CN109342545B - A kind of ginseng recognition methods based on the regulation of difference ion mobility spectrometry gas dressing agent - Google Patents
A kind of ginseng recognition methods based on the regulation of difference ion mobility spectrometry gas dressing agent Download PDFInfo
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- CN109342545B CN109342545B CN201811100590.XA CN201811100590A CN109342545B CN 109342545 B CN109342545 B CN 109342545B CN 201811100590 A CN201811100590 A CN 201811100590A CN 109342545 B CN109342545 B CN 109342545B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
- G01N27/624—Differential mobility spectrometry [DMS]; Field asymmetric-waveform ion mobility spectrometry [FAIMS]
Abstract
The invention discloses a kind of ginseng recognition methods based on the regulation of difference ion mobility spectrometry gas dressing agent.Ginseng to be measured is extracted and obtains ginseng to be measured extracting solution, using ginseng to be measured extracting solution as sample to be tested, the type and content that ginsenoside in separation sample to be tested is carried out using difference Ion mobility spectrometry, can identifying to ginseng to be measured by the type and content of the ginsenoside measured；Wherein, it in the difference Ion mobility spectrometry, is added in assisted electrospray gas and auxiliary aggregation gas using normal propyl alcohol as gas dressing agent.The present invention has the advantages that separation is stable, reproducible, the time is short to different ginsenosides and ginsenoside isomer.
Description
Technical field
The invention belongs to the detection techniques of ginseng, are related to the detection of ginseng type, and in particular to one kind is based on difference ion
The ginseng recognition methods of migration spectrum gas dressing agent regulation.
Background technique
Ginseng is a kind of famous natural prodcuts, and more than one thousand years has been widely used in Asian countries.Largely about people
Ginseng research shows that ginseng has an extensive, complicated pharmacological action, including but not limited to anticancer, it is anti-oxidant, improve cardiovascular status
And immune function.Relevant pharmacological research confirms that many ginsenosides are the masters that ginseng has so many pharmacological action
Want active constituent.Ginsenoside is a kind of steroid compound of diversification, triterpenoid saponin or steroid saponin.So far, exist
100 kinds of ginsenoside has been had more than in the ginseng of each kind to be extracted and detect.Ginsenoside affects multiple
Metabolic pathway, efficiency are and its complicated, it should be noted that the monomer component of various ginsenosides is difficult to separate.
The fitochemical studies that structural characterization and isomer about ginsenoside are distinguished are always ginseng research in recent decades
Hot spot.Relevant fitochemical studies show that the structure function of ginsenoside and chemistry and pharmacology diversity are to be closely related
's.
At present in the lab, identify asia ginseng (Panax ginseng), U.S. ginseng (panax
Quinquefolius) and relevant ginseng product is mainly the identification and differentiation for relying on its chemical feature.Such as ginsenoside
Rf is existed only in asia ginseng, isomer pseudo-ginsenoside F11(psudoginsenoside F11) it is present in the U.S.
In ginseng, it is not present in asia ginseng or content is extremely low, and its other isomer ginsenoside Rg1, at two
All exist in the ginseng of kind, but the content of opposite ginsenoside Re has significant difference.Researcher develops many ginsengs
Saponin separation method, including based on liquid chromatography-mass spectrography (Liquid chromatography-mass spectrometry,
LC-MS method), second order ms (Tandem mass spectrometry, MS/MS), thin-layer chromatography (Thin-layer
Chromatography, TLC), gas-chromatography (Gas Chromatography, GC), near infrared spectrum (Near infrared
Spectroscopy, NIRS) and enzyme immunoassay (EIA) (Enzyme immunoassay).But these methods have corresponding limitation
Property, or part ginsenoside can only be obtained and be efficiently separated or separating effect is limited and analysis time is longer, or cannot
Separate certain ginsenoside isomers.
