CN110824028A - Method for identifying sulfured radix angelicae and unvulcanized radix angelicae - Google Patents
Method for identifying sulfured radix angelicae and unvulcanized radix angelicae Download PDFInfo
- Publication number
- CN110824028A CN110824028A CN201810920375.8A CN201810920375A CN110824028A CN 110824028 A CN110824028 A CN 110824028A CN 201810920375 A CN201810920375 A CN 201810920375A CN 110824028 A CN110824028 A CN 110824028A
- Authority
- CN
- China
- Prior art keywords
- radix angelicae
- solution
- methanol
- detected
- authentication method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Abstract
The invention discloses a method for identifying sulfured radix angelicae and unvulcanized radix angelicae. The identification method comprises the following operation steps: 1) preparation of control solutions: preparing oxypeucedanin into a reference solution by using methanol; 2) preparation of a test solution: taking a sample to be detected, and extracting with methanol to obtain a test solution; 3) and (3) detection: detecting by UPLC chromatography. Compared with the common HPLC detection method, the UPLC detection method for judging whether the radix angelicae is sulfured or not has the advantages of better stability, higher accuracy, shorter detection time and higher efficiency, reduces the detection cost, and provides a new method for the quality control of the radix angelicae.
Description
Technical Field
The invention particularly relates to a method for identifying sulfured radix angelicae and unvulcanized radix angelicae.
Background
Radix Angelicae Dahuricae is dried root of Angelica dahurica (Fisch. ex Hoffm.) Benth.ethook.f. or Angelica dahurica (Fisch. ex Hoffm.) Benth.ethook.f. var.fortusana (Boiss.) Shann et Yuan of Umbelliferae. The angelica dahurica is mainly produced in Sichuan, Anhui, Henan, Hebei and other places, and the angelica dahurica which is currently circulated in the market is mainly smoked sulfur angelica dahurica. Although sulfur fumigation can effectively prevent the angelica dahurica from being verminous and mildewing, a large number of researches show that the sulfur fumigation causes the change of the characters and the smell of the medicinal materials, the content of effective components is reduced, the drug effect is reduced, and SO is generated2The residue content exceeds the standard, and the method is not suitable for processing the angelica dahurica.
At present, HPLC is adopted to detect the component difference of the smoked radix angelicae and the unvulcanized radix angelicae, but the detection time is long, and the detection efficiency is low under the condition of large sample amount.
Disclosure of Invention
In order to solve the problems, the invention provides a novel detection method of the sulfured radix angelicae and the unvulcanized radix angelicae.
The invention relates to a method for identifying sulfured angelica dahurica and unvulcanized angelica dahurica, which comprises the following operation steps:
1) preparation of control solutions: preparing oxypeucedanin into a reference solution by using methanol;
2) preparation of a test solution: taking a sample to be detected, and extracting with methanol to obtain a test solution;
3) and (3) detection: detecting by using UPLC chromatography under the following chromatographic conditions: a chromatographic column: c18A chromatographic column; the mobile phase comprises an A phase and a B phase, the A phase is acetonitrile, the B phase is pure water, and the gradient elution is carried out by the following procedures: 0-2 min, 35% A; 2-3 min, 35% -40% A; 3-6 min, 40% -50% A; 6-9 min, 50% -57% A; 9-11 min, 57% -58% A; 11-12 min, 58% -70% A; 12-15 min, 70% -90% A; 15-16 min, 90% -100% A; detection wavelength: 305 nm;
4) and judging according to the detection result: if the oxidized decursin is detected in the sample to be detected, the radix angelicae dahuricae is not fumigated, and if the oxidized decursin is not detected, the radix angelicae dahuricae is fumigated.
In the step 1), the reference solution is a solution containing 0.05-0.15 mg of oxypeucedanin per 1 mL. Preferably, the control solution is a solution containing 0.1mg of oxypeucedanin per 1 mL.
In the step 2), the methanol extraction method comprises the following steps: taking a sample to be detected, adding 70-110 times v/w of methanol, ultrasonically extracting for 0.5-2 h, filtering, and taking a subsequent filtrate. Preferably, the using amount of the methanol is 90 times of that of a sample to be detected; the time of ultrasonic extraction is 1 h.
