CN112782300B - Cholanic acid isomer and detection method and application thereof - Google Patents
Cholanic acid isomer and detection method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses an isomer of cholanic acid, a detection method and application thereof, wherein a new cholanic acid isomer 3 beta type cholanic acid is found in a swine bile substance used as a raw material of a Naoliqing preparation, the by-product widely exists in swine bile powder and swine bile paste medicinal materials and can be transferred into the Naoliqing preparation along with a production feeding process, and the quality risk caused by component change can be avoided by using the substance as an index for detecting the quality of the swine bile raw material.
Description
Technical Field
The invention relates to an isomer of cholanic acid and a detection method and application thereof, belonging to the field of analytical chemistry.
Background
The spatial configuration of the functional group has a decisive effect on the action mechanism and clinical curative effect of the compound, and the teratogenic effect of the international and historical famous phytotoxicity event, namely 'reaction stoppage', is the most typical case. Thalidomide, the "Ready" form, exhibits distinct pharmacological and toxicological effects in its two spatial configurations, with R-form corresponding to a good sedative effect and S-form having a strong teratogenic effect. Thus, in the early 19 th century, the study of spatial configuration was not yet thorough, and the combination of two isomers of thalidomide led to the birth of a large number of "seal" molecules. Another typical drug, glycyrrhizic acid, is widely used clinically as the first-line drug for treating chronic liver injury at present. The alpha and beta configurations of the 18-site hydrogen in the structure of the compound also dominate the difference expression of the two isomers in the aspects of pharmacological activity, bioavailability and adverse reaction incidence.
The Naoliqing pill (capsule or tablet) is prepared from ten Chinese medicinal materials of magnetite, pinellia tuber, menthol, pig bile (pig bile powder and pig bile paste) and the like, wherein the pig bile is an adjuvant drug in the prescription for clearing heat, cooling liver, calming endogenous wind and relieving spasm. Because fresh pig bile is inconvenient to store and transport, Chinese patent medicine production enterprises mostly replace pig bile with pig bile powder or pig bile paste to produce and feed materials. The pig bile powder is dried product of pig bile, and the pig is slaughtered, and the gallbladder is collected, hung and dried, or the pig bile is filtered, directly dried and pulverized to obtain yellow and gray yellow powder, which has light fishy smell, bitter taste and easy moisture absorption. The pig bile paste is a dried product of pig bile, and is in a paste block shape without being crushed.
The detection of the pig bile substances in the existing quality standard of the Naoliqing preparation is usually to identify the truth of the pig bile medicinal materials by using thin-layer identification to control the problem that the pig bile is replaced by the ox and sheep bile, but the quality risk caused by the change of components in the raw materials such as the pig bile, the pig bile powder, the pig bile paste and the like in the Naoliqing preparation cannot be detected, and the impurity condition in the raw materials cannot be correspondingly detected and evaluated.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a cholanic acid isomer, a detection method and application thereof, and the cholanic acid isomer is a new cholanic acid isomer 3 beta type found in swine bile substances used as raw materials of a brain-invigorating preparation, the by-product widely exists in swine bile powder and swine bile paste medicinal materials and can be transferred into the brain-invigorating preparation along with the production and feeding process, and the quality risk caused by component change can be avoided by using the cholanic acid isomer as an index for detecting the quality of the swine bile raw materials.
An isomer of cholanic acid, which is represented by the following:
further, the method for detecting an isomer of cholanic acid comprises the following steps:
1) weighing 0.1-1g of a pig gall product, adding 40-50mL of 70% methanol solution, performing ultrasonic treatment, shaking up, and filtering to obtain a solution to be detected;
2) weighing 0.1-1g of fresh pig bile, adding 40-50mL of 70% methanol solution, performing ultrasonic treatment, shaking up, and filtering to obtain a solution to be detected;
3) respectively taking 1 mu L of the solution to be detected obtained in the step 1) and 1 mu L of the solution to be detected obtained in the step 2), injecting the solution to be detected into a liquid chromatograph, setting appropriate chromatographic conditions for analysis, and obtaining a chromatogram for comparing the two solutions to be detected;
4) comparing the chromatograms of the two solutions to be detected obtained in the step 3), wherein the difference peak is the isomer of cholanic acid.
Further, the pig gall product in the step 1) is one of commercially available pig gall powder and commercially available pig gall paste.
Further, the fresh pig bile in the step 2) is fresh bile of Sus scrofadosteica Brisson of a pig of the family Sus domestica.
Further, the chromatographic conditions in the step 3) above are: the chromatographic column was a Thermo Hypersil Gold chromatographic column (4.6 mm. times.250 mm, 5 μm), the column temperature was 30 ℃, methanol was used as the mobile phase-0.1% phosphoric acid solution (35: 65) was used as the mobile phase, the flow rate was 1.0mL/min, a diode array detector was used, and the detection wavelength was 200 nm.