Difference ion mobility spectrometry (Differential Ion Mobility Spectrometry) is that one kind works in greatly
Ion mobility spectrometry under air pressure environment is a kind of quick separating detection technique occurred in early 1980s, initially
It is used in the detection of explosive substance such as 2,4,6- trinitrotoluene (TNT).It connect, makees with liquid chromatograph-mass spectrometer device in recent years
For a kind of new instrument of biochemistry domain analysis test, usual available more biological informations.We study at present
Difference ionic migration spectrometer mainly as where ion source ion source cavity, auxiliary aggregation gas where auxiliary assemble air cavity
Difference ion mobility spectrometry cavity composition where body, a pair of of stainless steel parallel electrode plate.The ion that ion source generates is in auxiliary electricity
Ionization Efficiency and stability are enhanced under the action of spraying gas and auxiliary aggregation gas, and reduces and is entering difference Ion transfer
The expansion of ion cloud before composing cavity, therefore enhance ion transmission efficiency and reduce the peak of difference ion mobility spectrometry signal peak
It is wide.Ion enters in the high electric field field strength and existing fringing field field strength of difference ion mobility spectrometry, and there are nonlinear changes for ionic mobility
Change thus it is unequal, the difference of ionic mobility is also referred to as difference ionic mobility (Differential Mobility), because
This difference ionic migration spectrometer is for separating the different ion of differential mobility.Difference ion mobility spectrometry is mended using a direct current
Voltage (Compensation Voltage, CV) is repaid, such as -50 volts to+100 volts, the longitudinal drift of counterion.Pass through compensation electricity
Pressure is assured that the presence of analysis target substance, and applies peak area or peak height that can carry out a sxemiquantitative or quantitative grind
Study carefully.
Summary of the invention
There is, analysis time longer deficiency limited to ginsenoside separating effect, mesh of the invention for the prior art
One of be to provide the method for separation detection ginsenoside and/or ginsenoside isomer a kind of, this method is to different people
Ginseng saponin(e and ginsenoside isomer have the advantages that separation is stable, reproducible, the time is short.
To achieve the goals above, the technical solution of the present invention is as follows:
The separation method of a kind of ginsenoside and/or ginsenoside isomer, to contain at least two ginsenosides
Mixture as sample to be tested, separated using difference Ion mobility spectrometry；Wherein, the difference ion mobility spectrometry skill
In art, it is added in assisted electrospray gas and auxiliary aggregation gas using normal propyl alcohol as gas dressing agent.
The present invention uses difference Ion mobility spectrometry to separate different ginsenosides for the first time.In research process,
It was found that simply directlying adopt, difference Ion mobility spectrometry can not (especially ginsenoside be different with dividing to different ginsenosides
Structure body) it is separated.In order to separate different ginsenosides, the present invention is added to gas dressing agent into carrier gas, is envisaged for
The separation of different ginsenosides finds that normal propyl alcohol is to ginsenoside by gas with various dressing agents such as addition normal propyl alcohol, acetonitriles
Separating property it is best.It finds after further research, it is high in the high field intensity asymmetric waveform radio frequency of difference ionic migration spectrometer
The periods of low pressure of pressure, normal propyl alcohol molecule and ginsenoside ion form more cluster ions by active force between ionic molecule；In High-Field
More cluster ions that the high pressure phase of strong asymmetric waveform radio frequency high tension, normal propyl alcohol molecule and ginsenoside ion are formed are by high electric field
It influences and more cluster ion dissociation occurs.This special phenomenon makes point to different ginsenosides of difference ion mobility spectrometry
It is promoted from ability.
The second object of the present invention is to provide a kind of separator for realizing the above method, by difference ionic migration spectrometer and
Evaporator composition, the gas circuit phase of the steam (vapor) outlet of evaporator and the assisted electrospray gas of difference ion mobility spectrometry and auxiliary aggregation gas
It connects, is connected by pipeline with the sample introduction needle equipped with normal propyl alcohol solution in the evaporator.