In step 3), the C18The chromatographic column is Agilent Poroshell 120EC-C18,Kinetex XB C18, CORTECTMTM C18, preferably Agilent Poroshell 120 EC-C18.
In the step 3), the column temperature of the chromatographic condition is 26-34 ℃, and preferably 30 ℃.
In the step 3), the flow rate of the chromatographic conditions is 0.95 mL/min-1～1.05mL·min-1Preferably 1.00 mL/min-1。
Preferably, the method also comprises a detection method using imperatorin and isoimperatorin as reference substances, and in the step 1), the reference substance solution is a solution containing 0.05-0.15 mg of imperatorin, 0.05-0.15 mg of isoimperatorin and 0.05-0.15 mg of oxidized imperatorin per 1 mL. Further preferably, the control solution is a solution containing 0.1mg imperatorin, 0.1mg isoimperatorin and 0.1mg oxypeucedanin per 1 mL.
The invention provides a method for judging whether radix angelicae is smoked and sulfurized, whether a sample to be detected is the smoked and sulfurized radix angelicae can be judged according to whether the oxypeucedanin is detected, quantification is not needed, the detection method is simple, precision is high, accuracy is high, detection time is short, efficiency is high, detection cost is reduced, and the application prospect is good.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 shows a chromatogram of a control, 1-hydrated oxidized decursin 2. oxidized decursin 3. imperatorin 4. isodecursin
FIG. 2 shows fingerprint of radix Angelicae Dahuricae without sulfuration
FIG. 3 shows fingerprint comparison of radix Angelicae Dahuricae without sulfuration
FIG. 4 fingerprint of radix Angelicae Dahuricae
FIG. 5 fingerprint comparison of radix Angelicae Dahuricae
FIG. 6 comparison of finger prints of radix Angelicae Dahuricae with and without sulfuration
Detailed Description
Example 1 method for identifying sulfured and unvulcanized angelica dahurica
1. Detection method
1) Preparation of control solutions:
precisely weighing 1.19mg of the oxypeucedanin reference substance, adding methanol to obtain a solution containing 0.1mg of the reference substance per 1mL, shaking, filtering with 0.22 μm microporous membrane, and collecting the filtrate.
2) Preparation of a test solution:
taking radix Angelicae Dahuricae powder (sieved with a third sieve) about 0.5g, precisely weighing, placing in a 50mL measuring flask, adding 45mL of methanol, ultrasonically treating l h, taking out, cooling, adding methanol to scale, shaking, filtering, and collecting the filtrate. Before injection, the mixture is filtered through a 0.22 mu m microporous membrane.
3) UPLC detection
Sucking 0.3ml of each of the reference solution and the sample solution to obtain mixed reference solution, injecting into UPLC chromatograph, and measuring. The chromatogram of the control is shown in FIG. 1.
The chromatographic conditions were as follows:
detection wavelength: 305 nm;
a chromatographic column: agilent Poroshell 120 EC-C18150X 4.6 mm;
the mobile phase comprises acetonitrile (A) and pure water (B), and gradient elution is carried out (0-2 min, 35% A, 2-3 min, 35-40% A, 3-6 min, 40-50% A, 6-9 min, 50-57% A, 9-11 min, 57-58% A, 11-12 min, 58-70% A, 12-15 min, 70-90% A, 15-16 min and 90-100% A);
column temperature: 30 ℃;
flow rate: 1.0 mL/min-1。
4) Result judgment
If the oxidized decursin is detected in the sample to be detected, the radix angelicae dahuricae is not fumigated, and if the oxidized decursin is not detected, the radix angelicae dahuricae is fumigated.
Example 2 method for identifying sulfured and unvulcanized angelica dahurica
1. Detection method
1) Preparation of control solutions:
precisely weighing 1.06mg, 1.01mg and 1.19mg of imperatorin, isoimperatorin and oxidized imperatorin reference substances respectively, adding methanol to obtain solutions containing 0.1mg of reference substances per 1mL, shaking, filtering with 0.22 μm microporous membrane, and collecting the filtrate.