The application of the isomers of the cholanic acid or the detection method of the isomers of the cholanic acid in detecting/evaluating the quality of the pig bile, the pig bile powder and the pig bile paste in the brain clearing preparation.
Has the advantages that:
(1) an isomer 3 beta type cholanic acid of cholanic acid is obtained through analysis, although the pharmacological and toxicological effects of the component are not reported in relevant documents, the isomer by-product 3 beta type cholanic acid is widely detected in a brain-based clearance preparation, potential risks are brought to the safety and effectiveness of the preparation, and attention should be paid to the isomer.
(2) The invention verifies the generation source of 3 beta-cholanic acid, which is the result of configuration conversion with temperature as the main driving force, and suggests that a reasonable drying mode for thinning the pig gall powder is required in the current standard and processing specification of the pig gall powder and the pig gall ointment, so as to ensure that the pig gall powder and the fresh bile are consistent in main components, and avoid the quality risk caused by component change.
Drawings
FIG. 1: and (4) comparing HPLC chromatograms of the pig gall powder and the pig gall.
FIG. 2: glycine-3 β -hydroxy-6-oxo-cholanic acid.
FIG. 3: the drying temperature was 150 ℃ and the two configurations were plotted against time.
FIG. 4: the drying time was 8 hours and the two configurations were plotted as a function of temperature.
FIG. 5: enterprise a nominally bases the chromatogram of the Naoliqing capsule dosed with swine bile.
FIG. 6: enterprise B nominally bases the chromatogram of the Naoliqing capsule dosed with swine bile.
FIG. 7: nuclear magnetic resonance hydrogen spectrum.
FIG. 8: nuclear magnetic resonance carbon spectrum.
FIG. 9: nuclear magnetic resonance HMBC spectra.
FIG. 10: HMQC spectra of nuclear magnetic resonance.
FIG. 11: nuclear magnetic resonance H-H COSY spectrogram
FIG. 12: NOE spectrum of nuclear magnetic resonance.
Detailed Description
In order to make the technical solutions in the present application better understood, the present invention is further described below with reference to examples, which are only a part of examples of the present application, but not all examples, and the present invention is not limited by the following examples.
Example 1 detection of isomers of cholanic acid
Analysis of composition of pig bile, pig bile powder and pig bile paste
1. Instrument, reagent and sample information
The instrument comprises the following steps: shimadzu LC-20A high performance liquid chromatograph, diode array detector;
sartorius CP225D electronic balance
Reagent: the methanol and the phosphoric acid are chromatographically pure, and the other reagents are analytically pure.
Sample preparation: 13 batches of pig bile powder, 2 batches of pig bile and 1 batch of pig bile paste are collected together by means of market collection, enterprise supply, self-control in a laboratory and the like.
Comparison products: taurolimus hyocholic acid sodium salt (screening standard organism, batch number: ZS-20025), taurolimus hyodeoxycholic acid (China food and drug testing institute, batch number: 111943-201802), and taurolimus chenodeoxycholic acid (China food and drug testing institute, batch number: 110846-201007). Glycine hyodeoxycholic acid (screening quasi-organism, batch number: ZZS-19-007-A2), glycocholic acid sodium salt (screening quasi-organism, batch number: ZS-20022), glycochenodeoxycholic acid sodium salt (screening quasi-organism, batch number: ZZS 19090407).
A chromatographic column: thermo Hypersil Gold chromatography column (4.6 mm. times.250 mm, 5 μm); column temperature: 30 ℃; methanol is taken as a mobile phase-0.1 percent phosphoric acid solution (35: 65) is taken as a mobile phase, and the flow rate is 1.0 ml/min; a diode array detector is adopted; the detection wavelength was 200 nm.
2. Preparation of solutions
Test solution: precisely weighing fel Sus Domestica powder or fel Sus Domestica paste powder 0.1g, or fel Sus Domestica 1g, precisely adding 70% methanol 50ml, ultrasonic treating for 10 min, shaking, and filtering.
Control solution: accurately weighing the above reference substances, and adding 70% methanol solution to obtain 1mg/ml reference substance solution.
3. Chromatogram analysis
The control and test solutions were measured to 1. mu.l each and injected into a liquid chromatograph for analysis. The chromatogram of fel Sus Domestica and fel Sus Domestica powder is shown in figure 1.
