CN102323370A - Identification method for rapidly judging sulphur fumigation of ginseng - Google Patents
Identification method for rapidly judging sulphur fumigation of ginseng Download PDFInfo
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- CN102323370A CN102323370A CN201110131403A CN201110131403A CN102323370A CN 102323370 A CN102323370 A CN 102323370A CN 201110131403 A CN201110131403 A CN 201110131403A CN 201110131403 A CN201110131403 A CN 201110131403A CN 102323370 A CN102323370 A CN 102323370A
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Abstract
The invention belongs to the field of authenticity and amerits identification of Chinese herbal medicines and decoction pieces, in particular relates to an identification method for judging quality of Chinese herbal medicines and decoction pieces through characteristic chemical ingredients. Irregularities for sulphur fumigation of ginseng often happen, therefore, a rapid identification method is in need. The method comprises the following steps of: based on the two new characteristic ingredients with the molecular weights of 898 and 1044, generated after the ginseng is subjected to sulphur fumigation, carrying out ultrasonic extraction on a ginseng sample by adopting 50% methanol; determining by adopting a reversed phase liquid chromatography and mass spectrometry analysis technology; and judging whether the ginseng is subjected to sulphur fumigation through observing whether two chromatographic peaks with deprotonated quasi-molecular ion mass-to-charge ratios of 897 and 1043 exist in a ginseng sample chromatogram. According to the identification method, whether the ginseng is subjected to sulphur fumigation can be rapidly judged, and the safety and the efficiency for clinical medication can be ensured.
Description
[technical field]
The invention belongs to the good and bad evaluation of the Chinese crude drug and the medicine materical crude slice true and false field, especially use characteristic chemical constitution and judge Chinese crude drug and the good and bad discrimination method of prepared slice quality.
[background technology]
Sulfur fumigation is as the maintenance process of a kind of traditional Chinese medicines material, have brighten, insect protected, anticorrosion and anti-effect such as go mouldy, in the processing and storage process of Chinese crude drug and medicine materical crude slice, use general.Yet discovering in recent years, Chinese crude drug and medicine materical crude slice be meeting residual toxicity sulphuric dioxide behind sulfur fumigation, and the change of intrinsic bioactive ingredients meeting generating capacity or matter, causes medicinal material and prepared slice quality to change, and pharmacological effect descends, even toxicity increases.State Food and Drug Administration has been regarded as substandard drug with the medicinal material behind the sulfur fumigation in 2004." Chinese pharmacopoeia (an one) has been cancelled the stove drying technology of Chinese crude drugs such as Chinese yam, the root of kudzu vine to version in 2005." increased the detection method of sulfur dioxide residual quantity in the Chinese pharmacopoeia appendix at 2010 editions.This shows that country no longer allows to use the method for sulfur fumigation for the processing and storage of Chinese crude drug and medicine materical crude slice.
Genseng is a kind of clinical valuable Chinese crude drug commonly used, and the illegal retailer of part is for reducing production costs, reach brighten, insect protected, anticorrosion and anti-purpose of going mouldy, when ginseng crude drug's preliminary working, still can adopt the method for sulfur fumigation.Therefore, the detection method of setting up genseng and whether be the sulfur fumigation article is not still guaranteed the needs of genseng curative effect and clinical drug safety, is the important technical of hitting illegal retailer yet.
At present people judge whether genseng mainly leans on through the method for sulfur fumigation and observe appearance color, the trial test smell, and subjectivity is strong, the deficiency in objective foundation.2010 editions " adopt titration measuring in the Chinese pharmacopoeia appendix IXU sulfur dioxide residual quantity determination method, sensitivity is low, sample quantity of sampling quantity also big (10 gram).In addition, the ginseng crude drug is behind sulfur fumigation, and along with the prolongation of resting period, gas might detect less than the sulphuric dioxide composition after waving and loosing, and false negative result occurs.
[summary of the invention]
Technical matters to be solved by this invention is a utilization modern analysis detection technique, uses specific discrimination method, judges whether genseng passes through sulfur fumigation.