2) Preparation of a test solution:
taking radix Angelicae Dahuricae powder (sieved with a third sieve) about 0.5g, precisely weighing, placing in a 50mL measuring flask, adding 45mL of methanol, ultrasonically treating l h, taking out, cooling, adding methanol to scale, shaking, filtering, and collecting the filtrate. Before injection, the mixture is filtered through a 0.22 mu m microporous membrane.
3) UPLC detection
Sucking 0.3ml of each of the reference solution and the sample solution to obtain mixed reference solution, injecting into UPLC chromatograph, and measuring. The chromatogram of the control is shown in FIG. 1.
The chromatographic conditions were as follows:
detection wavelength: 305 nm;
a chromatographic column: agilent Poroshell 120 EC-C18150X 4.6 mm;
the mobile phase comprises acetonitrile (A) and pure water (B), and gradient elution is carried out (0-2 min, 35% A, 2-3 min, 35-40% A, 3-6 min, 40-50% A, 6-9 min, 50-57% A, 9-11 min, 57-58% A, 11-12 min, 58-70% A, 12-15 min, 70-90% A, 15-16 min and 90-100% A);
column temperature: 30 ℃;
flow rate: 1.0 mL/min-1。
4) Result judgment
If the content of the imperatorin and the peak of isoimperatorin is high, the radix angelicae is not fumigated, and if the content of the imperatorin and the peak of isoimperatorin is low, the radix angelicae is fumigated.
Example 3 method for identifying sulfured and unvulcanized angelica dahurica
1) Establishing a reference substance map:
a. preparation of control solutions:
precisely weighing imperatorin, isoimperatorin, oxypeucedanin and hydrated oxypeucedanin reference substances 1.06mg, 1.01mg, 1.19mg and 0.21mg respectively, adding methanol to prepare solutions containing 0.1mg of the reference substances per 1mL, shaking uniformly, filtering with 0.22 μm microporous membrane, and collecting the subsequent filtrate.
b. Determination of the control solutions:
sucking 0.3ml of each control solution to obtain mixed control solution, injecting into UPLC chromatograph, and measuring. The chromatogram of the control is shown in FIG. 1.
The chromatographic conditions were as follows:
detection wavelength: 305 nm;
a chromatographic column: agilent Poroshell 120 EC-C18150X 4.6 mm;
the mobile phase comprises acetonitrile (A) and pure water (B), and gradient elution is carried out (0-2 min, 35% A, 2-3 min, 35-40% A, 3-6 min, 40-50% A, 6-9 min, 50-57% A, 9-11 min, 57-58% A, 11-12 min, 58-70% A, 12-15 min, 70-90% A, 15-16 min and 90-100% A);
column temperature: 30 ℃;
flow rate: 1.0 mL/min-1；
2) Analyzing the fingerprint spectrum of the unvulcanized angelica dahurica medicinal material:
c. preparing an unvulcanized angelica dahurica medicinal material solution:
taking radix Angelicae Dahuricae powder (sieved with a third sieve) about 0.5g, precisely weighing, placing in a 50mL measuring flask, adding 45mL of methanol, ultrasonically treating l h, taking out, cooling, adding methanol to scale, shaking, filtering, and collecting the filtrate. Before injection, the mixture is filtered through a 0.22 mu m microporous membrane.
Preparing a sample of the radix angelicae solution without fumigating. The sample sources are shown in table 1:
TABLE 1 sample Source Table
d. Matching fingerprint spectrums of the unvulcanized angelica dahurica medicinal material:
and (c) injecting the solution of the unvulcanized radix angelicae into an UPLC chromatograph, detecting under the same chromatographic conditions in the step b, and comparing chromatographic peaks of the fingerprint of the unvulcanized radix angelicae by adopting a Chinese medicine chromatographic fingerprint similarity evaluation system (2004A) of the State pharmacopoeia Committee. The fingerprint and fingerprint reference chromatogram of radix Angelicae Dahuricae without sulfuration are shown in figure 2 and figure 3 respectively.
e. Identification of common peaks of fingerprint spectrums of radix angelicae dahuricae medicinal materials without sulfuring
According to the UPLC fingerprint, 10 common peaks of the radix Angelicae Dahuricae without sulfuration are shown, and 4 common peaks are identified by combining with the chromatogram of the reference, and the result is shown in Table 2.