The third object of the present invention is to provide the separation detection side of a kind of ginsenoside and/or ginsenoside isomer
Method, to contain the mixtures of at least two ginsenosides as sample to be tested, using difference ion mobility spectrometry tandem mass spectrometry
It is detected；Wherein, in the difference ion mobility spectrometry, assisted electrospray gas is added to as gas dressing agent using normal propyl alcohol
In auxiliary aggregation gas.
The fourth object of the present invention is to provide a kind of separation detecting device for realizing the above method, by difference ion mobility spectrometry
Instrument, mass spectrograph and evaporator composition, difference ionic migration spectrometer and mass spectrograph are sequentially connected in series, the steam (vapor) outlet and difference of evaporator
The assisted electrospray gas of ion mobility spectrometry is connected with the gas circuit of auxiliary aggregation gas, by pipeline and equipped with just in the evaporator
The sample introduction needle of propanol solution is connected.
The fifth object of the present invention is to provide a kind of above-mentioned separation method, separator, method for separating and detecting or separation inspection
It surveys device and is identifying the application in different types of ginseng.
Due to the ginsenoside (especially asia ginseng and U.S.'s ginseng) in variety classes ginseng type and content simultaneously
It is not identical, and the above method or device can will separate different ginsenosides even ginsenoside isomer,
So can be identified using the above method or device to different types of ginseng.
The sixth object of the present invention is to provide a kind of ginseng identification based on the regulation of difference ion mobility spectrometry gas dressing agent
Ginseng to be measured is extracted and obtains ginseng to be measured extracting solution by method, using ginseng to be measured extracting solution as sample to be tested, in use
The type and content for stating the ginsenoside in method for separating and detecting detection sample to be tested, by the type of ginsenoside that measures and
Content can identifying to ginseng to be measured.
The invention has the benefit that
1. the present invention is by adding normal propyl alcohol as gas dressing agent, in the high field intensity asymmetry of difference ionic migration spectrometer
The periods of low pressure of waveform radio frequency high pressure, normal propyl alcohol molecule and ginsenoside ion by active force between ionic molecule formed more clusters from
Son；In the high pressure phase of high field intensity asymmetric waveform radio frequency high tension, more clusters that normal propyl alcohol molecule and ginsenoside ion are formed from
Son is influenced and more cluster ions are occurred and are dissociated by high electric field；By this special phenomenon, so that the separation of difference ion mobility spectrometry
Ability is promoted, and carries out detection separation to different ginsenosides using difference Ion mobility spectrometry for the first time to realize.
2. difference ion mobility spectrometry can quickly distinguish ginsenoside isomer, separation is stablized and repeatability is preferable,
Therefore it can be used as a kind of new method for identifying ginseng kind in laboratory.Difference ion mobility spectrometry is compared with liquid chromatogram, only
The data acquisition time for needing several seconds, time needed for substantially reducing separation.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is that difference ion moves under 7000V radio-frequency voltage, positive ion mode, 0% concentration normal propyl alcohol gas dressing agent mode
Move the difference ion mobility spectrometry spectrogram of spectrum detection ginseng saponin Rh 2, CK mixture.
Fig. 2 be 7000V radio-frequency voltage, positive ion mode, under 0.02% concentration normal propyl alcohol gas dressing agent mode difference from
The difference ion mobility spectrometry spectrogram of sub- migration spectrum detection ginseng saponin Rh 2, CK mixture.
Fig. 3 be 7000V radio-frequency voltage, positive ion mode, under 0.08% concentration normal propyl alcohol gas dressing agent mode difference from
The difference ion mobility spectrometry spectrogram of sub- migration spectrum detection ginseng saponin Rh 2, CK mixture.
Fig. 4 is that difference ion moves under 7000V radio-frequency voltage, positive ion mode, 0% concentration normal propyl alcohol gas dressing agent mode
Move the difference ion mobility spectrometry spectrogram of spectrum detection ginsenoside Rf, pseudo-ginsenoside F 11 mixture.
Fig. 5 be 7000V radio-frequency voltage, positive ion mode, under 0.10% concentration normal propyl alcohol gas dressing agent mode difference from
Sub- migration spectrum detects the difference ion mobility spectrometry spectrogram of ginsenoside Rf, pseudo-ginsenoside F 11 mixture.
