CN112730670A - Method for detecting Shunaoxin dropping pills - Google Patents

Method for detecting Shunaoxin dropping pills Download PDF

Info

Publication number
CN112730670A
CN112730670A CN202011537296.2A CN202011537296A CN112730670A CN 112730670 A CN112730670 A CN 112730670A CN 202011537296 A CN202011537296 A CN 202011537296A CN 112730670 A CN112730670 A CN 112730670A
Authority
CN
China
Prior art keywords
peak
shunaoxin
precisely
chromatogram
ethyl acetate
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.)
Granted
Application number
CN202011537296.2A
Other languages
Chinese (zh)
Other versions
CN112730670B (en
Inventor
刘丹
韩志峰
刘彤
陈妤
杨柳
陈素琳
王金磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
No 6 Traditional Chinese Medicine Factory Of Tianjin Zhongxin Pharmaceutical Group Co ltd
Original Assignee
No 6 Traditional Chinese Medicine Factory Of Tianjin Zhongxin Pharmaceutical Group Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by No 6 Traditional Chinese Medicine Factory Of Tianjin Zhongxin Pharmaceutical Group Co ltd filed Critical No 6 Traditional Chinese Medicine Factory Of Tianjin Zhongxin Pharmaceutical Group Co ltd
Priority to CN202011537296.2A priority Critical patent/CN112730670B/en
Publication of CN112730670A publication Critical patent/CN112730670A/en
Application granted granted Critical
Publication of CN112730670B publication Critical patent/CN112730670B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8624—Detection of slopes or peaks; baseline correction
    • G01N30/8631—Peaks
    • G01N30/8634—Peak quality criteria
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
    • G01N30/8686—Fingerprinting, e.g. without prior knowledge of the sample components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8696—Details of Software
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention relates to a method for detecting Shunaoxin dripping pills, which adopts gas chromatography and comprises the following steps: step 1, preparation of a test solution: taking a finished product of the Shunaoxin dripping pill, adding diatomite and ethyl acetate, uniformly mixing, and filtering to obtain a subsequent filtrate; step 2, detection: absorbing the test solution, and injecting the test solution into a gas chromatograph to obtain a chromatogram; step 3, comparative analysis: comparing the chromatogram obtained in the step 2 with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, wherein the coincidence rate is more than 80 percent and is qualified, wherein the chromatographic conditions of the gas chromatograph are as follows: the capillary column using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase is heated by program and divided into two parts for sampling.