TABLE 2 fingerprint spectrum common peak identification results of radix Angelicae Dahuricae without sulfuration
f. Calculation of fingerprint similarity of unvulcanized angelica dahurica medicinal material
TABLE 3 fingerprint similarity calculation results for radix Angelicae Dahuricae without sulfuration
3) Analyzing the fingerprint spectrum of the fuming radix angelicae:
h. preparing a sulfured radix angelicae medicinal material solution:
taking radix Angelicae Dahuricae powder (sieved with a third sieve) about 0.5g, precisely weighing, placing in a 50mL measuring flask, adding 45mL of methanol, ultrasonically treating l h, taking out, cooling, adding methanol to scale, shaking, filtering, and collecting the filtrate. Before injection, the mixture is filtered through a 0.22 mu m microporous membrane. Preparing a sample of a fumigated sulfur angelica dahurica medicinal material solution. The sample sources are shown in Table 4:
table 4 sample sources table
i. Matching the fingerprint spectrums of the fuming and sulfur-curing angelica dahurica medicinal material:
and (c) injecting the sulfurated angelica dahurica medicinal material solution into an UPLC chromatograph, detecting under the same chromatographic conditions in the step b, and comparing chromatographic peaks of the fingerprint of the sulfurated angelica dahurica medicinal material by adopting a Chinese medicine chromatographic fingerprint similarity evaluation system (2004A) of the State pharmacopoeia Committee. The finger print and the finger print reference of radix Angelicae Dahuricae with sulfur are shown in figure 4 and figure 5 respectively.
j. Identification of fingerprint spectrum common peak of fuming radix angelicae dahuricae
According to the UPLC fingerprint, 8 common peaks of the fumitory radix angelicae medicinal material are shown, 3 common peaks are identified by combining a reference chromatogram, and the result is shown in Table 5.
TABLE 5 finger print common peak identification result of radix Angelicae Dahuricae with sulfuration
k. Calculation of similarity of fingerprint spectrums of smoke sulfur angelica dahurica medicinal materials
TABLE 6 Fumigation radix Angelicae Dahuricae fingerprint similarity calculation results
4) Comparison analysis of fingerprint spectra of radix Angelicae Dahuricae with sulfured and non-sulfured radix Angelicae Dahuricae
Comparing the fingerprint of the radix Angelicae Dahuricae with the fingerprint of the radix Angelicae Dahuricae without sulfuration, see FIG. 6, it can be seen that the chromatographic peak of the radix Angelicae Dahuricae with sulfuration is significantly lower than that of the radix Angelicae Dahuricae without sulfuration, and the number of the chromatographic peaks of the radix Angelicae Dahuricae with sulfuration is less than that of the radix Angelicae Dahuricae with no sulfuration.
5) Results and analysis
The fingerprint of the radix angelicae dahuricae after the fumigation is obviously different from that of the radix angelicae dahuricae without the fumigation, the peak areas of imperatorin and isoimperatorin in the radix angelicae dahuricae after the fumigation are obviously reduced, and the peak of the oxypeucedanin disappears. Therefore, the UPLC chromatography can be used for judging whether the radix angelicae is smoked or not. The UPLC fingerprint spectrum method has short detection time of a sample, and improves the detection efficiency; the sampling amount is small, and the detection cost is saved; the separation degree of each spectrum peak in the spectrum is increased, and the method is a new method for analyzing the analysis of the angelica dahurica medicinal material.
In conclusion, the method for judging whether the radix angelicae is smoked or not can judge whether the sample to be detected is the smoked radix angelicae according to whether the oxypeucedanin is detected or not, quantification is not needed, the detection method is simple, the precision and the accuracy are high, the detection time is short, the efficiency is high, the detection cost is reduced, and the application prospect is good.
