CN107144652A - The method of smilax and its product of the detection through sulfur fumigation - Google Patents
The method of smilax and its product of the detection through sulfur fumigation Download PDFInfo
- Publication number
- CN107144652A CN107144652A CN201710347862.5A CN201710347862A CN107144652A CN 107144652 A CN107144652 A CN 107144652A CN 201710347862 A CN201710347862 A CN 201710347862A CN 107144652 A CN107144652 A CN 107144652A
- Authority
- CN
- China
- Prior art keywords
- sample solution
- product
- smilax
- sulfur fumigation
- sulfur
- 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
Links
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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
-
- 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
-
- 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
-
- 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
- G01N30/8641—Baseline
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a kind of method of the detection through the smilax of sulfur fumigation or its product, comprise the following steps：Step 1: preparing the sample solution a through the smilax of sulfur fumigation or its product and sample solution b without the smilax of sulfur fumigation or its product；Step 2: mass spectrometric data collection is carried out to sample solution a and sample solution b respectively using method associated with ultra performance liquid chromatography quadrupole rod flight time mass spectrum, wherein the collision voltage selected is 35~50V；Step 3: using the method for multi-variate statistical analysis, contrast determines that sample solution a is the mass spectrometric data comprising significant sulfur product or its fragment compared to the poor inhomogeneous mass spectrometric data occurred in sample solution b.The present invention realizes the quick detection of sulfur fumigation smilax and its product first, while sample treatment is easy, analysis time is short, high specificity, testing result are accurate.
Description
Technical field
The present invention relates to field of traditional Chinese medicine detection.It is more particularly related to a kind of native Fu of the detection through sulfur fumigation
Siberian cocklebur and its method for product.
Background technology
Smilax is the dry rhizome of Liliaceae smilax plant smilacis glabra, is medicine-food two-purpose resource, Return liver, stomach,
With dehumidifying, removing toxic substances, it is easing joint movement the effects such as.Modern study shows that Tu Huo Cutters have extensive pharmacological activity, is mainly manifested in
It is clinical in terms of cardiovascu- lar effects, antitumor, anti-inflammatory, immunological regulation, anti-oxidant, antibacterial, anti-trioxypurine, protection renal function
On be mainly used in treating microorganism infection, urogenital system, connective tissue system, skin disease, the disease in terms of digestive system
Disease.Conventional smilax tonic among the people or as health products, especially in southern china, is also generally used for Baoshang as soup stock.In addition,
The important raw and processed materials of smilax or Guiling Jelly, Guiling Jelly is as a kind of traditional characteristicses functional food, by China, Japan, Korea Spro
The popular welcome of the country in Southeast Asia such as state, Singapore.
Research shows, the compositions such as flavonoids, talan, Phenylpropanoid Glycosides class is mainly contained in smilax, and show a variety of
Bioactivity, such as astilbin have diuresis, analgesia, an anti-inflammatory, immunosupress, antitumor isoreactivity, major flavans alcohol component,
Epicatechin has anti-oxidant, regulation blood lipid level, antitumor isoreactivity, and 5-O- coffee acyls shikimic acid and engelitin have anti-
Tumour, antioxidation.
With the increase of smilax consumption and storage capacity, plantation casual household among the people continues to use the phenomenon of traditional sulfur fumigation maintenance still
It is more universal.Appropriate sulfur fumigation can reach the purpose of Vermins-proof mildew-proof, but some medicinal herb growers and dealer are economical sharp in order to pursue
Benefit, with the prolonged and repeated stifling quality for having had a strong impact on medicinal material of industrial sulphur.During modern study is proved before and after sulfur fumigation
There is change more the character of medicinal material and medicine materical crude slice, and can make wherein to remain the heavy metal such as substantial amounts of sulfur dioxide and arsenic, mercury, to human body
With a variety of harm；, may be with containing carbonyl in Chinese medicine because sulfur dioxide is a kind of strong reductant, the composition of carboxyl occurs
Chemical reaction, causes the loss of active ingredient, it is thus possible to change the nature and flavor of medicine, curative effect of medication is reduced, so as to directly affect
The quality of the prepared slices of Chinese crude drugs.2012, Guangzhou was discovered and seized a collection of " pesticide-clay mixture Poria cocos ", and black-labour factory will smoke obtained " poison through poisonous sulphur
Smilax " largely comes into the market, and enters as soup stock in daily life.It is reported that the Chinese medicine that edible sulfur fumigation is crossed
Material, food etc. can cause damage to alimentary canal and respiratory system mucous membrane, cause to vomit, suffer from diarrhoea, the symptom such as nausea, seriously even
Liver, the kidney of people can be endangered.The content of beary metal such as lead, the mercury of some sulphur inferior are exceeded, long-term consumption can cause it is chronic in
Poison.