Fig. 6 be 7000V radio-frequency voltage, positive ion mode, under 0.40% concentration normal propyl alcohol gas dressing agent mode difference from
Sub- migration spectrum detects the difference ion mobility spectrometry spectrogram of ginsenoside Rf, pseudo-ginsenoside F 11 mixture.
Fig. 7 be 7000V radio-frequency voltage, positive ion mode, under 0.13% concentration normal propyl alcohol gas dressing agent mode difference from
The difference ion mobility spectrometry spectrogram of sub- migration spectrum detection U.S.'s samples of Ginseng.
Fig. 8 be 7000V radio-frequency voltage, positive ion mode, under 0.13% concentration normal propyl alcohol gas dressing agent mode difference from
The difference ion mobility spectrometry spectrogram of sub- migration spectrum detection Northeast China ginseng sample.
Fig. 9 is difference ion under 7000V radio-frequency voltage, positive ion mode, 0.50% concentration acetonitrile gas dressing agent mode
Migration spectrum detects the difference ion mobility spectrometry spectrogram of ginseng saponin Rh 2, CK mixture.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Ginsenoside isomer described herein refers to the ginsenoside that chemical formula is identical, chemical structure is different.
The carrier gas that difference ion mobility spectrometry uses in the application is divided into assisted electrospray gas and auxiliary aggregation gas, the carrier gas
For the nitrogen of 99.999% purity.
As background technique is introduced, exist in the prior art, analysis time limited to ginsenoside separating effect compared with
Long deficiency, in order to solve technical problem as above, present applicant proposes one kind to be based on difference ion mobility spectrometry gas dressing agent
The ginseng recognition methods of regulation.
A kind of exemplary embodiment of the application provides a kind of ginsenoside and/or ginsenoside isomer
Separation method, to contain the mixtures of at least two ginsenosides as sample to be tested, using difference Ion mobility spectrometry into
Row detection；Wherein, in the difference Ion mobility spectrometry, assisted electrospray is added to as gas dressing agent using normal propyl alcohol
In gas and auxiliary aggregation gas.The mechanism of ginsenoside separation may be implemented in normal propyl alcohol are as follows: in the High-Field of difference ionic migration spectrometer
The periods of low pressure of strong asymmetric waveform radio frequency high tension, normal propyl alcohol molecule and ginsenoside ion pass through active force shape between ionic molecule
At more cluster ions；In the high pressure phase of high field intensity asymmetric waveform radio frequency high tension, normal propyl alcohol molecule is formed with ginsenoside ion
More cluster ions influenced and more cluster ions are occurred and are dissociated by high electric field.Because of the space structure of different ginsenoside ions, ionization position
Difference is set, therefore during this more cluster ion formation/dissociation, the journey that the space structure of more cluster ions, more cluster ions are formed
Interaction force is different between degree, ionic molecule, thus facilitates the separation of ginsenoside ion.
The application uses difference Ion mobility spectrometry to separate different ginsenosides for the first time.In research process,
It was found that simply directlying adopt, difference Ion mobility spectrometry can not (especially ginsenoside be different with dividing to different ginsenosides
Structure body) it is separated.In order to separate different ginsenosides, the application is added to gas dressing agent into carrier gas, is envisaged for
The separation of different ginsenosides finds that normal propyl alcohol is to ginsenoside by gas with various dressing agents such as addition normal propyl alcohol, acetonitriles
Separating effect it is best.It finds after further research, it is high in the high field intensity asymmetric waveform radio frequency of difference ionic migration spectrometer
The periods of low pressure of pressure, normal propyl alcohol molecule and ginsenoside ion form more cluster ions by active force between ionic molecule；In High-Field
More cluster ions that the high pressure phase of strong asymmetric waveform radio frequency high tension, normal propyl alcohol molecule and ginsenoside ion are formed are by high electric field
It influences and more cluster ion dissociation occurs.This special phenomenon makes point to different ginsenosides of difference ion mobility spectrometry
It is promoted from ability.