Claims (10)
1. A method for identifying sulfured radix angelicae and unvulcanized radix angelicae is characterized by comprising the following steps: the method comprises the following operation steps:
1) preparation of control solutions: preparing oxypeucedanin into a reference solution by using methanol;
2) preparation of a test solution: taking a sample to be detected, and extracting with methanol to obtain a test solution;
3) and (3) detection: detecting by using UPLC chromatography under the following chromatographic conditions: a chromatographic column: c18A chromatographic column; the mobile phase comprises an A phase and a B phase, the A phase is acetonitrile, the B phase is pure water, and the gradient elution is carried out by the following procedures: 0-2 min, 35% A; 35 to 40 percent of the total amount of the mixture for 2 to 3min% A; 3-6 min, 40% -50% A; 6-9 min, 50% -57% A; 9-11 min, 57% -58% A; 11-12 min, 58% -70% A; 12-15 min, 70% -90% A; 15-16 min, 90% -100% A; detection wavelength: 305 nm;
4) and judging according to the detection result: if the oxidized decursin is detected in the sample to be detected, the radix angelicae dahuricae is not fumigated, and if the oxidized decursin is not detected, the radix angelicae dahuricae is fumigated.
2. The authentication method according to claim 1, wherein: in the step 1), the reference solution is a solution containing 0.05-0.15 mg of oxypeucedanin per 1 mL.
3. The authentication method according to claim 2, wherein: the control solution is a solution containing 0.1mg of oxypeucedanin per 1 mL.
4. The authentication method according to claim 1, wherein: in the step 2), the methanol extraction method comprises the following steps: taking a sample to be detected, adding 70-110 times v/w of methanol, ultrasonically extracting for 0.5-2 h, filtering, and taking a subsequent filtrate.
5. The authentication method according to claim 1, wherein: the using amount of the methanol is 90 times of that of a sample to be detected; the time of ultrasonic extraction is 1 h.
6. The authentication method according to claim 1, wherein: in step 3), the C18The chromatographic column is AgilentPoroshell 120EC-C18,Kinetex XB C18, CORTECTMTM C18, preferably Agilent Poroshell 120 EC-C18.
7. The authentication method according to claim 1, wherein: in the step 3), the column temperature of the chromatographic condition is 26-34 ℃, and preferably 30 ℃.
8. The authentication method according to claim 1, wherein: in step 3), theThe flow rate under the chromatographic conditions was 0.95 mL. min-1～1.05mL·min-1Preferably 1.00 mL/min-1。
9. The authentication method according to claim 1, wherein: the method also comprises a detection method using imperatorin and isoimperatorin as reference substances, wherein in the step 1), the reference substance solution is a solution containing 0.05-0.15 mg of imperatorin, 0.05-0.15 mg of isoimperatorin and 0.05-0.15 mg of oxidized imperatorin in every 1 mL.
10. The authentication method according to claim 1, wherein: the control solution was a solution containing 0.1mg imperatorin, 0.1mg isoimperatorin and 0.1mg oxypeucedanin per 1 mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810920375.8A CN110824028A (en) | 2018-08-13 | 2018-08-13 | Method for identifying sulfured radix angelicae and unvulcanized radix angelicae |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810920375.8A CN110824028A (en) | 2018-08-13 | 2018-08-13 | Method for identifying sulfured radix angelicae and unvulcanized radix angelicae |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110824028A true CN110824028A (en) | 2020-02-21 |
Family
ID=69547105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810920375.8A Pending CN110824028A (en) | 2018-08-13 | 2018-08-13 | Method for identifying sulfured radix angelicae and unvulcanized radix angelicae |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110824028A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003075938A1 (en) * | 2002-03-14 | 2003-09-18 | Beijing Tongyuan Pharmaceutical Co., Ltd. | Coumarins extractions and their uses for treating hypertension disease |
| KR20160150250A (en) * | 2015-06-19 | 2016-12-29 | 서울대학교산학협력단 | A composition comprising extract of Angelica dahurica or furanocoumarins isolated therefrom for preventing or treating Avian influenza, Swine influenza or Corona virus |
