CN1731163A - Chinese herbal medicine NMR fingerprint discrimination method - Google Patents
Chinese herbal medicine NMR fingerprint discrimination method Download PDFInfo
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- CN1731163A CN1731163A CN 200510044396 CN200510044396A CN1731163A CN 1731163 A CN1731163 A CN 1731163A CN 200510044396 CN200510044396 CN 200510044396 CN 200510044396 A CN200510044396 A CN 200510044396A CN 1731163 A CN1731163 A CN 1731163A
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Abstract
The invention discloses a Chinese herbal nuclear magnetic resonance fingerprint pattern discriminate method, which is characterized in that: extracting 5-20 gram sample, adding 50-200 millimeter polar solvent with low molecular weight, flowing-back about 30-120 minutes on water-bath, filtering the extracting liquid, volatizing the reagent and weighting the oddments. Extracting 1-15 milligram oddments to do nuclear magnetic resonance analysis and comparing it with the nuclear magnetic resonance graph. The polar solvent with low molecular weight is alcohol, carbinol, water, chloroform, methyl acetyl, butyl acetate, butanol and so on. The method can be applied to identify the amalgamate and the genuine-fake of the Chinese patent drug, the traditional drug, each extractor and addictive which use nature plate as main materials.
Description
Technical field: the invention belongs to the magnetic nuclear resonance method in the instrument analytical method, specifically about the Chinese herbal medicine NMR fingerprint discrimination method.
Background technology: Chinese herbal medicine is the material base that the traditional Chinese medical science is used for disease preventing and treating, and its true and false quality is not only directly determining clinical efficacy and even patient's life safety, and the development based on inheritance and the Chinese medicine that also have a strong impact on science of Chinese materia medica go to the world.Therefore has only the quality control of the science under the Modern Significance that Chinese crude drug is carried out, could ensure the quality of the prepared slices of Chinese crude drugs and patent medicine better, realize the safe, effective, stable, controlled of traditional Chinese medicine quality, the obstacle that cleaning restriction Chinese medicine goes to the world lays a good foundation for Chinese medicine goes to the world.System testing, the standard finger-print on the analysis result that wherein is based upon traditional Chinese medicine ingredients is effective means comprehensive, objective evaluation reflection Chinese medicine inherent quality, also easily accepted by international community simultaneously.Fingerprint pattern technology also is the best solution of Chinese crude drug, Chinese patent drug being carried out strict quality control under existing technical conditions.It can be from the cultivation of crude drug, introduce a fine variety, the standard and the optimization of production technology the Chinese patent drug production run, provides omnibearing quality assurance to the formulation of target level of product quality.Be extensive use of by the U.S., Europe, India, Japan and other countries at present, and admitted by the pharmacopeia of a plurality of countries.The foundation that therefore can really reflect the finger-print of Chinese crude drug, Chinese patent drug inherent quality is the key that realizes the modernization of Chinese medicine.For other spectrum such as ultraviolet, infrared, fluorescence, atomic absorption and chromatography such as gas chromatography, high performance liquid chromatography, chromatogram-spectrum coupling method, also can carry out the research of medicine quality evaluated.The difference of the whole bag of tricks performance causes its identification result also to differ from one another.Every kind of collection of illustrative plates discrimination method all has its limitation and relative advantage.The complexity of distinct methods, the angle of dealing with problems, testing cost and identification result be difference to some extent all.For qualitative, the quantitative test of Chinese herbal medicine composition, chromatogram-mass spectrometric hyphenated technique is better.And for the cultivar identification and real and fake discrimination of single medicinal material or Chinese patent drug, when particularly its characteristic was relatively poor, reliable, sensitive, easy, inexpensive, favorable reproducibility, the discrimination method that characteristic is strong did not appear in the newspapers as yet.
Summary of the invention: the present invention is directed to the above-mentioned shortcoming that present prior art exists, a kind of reliable, sensitive, easy, inexpensive, favorable reproducibility, Chinese herbal medicine NMR fingerprint discrimination method that characteristic is strong are provided.
The object of the present invention is achieved like this: the present invention includes sample is extracted with low-molecular-weight polar solvent, the nuclear magnetic resonance map of Test extraction thing respectively compares with the nuclear magnetic resonance map of corresponding reference substance, can obtain identification result.Described low-molecular-weight polar solvent is meant ethanol, methyl alcohol, water, chloroform, acetone, ethyl acetate, normal butyl alcohol etc.