The chromatogram of the pig bile and the low-temperature home-made pig bile powder shows 7 main chromatographic peaks, and the commercially available pig bile powder and the commercially available pig bile paste respectively show 8 chromatographic peaks, including 7 common peaks of the pig bile powder and a No. 8 differential peak of the pig bile powder. The total 6 main chromatographic peaks are identified as shown in figure 1 by comparison with the chromatogram of the control single-standard solution; the common peak 5 is deduced to be the glycine-3 alpha-hydroxy-6-oxo-cholanic acid by consulting the pig bile related literature and combining the analysis of an IT-TOF mass spectrometer, and no relevant information is reported in the literature for the peak No. 8 of the difference peak.
In order to find out the different components in the commercially available pig bile powder and pig bile paste, the analysis is carried out by IT-TOF mass spectrometry. Mass spectrum conditions: ESI ion source; scanning negative ions; scanning range: m/z is 100-1000; ion source voltage: negative ion mode-3.5 kv; heating module temperature: 200 ℃; CDL temperature: 200 ℃; flow rate of atomizing gas: 1.5ml/min, detector voltage 1.57 kv. Chromatographic conditions are as follows: thermo Hypersil Gold chromatography column (4.6 mm. times.250 mm, 5 μm); column temperature: 30 ℃; methanol was used as the mobile phase-0.1% formic acid solution (35: 65) was used as the mobile phase, and the flow rate was 1.0 ml/min.
The peak of difference peak No. 8 and the peak of common peak No. 5 have the same excimer ion peak M/z 446.2827[ M-H ]]-, deducing the formula C26H41NO5(calc.447.62). And 5 peak glycine-3 alpha-hydroxy-6-oxo-cholanic acid are isomer structures. The structure search was performed by Scifinder and all isomers of the structure were void of nuclear magnetic data reports.
4. Determination of No. 8 peak Structure of Difference component
And extracting and separating the components corresponding to the No. 8 peak by adopting a gel column chromatography and a semi-preparative liquid chromatography mode. This fraction was obtained in 98% purity as a solid, designated ZDF-1. About 8mg of ZDF-1 was weighed, vacuum-dried for 20 hours, and then dissolved in 1ml of deuterated methanol, and then subjected to nuclear magnetic hydrogen spectrometry, carbon spectrometry, HSQC spectrometry, HMBC spectrometry, H-H cosy and NOE analysis.
The hydrogen spectrum (fig. 7) shows a structure containing 2 monomodal methyl groups (δ H0.72, 0.74), 1 bimodal methyl group (δ H0.99, d, J ═ 6.6Hz), 1 methylene group with oxygen or nitrogen linkage (δ H3.88) and 1 methine group with oxygen or nitrogen linkage (δ H4.05). The compound carbon spectrum (fig. 8) shows 26 carbon signals, including 1 ketocarbonyl carbon (δ C215.5) and 2 amide or ester carbonyl groups (δ C173.1,177.1), as well as the other 23 saturated carbon signals. In conjunction with the HSQC spectrum (fig. 10), it was determined that the compound structure consists of the following structural units: 3 methyl groups (2 singlet and 1 doublet), 11 methylene groups (1 vicinal oxygen or nitrogen), 7 methine groups (1 vicinal oxygen), 2 quaternary carbons and 3 carbonyl groups (1 ketocarbonyl and 2 amide or ester carbonyl groups). Based on the isolated source of the compound, and by consulting the analog literature, peak 8 compound was determined to be glycine-3 β -hydroxy-6-oxo-5 β -cholanic acid. Further analysis of the two-dimensional NMR spectrum 1H-1H COSY (FIG. 11), HSQC (FIG. 10) and HMBC (FIG. 9) confirmed the structure of the compound again, as shown in FIG. 2.
5. Differential component source analysis
The component is supposed to be 3 beta type cholanic acid converted from 3 alpha type cholanic acid naturally existing in the bile as a precursor substance in the preparation process of the pig bile powder, because no obvious No. 8 peak exists in fresh pig bile, but the component generally appears in commercial pig bile powder, and the No. 8 peak and the No. 5 peak are isomers with each other, and the difference is only that the configuration of a 3-position hydroxyl group is changed from alpha position to beta position.
The pig gall powder is collected in the 2015 edition of Chinese pharmacopoeia, and the preparation process is described as the steps of taking pig gall, filtering, drying and crushing. Wherein, the drying process is accompanied by the temperature rise, which is most easy to change the components of the raw materials. Therefore, it is presumed that the drying temperature is an important factor for the generation of new components in the production of the powder of the pig gall from the juice.