Description

Method for detecting Shunaoxin dropping pills
The technical field is as follows:
the invention relates to a detection method of a traditional Chinese medicine preparation, in particular to a detection method of a gas phase characteristic spectrum of a Shunaoxin dripping pill.
Background art:
the Shunaoxin dripping pill (Chinese medicine standard character Z20050041) is also called as: chuan Gui dripping pill or Xiong Gui dripping pill. Shu its function is mainly indicated: regulating qi-flowing, promoting blood circulation, removing blood stasis and relieving pain. Can be used for treating migraine caused by blood deficiency and blood stasis, with symptoms of headache, dizziness, blurred vision, amnesia, insomnia, etc. Specification: each pill weighed 42 mg. The usage and dosage are as follows: is administered orally. 4 granules at a time, 3 times a day.
The Shunaoxin dripping pill is prepared by extracting radix Angelicae sinensis and rhizoma Ligustici Chuanxiong with ethanol and diethyl ether or by supercritical carbon dioxide extraction, and has entered the clinic in the 1980 s and been approved by the drug administration in 2005 to be marketed, and the main active ingredient of the dripping pill is volatile oil of radix Angelicae sinensis and rhizoma Ligustici Chuanxiong.
The research on angelica and ligusticum wallichii is more, the detection method is also in the pharmacopoeia, but the research on the detection method of the volatile oil of angelica and ligusticum wallichii is less. The existing detection method of radix Angelicae sinensis and rhizoma Ligustici Chuanxiong can be found in the following documents, the study literature of radix Angelicae sinensis and rhizoma Ligustici Chuanxiong shows that the fingerprint chromatogram is insufficient for 10 years, the comparison of fingerprint chromatograms of extracts of radix Angelicae sinensis, rhizoma Ligustici Chuanxiong and Carthami flos in different combination modes, the study of fingerprint chromatogram of co-decoction of rhizoma Ligustici Chuanxiong and radix Angelicae sinensis in different proportions, the study of chemical components of rhizoma Ligustici Chuanxiong and radix Angelicae sinensis in HPLC fingerprint chromatogram comparison, the study of radix Angelicae sinensis-rhizoma Ligustici Chuanxiong drug pair based on near infrared diffuse reflection spectrum fingerprint chromatogram, and the study of compound radix Angelicae sinensis and rhizoma Ligustici Chuanxiong injection specific (fingerprint) chromatogram
The volatile oil of angelica and ligusticum wallichii is complex in components and mainly comprises the following components: ligustilide, butylphthalide, neocnidilide, ethyl palmitate, senkyunolide A, senkyunolide I, etc. the prior art is lack of understanding on the research and detection methods of the components and needs further research.
The invention aims to ensure that the Shunaoxin dripping pills are monitored in the production process all the time, researches a method for quickly detecting the Shunaoxin dripping pills, establishes a Shunaoxin dripping pill standard gas-phase characteristic map, and detects a sample in production at any time through the gas-phase characteristic map so as to confirm that the sample meets the standard.
In order to facilitate the application of the standard gas phase characteristic spectrum of the Shunaoxin dripping pill, the inventor researches the chromatographic conditions of gas chromatography. The pretreatment method of the Shunaoxin dripping pill is determined by examining the conditions of the extraction mode of a sample, the type of an extraction solvent, the addition amount of the solvent, the extraction time and the like. The feasibility of the method is determined by negative interference, precision, stability, reproducibility, durability and other tests. Respectively measuring a plurality of batches of Shunaoxin dripping pills, angelica and ligusticum wallichii medicinal materials according to a determined gas phase characteristic spectrum method, analyzing and concluding common peaks of a plurality of batches of samples, analyzing medicinal material sources of the common peaks of the dripping pills, selecting chromatographic peaks with effective components, large peak areas and good separation degrees as characteristic peaks, and performing component identification on the characteristic peaks to finally determine the standard gas phase characteristic spectrum of the Shunaoxin dripping pills.
The invention content is as follows:
the invention provides a method for detecting Shunaoxin dripping pills, which is used for judging whether a finished product of the Shunaoxin dripping pills meets standard requirements or not, wherein the finished product of the Shunaoxin dripping pills is a final product produced.
The detection method adopts gas chromatography, and comprises the following steps:
step 1, preparation of a test solution:
taking a finished product of the Shunaoxin dripping pill, adding diatomite and ethyl acetate, uniformly mixing, and filtering to obtain a subsequent filtrate;
step 2, detection:
absorbing the test solution, and injecting the test solution into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis
Comparing the chromatogram obtained in the step 2 with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, and determining that the coincidence rate is more than 80 percent as qualified.
Wherein the chromatographic conditions of the gas chromatograph are as follows:
the capillary column using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase is heated by program and divided into two parts for sampling.
Wherein, the standard gas phase characteristic spectrum of the Shunaoxin dripping pill in the step 3 is established according to the following method:
(1) preparation of reference solutions
Taking appropriate amount of ligustilide reference substance, and preparing into ligustilide ethyl acetate solution with ethyl acetate;
(2) preparation of test solution
Taking multiple batches of qualified Shunaoxin dripping pills, adding diatomite and ethyl acetate, uniformly mixing, and filtering to obtain a subsequent filtrate;
(3) measurement of
And precisely absorbing the reference substance solution and the test solution respectively, injecting into a gas chromatograph, and measuring to obtain a chromatogram.
(4) Standard gas phase fingerprint
Finding out common peaks from gas chromatogram maps of at least 10 batches of qualified Shunaoxin dripping pills, and obtaining a standard gas phase characteristic map through calculation and fitting.
Wherein, the qualified sulnaoxin dripping pills in the multiple batches are at least 10 batches, preferably 30 batches and 50 batches.
Preferably, the detection method of the present invention comprises the following steps:
step 1, preparation of a test solution:
precisely weighing 0.5-2g of Shunaoxin dripping pill, precisely adding 1.5-3 times of diatomite, grinding, precisely weighing 1-2g, placing into 40-60ml conical flask with plug, precisely adding 5-15ml of ethyl acetate, performing ultrasonic treatment for 20-40min, standing to room temperature, shaking, filtering, and collecting filtrate;
step 2, detection:
precisely sucking 1-5 μ l of sample solution, and injecting into a gas chromatograph to obtain chromatogram;
step 3, comparative analysis
And (3) comparing the chromatogram obtained in the step (2) with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, wherein the conformity rate of more than 85 percent is qualified.
Wherein the chromatographic conditions of the gas chromatograph are as follows:
a capillary column (column length is 30m, column inner diameter is 0.25mm, and membrane thickness is 0.25 μm) using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase; temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1.
wherein, the standard gas phase characteristic spectrum of the Shunaoxin dripping pill in the step 3 is established according to the following method:
(1) preparation of reference solutions
Taking appropriate amount of ligustilide reference substance, and making into solution containing 2mg per 1ml with ethyl acetate;
(2) preparation of test solution
Taking about 1g of multiple batches of qualified Shunaoxin dripping pills, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (power of 260W and frequency of 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
(3) measurement of
Precisely sucking 1 μ l of reference solution and sample solution respectively, injecting into gas chromatograph, and measuring to obtain chromatogram.
(4) Standard gas phase fingerprint
Finding out common peaks from gas chromatogram maps of at least 10 batches of qualified Shunaoxin dripping pills, and obtaining a standard gas phase characteristic map through calculation and fitting.
Most preferably, the detection method of the present invention comprises the following steps:
step 1, preparation of a test solution:
taking about 1g of finished Shunaoxin dripping pills, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (power of 260W and frequency of 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
step 2, detection:
precisely sucking 1 mu l of sample solution, and injecting into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis
Comparing the chromatogram obtained in the step 2 with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, and determining that the coincidence rate is more than 90 percent.
Wherein the chromatographic conditions of the gas chromatograph are as follows:
a capillary column (column length is 30m, column inner diameter is 0.25mm, and membrane thickness is 0.25 μm) using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase; temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1.
wherein, the standard gas-phase fingerprint spectrum of the Shunaoxin dripping pill in the step 3 is established according to the following method:
(1) preparation of reference solutions
Taking appropriate amount of ligustilide reference substance, and making into solution containing 2mg per 1ml with ethyl acetate;
(2) preparation of test solution
Taking about 1g of multiple batches of qualified Shunaoxin dripping pills, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (power of 260W and frequency of 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
(3) measurement of
Precisely sucking 1 μ l of reference solution and sample solution respectively, injecting into gas chromatograph, and measuring to obtain chromatogram.
(4) Standard gas phase fingerprint
And (3) taking the relative retention time of each characteristic peak in the gas chromatogram of at least 10 batches of qualified Shunaoxin dropping pills as a calculated base value, and comparing the maximum value and the minimum value of the relative retention time in each experiment in methodological verification with the maximum value and the minimum value to calculate the relative retention time deviation value of the characteristic peak.
The chromatogram of the test sample in the gas chromatogram provided by the invention shows 8 characteristic peaks, wherein the peak corresponding to the ligustilide reference peak is an S peak, the relative retention time of each characteristic peak and the S peak is calculated, the relative retention time of No. 1-7 peaks is within +/-5% of a specified value, and the relative retention time of No. 8 peak is within +/-10% of the specified value.
The above presents 8 characteristic peaks, the specified values being: the gas phase fingerprint patterns of 0.86 (peak 1), 0.89 (peak 2), 0.92 (peak 3), 0.97 (peak 4), 0.98 (peak 5), 1.00 (peak S), 1.09 (peak 7) and 1.27 (peak 8) are the standard gas phase characteristic patterns of the invention. (the standard gas phase characteristic spectrum of the Shunaoxin dripping pill is shown in figure 1 and figure 2)
The invention relates to a method for detecting Shunaoxin dripping pills and a method for establishing a standard gas phase characteristic spectrum, which are obtained by screening by the inventor, wherein the screening process comprises the following steps:
2. experimental methods and results
2.1 reagent and instrumentation
2.1.1 reagent
Shunaoxin dripping pills: the sixth Chinese medicine factory, Tianjin Chinese medicine industry group GmbH.
Brain soothing extract: the sixth Chinese medicine factory, Tianjin Chinese medicine industry group GmbH.
2.1.2 instrumentation
The instrument comprises the following steps: GC-2010 gas chromatograph (GCsolutions workstation), Shimadzu corporation, Japan
A chromatographic column: DB-1 column (30 m.times.0.25 mm.times.0.25 μm), Agilent Technologies Inc
DB-5 column (30 m.times.0.25 mm.times.0.25 μm), Agilent Technologies Inc
DB-17 column (30 m.times.0.25 mm.times.0.25 μm), Agilent Technologies Inc
ZB-5 column (30 m.times.0.25 mm.times.0.25 μm), phenomenex
TR-5 column (30 m.times.0.25 mm.times.0.25 μm), Thermo Scientific
2.2 contents of the experiment
2.2.1.1 inspection of chromatographic conditions
2.2.1.1.1 column selection
Precisely weighing about 1g (lot number is 677033), precisely weighing, precisely adding 2 times of diatomaceous earth, grinding, precisely weighing 1.5g, placing in 50ml conical flask with plug, precisely adding 10ml of ethyl acetate, performing ultrasonic treatment (power 260W, frequency 40kHz) for 20min, standing to room temperature, shaking, filtering, and measuring the filtrate with chromatographic columns DB-1, DB-5 and DB-17 according to the following temperature rise program.
DB-1 column: the initial temperature was 120 ℃ and held for 2 minutes; heating to 280 deg.C at a rate of 4 deg.C per minute, maintaining for 18min, and feeding into 250 deg.C; the temperature of the detector is 300 ℃; split-flow sample injection, split-flow ratio 10: 1.