Concrete operation method is as follows: gets 5-20 gram sample, adds the low-molecular-weight polar solvent of 50-200 milliliter, and in water-bath reflux 30-120 minute, the leaching extract, with solvent evaporates, residue is weighed.Get 1-50 milligram residue and carry out nuclear magnetic resonance spectroscopy, compare with the nuclear magnetic resonance map of corresponding reference substance.
Applicable object of the present invention comprises the solid sample that can be ground into powder, as Chinese crude drug or based on the tablet of the Chinese patent drug of crude drug, powder, capsule, water-bindered pill agent, lozenge etc.; The viscous solid sample need shred sample, as honey pill agent of Chinese patent drug etc.; Fluid sample then can directly select suitable solvent to extract.The most frequently used solvent is methyl alcohol, second alcohol and water.
Description of drawings: Fig. 1: the NMR fingerprint of different cultivars honeysuckle
Fig. 2: the NMR fingerprint of different quality honeysuckles
Fig. 3: the NMR fingerprint of radix glehniae
Fig. 4: the NMR fingerprint of different manufacturers Liuwei Dihuang Wan
Among the figure:
1-covers the proton nmr spectra of flower (big hair flower)
The proton nmr spectra of 2-first-filial generation
The standard proton nmr spectra of 3-honeysuckle
4-covers the carbon-13 nmr spectra of flower (big hair flower)
The carbon-13 nmr spectra of 5-first-filial generation
The standard carbon-13 nmr spectra of 6-honeysuckle
The standard proton nmr spectra of 7-honeysuckle
8-becomes damp and rotten and covers the proton nmr spectra of flower (big hair flower)
The standard carbon-13 nmr spectra of 9-honeysuckle
10-becomes damp and rotten and covers the carbon-13 nmr spectra of flower (big hair flower)
Embodiment:
The NMR fingerprint of 1. pairs of different cultivars honeysuckles of embodiment
Sample is pulverized, crossed 40 mesh sieves, take by weighing sample 5 grams, add 50ml ethanol, refluxed 30 minutes in water-bath, the leaching extract will obtain extract after the solvent evaporates.The Test extraction thing
1HNMR (seeing Fig. 1-1,2) spectrum and
13CNMR composes (seeing Fig. 2-4,5), and with itself and honeysuckle control medicinal material
1HNMR (seeing Fig. 1-3) spectrum and
13CNMR (seeing Fig. 2-6) composes relatively, judges its true and false according to similarity degree.
The NMR fingerprint of 2. pairs of different quality honeysuckles of embodiment
Used honeysuckle inferior is the honeysuckle of becoming damp and rotten in the preservation process, and sample is pulverized, and crosses 40 mesh sieves, takes by weighing sample 5 grams, adds 50ml ethanol, refluxes 30 minutes in water-bath, and the leaching extract will obtain extract after the solvent evaporates.The Test extraction thing
1HNMR spectrum (seeing Fig. 3-7) and
13CNMR composes (seeing Fig. 4-9), and with itself and honeysuckle control medicinal material
1HNMR spectrum (seeing Fig. 3-8) and
13CNMR spectrum (seeing Fig. 4-10) is relatively judged its quality according to similarity degree.
The NMR fingerprint of embodiment 3. radix glehniaes
Sample is pulverized, crossed 40 mesh sieves, take by weighing sample 5 grams, add 50ml methyl alcohol, refluxed 30 minutes in water-bath, the leaching extract will obtain extract after the solvent evaporates.The Test extraction thing
1HNMR spectrum and
13CNMR spectrum, and with itself and radix glehniae control medicinal material
1HNMR spectrum and
13CNMR composes relatively, judges its true and false according to similarity degree.
The NMR fingerprint of embodiment 4. different manufacturers Liuwei Dihuang Wans
With the sample chopping, cross 40 mesh sieves, take by weighing sample 5 grams, add 50ml methyl alcohol, in water-bath, refluxed 30 minutes, the leaching extract will obtain extract after the solvent evaporates.The Test extraction thing
1HNMR spectrum and
13CNMR spectrum, and with itself and radix glehniae control medicinal material
1HNMR spectrum and
13CNMR composes relatively, judges its true and false according to similarity degree.
5. couples of embodiment only contain the NMR fingerprint of the fluid sample danshen injections of the hydrotrope
Get parenteral solution 10ml, the water evaporate to dryness is obtained extract.The Test extraction thing
1HNMR spectrum and
13CNMR spectrum, and with itself and danshen injections reference substance
1HNMR spectrum and
13CNMR composes relatively, judges its true and false according to similarity degree.