Normal propyl alcohol after constant-temperature evaporation by being added in the application, and after avoiding heating evaporation, solution is condensate in pipeline
In difference ion mobility spectrometry apparatus, impact analysis performance and equipment operation stability.
In one or more embodiments of the embodiment, the concentration of normal propyl alcohol is 0~0.8%, and concentration is not 0.This
The application concentration refers to the molar ratio of normal propyl alcohol and carrier gas.Under the range, it can guarantee different ginseng saponin separation effects
And the intensity of detection signal.
In one or more embodiments of the embodiment, in the difference Ion mobility spectrometry, using nanoelectrospray
Ion source, positive ion mode.
In one or more embodiments of the embodiment, the detection parameters of the difference Ion mobility spectrometry are as follows: poor
The spacing between plates of ion mobility spectrum is 1.4mm, migration section length is 80mm, migration sector width is 20mm, is penetrated under working condition
Frequency electric field magnitude is 7kV, frequency 750kHz, and the sweep interval of offset voltage is -50V~+100V.
The another embodiment of the application provides a kind of separator for realizing the above method, is moved by difference ion
Spectrometer and evaporator composition are moved, the steam (vapor) outlet of evaporator and the assisted electrospray gas of difference ion mobility spectrometry and auxiliary assemble gas
Gas circuit be connected, in the evaporator by pipeline be equipped with normal propyl alcohol solution sample introduction needle be connected.
Embodiment there is provided points of a kind of ginsenoside and/or ginsenoside isomer for the third of the application
From detection method, the mixture to contain at least two ginsenosides is connected as sample to be tested using difference ion mobility spectrometry
Mass-spectrometric technique is detected；Wherein, in the difference ion mobility spectrometry, auxiliary is added to as gas dressing agent using normal propyl alcohol
In EFI fog and auxiliary aggregation gas.
In one or more embodiments of the embodiment, the concentration of normal propyl alcohol is 0~0.8%, and concentration is not 0.This
The application concentration refers to the molar ratio of normal propyl alcohol and carrier gas.Under the range, it can guarantee different ginseng saponin separation effects
And the intensity of detection signal.
In one or more embodiments of the embodiment, in difference ion mobility spectrometry, using nanoelectrospray ion source, just
Ion mode.
In one or more embodiments of the embodiment, the detection parameters of difference Ion mobility spectrometry are as follows: difference from
The spacing between plates of sub- migration spectrum is 1.4mm, migration section length is 80mm, migration sector width is 20mm, radio frequency electrical under working condition
Amplitude is 7kV, frequency 750kHz, and the sweep interval of offset voltage is -50V~+100V.
In one or more embodiments of the embodiment, mass spectrographic parameter are as follows: detection 500~3000 ion of mass-to-charge ratio
Standard method parameter: mass spectrum entrance is 0V, and temperature is 150 DEG C, and reversed drying nitrogen air-flow velocity is 1.3L/min, collision cell electricity
It is overstocked automatic adjustment when being pressed in second order ms using standard electric, is -3V in first mass spectrometric.
The 4th kind of the application embodiment there is provided a kind of separation detecting device for realizing the above method, by difference from
Sub- mobility spectrometer, mass spectrograph and evaporator composition, difference ionic migration spectrometer and mass spectrograph are sequentially connected in series, and the steam of evaporator goes out
Mouth is connected with the gas circuit of the assisted electrospray gas of difference ion mobility spectrometry and auxiliary aggregation gas, and positive third is filled in the evaporator
Alcohol.
The 5th kind of the application embodiment there is provided a kind of above-mentioned separation method, separator, method for separating and detecting or
Separation detecting device is identifying the application in different types of ginseng.