-
2018
- 2018-08-13 CN CN201810920375.8A patent/CN110824028A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003075938A1 (en) * | 2002-03-14 | 2003-09-18 | Beijing Tongyuan Pharmaceutical Co., Ltd. | Coumarins extractions and their uses for treating hypertension disease |
| CN1445228A (en) * | 2002-03-14 | 2003-10-01 | 北京同源医药科技有限公司 | Application of active ingredient of coumarin category distilled from dahurian angelica in preparing medicine for curing high blood pressure and its extracting method |
| KR20160150250A (en) * | 2015-06-19 | 2016-12-29 | 서울대학교산학협력단 | A composition comprising extract of Angelica dahurica or furanocoumarins isolated therefrom for preventing or treating Avian influenza, Swine influenza or Corona virus |
Non-Patent Citations (3)
| Title |
|---|
| YUN WEI 等: "Preparative isolation of imperatorin, oxypeucedanin and isoimperatorin from traditional Chinese herb"bai zhi"Angelica dahurica (Fisch. ex Hoffm) Benth. et Hook using multidimensional high-speed counter-current chromatography", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 卢晓琳 等: "熏硫与未熏硫白芷的体内外HPLC图谱对比分析", 《中药与临床》 * |
| 张静 等: "基于化学计量学的RRLC 指纹图谱在川白芷硫熏前后质量控制和识别中的应用", 《中国药学杂志》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101140268B (en) | Analysis method for semi-volatility component in cigarette main stream flue gas | |
| US20060292246A1 (en) | Characteristic mass spectral fingerprint setting method and rapid identification method for Chinese herbal medicines and prescriptions | |
| CN107356691B (en) | Method for detecting fingerprint of Jianqu | |
| CN104634888B (en) | A kind of intensified loquet distillate fingerprint pattern quality control method | |
| CN105203654A (en) | Method for measuring content of 11 illegally added medicaments in veterinary drug powder | |
| CN106198832B (en) | A kind of quality of production control method of intensified loquet distillate | |
| CN110824029A (en) | UPLC and one-test-multiple-evaluation method based detection of content of coumarins in radix angelicae medicinal material | |
| CN107478755B (en) | The method for preparing purified of crystal methamphetamine standard substance for forensic science illicit drugs inspection | |
| CN107132304B (en) | A kind of Polygala tenuifolia finger-print and index component content method for measuring | |
| CN109884232A (en) | The analysis method of volatile component in a kind of Blumea balsamifera | |
| CN110346462A (en) | Leaf of Moringa UPLC fingerprint and its UPLC finger-print | |
| CN105929082A (en) | Method for separating and determining pyrazine substances and pyridine substances in saliva | |
| CN103115984A (en) | Quality control method of medicament for treating leukopenia | |
| CN104849363A (en) | Cordate houttuynia wall-breaking decoction pieces fingerprinting construction and quality detection method thereof | |
| CN110824028A (en) | Method for identifying sulfured radix angelicae and unvulcanized radix angelicae | |
| CN102552515A (en) | Quality detection method for blood-nourishing Chinese angelica syrup | |
| Maimaiti et al. | Quantitative determination of marker compounds and fingerprint analysis of the seeds of Vernonia anthelmintica | |
| CN103630614A (en) | High performance liquid chromatography detection method of Yangxueqingnao granule | |
| CN203479772U (en) | High performance liquid chromatography fingerprint measuring device of dendrobium candidum | |
| CN108982738B (en) | Construction method and detection method of intermediate characteristic spectrum of Zhenqi Fuzheng granule or Zhenqi Fuzheng granule fingerprint | |
| CN103983714B (en) | A kind of method measuring cumarin and safrole content in tobacco product | |
| CN109991347B (en) | HPLC fingerprint spectrum establishment method of eclipta medicinal material | |
| CN105548384A (en) | Detection method of nasal and oral cavity spray | |
| CN104897811A (en) | Detection method for musk Xintongning preparation | |
| CN105486761A (en) | Method for determining scutelloside content in traditional Chinese medicine granules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200221 |
|
| RJ01 | Rejection of invention patent application after publication |