The NMR fingerprint of embodiment 6. ginkgo leaves
Sample is pulverized, crossed 40 mesh sieves, take by weighing sample 5 grams, add 50ml acetone, refluxed 30 minutes in water-bath, the leaching extract obtains extract with solvent evaporates.The Test extraction thing
1HNMR spectrum and
13CNMR spectrum, and with itself and ginkgo control medicinal material
1HNMR spectrum and
13CNMR composes relatively, judges its true and false according to similarity degree.
Advantage of the present invention is based on the characteristics of magnetic resonance detection method, and nuclear magnetic resonance map has unicity, and promptly the spectrum peak of hydrogen spectrum and carbon spectrum and each hydrogen and carbon all have strict corresponding relationship; Comprehensive, promptly the arbitrary proton in institute's test sample product all has its relevant spectrum peak with carbon atom; Quantitative property, the i.e. relative content of each component in the strong and weak relatively reflection potpourri of the signal of spectrogram; The easy property distinguished, i.e. structural research by compound can belong to each signal in the finger-print.Therefore under the separating extraction program of standard, have strict corresponding relationship between the nuclear magnetic resonance map of Chinese medicament extract and botanical herbs kind, can provide reflect molecular structure the one-dimensional characteristic signal (for example
1HNMR and
13CNMR) and two dimensional character signal (gHMQC for example, gHMBC etc.), the advantage that magnetic resonance detection can provide the multidimensional of reflection molecular characterization to cease characteristic signal more, make the NMR fingerprint authentication technique can provide the number of characteristics signal from many aspects, multi-angle is described the structures of samples feature, thus make Chinese medicine NMR fingerprint authentication technique really reached repeated height, characteristic strong, contain much information, usable range is wide, identification result advantage accurately.
The present invention is by measuring the nuclear magnetic resonance map of inspection product, compare with the nuclear magnetic resonance map of its collection of illustrative plates and its reference substance or with the standard nuclear magnetic resonance spectrum storehouse of Chinese crude drug of having set up and Chinese patent drug, simultaneously also can utilize computer checking wave spectrum storehouse to carry out auxiliary judgment, determine the true and false quality of inspection product.
Use the present invention can make natural plants or based on the Chinese crude drug of natural plant raw material, Chinese patent drug with and various extract and adjuvant obtain the NMR fingerprint of its feature.This collection of illustrative plates can be used for the cultivar identification of Chinese medicine sample and real and fake discrimination and to the study on the stability of product quality.Different medicinal material nmr spectrums are stacks of its all the components magnetic resonance spectrogram, are the reflections of Chinese crude drug overall chemical feature.The profile of every kind of medicinal material nmr spectrum is relatively-stationary, therefore can be regarded as a stable spectrogram, in this sense, the NMR fingerprint authentication technique just becomes macroscopical form discrimination method of the special graph of similar medicinal material profile discriminating, but it is independent of outside the traditional morphology and histologic characteristics, its accuracy then can reduce the mistake that people's subjective judgement causes effectively, thereby makes the difference of its figure spectrum signature have more intuitive than its morphological feature difference.The characteristic peak of diverse location has then reflected the existence and the architectural feature of the feature chemical constitution that Chinese medicine contains on the while nuclear magnetic resonance map, from the chemical feature of microcosmic reflection Chinese medicine.
Method of the present invention can be carried out omnidistance quality control to Chinese medicine production, storage, processing and final products, thereby guarantees the quality of product, improves the prestige of product.
Claims (4)
1, a kind of Chinese herbal medicine NMR fingerprint discrimination method is characterized in that: gets 5-20 gram sample, adds the low-molecular-weight polar solvent of 50-200 milliliter, and in water-bath reflux 30-120 minute, the leaching extract, with solvent evaporates, residue is weighed.Get 1-15 milligram residue and carry out nuclear magnetic resonance spectroscopy, compare with the nuclear magnetic resonance map of corresponding reference substance.
2. Chinese herbal medicine NMR fingerprint discrimination method according to claim 1 is characterized in that described low-molecular-weight polar solvent is a methyl alcohol.
3. Chinese herbal medicine NMR fingerprint discrimination method according to claim 1 is characterized in that described low-molecular-weight polar solvent is an ethanol.