Ultimate principle of the present invention:
We compare the samples of Ginseng before and after sulfur fumigation and discover; Genseng is behind sulfur fumigation; Can produce two new chemical constitutions, these two new components show on reversed-phase liquid chromatography than the shorter retention time of former genseng saponin component, see Fig. 1-1, Fig. 1-2.
Mass spectrometric data shows that the deprotonation quasi-molecular ion mass-to-charge ratio of these two new components is respectively 897 and 1043, sees Fig. 2-1, Fig. 2-2.
The present invention promptly is through measuring this two characteristic chemical constitutions, judging whether genseng passes through sulfur fumigation.
Technical scheme of the present invention:
Adopt 50% methyl alcohol Extraction by Ultrasound samples of Ginseng; Extract is used the teflon filtering with microporous membrane; Filtrating adopts reversed-phase liquid chromatography-mass spectrometry analytical technology to measure; Record chromatogram and mass spectrogram is characterized by: whether to have deprotonation quasi-molecular ion mass-to-charge ratio among the genseng sample chromatogram figure be that two chromatographic peaks of 897 and 1043 judge whether genseng adopts sulfur fumigation through observing.As have the chromatographic peak of these two kinds of deprotonation quasi-molecular ions, this samples of Ginseng sulfur fumigation is described; As do not occur, can judge that then this genseng is without sulfur fumigation.
Whether the present invention and the existing ginseng crude drug of judgement compare through the detection method of sulfur fumigation, have sampling amount little (0.1 gram), specificity is strong, sample preparation is simple and the result precision advantages of higher, is a kind of sensitivity and exclusive discrimination method.
Description of drawings
Fig. 1-1 is without sulfur fumigation samples of Ginseng HPLC-ESI (-)-MS chromatogram
Fig. 1-2 sulfur fumigation samples of Ginseng HPLC-ESI (-)-MS chromatogram, wherein 1,2 is two new characteristic component chromatographic peaks that produce
New characteristic component 1 mass spectrogram that produces of Fig. 2-1
New characteristic component 2 mass spectrograms that produce of Fig. 2-2
Among Fig. 3-1 embodiment 1 without sulfur fumigation samples of Ginseng HPLC-ESI (-)-MS chromatogram
Sulfur fumigation samples of Ginseng HPLC-ESI (-) among Fig. 3-2 embodiment 1-MS chromatogram, wherein 1,2 is two new characteristic component chromatographic peaks that produce
Among Fig. 4-1 embodiment 2 without sulfur fumigation samples of Ginseng HPLC-ESI (-)-MS chromatogram
Sulfur fumigation samples of Ginseng HPLC-ESI (-) among Fig. 4-2 embodiment 2-MS chromatogram, wherein 1,2 is two new characteristic component chromatographic peaks that produce
Among Fig. 5-1 embodiment 3 without sulfur fumigation samples of Ginseng HPLC-ESI (-)-MS chromatogram
Sulfur fumigation samples of Ginseng HPLC-ESI (-) among Fig. 5-2 embodiment 3-MS chromatogram, wherein 1,2 is two new characteristic component chromatographic peaks that produce
[embodiment]
Embodiment one
1. chromatographic system:
Waters ACQUITY UPLC-PDA system.Chromatographic column: Waters ACQUITY HSS T3 (2.1 * 100mm, 1.8 μ m).Moving phase consists of 0.1% formic acid water and 0.1% formic acid acetonitrile.Gradient elution: see table 1.Elution flow rate is 0.6ml/min.Column oven and sample chamber temperature are respectively 35 ℃ and 10 ℃.The sample feeding amount is 2 μ l.
Table 1 gradient elution table
2. mass spectrum condition
Waters Q-TOF Premier mass spectrometer; ESI
-Ion gun; The spraying gas velocity is made as 700I/h, 300 ℃ of temperature.The taper hole air-flow is made as 10I/h; Capillary voltage and taper hole voltage are made as 3500V and 45V respectively.The Q-TOF sweep velocity is 0.2s, and the scan delay interval time is 0.02s; Collision gas (argon gas) pressure is 7.066 * 10
-3Pa.Collision (CID) energy is made as 5 respectively, 45eV.