DB-5 column: the initial temperature was 120 ℃ and held for 2 minutes; heating to 280 deg.C at a rate of 4 deg.C per minute, maintaining for 18min, and feeding into 250 deg.C; the temperature of the detector is 300 ℃; split-flow sample injection, split-flow ratio 10: 1.
DB-17 column: the initial temperature was 120 ℃ and held for 2 minutes; heating to 270 deg.C at a rate of 4 deg.C per minute, and maintaining for 20.5min with a sample inlet temperature of 250 deg.C; the temperature of the detector is 300 ℃; split-flow sample injection, split-flow ratio 10: 1.
the results show that columns DB-1 and DB-5 separated more peaks than DB-17 and that DB-17 column has a lower maximum tolerance temperature, and therefore DB-17 column is not considered. In addition, the separation effect of the DB-5 column was better than that of DB-1, and finally the DB-5 column was confirmed to be an experimental column.
2.2.1.1.2 chromatographic condition optimization
Precisely weighing about 1g (lot number is 677033), precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, performing ultrasonic treatment (power is 260W, frequency is 40kHz) for 20 minutes, standing to room temperature, uniformly shaking, filtering, taking subsequent filtrate, and respectively determining according to the chromatographic condition optimization scheme shown in Table 1.
TABLE 1 chromatographic Condition optimization protocol
Figure BDA0002853477820000061
It can be seen from comparison conditions 1, 2, and 3 that changing the temperature of the sample inlet and the detector does not affect the number of chromatographic peaks, the peak separation degree, etc., and combining the usage rule of the gas chromatographic column, the temperature of the detector is higher than the temperature of the chromatographic column and higher than the temperature of the sample inlet, and the temperature of the upper stage is generally higher than the temperature of the lower stage by 20-30 ℃, so that the higher temperature of the sample inlet is selected, and the temperature of the sample inlet is determined to be 280 ℃ and the temperature of the detector is determined to be 320 ℃.
In contrast conditions 3, 4 and 5, it can be seen that increasing the split ratio is beneficial to improving the resolution of chromatographic peaks, but an excessively large split ratio can reduce the number of chromatographic peaks, so that the split ratio with better resolution is selected while the number of chromatographic peaks is ensured, and the split ratio is determined to be 20: 1.
As can be seen by comparing conditions 5, 6 and 7, the separation effect of chromatographic peaks is basically consistent at the initial temperature of 80 ℃ and 100 ℃, and is slightly superior to that at the initial temperature of 120 ℃; the initial temperature was determined to be 100 deg.c, considering that the retention time of the chromatographic peak was longer at an initial temperature of 80 deg.c.
As can be seen from comparison conditions 7 and 8, the retention time of the initial temperature has no influence on the separation of chromatographic peaks, and the retention time of the initial temperature is determined to be 0min in order to reduce the acquisition time and improve the detection efficiency.
Comparing conditions 8, 9, 10 and 11, it can be seen that peak wrapping phenomena occur in the 4 th peak and the 5 th peak in conditions 8, 9 and 10, and since the 5 th peak has a high possibility of being a characteristic peak of the ligusticum wallichii medicinal material and should be completely separated as much as possible, the condition 11 is determined to be the best temperature raising program.
In summary, the chromatographic conditions determined were: a capillary column (column length is 30m, column inner diameter is 0.25mm, and membrane thickness is 0.25 μm) using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase; temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1.
2.2.1.2 examination of pretreatment method of test sample
2.2.1.2.1 examination of extraction mode
Taking about 1g of the product (lot number is 677033), paralleling 3 parts, precisely weighing, precisely adding 2 times of diatomite, grinding uniformly, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, respectively refluxing, ultrasonically treating (power is 260W, frequency is 40kHz), oscillating for 30 minutes, standing to room temperature, shaking uniformly, filtering, taking the subsequent filtrate, and determining according to the proposed chromatographic conditions.
Experimental results show that the extraction effects of the three extraction modes are basically consistent. Considering that a large amount of polyethylene glycol is separated out after the reflux sample is placed overnight; the oscillation device is not easily standardized and is less convenient to operate than ultrasound, and therefore ultrasound is selected as the extraction means.
2.2.1.2.2 ultrasonic Power investigation
About 1g (lot number is 677033) of the product is taken, 2 parts are parallelly taken and precisely weighed, 2 times of diatomite is precisely added, the mixture is uniformly ground, 1.5g is precisely weighed and placed in a 50ml conical flask with a plug, 10ml of ethyl acetate is precisely added, the mixture is respectively treated for 30 minutes under the power of 260W and the power of 500W, the mixture is stood to the room temperature, shaken uniformly and filtered, and subsequent filtrate is taken and is measured according to the set chromatographic conditions, and the result is shown in the table 2.
TABLE 2 influence of ultrasonic power on the test article Peak area
Figure BDA0002853477820000071
Figure BDA0002853477820000081
The experimental result shows that the relative deviation of peak areas of other chromatographic peaks under two powers is less than 3% except for chromatographic peaks No. 1, No. 3, No. 7, No. 15, No. 16, No. 17, No. 18 and No. 20, and no obvious difference exists. The extraction effect that the peak 1 in the 8 chromatographic peaks with large difference is high-power (500W) is good, and the extraction effect that the other 7 chromatographic peaks are low-power (260W) is good. In addition, polyethylene glycol was precipitated in large amounts after the high power (500W) ultrasonic sample was left overnight. Combining the above comparison results, 260W was selected as the extraction power.
2.2.1.2.3 investigation of solvent species
Taking about 1g (batch number is 677033), paralleling 4 parts, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, respectively and precisely adding 10ml of trichloromethane, ethyl acetate, diethyl ether and acetone, ultrasonically treating (power is 260W and frequency is 40kHz) for 30 minutes, standing to room temperature, uniformly shaking, filtering, taking the subsequent filtrate, and determining according to the preset chromatographic conditions.
