordingly, the present application can be applied to distinguish the Baiyaojian and the main raw material sumac thereof.

[0077] Example 2

[0078] Methodology verification

[0079] (1) Precision test

[0080] Take the same test solution, continuously sample 6 times according to the chromatographic conditions under item "2.1", and take peak 1 as the reference peak. The relative retention time RSD value of peak S is in the range of 0.07% to 0.08%, the relative peak area RSD value is in the range of 0.37% to 2.86%, and the RSD is less than 3.0%, indicating that the precision of the sampler is good.

[0081] (2) Reproducibility test

[0082] Take about 0.2 g of the same test powder, 6 parallel parts, prepare the test solution according to the method determined under item "2.3", and determine according to the chromatographic conditions under item "2.1". Take peak 1 as the reference peak of peak S. The relative retention time RSD value of peak S is in the range of 0.07% to 0.08%, the relative peak area RSD value is in the range of 0.37% to 2.86%, and the RSD is less than 3%, indicating that the method has good reproducibility.

[0083] (3) Stability test

[0084] Take the same test solution, under the chromatographic conditions of "2.1", respectively, 0, 2, 4, 8, 12, 24h sample determination, with peak 1 as the reference peak S, the relative retention time RSD value in the range of 1.04% to 1.13%, the relative peak area RSD value in the range of 0.49% to 2.05%, RSD <3%, indicating that the test solution is stable within 24h.

[0085] (4) Intermediate precision test

[0086] By different analysts on different dates on different instruments, take the same test sample powder about 0.2g, parallel 6 times, according to the test sample solution preparation method determined under "2.3" to prepare 6 test sample solutions, according to the chromatographic conditions under "2.1" sample analysis, with peak 1 as the reference peak S, the relative retention time RSD value in the range of 0.14% to 0.34%, the relative peak area RSD value in the range of 0.37% to 1.12%. The relative retention time and the RSD value of the repeatability test 6 data are in the range of 1.33% to 2.22%, the relative peak area and the RSD value of the repeatability test 6 data are in the range of 0.97% to 4.83%, RSD <5%, indicating that the intermediate precision of the method is good.

[0087] In summary, the characteristic spectrum of the hundred medicine decoction pieces and the formula granules is established for the first time, which can fully display the chemical composition characteristics of the hundred medicine decoction pieces and the formula granules, the characteristic peak information is rich, and the quality information of the hundred medicine decoction pieces and the formula granules can be comprehensively reflected, so as to achieve the purpose of comprehensively and effectively controlling the quality of the hundred medicine decoction pieces and the formula granules. And it can realize the identification and differentiation of the hundred medicine decoction pieces and the formula granules and the sumac medicinal materials, and provide a reference for the identification of the hundred medicine decoction pieces and the formula granules and the sumac medicinal materials.

[0088] The above is the preferred embodiment of the application, it should be pointed out that, for those skilled in the ordinary skill of the art, without departing from the principles of the present application, can make a number of improvements and refinements, these improvements and refinements also regarded as the protection scope of the present application.

Claims

1. A method for constructing a characteristic spectrum of a decoction of various herbs and its formulation granules, characterized in that, Includes the following steps: Prepare a reference solution, wherein the reference solution includes a reference solution of control medicinal slices and a reference solution of gallic acid reference standard; Take Baiyaojian decoction pieces or Baiyaojian formula granules, grind them and pass them through a 45-55 mesh sieve. Then weigh 0.1g-0.3g and mix them with 50%-70% methanol. The amount of methanol added is 95mL-105mL. After ultrasonic treatment for 25min-35min, cool, shake well, filter, and take the filtrate to prepare the test solution. Pre-defined amounts of reference solution and test solution were injected into a liquid chromatograph (LC). The LC used octadecylsilane-bonded silica gel as the packing material, with a column length of 100 mm, an inner diameter of 2.1 mm, and a particle size of 1.7 μm. The UV detection wavelength of the LC was 270 nm. The LC used methanol as mobile phase A and phosphoric acid solution as mobile phase B for gradient elution to establish a characteristic chromatogram. The volume concentration of the phosphoric acid solution was 0.05%–0.15%. The gradient elution is performed according to the following procedure: 0-5 min, mobile phase A is 2%, mobile phase B is 98%; In 5-10 minutes, mobile phase A decreased from 2% to 16%, and mobile phase B decreased from 98% to 84%. Between 10 and 20 minutes, mobile phase A decreased from 16% to 22%, and mobile phase B decreased from 84% to 78%. Between 20 and 22 minutes, mobile phase A decreased from 22% to 90%, while mobile phase B decreased from 78% to 10%. 22-25 min, mobile phase A is 90%, mobile phase B is 10%.

2. The method for constructing the characteristic spectrum of the herbal decoction pieces and formula granules as described in claim 1, characterized in that, The phosphoric acid solution has a volume concentration of 0.1%.

3. The method for constructing the characteristic spectrum of the herbal decoction pieces and formula granules as described in claim 1, characterized in that, The preset volume of the reference solution and the test solution is 0.5 μL-1.5 μL; The column temperature of the liquid chromatograph is 24℃-26℃; During gradient elution, the flow rate of the mobile phase is 0.24 mL / min to 0.26 mL / min.

4. The method for constructing the characteristic spectrum of the herbal decoction pieces and formula granules as described in claim 1, characterized in that, The gallic acid reference solution was prepared according to the following method: Prepare a gallic acid reference solution containing 0.1 mg gallic acid per 1 mL by adding 40%-60% methanol to gallic acid reference standard. The reference solution of the control medicinal slices was prepared by the following method: Weigh 0.1g-0.3g of the Baiyao Decoction reference slices, add 45-55mL of water, heat under reflux for 25min-35min, filter, evaporate the filtrate to dryness, and mix the residue with 40%-60% methanol (95mL-105mL), sonicate for 25min-35min, cool, shake well, filter, and collect the filtrate to obtain the reference solution of the reference slices.

5. The method for constructing the characteristic spectrum of the herbal decoction pieces and formula granules as described in claim 1, characterized in that, The characteristic spectrum of the Baiyaojian decoction tablets or Baiyaojian formula granules includes 8 common peaks, of which peak 1 corresponds to gallic acid.

6. The method for constructing the characteristic spectrum of the herbal decoction tablets and formula granules as described in claim 5, characterized in that, The characteristic chromatogram of the Baiyaojian decoction tablets or Baiyaojian formula granules uses peak 1 as reference peak S. The specified values ​​for the relative retention times of peaks 2, 3, 4, 5, 6, 7, and 8 with peak S are as follows: peak 2 is 3.28, peak 3 is 3.52, peak 4 is 3.61, peak 5 is 3.78, peak 6 is 3.97, peak 7 is 5.59, and peak 8 is 5.

84. The error range of the specified values ​​is ±15%.

7. The method for constructing the characteristic spectrum of Baiyao decoction pieces and formula granules as described in any one of claims 1 to 6 is used in distinguishing Baiyao decoction pieces and formula granules from gallnut medicinal material.

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