3. samples of Ginseng is measured formulations prepared from solutions and detection
Samples of Ginseng 0.1g adds 50% methyl alcohol 5ml, and room temperature ultrasonic Extraction 60min, extract are through 0.2 μ m teflon membrane filtration, and sample introduction writes down chromatogram.
4. chromatogram
See Fig. 3-1, Fig. 3-2, be two chromatographic peaks of 897 and 1043 without there not being deprotonation quasi-molecular ion mass-to-charge ratio in the sulfur fumigation samples of Ginseng chromatographic peak, and in sulfur fumigation samples of Ginseng chromatographic peak, have these two chromatographic peaks.
Embodiment two
1. chromatographic system
Waters ACQUITY UPLC-PDA system.Chromatographic column: Waters ACQUITY BEHC18 (2.1 * 100mm, 1.7 μ m).Moving phase consists of 0.2% formic acid water and 0.2% formic acid acetonitrile.Gradient elution: see table 2.Elution flow rate is 0.6ml/min.Column oven and sample chamber temperature are respectively 35 ℃ and 10 ℃.The sample feeding amount is 2 μ l.
Table 2 gradient elution table
2. mass spectrum condition
Waters Q-TOF Premier mass spectrometer; ESI
-Ion gun; The spraying gas velocity is made as 700I/h, 300 ℃ of temperature.The taper hole air-flow is made as 10I/h; Capillary voltage and taper hole voltage are made as 3500V and 45V respectively.The Q-TOF sweep velocity is 0.2s, and the scan delay interval time is 0.02s; Collision gas (argon gas) pressure is 7.066 * 10
-3Pa.Collision (CID) energy is made as 5 respectively, 45eV.
3. samples of Ginseng is measured formulations prepared from solutions and detection
Samples of Ginseng 0.1g adds 50% methyl alcohol 5ml, and room temperature ultrasonic Extraction 60min, extract are through 0.2 μ m teflon membrane filtration, and sample introduction writes down chromatogram.
4. spectrogram
See Fig. 4-1, Fig. 4-2, be two chromatographic peaks of 897 and 1043 without there not being deprotonation quasi-molecular ion mass-to-charge ratio in the sulfur fumigation samples of Ginseng chromatographic peak, and in sulfur fumigation samples of Ginseng chromatographic peak, have these two chromatographic peaks.
Embodiment three
1. chromatographic system
Waters ACQUITY UPLC-PDA system.Chromatographic column: Waters ACQUITY BEHC8 (2.1 * 100mm, 1.7 μ m).Moving phase consists of water and methyl alcohol.Gradient elution: see table 3.Elution flow rate is 0.6ml/min.Column oven and sample chamber temperature are respectively 35 ℃ and 10 ℃.The sample feeding amount is 2 μ l.
Table 3 gradient elution table
2. mass spectrum condition
Waters Q-TOF Premier mass spectrometer; ESI
-Ion gun; The spraying gas velocity is made as 700I/h, 300 ℃ of temperature.The taper hole air-flow is made as 10I/h; Capillary voltage and taper hole voltage are made as 3500V and 45V respectively.The Q-TOF sweep velocity is 0.2s, and the scan delay interval time is 0.02s; Collision gas (argon gas) pressure is 7.066 * 10
-3Pa.Collision (CID) energy is made as 5 respectively, 45eV.
3. samples of Ginseng is measured formulations prepared from solutions and detection
Samples of Ginseng 0.1g adds 50% methyl alcohol 5ml, and room temperature ultrasonic Extraction 60min, extract are through 0.2 μ m teflon membrane filtration, and sample introduction writes down chromatogram.