The polarity sequence of the four solvents is acetone, ethyl acetate, diethyl ether and chloroform, and the experimental result shows that the extraction effect of the four solvents is basically consistent, and the ethyl acetate is selected as the extraction solvent because the chloroform, the diethyl ether and the acetone are easy-to-detoxify reagents and are not easy to purchase.
2.2.1.2.4 investigation of solvent addition
About 1g (lot number is 677033) of the product is taken, 3 parts are parallelly taken and precisely weighed, 2 times of diatomite is precisely added, the mixture is uniformly ground, 1.5g is precisely weighed, the mixture is placed in a 50ml conical flask with a plug, 5ml, 10ml and 20ml of ethyl acetate are precisely added respectively, ultrasonic treatment (power is 260W and frequency is 40kHz) is carried out for 30 minutes, the mixture is kept stand to room temperature, shaking is carried out uniformly, filtering is carried out, a filtrate is taken, and determination is carried out according to the set chromatographic conditions, and the result is shown in Table 3.
TABLE 3 influence of solvent addition on the test article Peak area
Figure BDA0002853477820000091
Figure BDA0002853477820000101
The experimental result shows that the extraction effect of the addition amount of the three solvents is basically consistent, and considering that when the addition amount of the solvent is 5ml, the concentration of polyethylene glycol in a sample is too high, a large amount of polyethylene glycol is separated out after the sample is placed overnight, and the sample is unstable; when the solvent addition amount is 20ml, the sample is too dilute, the peak area is small, and as shown in fig. 12, the chromatographic peak marked by the dotted line is easy to lose the chromatographic peak with small peak area when detecting multiple batches of samples in the future, so 10ml is selected as the solvent addition amount.
2.2.1.2.6 extraction time
About 1g (lot number is 677033) of the product is taken, 3 parts are parallelly taken and precisely weighed, 2 times of diatomite is precisely added, the mixture is uniformly ground, 1.5g is precisely weighed, the mixture is placed in a 50ml conical flask with a plug, 10ml of ethyl acetate is precisely added, ultrasonic treatment (power is 260W, frequency is 40kHz) is respectively carried out for 20 minutes, 30 minutes and 40 minutes, the mixture is kept stand to room temperature, shaking is uniformly carried out, filtering is carried out, a filtrate is taken, and determination is carried out according to the set chromatographic conditions, and the result is shown in a table 4.
TABLE 4 influence of different extraction times on the test article peak area
Figure BDA0002853477820000102
Figure BDA0002853477820000111
Experimental results show that the extraction effects are different in different extraction times, wherein the relative standard deviation of the chromatographic peaks No. 1, No. 3, No. 8, No. 11, No. 12, No. 15, No. 17, No. 19 and No. 20 is more than 3%, the extraction effect of the chromatographic peaks No. 1, No. 3 and No. 8 is better in 20min, the extraction effect of the chromatographic peaks No. 11, No. 12, No. 15, No. 17 and No. 19 is better in 40min, and the extraction time is selected to be 30min in view of the fact that the extraction effects of the peaks 30min are relatively balanced.
In summary, the determined pretreatment method comprises: precisely weighing about 1g (lot number is 677033), precisely weighing, precisely adding 2 times of diatomaceous earth, grinding, precisely weighing 1.5g, placing in 50ml conical flask with plug, precisely adding 10ml of ethyl acetate, performing ultrasonic treatment (power 260W, frequency 40kHz) for 30min, standing to room temperature, shaking, filtering, and collecting the filtrate.
2.2.1.3 selection of reference
In order to accurately describe the characteristic spectrum (relative retention time) of the product, a relatively large peak area is adopted, and a relatively stable ligustilide peak is taken as a reference substance peak.
2.2.1.4 inspection of chromatogram recording time
Injecting 1 μ l of the sample solution into a gas chromatograph, detecting by a proposed method, recording chromatogram for 2 hours, and displaying that no chromatographic peak flows out after 60 minutes, thus determining the recording time of chromatogram as 60 minutes.
2.2.2.6 System Adaptation experiments
A capillary column using (5% -phenyl) -methyl polysiloxane as a stationary phase (the column length is 30m, the inner diameter of the column is 0.25mm, and the thickness of the membrane is 0.25 μm); temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1. the theoretical plate number is calculated according to the reference peak (ligustilide), and is shown in Table 5.
TABLE 5 theoretical plate number calculation result table
Chromatographic columns of different manufacturers Agilent (DB-5) Feilou door (ZB-5) Saimei Feishale (TR-5)
Number of theoretical plate 286678 727477 400274
In combination with the above results, the number of theoretical plates should be not less than 270000 as calculated from the peak of the reference.
2.2.3 fingerprint and technical parameters
2.2.3.1 calibration of common peaks
According to the related parameters given by the gas chromatograms of 11 batches of samples, determining 18 common peaks, wherein the number of the common peaks is 1, 2, and N, and the number of the reference peak (ligustilide) is 14 (S).
2.2.3.2 common peak relative retention time
The relative retention time and relative peak area ratio of the common peak of 11 test samples were calculated by using peak 7 (ligustilide) as reference, and the results are shown in Table 6.
TABLE 6 consensus peak relative retention time
Figure BDA0002853477820000121
The results show that the relative retention time has better reproducibility, and the difference between the relative retention time of each common peak and the mean value thereof is less than 0.3%.
2.2.3.3 ratio of the common Peak areas
According to the related parameters given by 11 test sample gas chromatogram spectra, 18 common chromatogram peaks with characteristics are selected, and the peak areas of the peaks are compared by the ratio of the peak areas of the peak 1, the peak 2, the peak 3, the peak 4, the peak 5, the peak 6, the peak 7 (reference peak), the peak 8, the peak 9, the peak 11, the peak 12, the peak 13, the peak 14, the peak 15, the peak 16, the peak 17 and the peak 18; a common peak with a single peak area accounting for more than or equal to 20% of the total peak area is peak No. 7 (reference peak); the unimodal area accounts for more than or equal to 10% of the total peak area, and less than 20% of the common peak is the No. 5 peak; the area of the single peak of each other peak accounts for less than 5 percent of the total peak area.