To confirm the presumption, the subject group concentrated and dried the collected pig bile under low temperature condition to prepare the pig bile powder, and the measurement and observation are carried out according to the experimental conditions, and only the base line fluctuation with the signal-to-noise ratio less than 3 appears at the position of No. 8 peak of the 3 beta cholanic acid. Weighing 6 parts of home-made pig gall powder, 2g of each part, flatly paving the home-made pig gall powder in a culture dish, respectively placing the home-made pig gall powder in an electric heating constant-temperature air blast drying oven at the temperature of 120-150 ℃ for drying treatment, sampling 1 time every 1 hour, and totally carrying out 8 hours. Performing liquid phase analysis on samples at different temperatures and different time points, and observing the peak area value change rule of the original 3 alpha-cholanic acid and the newly generated 3 beta-cholanic acid, which is shown in the figure 3-4
As can be seen, the production of 3 β cholanic acid was accompanied by a decrease in 3 α cholanic acid and was positively correlated with temperature and time, confirming the foregoing speculation.
Example 2 distribution of by-product 3 beta-cholanic acid in pig gall series products and Naoliqing preparation
The ratio of the peak area of the byproduct 3 beta-type cholanic acid to the sum of the peak areas of the cholanic acids with two configurations is taken as the conversion rateThe criterion is that the conversion rate is Aβ/(Aα+Aβ) X 100%. Three additional batches of high temperature home-made pig gall powder (boiled and concentrated for 24 hours, dried at 121 ℃ for 8 hours) were prepared, and the average conversion rate was found to be 10% as a limit.
The analysis of the pig gall series products shows that: firstly, fresh pig bile is collected in the market, and the conversion rate is lower than 1%; ② the conversion rate of all the commercially available pig bile powder and pig bile paste is higher than 10%, and the highest conversion rate can be up to 75%. Therefore, the by-product 3 beta cholanic acid is widely existed in the medicinal materials of the pig gall powder and the pig bile paste.
Through investigating and researching the process and feeding information of the enterprises, it is found that 13 enterprises of 15 enterprises collected at this time are fed with pig gall powder or pig gall paste, and 2 enterprises are fed with pig gall. Analysis is carried out on the 88 batches of samples collected this time, and the results show that: the conversion rate of byproducts of all batches of samples of 13 enterprises which are fed with the nominal pig gall powder or pig gall paste is higher than 10 percent and is consistent with the condition of raw materials; ② in 2 enterprises of nominal pig bile feeding, the Naoliqing capsule of the enterprise A has a byproduct conversion rate of less than 10 percent, which is consistent with the raw material condition; the conversion rate of the Naoliqing capsules produced by the enterprise B is higher than 10%, which is not consistent with the condition of raw materials, and is shown in figures 5-6.
In 87 batches of cephalocathartic samples in total, the conversion rate of the by-product 3 beta cholanic acid is higher than a set limit value, and accounts for 98.9 percent, so that the by-product generated by processing raw materials is widely transferred into a preparation along with the production and feeding process.
Claims (4)
1. A method for detecting an isomer of cholanic acid, comprising the steps of:
1) weighing 0.1-1g of a pig gall product, adding 40-50mL of 70% methanol solution, performing ultrasonic treatment, shaking up, and filtering to obtain a solution to be detected;
2) weighing 0.1-1g of fresh pig bile, adding 40-50mL of 70% methanol solution, performing ultrasonic treatment, shaking up, and filtering to obtain a solution to be detected;
3) respectively taking 1 mu L of the solution to be detected obtained in the step 1) and 1 mu L of the solution to be detected obtained in the step 2, injecting the solution to be detected into a liquid chromatograph, setting appropriate chromatographic conditions for analysis, and obtaining a chromatogram for comparing the two solutions to be detected; the chromatographic conditions are as follows: the chromatographic column is a Thermo Hypersil Gold chromatographic column, the column temperature is 30 ℃, methanol is used as a mobile phase-0.1% phosphoric acid solution is used as a mobile phase, the flow rate is 1.0mL/min, a diode array detector is adopted, and the detection wavelength is 200 nm; the parameters of the chromatographic column are 4.6mm multiplied by 250mm and 5 mu m; methanol and 0.1% phosphoric acid solution in the mobile phase in a volume ratio of 35: 65 mixing;
4) comparing chromatograms of the two solutions to be detected obtained in the step 3), wherein a difference peak is an isomer of cholanic acid;
the isomers of cholanic acid are characterized in that the structural formula of the isomers of cholanic acid is as follows:
2. the detection method according to claim 1, wherein the swine bile product of step 1) is one of commercially available swine bile powder and commercially available swine bile paste.
3. The test method according to claim 1, wherein the fresh pig bile in step 2) is fresh bile of Sus scrofadomastia Brisson, a porcine animal.
4. The use of the assay of claim 1 to detect/evaluate the quality of fel Sus domestica, fel Sus domestica powder, and fel Sus domestica paste in a Naoliqing preparation.
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