4. Chinese herbal medicine NMR fingerprint discrimination method according to claim 1 is characterized in that described low-molecular-weight polar solvent is a water.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102147378A (en) * | 2011-02-28 | 2011-08-10 | 周至譓 | Method for analyzing traditional Chinese medicine dimethyl sulfoxide extracting solution by nuclear magnetic resonance technology |
| CN102749348A (en) * | 2012-06-18 | 2012-10-24 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying active components in medicinal plant |
| CN103048347A (en) * | 2012-08-15 | 2013-04-17 | 河南省科高植物天然产物开发工程技术有限公司 | Method for distinguishing root-bark medicinal materials of celastrus angulatus |
| CN103134827A (en) * | 2013-01-29 | 2013-06-05 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying angled bittersweet seed medicinal materials |
| CN103149232A (en) * | 2013-01-30 | 2013-06-12 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying pyrethrum derivatives |
| CN103674996A (en) * | 2012-10-24 | 2014-03-26 | 河南省科高植物天然产物开发工程技术有限公司 | Method for distinguishing salvia miltiorrhiza medicinal material or derivative |
| CN103698353A (en) * | 2013-12-30 | 2014-04-02 | 厦门出入境检验检疫局检验检疫技术中心 | Bird's nest identification method |
| CN104122287A (en) * | 2014-08-01 | 2014-10-29 | 山西大学 | Method for distinguishing wild radix astragali from cultured radix astragali |
| CN104181186A (en) * | 2014-09-03 | 2014-12-03 | 山西大学 | Construction method of <1>H-NMR fingerprint of radix astragali injection |
| CN104297277A (en) * | 2013-07-15 | 2015-01-21 | 天士力制药集团股份有限公司 | 1H-NMR fingerprint spectrum of compound red sage root dropping pill |
| CN107003375A (en) * | 2014-11-27 | 2017-08-01 | 皇家飞利浦有限公司 | Magnetic resonance finger print data is collected and analysis system |
-
2005
- 2005-08-10 CN CN 200510044396 patent/CN1731163A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102147378A (en) * | 2011-02-28 | 2011-08-10 | 周至譓 | Method for analyzing traditional Chinese medicine dimethyl sulfoxide extracting solution by nuclear magnetic resonance technology |
| CN102749348A (en) * | 2012-06-18 | 2012-10-24 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying active components in medicinal plant |
| CN103048347A (en) * | 2012-08-15 | 2013-04-17 | 河南省科高植物天然产物开发工程技术有限公司 | Method for distinguishing root-bark medicinal materials of celastrus angulatus |
| CN103048347B (en) * | 2012-08-15 | 2014-06-11 | 河南省科高植物天然产物开发工程技术有限公司 | Method for distinguishing root-bark medicinal materials of celastrus angulatus |
| CN103674996A (en) * | 2012-10-24 | 2014-03-26 | 河南省科高植物天然产物开发工程技术有限公司 | Method for distinguishing salvia miltiorrhiza medicinal material or derivative |
| CN103674996B (en) * | 2012-10-24 | 2016-02-10 | 河南省科高植物天然产物开发工程技术有限公司 | A kind of method differentiating red rooted salvia or spin-off |
| CN103134827B (en) * | 2013-01-29 | 2015-07-01 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying angled bittersweet seed medicinal materials |
| CN103134827A (en) * | 2013-01-29 | 2013-06-05 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying angled bittersweet seed medicinal materials |
| CN103149232A (en) * | 2013-01-30 | 2013-06-12 | 河南省科高植物天然产物开发工程技术有限公司 | Method for identifying pyrethrum derivatives |
| CN104297277A (en) * | 2013-07-15 | 2015-01-21 | 天士力制药集团股份有限公司 | 1H-NMR fingerprint spectrum of compound red sage root dropping pill |
| CN104297277B (en) * | 2013-07-15 | 2018-07-06 | 天士力医药集团股份有限公司 | Compound danshen dripping pills 1H-NMR finger-prints |
| CN103698353A (en) * | 2013-12-30 | 2014-04-02 | 厦门出入境检验检疫局检验检疫技术中心 | Bird's nest identification method |
| CN103698353B (en) * | 2013-12-30 | 2016-08-17 | 厦门出入境检验检疫局检验检疫技术中心 | A kind of Nidus collocaliae authentication method |
| CN104122287A (en) * | 2014-08-01 | 2014-10-29 | 山西大学 | Method for distinguishing wild radix astragali from cultured radix astragali |
| CN104181186A (en) * | 2014-09-03 | 2014-12-03 | 山西大学 | Construction method of <1>H-NMR fingerprint of radix astragali injection |
| CN104181186B (en) * | 2014-09-03 | 2016-08-24 | 山西大学 | A kind of Radix Astragali injection1the construction method of H-NMR finger printing |
| CN107003375A (en) * | 2014-11-27 | 2017-08-01 | 皇家飞利浦有限公司 | Magnetic resonance finger print data is collected and analysis system |
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