The chromatogram of the product selects the peak area of the relatively large and stable chromatographic peak (No. 7 common peak) as 1, and calculates the ratio of other common peak areas, as shown in Table 7.
TABLE 7 ratio of the common Peak areas
Figure BDA0002853477820000131
2.2.3.4 non-shared peak area
The percentage of the total area of the non-common peaks to the total peak area is shown in Table 8, and the results show that the maximum percentage of the total area of the non-common peaks to the total peak area is 1.33%.
TABLE 8 percentage of total area of non-common peaks to total peak area
Figure BDA0002853477820000141
2.2.3.5 similarity of finger prints
The chromatogram of 11 batches of samples of the Shunaoxin dripping pills are calculated and processed by a traditional Chinese medicine chromatogram fingerprint similarity evaluation system 2012.130723 version to obtain the gas chromatogram comparison fingerprint of each batch of dripping pills, and the similarity between each batch of test products and the comparison fingerprint is more than or equal to 0.99. The similarity results are shown in Table 9.
TABLE 9 Shunaoxin dripping pills 11 batches of the results of similarity of fingerprint pattern with the reference fingerprint pattern
Figure BDA0002853477820000142
2.2.6.1.1 selection of characteristic peaks
By referring to the correlation analysis of common peaks and combining the analysis result of the source of chromatographic peaks, the common peaks of the dripping pills with better separation degree and larger peak area and containing the specific peaks of the two medicinal materials are selected, so that the No. 2 peak, the No. 3 peak, the No. 4 peak, the No. 5 peak, the No. 6 peak, the No. 7 peak, the No. 8 peak and the No. 12 peak are determined as the characteristic peaks of the characteristic spectrum of the Shunaoxin dripping pills.
2.2.6.1.2 confirmation of chemical composition of characteristic peaks
TABLE 10 calibration chart of characteristic peaks
Peak number Identification result
1 Butylphthalide
2 Butylene phthalide
3 -
4 Senkyunolide A
5 Novel cnidium lactone
6(S) Ligustilide
7 -
8 Senkyunolide I
2.2.6.2 creation of characteristic map
(1) Preparation of reference solutions
Taking appropriate amount of ligustilide control, and making into solution containing 2mg per 1ml with ethyl acetate.
(2) Preparation of test solution
Precisely weighing about 1g of the product, precisely adding 2 times of diatomite, grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, performing ultrasonic treatment (power 260W and frequency 40kHz) for 30min, standing to room temperature, shaking, filtering, and collecting the subsequent filtrate.
(3) Measurement of
Precisely sucking 1 μ l of each of the reference solution and the sample solution, and injecting into a gas chromatograph. And (5) measuring to obtain the product.
The relative retention time of each characteristic peak in 11 batches of the dripping pill samples is taken as a calculated base value, and the maximum value and the minimum value of the relative retention time in each experiment in methodological verification are compared with each other to calculate the deviation value of the relative retention time of the characteristic peak, which is shown in table 11.
TABLE 11 calculation of relative retention time difference
Figure BDA0002853477820000151
Figure BDA0002853477820000161
8 characteristic peaks are presented in the chromatogram of the test sample, wherein the peak corresponding to the ligustilide reference peak is an S peak, the relative retention time of each characteristic peak and the S peak is calculated, the relative retention time of No. 1-7 peaks is within +/-5% of a specified value, and the relative retention time of No. 8 peaks is within +/-10% of the specified value. The specified values are: 0.86 (peak 1), 0.89 (peak 2), 0.92 (peak 3), 0.97 (peak 4), 0.98 (peak 5), 1.00 (peak S), 1.09 (peak 7), 1.27 (peak 8). The obtained map is the standard gas phase characteristic map of the invention (see figure 1 and figure 2).
Description of the drawings:
FIG. 1 Standard gas phase characteristic spectrum of Shunaoxin dripping pills
FIG. 2 shows a standard gas phase characteristic spectrum of Shunaoxin dripping pills (partially enlarged view)
Peak 1: butylphthalide, peak 2: butenylphthalide, peak 4: senkyunolide a, peak 5: neocnidilide, peak 6: ligustilide, peak 8; senkyunolide I
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
Step 1, preparation of a test solution:
taking about 1g of finished Shunaoxin dripping pills with the batch number of 67940, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing into a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (the power is 260W, the frequency is 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
step 2, detection:
precisely sucking 1 mu l of sample solution, and injecting into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis
And (3) comparing the chromatogram obtained in the step (2) with the standard gas-phase fingerprint of the Shunaoxin dripping pill by using fingerprint similarity software, wherein the coincidence rate is 99.6%.
Wherein the chromatographic conditions of the gas chromatograph are as follows:
a capillary column (column length is 30m, column inner diameter is 0.25mm, and membrane thickness is 0.25 μm) using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase; temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1.
example 2
Step 1, preparation of a test solution:
taking about 1g of the finished Shunaoxin dripping pills with the batch number of 679041, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (the power is 260W and the frequency is 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the finished product;
step 2, detection:
precisely sucking 1 mu l of sample solution, and injecting into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis
And (3) comparing the chromatogram obtained in the step (2) with the standard gas-phase fingerprint of the Shunaoxin dripping pill by using fingerprint similarity software, wherein the coincidence rate is 99.6%.
The chromatographic conditions were the same as in example 1.
Example 3
Step 1, preparation of a test solution:
taking about 1g of the finished Shunaoxin dripping pills with the batch number of 679042, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (the power is 260W and the frequency is 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the finished product;
step 2, detection:
precisely sucking 1 mu l of sample solution, and injecting into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis
And (3) comparing the chromatogram obtained in the step (2) with the standard gas-phase fingerprint of the Shunaoxin dripping pill by using fingerprint similarity software, wherein the coincidence rate is 99.8%.
The chromatographic conditions were the same as in example 1.