Embodiment there is provided a kind of people based on the regulation of difference ion mobility spectrometry gas dressing agent for the 6th kind of the application
Join recognition methods, ginseng to be measured is extracted and obtains ginseng to be measured extracting solution, using ginseng to be measured extracting solution as sample to be tested,
Using the type and content of the ginsenoside in above-mentioned method for separating and detecting detection sample to be tested, pass through the ginsenoside that measures
Type and content can identifying to ginseng to be measured.
When identifying asia ginseng and U.S.'s ginseng, the concentration of normal propyl alcohol is 0.13%.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment and comparative example of body.
The device used in the embodiment of the present application and comparative example is difference ionic migration spectrometer and Brooker 9.4T FTMS matter
Spectrometer device is connected.Flight sequence of the difference ionic migration spectrometer according to ion is followed successively by ion source cavity, auxiliary aggregation air cavity
Body, difference ion mobility spectrometry cavity be linked in sequence setting, sampling system mainly include 250 microlitres of sample introduction needles, sample feeding pump and
Solution conveyor tube road composition.Carrier gas system is mainly by carrier gas transfer pipeline, gas dressing agent evaporator and five milliliters of solution sample introductions
Needle, solution conveyor tube road composition.
The principle of embodiment be with difference Ion mobility spectrometry be basic detection technique, using nanoelectrospray ion source,
Positive ion mode selects normal propyl alcohol to be added to the assisted electrospray gas and auxiliary of difference ionic migration spectrometer as gas dressing agent
Assemble in the gas circuit of gas (the adjustable concentration value of minimum is 0.01%, and it is 0%~0.8% that concentration range, which is adjusted).Assist EFI
Fog is added in enclosed nanoelectrospray ion source, and auxiliary generates stable electron spray, and assembles ion cloud and pass through difference
The entrance of ion mobility spectrum；Auxiliary aggregation gas is added to after the entrance of nanoelectrospray ion source, to the ion cloud of expansion
Secondary aggregation is done, ion transmission efficiency is improved.Normal propyl alcohol molecule and ginsenoside ion pass through active force shape between ionic molecule
At more cluster ions；In the high pressure phase of high field intensity asymmetric waveform radio frequency high tension, normal propyl alcohol molecule is formed with ginsenoside ion
More cluster ions influenced and more cluster ions are occurred and are dissociated by high electric field.This special phenomenon makes point of difference ion mobility spectrometry
It is promoted from ability.Using the carrier gas of the dressing agent of gas containing various concentration, ginsenoside isomer is moved in difference ion
The drift that the top of signal peak can be regular to deserved offset voltage value in shifting spectrum.The separation of ginsenoside isomer
It is influenced by gas dressing agent concentration, and condition is relatively harsh；When using the carrier gas of a certain concentration gases dressing agent, ginseng soap
The available separation of glycosides isomer.
Detection parameters in embodiment are as follows:
Difference ion mobility spectrometry: the spacing between plates of the difference ion mobility spectrometry be 1.4mm, migration section length be 80mm,
Migration sector width is 20mm, under working condition rf electric field amplitude be 7kV, frequency 750kHz, the sweep interval of offset voltage
It is -50V~+100V.The carrier gas overall flow rate of the dressing agent containing gas is 1.2L/min, and carrier gas uses the nitrogen of 99.999% purity,
Two points are assisted electrospray gas and auxiliary aggregation gas, are respectively 600mL/min.
Mass spectrum: the mass spectrometer is Brooker 9.4T FTMS mass spectrum, and parameter used is detection in addition to following parameter
The standard method parameter of 500~3000 ion of mass-to-charge ratio: mass spectrum entrance is 0V, and temperature is 150 DEG C, reversed drying nitrogen air-flow stream
Speed is 1.3L/min, and collision cell voltage is overstocked automatic adjustment in second order ms using standard electric, is -3V in first mass spectrometric.
