WO2014067478A1 - 一种参芪扶正注射液指纹图谱的建立方法 - Google Patents
一种参芪扶正注射液指纹图谱的建立方法 Download PDFInfo
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- WO2014067478A1 WO2014067478A1 PCT/CN2013/086405 CN2013086405W WO2014067478A1 WO 2014067478 A1 WO2014067478 A1 WO 2014067478A1 CN 2013086405 W CN2013086405 W CN 2013086405W WO 2014067478 A1 WO2014067478 A1 WO 2014067478A1
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- Prior art keywords
- peak
- mobile phase
- fingerprint
- shenqi fuzheng
- injection
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Links
- 238000002347 injection Methods 0.000 title claims abstract description 93
- 239000007924 injection Substances 0.000 title claims abstract description 93
- 239000008687 shenqi fuzheng Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000001228 spectrum Methods 0.000 title abstract description 3
- 239000000243 solution Substances 0.000 claims abstract description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010828 elution Methods 0.000 claims abstract description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical compound CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004811 liquid chromatography Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 230000014759 maintenance of location Effects 0.000 claims description 27
- 229930182478 glucoside Natural products 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- QMNWISYXSJWHRY-YLNUDOOFSA-N astragaloside IV Chemical compound O1[C@H](C(C)(O)C)CC[C@]1(C)[C@@H]1[C@@]2(C)CC[C@]34C[C@]4(CC[C@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)CO4)O)C4(C)C)[C@H]4[C@@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O4)O)C[C@H]3[C@]2(C)C[C@@H]1O QMNWISYXSJWHRY-YLNUDOOFSA-N 0.000 claims description 15
- QMNWISYXSJWHRY-BCBPIKMJSA-N astragaloside IV Natural products CC(C)(O)[C@@H]1CC[C@@](C)(O1)[C@H]2[C@@H](O)C[C@@]3(C)[C@@H]4C[C@H](O[C@@H]5O[C@H](CO)[C@H](O)[C@@H](O)[C@H]5O)[C@H]6C(C)(C)[C@H](CC[C@@]67C[C@@]47CC[C@]23C)O[C@@H]8OC[C@@H](O)[C@H](O)[C@H]8O QMNWISYXSJWHRY-BCBPIKMJSA-N 0.000 claims description 15
- PFKIBRPYVNVMRU-UHFFFAOYSA-N cyclosieversioside F Natural products CC(C)(O)C1COC(C)(C1)C2C(O)CC3(C)C4CC(OC5OC(CO)C(O)C(O)C5O)C6C(C)(C)C(CCC67CC47CCC23C)OC8OCC(O)C(O)C8O PFKIBRPYVNVMRU-UHFFFAOYSA-N 0.000 claims description 15
- -1 calycosin glucoside Chemical class 0.000 claims description 14
- 239000012085 test solution Substances 0.000 claims description 14
- 239000013558 reference substance Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000012088 reference solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 6
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 5
- 238000004949 mass spectrometry Methods 0.000 claims description 5
- 150000008131 glucosides Chemical class 0.000 claims description 4
- 239000012982 microporous membrane Substances 0.000 claims description 4
- 229930182470 glycoside Natural products 0.000 claims description 2
- ZZAJQOPSWWVMBI-UHFFFAOYSA-N Calycosin Natural products C1=C(O)C(OC)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZZAJQOPSWWVMBI-UHFFFAOYSA-N 0.000 claims 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- QUQPHWDTPGMPEX-UHFFFAOYSA-N Hesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(COC4C(C(O)C(O)C(C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-UHFFFAOYSA-N 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 150000002338 glycosides Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000012925 reference material Substances 0.000 claims 1
- KDSWDGKIENPKLB-QJDQKFITSA-N verbascoside Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC(=O)CCC=2C=C(O)C(O)=CC=2)[C@@H](CO)O[C@@H](OCCC=2C=C(O)C(O)=CC=2)[C@@H]1O KDSWDGKIENPKLB-QJDQKFITSA-N 0.000 claims 1