Claims (6)

1. A method for detecting Shunaoxin dripping pills adopts gas chromatography, and comprises the following steps:
step 1, preparation of a test solution:
taking a finished product of the Shunaoxin dripping pill, adding diatomite and ethyl acetate, uniformly mixing, and filtering to obtain a subsequent filtrate;
step 2, detection:
absorbing the test solution, and injecting the test solution into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis:
comparing the chromatogram obtained in the step 2 with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, wherein the qualification rate of more than 80 percent is qualified;
wherein the chromatographic conditions of the gas chromatograph are as follows:
the capillary column using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase is heated by program and divided into two parts for sampling.
2. The detection method according to claim 1, wherein the Shunaoxin dripping pill standard gas phase characteristic spectrum in the step 3 is established according to the following method:
(1) preparation of reference solutions
Taking appropriate amount of ligustilide reference substance, and preparing into ligustilide ethyl acetate solution with ethyl acetate;
(2) preparation of test solution
Taking multiple batches of qualified Shunaoxin dripping pills, adding diatomite and ethyl acetate, uniformly mixing, and filtering to obtain a subsequent filtrate;
(3) measurement of
Precisely absorbing the reference solution and the test solution respectively, injecting into a gas chromatograph, and measuring to obtain a chromatogram;
(4) standard gas phase fingerprint
Finding common peaks of gas chromatogram maps of at least 10 batches of qualified Shunaoxin dripping pills, and obtaining a standard gas phase characteristic map through calculation and fitting;
wherein, the qualified sulnaoxin dripping pills in the multiple batches are at least 10 batches, preferably 30 batches and 50 batches.
3. The detection method according to claim 1, characterized in that the method steps are as follows:
step 1, preparation of a test solution:
precisely weighing 0.5-2g of Shunaoxin dripping pill, precisely adding 1.5-3 times of diatomite, grinding, precisely weighing 1-2g, placing into 40-60ml conical flask with plug, precisely adding 5-15ml of ethyl acetate, performing ultrasonic treatment for 20-40min, standing to room temperature, shaking, filtering, and collecting filtrate;
step 2, detection:
precisely sucking 1-5 μ l of sample solution, and injecting into a gas chromatograph to obtain chromatogram;
step 3, comparative analysis:
comparing the chromatogram obtained in the step 2 with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, and determining that the coincidence rate is more than 85 percent as qualified;
wherein the chromatographic conditions of the gas chromatograph are as follows:
a capillary column (column length is 30m, column inner diameter is 0.25mm, and membrane thickness is 0.25 μm) using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase; temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1.
4. the detection method according to claim 3, wherein the Shunaoxin pill standard gas phase characteristic spectrum in the step 3 is established according to the following method:
(1) preparation of reference solutions
Taking appropriate amount of ligustilide reference substance, and making into solution containing 2mg per 1ml with ethyl acetate;
(2) preparation of test solution
Taking about 1g of multiple batches of qualified Shunaoxin dripping pills, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (power of 260W and frequency of 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
(3) measurement of
Precisely absorbing 1 μ l of reference solution and sample solution respectively, injecting into gas chromatograph, and measuring to obtain chromatogram;
(4) standard gas phase fingerprint
Finding out common peaks from gas chromatogram maps of at least 10 batches of qualified Shunaoxin dripping pills, and obtaining a standard gas phase characteristic map through calculation and fitting.
5. The detection method according to claim 1, characterized in that the method steps are as follows:
step 1, preparation of a test solution:
taking about 1g of finished Shunaoxin dripping pills, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (power of 260W and frequency of 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
step 2, detection:
precisely sucking 1 mu l of sample solution, and injecting into a gas chromatograph to obtain a chromatogram;
step 3, comparative analysis:
comparing the chromatogram obtained in the step 2 with the standard gas phase characteristic spectrum of the Shunaoxin dripping pill through fingerprint similarity software, wherein the coincidence rate is more than 90 percent and is qualified;
wherein the chromatographic conditions of the gas chromatograph are as follows:
a capillary column (column length is 30m, column inner diameter is 0.25mm, and membrane thickness is 0.25 μm) using (5% -phenyl) -methyl polysiloxane (DB-5) as stationary phase; temperature programming: the initial temperature is 100 ℃; heating to 170 deg.C at a rate of 2 deg.C per minute, heating to 300 deg.C at a rate of 10 deg.C per minute, and maintaining for 12 min; the temperature of a sample inlet is 280 ℃; the temperature of the detector is 320 ℃; split-flow sample injection, split ratio 20: 1.
6. the detection method according to claim 5, wherein the Shunaoxin pill standard gas-phase fingerprint in step 3 is established according to the following method:
(1) preparation of reference solutions
Taking appropriate amount of ligustilide reference substance, and making into solution containing 2mg per 1ml with ethyl acetate;
(2) preparation of test solution
Taking about 1g of multiple batches of qualified Shunaoxin dripping pills, precisely weighing, precisely adding 2 times of diatomite, uniformly grinding, precisely weighing 1.5g, placing in a 50ml conical flask with a plug, precisely adding 10ml of ethyl acetate, carrying out ultrasonic treatment (power of 260W and frequency of 40kHz) for 30min, standing to room temperature, uniformly shaking, filtering, and taking a subsequent filtrate to obtain the medicine;
(3) measurement of
Precisely absorbing 1 μ l of reference solution and sample solution respectively, injecting into gas chromatograph, and measuring to obtain chromatogram;
(4) standard gas phase fingerprint
Taking the relative retention time of each characteristic peak in the gas chromatogram of at least 10 batches of qualified Shunaoxin dripping pills as a calculated base value, and comparing the maximum value and the minimum value of the relative retention time in each experiment in methodological verification with the maximum value and the minimum value of the relative retention time to calculate the deviation value of the relative retention time of the characteristic peak;
the chromatogram of a test sample in the gas chromatogram provided by the invention shows 8 characteristic peaks, wherein the peak corresponding to the ligustilide reference peak is an S peak, the relative retention time of each characteristic peak and the S peak is calculated, the relative retention time of No. 1-7 peaks is within +/-5% of a specified value, and the relative retention time of No. 8 peak is within +/-10% of the specified value; the above presents 8 characteristic peaks, the specified values being: 0.86 (peak 1), 0.89 (peak 2), 0.92 (peak 3), 0.97 (peak 4), 0.98 (peak 5), 1.00 (peak S), 1.09 (peak 7), 1.27 (peak 8).
CN202011537296.2A 2020-12-23 2020-12-23 Detection method of sulbactam sodium dripping pill Active CN112730670B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011537296.2A CN112730670B (en) 2020-12-23 2020-12-23 Detection method of sulbactam sodium dripping pill