How correctly to recognize and handle sulfur fumigation problem, relation Chinese medicine Quality Safety, it would therefore be highly desirable to set up it is quick,
The method of effective detection sulfur fumigation smilax and its product.
Early-stage Study shows that sulfur fumigation can result in the content reduction of main active in smilax.2015 editions《In
State's pharmacopeia》The quality evaluation standard of the smilax recorded mainly includes several aspects such as character, discriminating, inspection, assay, its
Middle astilbin must not be less than 0.45%.The change on chemical constituents from Smilax glabra Roxb after sulfur fumigation is there is no in current existing report
The research of change, to the quick determination method of sulfur fumigation rhizoma smilacis glabrae medicinal material, there is not been reported.
The content of the invention
It is an object of the present invention to provide the mirror of a kind of sample treatment simplicity, analysis time shortening and high specificity
Determine the method for sulfur fumigation rhizoma smilacis glabrae medicinal material.
In order to realize that there is provided a kind of native Fu of the detection through sulfur fumigation according to object of the present invention and further advantage
The method of Siberian cocklebur or its product, comprises the following steps：
Step 1: preparing the sample solution a through the smilax of sulfur fumigation or its product and native Fu without sulfur fumigation
The sample solution b of Siberian cocklebur or its product；
Step 2: using method associated with ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry respectively to sample solution
A and sample solution b carries out mass spectrometric data collection, wherein the collision voltage selected is 35~50V；
Step 3: sample solution a and sample solution b raw mass spectrum data are pre-processed, contrast determines that sample is molten
Liquid a is significant sulfur product or the mass spectrum of its fragment compared to the poor inhomogeneous mass spectrometric data occurred in sample solution b
Data；
Step 4: preparing unknown smilax or the sample solution c of its product, and use ultra performance liquid chromatography-quadrupole
Method associated with bar-flight time mass spectrum gathers mass spectrometric data, and the mass spectrometric data of correlation marker sulfur product or its fragment is
Understand whether smilax is fumigated.
Preferably, in step one, sample solution a and sample solution b preparation method are specially：Learn from else's experience sulfur fumigation
Powder is respectively prepared in smilax or its product and smilax sample or its product without sulfur fumigation, and reusing volume fraction is
80% methanol is each configured to solution, using ultrasonic wave extraction 30min, and the methanol that same volume fraction is continuously added after cooling is determined
Hold for 10mg/ml, then shake up filtering, take subsequent filtrate to produce sample solution a and sample solution b.
Preferably, when ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry combination is carried out in step 2, ladder is taken
Spend the mode of elution.
Preferably, the A phases of gradient elution are the formic acid solution that volume fraction is 0.1% in step 2, and B phases are acetonitrile.
Preferably, the ratio of acetonitrile becomes and turned to：5-10%B (0-1.0min)；10-12%B (1-2.5min)；12–
25%B (2.5-7.0min)；25-35%B (7.0-7.5min)；35-48%B (7.5-11.5min)；48-70%B (11.5-
12.0min)；70-90%B (12.0-13.0min)；90-5%B (13.0-13.1min)；5%B (13.1-15.0min).
Preferably, when ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry combination is carried out in step 2, using negative
Ion MSEDrainage pattern.
Preferably, the parameter setting of progress calculating analysis is in step 3：Retention time scope is 1-10min, mass spectrum
Scope is m/z 100-1000, and quality tolerance is set as 0.01Da, and noise elimination of level is 6.00, and intensity threshold is set to
100, mass spectrum window is set to 0.02Da.
Preferably, to point of the poor inhomogeneous mass spectrometric data occurred in sample solution a and sample solution b in step 3
Analysis method is PCA and orthogonal PLS, wherein choosing variable weight value VIP>1 mass spectrometric data is mark
The mass spectrometric data of will sulfur product or its fragment.