- QFRYQWYZSQDFOS-UHFFFAOYSA-N verbascoside Natural products CC1OC(COC2C(O)C(COC3OC(C(O)C(O)C3O)C(=O)O)OC(Oc4cc(O)cc5OC(=CC(=O)c45)c6ccc(O)c(O)c6)C2O)C(O)C(O)C1O QFRYQWYZSQDFOS-UHFFFAOYSA-N 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 21
- 239000003814 drug Substances 0.000 description 17
- SMDOOINVMJSDPS-UHFFFAOYSA-N Astragaloside Natural products C1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)OC2C(C(OC3C(C(O)C(O)C(CO)O3)O)C(O)C(CO)O2)O)=C1 SMDOOINVMJSDPS-UHFFFAOYSA-N 0.000 description 12
- QMNWISYXSJWHRY-XWJCTJPOSA-N astragaloside Chemical compound O1[C@H](C(C)(O)C)CC[C@]1(C)[C@@H]1[C@@]2(C)CC[C@]34C[C@]4(CC[C@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)CO4)O)C4(C)C)C4[C@@H](O[C@H]4[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O4)O)CC3[C@]2(C)C[C@@H]1O QMNWISYXSJWHRY-XWJCTJPOSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- CJWQYWQDLBZGPD-UHFFFAOYSA-N isoflavone Natural products C1=C(OC)C(OC)=CC(OC)=C1C1=COC2=C(C=CC(C)(C)O3)C3=C(OC)C=C2C1=O CJWQYWQDLBZGPD-UHFFFAOYSA-N 0.000 description 8
- 235000008696 isoflavones Nutrition 0.000 description 8
- 239000000284 extract Substances 0.000 description 7
- 229930182490 saponin Natural products 0.000 description 7
- 150000007949 saponins Chemical class 0.000 description 7
- 235000017709 saponins Nutrition 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 6
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 244000132619 red sage Species 0.000 description 5
- WTPPRJKFRFIQKT-UHFFFAOYSA-N 1,6-dimethyl-8,9-dihydronaphtho[1,2-g][1]benzofuran-10,11-dione;1-methyl-6-methylidene-8,9-dihydro-7h-naphtho[1,2-g][1]benzofuran-10,11-dione Chemical compound O=C1C(=O)C2=C3CCCC(=C)C3=CC=C2C2=C1C(C)=CO2.O=C1C(=O)C2=C3CCC=C(C)C3=CC=C2C2=C1C(C)=CO2 WTPPRJKFRFIQKT-UHFFFAOYSA-N 0.000 description 4
- 229930003935 flavonoid Natural products 0.000 description 4
- 235000017173 flavonoids Nutrition 0.000 description 4
- 238000003908 quality control method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930182486 flavonoid glycoside Natural products 0.000 description 3
- 150000007955 flavonoid glycosides Chemical class 0.000 description 3
- 239000009798 Shen-Fu Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001474 liquid chromatography-evaporative light scattering detection Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 206010051602 Laziness Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 235000011135 Salvia miltiorrhiza Nutrition 0.000 description 1
- 208000005718 Stomach Neoplasms Diseases 0.000 description 1
- 208000012886 Vertigo Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000009098 adjuvant therapy Methods 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000036267 drug metabolism Effects 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 206010017758 gastric cancer Diseases 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010390 livzon Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 201000011549 stomach cancer Diseases 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 231100000889 vertigo Toxicity 0.000 description 1
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
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/15—Medicinal preparations ; Physical properties thereof, e.g. dissolubility
-
- 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
- G01N2030/8813—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 biological materials
Definitions
- the invention belongs to the technical field of drug detection, and particularly relates to a fingerprint of Shenqi Fuzheng injection
- the quality control of traditional Chinese medicine compound is one of the key issues that restrict the modernization of traditional Chinese medicine.
- the theory of traditional Chinese medicine emphasizes the overall effect of traditional Chinese medicine and attaches importance to the synergistic effect on the efficacy of medicine.