Experiment condition are as follows: difference ionic migration spectrometer cavity keeps room temperature, and assisted electrospray gas and auxiliary aggregation gas are
600mL/min, normal propyl alcohol gas dressing agent are added in carrier gas by gas dressing agent evaporator, and concentration range 0%~
0.8%.Ginsenoside sample feeding speed is 30 μ L/h, with nanoelectrospray ion source positive ion mode.Utilize standard items
The database of foundation obtains the top of ginsenoside isomer signal peak in difference ion mobility spectrometry to deserved compensation
Voltage value, so that it may confirm corresponding isomer type.
The separation detection of 1 ginseng saponin Rh 2 of embodiment, CK
Ginseng saponin Rh 2, CK are a pair of of isomers, and the link position for differing only in glycosyl is different.
Difference ionic migration spectrometer cavity keeps room temperature, and assisted electrospray gas and auxiliary aggregation gas are 600mL/min, just
Propyl alcohol gas dressing agent is added in carrier gas by gas dressing agent evaporator, concentration range 0%~0.1%.Ginsenoside sample
Product sample introduction speed is 30 μ L/h, with nanoelectrospray ion source positive ion mode.Ginseng saponin Rh 2, CK concentration are 1E-6M
(10-6Mol/L), it is mixed into mixed liquor.
Detection normal propyl alcohol concentration be respectively 0,0.02%, 0.08% result it is as shown in Figures 1 to 3, utilize 0% concentration positive third
It is high that alcohol gas dressing agent can be seen that ginsenoside signal strength, but two kinds of ginseng saponin Rh 2s, CK cannot be separated；And it is added
0.02% concentration normal propyl alcohol gas dressing agent can be seen that two kinds of ginseng saponin Rh 2s, CK is separated and signal strength is opposite
It is higher；Though continuing to improve normal propyl alcohol gas dressing agent concentration to 0.08% as can be seen that two kinds of ginseng saponin Rh 2s, CK are divided
From but signal strength continue to reduce.
2 ginsenoside Rf of embodiment, pseudo-ginsenoside F 11 separation detection
Ginsenoside Rf, pseudo-ginsenoside F 11 mixture are a pair of of isomers, differ only in the structure of side chain not
Together.Ginsenoside Rf is the marker of asia ginseng, and pseudo-ginsenoside F 11 is the marker of U.S.'s ginseng.If distinguishing ginseng
Saponin(e Rf, pseudo-ginsenoside F 11 then can identify asia ginseng, U.S.'s ginseng and relevant ginseng product for laboratory and mention
For a kind of completely new method.
Difference ionic migration spectrometer cavity keeps room temperature, and assisted electrospray gas and auxiliary aggregation gas are 600mL/min, just
Propyl alcohol gas dressing agent is added in carrier gas by gas dressing agent evaporator, concentration range 0%~0.5%.Ginsenoside sample
Product sample introduction speed is 30 μ L/h, with nanoelectrospray ion source positive ion mode.Ginsenoside Rf, pseudo-ginsenoside F 11 are dense
Degree is 1E-6M, is mixed into mixed liquor.
Detection normal propyl alcohol concentration be respectively 0,0.10%, 0.40% result as shown in figures 4-6, utilize 0% concentration positive third
It is high that alcohol gas dressing agent can be seen that ginsenoside signal strength, but two kinds of ginsenoside Rfs, pseudo-ginsenoside F 11s cannot get
Separation；And 0.10% concentration normal propyl alcohol gas dressing agent of addition can be seen that two kinds of ginsenoside Rfs, pseudo-ginsenoside F 11s and obtain
To separation and signal strength it is higher；Continue to improve normal propyl alcohol gas dressing agent concentration to 0.40% as can be seen that two kinds of ginseng soaps
Glycosides Rf, pseudo-ginsenoside F 11, which cannot separate, and signal strength continues reduces.
The identification of embodiment 3 asia ginseng and U.S.'s ginseng
Difference ionic migration spectrometer cavity keeps room temperature, and assisted electrospray gas and auxiliary aggregation gas are 600mL/min, just
Propyl alcohol gas dressing agent is added in carrier gas by gas dressing agent evaporator, concentration range 0%~0.5%.By samples of Ginseng
Extract liquor dilute 20 times after sample introduction, sample introduction speed be 30 microlitres per hour, with nanoelectrospray ion source positive ion mode.