Preferably, it is further comprising the steps of before step 2 after step one：It will distinguish in sample solution a and sample solution b
Add and contain 1.0 × 10-4The PBS cushioning liquid of mol/L catechols, the pH value of the PBS cushioning liquid of selection is 7.4, phosphorus
Acid group concentration is 0.1mol/L, and uses the three-electrode system using glass-carbon electrode as working electrode to delay respectively to adding PBS
The sample solution a and sample solution b for rushing solution carry out cyclic voltammetry scanning, and the parameter of scanning is set to：Initial potential-
It is 0.4V, maximum potential 1V, minimum point position -0.4V, final current potential -0.4V, sweep speed 0.05V/s, scanning times 2 times, sensitive
Degree 10-4A/V, stand-by period are 2s.
The present invention at least includes following beneficial effect：
1st, the quick detection of sulfur fumigation smilax and its product is realized first.
2nd, using second order mses, the characteristic ion fragment of various labeled components is found, component can be identified simultaneously.
3rd, the collision voltage selected of the present invention is 35-50V, now each group characteristic ion peak can detect and be formed it is broken
Piece ion peak areas is maximum, if collision voltage is too low, quasi-molecular ions is not enough to crush, and the fragment ion abundance of formation is low；If collision
Overtension, characteristic ion peak is also crushed therewith, it is impossible to differentiated.
4th, from 80% methanol as Extraction solvent, using ultrasonic extracting method, ultrasonic 30min.Target component is extracted
Effect is good, and method has simply been operated.
5th, using gradient elution, it is aided with the acetonitrile ratio delta data that the present invention is provided, at utmost can separates in solution
Various composition, testing result is more accurate.
6th, using PCA and orthogonal PLS, it is aided with the parameter setting calculated before analysis, can not only
Preferable place to go background noise, while result of calculation is accurately and reliably, compared to manually also greatling save the time to analysis of spectrum.
8th, before LC-MS analysis is carried out, the scanning of three electrode cycle voltammetries is carried out to sample solution, can quick separating
Heavy metal ion in solution, reduces the background noise of follow-up LC-MS analysis, makes testing result more accurate.
7th, empirical tests, the method degree of accuracy that provides of the present invention is high, can be to the rhizoma smilacis glabrae medicinal material and its product that are circulated in market
Whether detected by the progress of sulfur fumigation, to reach the purpose of quality control.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 is the mass spectrogram of sample solution a and sample solution b in embodiment 1；
The mass spectrometric data PCA analysis Scores shot charts that Fig. 2 is sample solution a and sample solution b in embodiment 1；
The mass spectrometric data OPLS-DA analysis S-plot figures that Fig. 3 is sample solution a and sample solution b in embodiment 1.
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
It should be noted that experimental method described in following embodiments, is conventional method unless otherwise specified, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
<Embodiment 1>：
Step 1: take fresh rhizoma smilacis glabrae medicinal material and the rhizoma smilacis glabrae medicinal material through sulfur fumigation to cut into slices dry respectively, Ran Houyan
Into powder, respectively take 0.5g to be respectively placed in 50ml volumetric flasks, 80% methanol 20mL is added, using being taken after ultrasonic extraction 20-30min
Go out, be cooled to room temperature, then be separately added into 80% methanol constant volume to scale, shake up, filter, take subsequent filtrate be sample solution a and
Sample solution b.
Step 2: using method associated with ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry respectively to sample solution
A and sample solution b carries out fragment ion mass spectrometric data collection, and wherein chromatographic condition is：Use ACQUITY UPLC HSS T3 colors
Compose post (2.1mm × 100mm, 1.8 μm)；By the way of gradient elution, A phases are 0.1% aqueous formic acid, B phases in mobile phase
For acetonitrile, the wherein ratio of acetonitrile becomes and turned to：5-10%B (0-1.0min)；10-12%B (1-2.5min)；12-25%B
(2.5–7.0min)；25-35%B (7.0-7.5min)；35-48%B (7.5-11.5min)；48-70%B (11.5-
12.0min)；70-90%B (12.0-13.0min)；90-5%B (13.0-13.1min)；5%B (13.1-15.0min), flowing
The flow velocity of phase is 0.5mLmin-1, 35 DEG C of the column temperature maintenance of chromatographic column, sample size is in 2 μ L.