- the use of one or two active ingredients in traditional Chinese medicine as a qualitative and quantitative indicator is far from being able to effectively control and evaluate the quality of traditional Chinese medicine, and it is more difficult to reflect its safety and effectiveness.
- Sex The traditional Chinese medicine compound is a compound preparation for the treatment of diseases with a combination of two or more traditional Chinese medicines.
- the quality control is more difficult than the single Chinese medicine.
- traditional Chinese medicine fingerprints and characteristic fingerprints have been widely used in quality control.
- Chinese medicine characteristic maps refer to the selection of characteristic peaks or chromatographic peaks from the fingerprints of traditional Chinese medicines to form characteristic fingerprints. There are no changes and changes to monitor the quality of Chinese medicine.
- the signature fingerprint has been applied to the quality control of various intermediate components of traditional Chinese medicine.
- Ultra High Performance Liquid Chromatography is a breakthrough in chromatographic technology. It is based on ultra-high speed, ultra-high sensitivity and ultra-high resolution. It uses faster column packing technology to achieve faster and more sensitive detection. The effect is widely used in agriculture, such as pesticide residues and drug metabolism, and is increasingly used in China.
- Chromatography-mass spectrometry is also a high-end analytical technology that has developed rapidly in recent years.
- LC-MS is gradually recognized after its extensive application in gas chromatography-mass spectrometry (GC-MS). And another combination of technologies accepted, but due to the high price of the instrument, it has not been widely used.
- the ionization technology used in the LC/MS instrument can not only solve the detection problems of some UV-free components, such as saponin components, but also obtain the precise molecular weight of the ionized components, and provide identification and confirmation of the components and their structures. Data support.
- Shenqi Fuzheng Injection is a large infusion of traditional Chinese medicine. It has the effect of supplementing Qi and strengthening the body. It is used for the fatigue caused by lung spleen qi deficiency, less gas laziness, self-sweating vertigo and lung cancer, gastric cancer see the above-mentioned syndrome for adjuvant treatment.
- [fingerprint] is detected by high performance liquid chromatography-ultraviolet detector, which has certain limitations.
- the main content of saponin is not absorbed in the ultraviolet, by adding high performance liquid chromatography-
- the evaporative light scattering detector can detect the saponin components, but the sample preparation is complicated and the analysis time is very long. It is impossible to monitor the main components comprehensively and quickly, and needs to be improved. Summary of the invention
- the technical problem to be solved by the present invention is to make up for the deficiencies of the prior art, and the purpose is to provide a method for establishing a fingerprint of Shenqi Fuzheng Injection.
- the fingerprint image established by this method can be used as a standard fingerprint map, and can be applied to identify Shenqi Fuzheng injection.
- a method for establishing a fingerprint of Shenqi Fuzheng injection which comprises using an ultrahigh pressure liquid chromatography mass spectrometer, such as an ultra performance liquid chromatography-quadrupole time-of-flight mass spectrometer for Shenqi Fuzheng injection Detection, wherein the chromatographic conditions include:
- the elution procedure is as follows, wherein the flow ratio is a volume percentage: 0 ⁇ 0.5min, mobile phase A is 95%, mobile phase B is 5%;
- the mobile phase A is 95% ⁇ 75%, and the mobile phase B is 5% ⁇ 25%;
- the mobile phase A is 75% ⁇ 45%, and the mobile phase B is 25% ⁇ 55%;
- the mobile phase A is 45% ⁇ 0%, and the mobile phase B is 55% ⁇ 100%.
- the mobile phase A is 0% and the mobile phase B is 100%.
- the chromatographic conditions further comprise:
- the flow rate is 0.35 ml/min
- the column temperature is 40 °C ;
- the injection volume is 5 ⁇ 1 .
- the conditions of the mass spectrum include: the ion source is ES, and the negative ion mode is detected;
- Atomizing gas pressure 35 psig
- Drying gas temperature 350 ° C;
- Dry gas flow rate lOL/min
- the method for establishing the fingerprint of the above-mentioned Shenqi Fuzheng injection further comprises the following steps Prepare the reference solution: take the appropriate amount of the reference substance of the isoflavone glucoside and the reference substance of the astragaloside, accurately weighed, add methanol to make a solution containing 0.004 mg of flavonoid glycosides per ml and 0.006 mg of astragaloside IV. .