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011537296.2A CN112730670B (en) 2020-12-23 2020-12-23 Detection method of sulbactam sodium dripping pill

Publications (2)

Publication Number Publication Date
CN112730670A true CN112730670A (en) 2021-04-30
CN112730670B CN112730670B (en) 2023-05-30

Family

ID=75604421

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011537296.2A Active CN112730670B (en) 2020-12-23 2020-12-23 Detection method of sulbactam sodium dripping pill

Country Status (1)

Country Link
CN (1) CN112730670B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060292246A1 (en) * 2005-06-20 2006-12-28 Rey-Yuh Wu Characteristic mass spectral fingerprint setting method and rapid identification method for Chinese herbal medicines and prescriptions
CN109350632A (en) * 2018-12-07 2019-02-19 四川省中医药科学院 A kind of Chinese medicine composition for antipyretic-antalgic
CN111796048A (en) * 2020-07-09 2020-10-20 中国科学院兰州化学物理研究所 Method for indirectly measuring content of ligustilide in traditional Chinese medicinal material or Chinese medicinal material by chemical conversion method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060292246A1 (en) * 2005-06-20 2006-12-28 Rey-Yuh Wu Characteristic mass spectral fingerprint setting method and rapid identification method for Chinese herbal medicines and prescriptions
CN109350632A (en) * 2018-12-07 2019-02-19 四川省中医药科学院 A kind of Chinese medicine composition for antipyretic-antalgic
CN111796048A (en) * 2020-07-09 2020-10-20 中国科学院兰州化学物理研究所 Method for indirectly measuring content of ligustilide in traditional Chinese medicinal material or Chinese medicinal material by chemical conversion method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BAIJUAN YANG等: "GC-MS fingerprints for discrimination of Ligusticum chuanxiong from Angelica", 《J. SEP. SCI.》 *
宋洁瑾等: "丹芪偏瘫胶囊挥发性成分的GC-MS指纹图谱研究", 《中国药房》 *
苏丽娜等: "舒脑欣滴丸中挥发性成分的GC-MS分析", 《中药材》 *

Also Published As

Publication number Publication date
CN112730670B (en) 2023-05-30

Similar Documents

Publication Publication Date Title
CN113791164B (en) Quality detection method for standard decoction of scalded rhizoma Cibotii
CN113917041B (en) Quality detection method for cortex moutan standard decoction
CN101028388B (en) Quality inspection of Chinese-medicinal preparation for treating shortsighness and asthenopia
CN111487344B (en) Method for detecting fingerprint spectrum of motherwort particles
CN102426205B (en) Detection method of thrombus sumalin capsules
CN102441057B (en) High performance liquid chromatography (HPLC) fingerprint detection method for blood-nourishing brain-refreshing grain
CN107727754A (en) A kind of HPLC fingerprint atlas detection methods of Xiaojing
CN110568108B (en) Multi-component content determination method of Ganfule preparation
CN110031564B (en) Quality detection method of natural plant anticoccidial feed additive based on HPLC fingerprint
CN106918673B (en) A kind of method for building up of the finger-print of Chinese medicine composition
CN114778739B (en) Method for detecting quality of fried chicken's gizzard-membrane standard decoction
CN113759015B (en) Preparation process and quality control method of Simiaoyongan decoction
CN112730670A (en) Method for detecting Shunaoxin dropping pills
CN102590423B (en) Fingerprint spectrum determination method of ligusticum wallichii tea-blending granular preparation
CN113341007B (en) HPLC (high Performance liquid chromatography) characteristic spectrum-based method for measuring content of all ingredients of jujube kernel nerve-soothing capsules
CN113759011B (en) Method for establishing characteristic spectrum of starwort root and preparation thereof
CN101028474B (en) Method for inspecting the quality of Chinese preparation with Yang-and kidney tonifying functions
CN110412162B (en) Construction method of HPLC (high performance liquid chromatography) characteristic spectrum of Baixiangdan capsule and quality detection method of Baixiangdan capsule
CN111487335B (en) Method for detecting fingerprint of Xiao' er Ganmaoshu granules
CN114965802A (en) Quality control method of climacteric syndrome-relieving tablet
CN103575823A (en) Detection method of 8 chemical components in Tangminling preparation
CN105929080A (en) Detection method of traditional Chinese medicine preparation for treating nerve-root type cervical spondylosis
CN108107130B (en) Method for measuring fingerprint spectrum of Shenzhiling preparation
CN114814059B (en) Agalloch eaglewood Shu Yupian gas chromatography standard reference fingerprint, construction method and application
CN113125620B (en) Fingerprint detection method of traditional Chinese medicine composition with kidney tonifying and yang strengthening effects

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
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 300401 Tianjin city Beichen District North Light

Applicant after: Jinyao Darentang Group Co.,Ltd. No 6 Chinese Medicine Factory

Address before: 300401 Tianjin city Beichen District North Light

Applicant before: No. 6 Traditional Chinese Medicine Factory of Tianjin Zhongxin Pharmaceutical Group Co.,Ltd.

GR01 Patent grant
GR01 Patent grant