Mass Spectrometry Conditions are：ESI-Ionization mode, capillary voltage 2.8kV, taper hole voltage 40V, except solvent temperature 350
DEG C, except solvent gas flow velocity 700Lh-1, 300 DEG C of ion source temperature, using MSEData acquisition modes, acquisition time 15min,
Scanning range：M/z 100~1500, sweep time 0.2s, collision energy：Low energy 4V, gradient 35~50V of high-energy, collision
Gas：High-purity argon gas.
Step 3: as shown in figure 1, sample solution a and sample solution b raw mass spectrum data are carried out into peak identification, peak pair
Together, Baseline wander and areas of peak normalization method pretreatment, then carry out multi-variate statistical analysis (PCA, OPLS-DA).Analytical parameters
Setting:Retention time scope is 1-10min, and mass ranges are m/z 100-1000, and quality tolerance is set as 0.01Da, made an uproar
Sound elimination of level is 6.00, and intensity threshold is set to 100, and mass spectrum window is set to 0.02Da.
Principal component analysis is carried out first using PCA to sulfur fumigation and without sulfur fumigation smilax in the present embodiment, is led to
R2X, R2Y, Q2 parameter evaluation pca model quality are crossed, wherein R2X, R2Y represents that model is more stable closer to 1, Q2>0.5 represents pre-
Survey rate is high.Pca model includes 7 principal components in this experiment, and its fitting parameter is R2X=0.735, R2Y=0.833, Q2=
0.658, show that constructed pca model stability and prediction rate are higher.As shown in Fig. 2 sulfur fumigation and without sulfur fumigation
Smilax is divided into two groups, shows that its chemical composition has notable difference.
In order to find out difference mark, OPLS-DA analyses are employed, further the overall otherness of two groups of data of analysis,
Utilize variable weight value (VIP>1) otherness mark is found.As shown in figure 3, each point in figure on S types curve is represented
1 compound, is to contribute difference in 2 groups of samples less composition close to center section, more remote from origin, represents it to 2
The difference contribution of group sample is bigger.In general, the data point at S type curves two ends represents confidence level highest in sample respectively
Difference mark, its time of occurrence and charge-mass ratio are respectively：a(tR=4.12min, m/z=529.0650)；b(tR=
1.79min, m/z=415.0333)；c(tR=2.94min, m/z=417.0491)；d(tR=6.39min, m/z=
449.1020)；e(tR=1.45min, m/z=439.0545)；f(tR=2.94min, m/z=415.0338)；g(tR=
2.06min, m/z=417.0489)；h(tR=5.85min, m/z=449.1091)；i(tR=5.67min, m/z=
449.1098)；j(tR=3.72min, m/z=335.0770), due in sample solution a include sulfur fumigation after feature into
Point, therefore mass spectrometric datas of a~g for significant sulfur product or its fragment can be determined, corresponding to 2 in Fig. 1,6,9,14,15,
21st, 26 peak position.
Step 4: from Chengdu, Hengxian County, the peaceful buying smilax sample respectively in Guangzhou, and according to step one and step
Method collection mass spectrometric data described in rapid two, then carry out the mark after peak identification, peak alignment, Baseline wander with being obtained in step 3
The mass spectrometric data of will sulfur product or its fragment is contrasted, and the smilax raw material that the results are shown in Table in 1,6 groups of experiments is
Fresh smilax without sulfur fumigation, the control test two-by-two after different disposal, it can be seen that the smilax after being fumigated
Recall rate be 100%.
The accuracy in detection assay of table 1, this method
In addition, for the specific material of clear and definite sulfur product, addition control group experiment：Precision weighs epicatechin, newly fallen
Bride's glycosides, astilbin, neoisoastilbin, engelitin, isoastilbin reference substance are appropriate, and the methanol for adding 50% is made respectively
Into containing epicatechin, neoastilbin, astilbin, neoisoastilbin, engelitin, isoastilbin 0.1mg/mL it is molten
Liquid is standby, then the method as described in step one and step 2 is respectively to containing epicatechin, neoastilbin, astilbin, new
Isoastilbin, engelitin, the methanol solution collection mass spectrometric data of isoastilbin, because prior art has been verified in smilax
Include flavones ingredient and flavane constituents, such as astilbin, epicatechin, 5-O- coffee acyl shikimic acids, therefore, only
The mass spectrometric data that control group need to be searched in corresponding database just can substantially clear and definite accordingly group, then by sample solution a's
Mass spectrometric data is compared with control group, so that it may know which group is made a variation, and in conjunction with sulfidation, can derive completely
The specific composition of sulfur product, as shown in table 2.