- the method for establishing the fingerprint of the above-mentioned Shenqi Fuzheng injection further comprises preparing the test solution by the following steps: taking Shenqi Fuzheng injection and filtering through a 0.22 um microporous membrane.
- the method for establishing the fingerprint of the above-mentioned Shenqi Fuzheng injection comprises the following steps:
- the chromatographic conditions include:
- the elution procedure is as follows, wherein the flow ratio is a volume percentage: 0 ⁇ 0.5min, mobile phase A is 95%, mobile phase B is 5%;
- the mobile phase A is 95% ⁇ 75%, and the mobile phase B is 5% ⁇ 25%;
- the mobile phase A is 75% ⁇ 45%, and the mobile phase B is 25% ⁇ 55%;
- the mobile phase A is 45% ⁇ 0%, and the mobile phase B is 55% ⁇ 100%.
- the mobile phase A is 0% and the mobile phase B is 100%.
- the chromatographic conditions further comprise:
- the flow rate is 0.35 ml/min
- the column temperature is 40 °C ;
- the conditions of the mass spectrum include:
- the ion source is ES, and the negative ion mode is detected;
- Atomizing gas pressure 35 psig
- Drying gas temperature 350 ° C;
- Dry gas flow rate lOL/min
- Capillary voltage 3500V
- the method for establishing the fingerprint of the Shenqi Fuzheng injection further comprises: comparing the fingerprints of the plurality of Shenqi Fuzheng injections, selecting a common characteristic peak, and obtaining a characteristic fingerprint of the Shenqi Fuzheng injection.
- the fingerprint fingerprint of the Shenqi Fuzheng injection liquid or the fingerprint of the Shenqi Fuzheng injection contains 18 characteristic peaks, and the retention times of the characteristic peaks are as follows:
- Peak 1 7.1 min, peak 2: 7.5 min, peak 3: 8.1 min, peak 4: 8.6 min, peak 5: 9.2 min, peak 6: 9.9 min, peak 7: 10.9 min, peak 8: 11.3 min, peak 9 : 11.7 min, peak 10: 12.7 min, peak 11: 13.4 min, peak 12: 13.7 min, peak 13: 14.4 min, peak 14: 14.8 min, peak 15: 15.1 min, peak 16: 15.5 min, peak 17: 15.9 Min, peak 18: 16.3min.
- the reference peak of the reference substance is calculated as the reference peak, and each characteristic peak is calculated.
- the relative retention time is as follows:
- Peak 1 0.52, peak 2: 0.54, peak 3: 0.59, peak 4: 0.62, peak 5: 0.66, peak 6: 0.72, peak 7: 0.79, peak 8: 0.82, peak 9: 0.85, peak 10: 0.92, Peak 11: 0.97, peak 12: 1.00, peak 13: 1.04, peak 14: 1.07, peak 15: 1.10, peak 16: 1.13, peak 17: 1.16, peak 18: 1.19.
- the peaks 2 and 12 are respectively the isoflavone glucoside and the astragaloside; preferably, the isoflavone glucoside and the astragaloside peak
- the ratio of the area to the corresponding reference peak area is between 0.5 and 1.5.
- the invention also provides a method for identifying Shenqi Fuzheng injection, which comprises comparing the fingerprint or characteristic fingerprint of the sample to be tested according to the above method with a standard fingerprint or a characteristic fingerprint established according to the above method to identify True or false.
- the present invention provides a method for establishing a fingerprint of Shenqi Fuzheng Injection, the method comprising the steps of:
- the above control solution and the test solution were analyzed by ultra performance liquid chromatography-quadrupole time-of-flight mass spectrometry.