The result of U.S.'s ginseng and asia ginseng that the normal propyl alcohol concentration of detection is 0.13% is as shown in Fig. 7~8, in spectrogram
It is ginsenoside Rg for the signal peak near the 7.5V to 8.0V of label1.In Fig. 7, the signal peak near 10V is pseudo-ginsenoside
F11Characteristic peak；In Fig. 8, the signal peak near 13V is pseudo-ginsenoside Rg1Characteristic peak.As can be seen that using containing 0.13%
Normal propyl alcohol gas dressing agent concentration, can distinguish U.S.'s ginseng and asia ginseng.
Comparative example
Difference ionic migration spectrometer cavity keeps room temperature, and assisted electrospray gas and auxiliary aggregation gas are 600mL/min, second
Nitrile gas dressing agent is added in carrier gas by gas dressing agent evaporator, concentration range 0%~1.5%.Ginsenoside sample
Sample introduction speed is 30 μ L/h, with nanoelectrospray ion source positive ion mode.Ginseng saponin Rh 2, CK concentration are 1E-6M,
It is mixed into mixed liquor.
It is as shown in Figure 9 to detect the result that acetonitrile concentration is 0.50%.It, can using 0% concentration acetonitrile gas dressing agent in Fig. 9
To find out, ginsenoside signal strength is high, but two kinds of ginseng saponin Rh 2s, CK cannot be efficiently separated.And in the concentration model of selection
It has been relatively good results, it can be seen that ginsenoside signal is strong using 0.50% concentration acetonitrile gas dressing agent in enclosing
Degree is still higher, but two kinds of ginseng saponin Rh 2s, CK still cannot be efficiently separated, and the range of drift of peak position is compared with normal propyl alcohol
It is smaller, it is unfavorable for the separation of ginsenoside.
Respectively by being carried out as gas dressing agent such as the identical experiment of acetonitrile, discovery isopropanol, second to isopropanol, ethyl alcohol
Ginseng saponin Rh 2, CK still can not be effectively separated by alcohol as gas dressing agent.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (5)
1. the separation method of a kind of ginsenoside and/or ginsenoside isomer, characterized in that contain at least two people
Join the mixture of saponin(e as sample to be tested, is separated using difference Ion mobility spectrometry；Wherein, the difference ion moves
It moves in spectral technology, using nanoelectrospray ion source, positive ion mode, auxiliary electricity is added to as gas dressing agent using normal propyl alcohol
In spraying gas and auxiliary aggregation gas, the concentration of normal propyl alcohol is 0~0.8%, and concentration is not 0.
2. the method for separating and detecting of a kind of ginsenoside and/or ginsenoside isomer, characterized in that contain at least two
The mixture of kind ginsenoside is detected as sample to be tested using difference ion mobility spectrometry tandem mass spectrometry；Wherein, institute
It states in difference ion mobility spectrometry, using nanoelectrospray ion source, positive ion mode, is added using normal propyl alcohol as gas dressing agent
Into assisted electrospray gas and auxiliary aggregation gas, the concentration of normal propyl alcohol is 0~0.8%, and concentration is not 0.
3. a kind of separation method described in claim 1 or method for separating and detecting as claimed in claim 2 are identifying variety classes
Ginseng in application.
4. a kind of ginseng recognition methods based on the regulation of difference ion mobility spectrometry gas dressing agent, characterized in that by ginseng to be measured
It extracts and obtains ginseng to be measured extracting solution, using ginseng to be measured extracting solution as sample to be tested, using as claimed in claim 2 point
Type and content from the ginsenoside in detection method detection sample to be tested, by the type and content of the ginsenoside measured
It can identifying to ginseng to be measured.
5. ginseng recognition methods as claimed in claim 4, characterized in that when identification asia ginseng and U.S.'s ginseng, normal propyl alcohol
Concentration be 0.13%.
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