The UPLC-QTOF-MS/MS accurate molecular weights and patch information of the feature sulfur product of table 2
<Embodiment 2>：
On the basis of embodiment 1, following steps are added after step one before step 2：By sample solution a and sample solution b
In be separately added into containing 1.0 × 10-4The PBS cushioning liquid of mol/L catechols, the pH value of the PBS cushioning liquid of selection is
7.4, phosphate concentration is 0.1mol/L, and uses three-electrode system using glass-carbon electrode as working electrode respectively to adding
The sample solution a and sample solution b of PBS cushioning liquid carry out cyclic voltammetry scanning, and the parameter of scanning is set to：Initial electricity
Position -0.4V, maximum potential 1V, minimum point position -0.4V, final current potential -0.4V, sweep speed 0.05V/s, scanning times 2 times, spirit
Sensitivity 10-4A/V, stand-by period are 2s.
Entered after above-mentioned steps, and further shorten ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry combination required
Time, while after heavy metal ion in quick separating sample solution, also eliminating the invalid mass spectrum of some effects analysis
Data.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the embodiment with description.
Claims (9)
1. a kind of method of the detection through the smilax of sulfur fumigation or its product, it is characterised in that comprise the following steps：
Step 1: prepare the sample solution a through the smilax of sulfur fumigation or its product and the smilax without sulfur fumigation or
The sample solution b of its product；
Step 2: using method associated with ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry respectively to sample solution a and
Sample solution b carries out mass spectrometric data collection, wherein the collision voltage selected is 35~50V；
Step 3: sample solution a and sample solution b raw mass spectrum data are pre-processed, contrast determines sample solution a phases
Poor inhomogeneous mass spectrometric data than occurring in sample solution b is the spectra count comprising significant sulfur product or its fragment
According to；
Step 4: prepare unknown smilax or the sample solution c of its product, and use ultra performance liquid chromatography-quadrupole rod-fly
Method associated with row time mass spectrum gathers mass spectrometric data, mass spectrometric data of the contrast comprising significant sulfur product or its fragment
Know whether smilax is fumigated.
2. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 1, it is characterised in that step one
In, sample solution a and sample solution b preparation method are specially：Learn from else's experience sulfur fumigation smilax or its product and without sulphur
Powder is respectively prepared in the stifling smilax sample of sulphur or its product, reuse volume fraction be each configured to for 80% methanol it is molten
Liquid, using ultrasonic wave extraction 30min, the methanol constant volume that same volume fraction is continuously added after cooling is 10mg/ml solution, so
After shake up filtering, take subsequent filtrate to produce sample solution a and sample solution b.
3. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 1, it is characterised in that step 2
During middle progress ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry combination, the mode of gradient elution is taken.
4. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 3, it is characterised in that step 2
The A phases of middle gradient elution are the formic acid solution that volume fraction is 0.1%, and B phases are acetonitrile.
5. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 4, it is characterised in that acetonitrile
Ratio, which becomes, to be turned to：5-10%B (0-1.0min)；10-12%B (1-2.5min)；12-25%B (2.5-7.0min)；25-35%B
(7.0–7.5min)；35-48%B (7.5-11.5min)；48-70%B (11.5-12.0min)；70-90%B (12.0-
13.0min)；90-5%B (13.0-13.1min)；5%B (13.1-15.0min).
6. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 1, it is characterised in that step 2
During middle progress ultra performance liquid chromatography-quadrupole time-of-flight mass spec-trometry combination, using anion MSEDrainage pattern.
7. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 1, it is characterised in that step 3
It is middle carry out calculate analysis parameter setting be：Retention time scope is 1-10min, and mass ranges are m/z 100-1000, quality
Tolerance is set as 0.01Da, and noise elimination of level is 6.00, and intensity threshold is set to 100, and mass spectrum window is set to 0.02Da.
8. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 1, it is characterised in that step 3
In to the analysis method of poor inhomogeneous mass spectrometric data that occurs in sample solution a and sample solution b for PCA and
Orthogonal PLS, wherein choosing variable weight value VIP>1 mass spectrometric data is significant sulfur product or its fragment
Mass spectrometric data.