- the chromatographic conditions were: The column was Agilent Zorbax Eclipse Plus CI 8 , 2.1 mm x 100 mm, 1.8 ⁇ m; the mobile phase was 0.1% formic acid in water and 0.1% formic acid in acetonitrile.
- the flow rate is 0.35 ml/min
- the column temperature is 40 °C ;
- the gradient elution step is: 0 ⁇ 0.5 minutes, the mobile phase acetonitrile-water is 5:95; 0.5 - 10 minutes, the mobile phase acetonitrile-water is changed from 5:95 to 25:75; 10 ⁇ 15 minutes, mobile phase
- the acetonitrile-water gradient was 55:45 at 25:75; for 15-18 minutes, the mobile phase acetonitrile-water was changed to 55:45 at 100:0; for 18-20 minutes, the mobile phase acetonitrile-water was 100:0.
- the characteristic fingerprint of Shenqi Fuzheng injection was determined to monitor Shenqi Fuzheng injection. The quality of the liquid.
- the step of gradient elution can also be represented by Table 1:
- the common characteristic peaks are found, and the extracted ion current map (EIC) is extracted by using these common characteristic peak ion mass numbers. , the retention time Rt of each common characteristic peak is marked, and the characteristic fingerprint of Shenqi Fuzheng injection is obtained.
- the common characteristic peak is 18, and the retention time Rt value and mass number are 7.1min ( 471.2083 ), 7.5min ( 491.1195 ), 8. lmin ( 441.1919 ), 8.6min ( 309.1555 ),
- the characteristic fingerprint map established by the invention can be applied to identify Shenqi Fuzheng injection.
- the present invention has the following beneficial effects:
- the fingerprints of Shenqi Fuzheng Injection were determined by high performance liquid chromatography-ultraviolet detection method, which achieved the purpose of monitoring its quality to a certain extent, but it accounted for the main content.
- the saponin component has no absorption in the ultraviolet; [Content determination]
- the content of total saponin is determined by vanillin-glacial acetic acid ultraviolet spectrophotometry, and the content of astragaloside IV is determined by high performance liquid chromatography-evaporative light scattering detection.
- the composition of saponins cannot be fully reflected.
- the saponin components can be monitored by adding high-performance liquid chromatography-evaporative light scattering detector to detect fingerprints, but the sample preparation needs to be increased, and the analysis time is also very long. .
- the method of the ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometric fingerprint standard of Shenqi Fuzheng Injection established by the method of the present invention can quickly and effectively monitor the quality of the drug through the presence and absence of common peaks in the characteristic fingerprint. Ensure that the quality is stable, uniform and controllable.
- the invention also has the characteristics of advanced method, stability and reproducibility.
- Figure 1 is a diagram showing the total ion current of the Shenqi Fuzheng injection of the present invention, wherein the arrows from left to right are characterized by characteristic peaks 1 to 18;
- Figure 2 is a diagram showing the extracted ion flow of Shenqi Fuzheng Injection. The arrows from left to right in the figure are characterized by characteristic peaks 1 to 18;
- Fig. 3 is a diagram showing the extracted ion flow of the mixed reference substance, wherein the peak numbers 2, 12 are sequentially indicated as flavonoid glucoside and astragaloside IV;
- Fig. 4 is a comparison diagram of the fingerprint and the counterfeit of the Shenqi Fuzheng injection of the present invention, wherein 1 is a genuine Shenqi Fuzheng injection, 2 is a fake (presumably Danshen injection), and 3 is a Danshen drip solution. detailed description
- Example 1 Instruments and reagents
- ion source is ESI source, negative ion mode detection; atomizing gas pressure: 35 psig, drying gas temperature: 350 °C, drying gas flow rate: 10 L/min, Vcap capillary voltage: 3500 V, capillary outlet voltage: 135V.