4. spectrogram
See Fig. 5-1, Fig. 5-2, be two chromatographic peaks of 897 and 1043 without there not being deprotonation quasi-molecular ion mass-to-charge ratio in the sulfur fumigation samples of Ginseng chromatographic peak, and in sulfur fumigation samples of Ginseng chromatographic peak, have these two chromatographic peaks.
Claims (6)
1. judge whether genseng passes through the authentication method of sulfur fumigation fast for one kind; Adopt 50% methyl alcohol Extraction by Ultrasound samples of Ginseng; Extract is used the teflon filtering with microporous membrane; Filtrating adopts reversed-phase liquid chromatography-mass spectrometry analytical technology to measure, and record chromatogram and mass spectrogram is characterized by: whether to have deprotonation quasi-molecular ion mass-to-charge ratio among the genseng sample chromatogram figure be that two chromatographic peaks of 897 and 1043 judge whether genseng adopts sulfur fumigation through observing.
2. as claimed in claim 1ly a kind ofly judge whether genseng adopts the authentication method of sulfur fumigation fast, the chromatographic column filler that it is characterized by the reversed-phase liquid chromatography method is carbon 18 or carbon eight bonded silica gels.
3. as claimed in claim 1ly a kind ofly judge whether genseng adopts the authentication method of sulfur fumigation fast, it is characterized by reversed-phase liquid chromatography moving phase is water and acetonitrile organic phase, or water and methyl alcohol organic phase.
4. as claimed in claim 3ly a kind ofly judge whether genseng adopts the authentication method of sulfur fumigation fast, it is characterized by the formic acid or the acetate that contain 0-1% in the reversed-phase liquid chromatography moving phase.
5. as claimed in claim 3ly a kind ofly judge whether genseng adopts the authentication method of sulfur fumigation fast, it is characterized by reversed-phase liquid chromatography moving phase water and organic phase and carry out gradient elution that method is that the variation range of water is 95%-5%.
6. as claimed in claim 1ly a kind ofly judge whether genseng adopts the authentication method of sulfur fumigation fast, it is characterized by mass spectrum ionization mode is electron spray, and scan pattern is negative ion scanning.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104880521A (en) * | 2015-02-02 | 2015-09-02 | 江苏省中医药研究院 | Identification method for judging whether Chinese angelica undergoes sulfur fumigation |
| CN107607652A (en) * | 2017-10-18 | 2018-01-19 | 北京理工大学 | A kind of method for determining flower of JINHUAKUI sulfur content |
| CN115651050A (en) * | 2022-10-17 | 2023-01-31 | 江苏省中医药研究院(江苏省中西医结合医院) | Chemical synthesis method of ginsenoside sulfur-containing derivative |
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| US20050276872A1 (en) * | 2001-08-31 | 2005-12-15 | Chan Pui-Kwong | Composition comprising Xanthoceras sorbifolia extracts, compounds isolated from same, methods for preparing same and uses thereof |
| CN101596275A (en) * | 2009-06-30 | 2009-12-09 | 贵州信邦制药股份有限公司 | The method of quality control of Radix Ginseng in the YIXINSHU Chinese medicine preparation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104880521A (en) * | 2015-02-02 | 2015-09-02 | 江苏省中医药研究院 | Identification method for judging whether Chinese angelica undergoes sulfur fumigation |
| CN107607652A (en) * | 2017-10-18 | 2018-01-19 | 北京理工大学 | A kind of method for determining flower of JINHUAKUI sulfur content |
| CN115651050A (en) * | 2022-10-17 | 2023-01-31 | 江苏省中医药研究院(江苏省中西医结合医院) | Chemical synthesis method of ginsenoside sulfur-containing derivative |
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Address after: 210028 No. 100 cross street, Nanjing, Jiangsu, Maigaoqiao Applicant after: Jiangsu Provincial Insititute of Traditional Chinese Medicine Address before: 210028, cross street, Hongshan Road, Jiangsu, Nanjing, 100 Applicant before: Jiangsu Provincial Insititute of Traditional Chinese Medicine |
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Application publication date: 20120118 |