9. the method through the smilax of sulfur fumigation or its product is detected as claimed in claim 1, it is characterised in that step one
It is further comprising the steps of before step 2 afterwards：It will be separately added into sample solution a and sample solution b containing 1.0 × 10-4Mol/L is adjacent
The PBS cushioning liquid of benzenediol, the pH value of the PBS cushioning liquid of selection is 7.4, and phosphate concentration is 0.1mol/L, and
Use the three-electrode system using glass-carbon electrode as working electrode respectively to adding the sample solution a and sample of PBS cushioning liquid
Solution b carries out cyclic voltammetry scanning, and the parameter of scanning is set to：Initial potential -0.4V, maximum potential 1V, minimum point position -
0.4V, final current potential -0.4V, sweep speed 0.05V/s, scanning times 2 times, sensitivity 10-4A/V, stand-by period are 2s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347862.5A CN107144652B (en) | 2017-05-17 | 2017-05-17 | Method for detecting rhizoma smilacis glabrae fumigated by sulfur and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347862.5A CN107144652B (en) | 2017-05-17 | 2017-05-17 | Method for detecting rhizoma smilacis glabrae fumigated by sulfur and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107144652A true CN107144652A (en) | 2017-09-08 |
| CN107144652B CN107144652B (en) | 2020-08-21 |
Family
ID=59777605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710347862.5A Expired - Fee Related CN107144652B (en) | 2017-05-17 | 2017-05-17 | Method for detecting rhizoma smilacis glabrae fumigated by sulfur and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107144652B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107782836A (en) * | 2017-12-22 | 2018-03-09 | 广东方制药有限公司 | A kind of UPLC MS MS rapid screening sulphuring root of herbaceous peonys and the method for non-sulphuring root of herbaceous peony otherness |
| CN109061004A (en) * | 2018-09-20 | 2018-12-21 | 广西壮族自治区药用植物园 | The content assaying method of calycosin glucoside in the antitoxin white mixture of liter |
| CN112683982A (en) * | 2019-10-18 | 2021-04-20 | 北京化工大学 | Intelligent total chlorine determination method based on cyclic voltammetry |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102100706A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for evaluating quality of Chinese patent medicament by using metabonomics |
| CN102288713A (en) * | 2011-07-29 | 2011-12-21 | 江苏省中医药研究院 | Authentication method for rapidly judging whether white paeony root is fumigated by sulfur or not |
| CN103149280A (en) * | 2011-12-07 | 2013-06-12 | 中国农业大学 | Method for evaluating animal individual nutriture by metabonomics |
| JP5689379B2 (en) * | 2011-07-19 | 2015-03-25 | 日清紡ホールディングス株式会社 | Catalyst support carrier, catalyst support, electrode and battery |
| 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 |
| CN106589041A (en) * | 2016-11-30 | 2017-04-26 | 江苏省中医药研究院 | Sulfur-containing compound used for identifying whether ginseng is fumigated with sulfur as well as preparation method and application of compound |
-
2017
- 2017-05-17 CN CN201710347862.5A patent/CN107144652B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102100706A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for evaluating quality of Chinese patent medicament by using metabonomics |
| JP5689379B2 (en) * | 2011-07-19 | 2015-03-25 | 日清紡ホールディングス株式会社 | Catalyst support carrier, catalyst support, electrode and battery |
| CN102288713A (en) * | 2011-07-29 | 2011-12-21 | 江苏省中医药研究院 | Authentication method for rapidly judging whether white paeony root is fumigated by sulfur or not |
| CN103149280A (en) * | 2011-12-07 | 2013-06-12 | 中国农业大学 | Method for evaluating animal individual nutriture by metabonomics |
| 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 |
| CN106589041A (en) * | 2016-11-30 | 2017-04-26 | 江苏省中医药研究院 | Sulfur-containing compound used for identifying whether ginseng is fumigated with sulfur as well as preparation method and application of compound |
Non-Patent Citations (3)
| Title |
|---|
| XUE JIANG等: "Sulfur fumigation, a better or worse choice in preservation of Traditional Chinese Medicine?", 《PHYTOMEDICINE》 * |
| 蔡皓等: "UHPLC-Q-TOF MS和化学计量学方法分析川芎硫磺熏蒸前后化学成分的变化", 《质谱学报》 * |