- the common characteristic peak is 18, and its retention time Rt value and mass number
- the other 'J is 7.1min ( 471.2083 ), 7.5min ( 491.1195 ), 8.1min ( 441.1919 ), 8.6min ( 309.1555 ), 9.2min ( 187.0976 ), 9.9min ( 441.1766 ), 10.9min ( 593.1876 ), 11.3min ( 507.1508 ), 11.7min ( 463.1610 ), 12.7min ( 991.5119 ), 13.4min ( 991.5119 ), 13.7min ( 829.4591 ), 14.4min ( 871.4697 ), 14.8min ( 871.4697 ), 15.1min ( 871.4697 ), 15.5min ( 913.4650 ) , 15.9min ( 913.4650 ), 16.3min ( 913.4650 ), wherein the chromatographic peaks with Rt value of 7.5min and 13.7min were confirmed as flavonoid glucoside and astragaloside, as shown in Figure 3; with reference
- the relative retention time should be within ⁇ 5% of the specified value, and the specified values are 0.52, 0.54, 0.59, 0.62, 0.66, 0.72, 0.79, 0.82. , 0.85, 0.92, 0.97, 1.00, 1.04, 1.07, 1.10, 1.13, 1.16, 1.19; the ratio of the peak area of the isoflavone glucoside and the astragaloside IV to the corresponding reference peak area should be between 0.5 and 1.5.
- Shenqi Fuzheng Injection In recent years, with the increasing use of Shenqi Fuzheng Injection in clinical practice, some lawless elements have been driven by economic interests, using other varieties of counterfeit Shenqi Fuzheng injection for sales, profiteering, causing very much to the brand of Shenqi Fuzheng Injection
- the big negative impact has brought great economic losses to enterprises that regularly produce and sell Shenfu Fuzheng Injection.
- These fake Shenfu Fuzheng injections are almost identical in appearance to the genuine ones, making it difficult to distinguish between authenticity and falsehood.
- Example 1 the method of Example 1 was used to detect the authenticity of Shenqi Fuzheng Injection (provided by Liv Pharmaceutical Group Limin Pharmaceutical Factory), suspected samples and Danshen drip solution, and the corresponding fingerprints were established. The results are shown in Figure 4. As shown, it can be seen that the suspected sample is completely different from the authentic Shenqi Fuzheng injection spectrum. The precise molecular weight provided by the mass spectrometer is used to infer the components contained in the counterfeit, and the basic locking component is derived from Salvia miltiorrhiza.
- the fingerprints established by the high-pressure liquid chromatography-mass spectrometry (UHPLC-MS) of Shenqi Fuzheng Injection can quickly and accurately identify the authenticity of Shenqi Fuzheng Injection, and can also characterize the fakes.
- Analysis basically lock the source of counterfeit products, if there are criminals using Danshen injection to impersonate Shenqi Fuzheng injection, use the above method to detect, compare it with the authentic Shenqi Fuzheng injection map, and then use the precise molecular weight provided by mass spectrometry, The components contained in the counterfeit are inferred, and the source of the counterfeit component can be basically locked.
- Shenqi Fuzheng injection UHPLC-MS fingerprint can effectively avoid production Counterfeit, guarantee the normal production and circulation order of the variety, and protect the legitimate rights and interests of the manufacturer.
- the above describes the method for establishing the fingerprint of Shenqi Fuzheng Injection provided by the present invention.
- the description of the above embodiment is only for helping to understand this.
- the method of invention and its core idea It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.
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US14/439,635 US20160054276A1 (en) | 2012-11-02 | 2013-11-01 | Method for establishing shenqi fuzheng injection fingerprint spectrum |
JP2015540037A JP6266637B2 (ja) | 2012-11-02 | 2013-11-01 | ShenqiFuzheng注射液の指紋的固有スペクトルを確立する方法 |
EP13851081.3A EP2916130B1 (en) | 2012-11-02 | 2013-11-01 | Method for establishing shenqi fuzheng injection fingerprint spectrum |
US16/361,136 US20190219550A1 (en) | 2012-11-02 | 2019-03-21 | System and Method for Identifying Shenqi Fuzheng Injection |
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US16/361,136 Continuation-In-Part US20190219550A1 (en) | 2012-11-02 | 2019-03-21 | System and Method for Identifying Shenqi Fuzheng Injection |
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