| 魏晓杰: "电吸附对中草药及酱油中金属元素的影响分析", 《中国优秀硕士论文全文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107782836A (en) * | 2017-12-22 | 2018-03-09 | 广东方制药有限公司 | A kind of UPLC MS MS rapid screening sulphuring root of herbaceous peonys and the method for non-sulphuring root of herbaceous peony otherness |
| CN109061004A (en) * | 2018-09-20 | 2018-12-21 | 广西壮族自治区药用植物园 | The content assaying method of calycosin glucoside in the antitoxin white mixture of liter |
| CN109061004B (en) * | 2018-09-20 | 2021-06-25 | 广西壮族自治区药用植物园 | Method for measuring content of calycosin glucoside in antitoxic leukogenic mixture |
| CN112683982A (en) * | 2019-10-18 | 2021-04-20 | 北京化工大学 | Intelligent total chlorine determination method based on cyclic voltammetry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107144652B (en) | 2020-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ćirić et al. | Evaluation of matrix effect in determination of some bioflavonoids in food samples by LC–MS/MS method | |
| Rychlinska et al. | Quantitative determination of arbutin and hydroquinone in different plant materials by HPLC | |
| Singh et al. | High‐performance liquid chromatography as a tool for the chemical standardisation of Triphala—an Ayurvedic formulation | |
| Klimek et al. | Simultaneous determination of flavonoids and phenylethanoids in the flowers of Verbascum densiflorum and V. phlomoides by high‐performance liquid chromatography | |
| Rao et al. | Hepatoprotective and antioxidant capacity of Melochia corchorifolia extracts | |
| CN107144652A (en) | The method of smilax and its product of the detection through sulfur fumigation | |
| Maldini et al. | A new approach to discriminate Rosmarinus officinalis L. plants with antioxidant activity, based on HPTLC fingerprint and targeted phenolic analysis combined with PCA | |
| CN106483215B (en) | Natural finds online and integrates antioxidant activity evaluation method in pawpaw medicinal material | |
| Salles et al. | Passiflora edulis leaf extract: evidence of antidiabetic and antiplatelet effects in rats | |
| Prando et al. | Ethnopharmacological investigation of the diuretic and hemodynamic properties of native species of the Brazilian biodiversity | |
| CN104897806B (en) | Judge Flos Chrysanthemi whether through the HPLC detection method of stove drying | |
| Jagtap et al. | Phytochemical screening and antioxidant activity of rhizome extracts of Costus speciosus (Koen.) JE Smith | |
| Chen et al. | Determination of marker constituents in radix Glycyrrhizae and radix Notoginseng by near infrared spectroscopy | |
| Avula et al. | Quantitative determination of flavonoids by column high-performance liquid chromatography with mass spectrometry and ultraviolet absorption detection in Artemisia afra and comparative studies with various species of Artemisia plants | |
| Karabat et al. | Zwitterion Chromatography-Hydrophilic Interaction Chromatography for Separation and Quantitative of Rutin and Quercetin from Herbs and Bee Products. | |
| CN102967670A (en) | Method for measuring cordycepin, adenosine and mannitol in cordyceps sinensis mycelium powder | |
| CN113155944B (en) | Method for analyzing pyrrolizidine alkaloids | |
| CN105954434B (en) | A kind of detection method of phenols fragrance | |
| Lee et al. | Subchronic toxicity evaluation of ethanol extract of Cassia tora L. seeds in rats | |
| Chauhan et al. | Simultaneous determination of bergenin and gallic acid in Bergenia ligulata wall by high-performance thin-layer chromatography | |
| Seal et al. | Identification and quantification flavonoids in three wild edible plants, Houttuynia cordata, Solanum gilo and Solanum kurzii of North-Eastern region in India, using high performance liquid chromatography with diode array detection | |
| CN104880521A (en) | Identification method for judging whether Chinese angelica undergoes sulfur fumigation | |
| Rode et al. | Quantification of piperine and 18-β glycyrrhetinic acid in herbal formulation “Eladi Gutika” | |
| Salazar et al. | Antioxidant activity of Stryphnodendron rotundifolium Mart. stem bark fraction in an iron overload model | |
| CN112147249A (en) | UPC2-PDA-Q-Tof/MS detection method for 31 effective components in waxberry wine |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200821 Termination date: 20210517 |