CN109270189A - The sample-pretreating method of perfluorochemical residual quantity in a kind of detection Chinese herbal medicine - Google Patents
The sample-pretreating method of perfluorochemical residual quantity in a kind of detection Chinese herbal medicine Download PDFInfo
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- CN109270189A CN109270189A CN201811346152.1A CN201811346152A CN109270189A CN 109270189 A CN109270189 A CN 109270189A CN 201811346152 A CN201811346152 A CN 201811346152A CN 109270189 A CN109270189 A CN 109270189A
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Abstract
The present invention provides a kind of sample-pretreating method for detecting perfluorochemical residual quantity in Chinese herbal medicine, belongs to technical field of analytical chemistry.The described method includes: acetonitrile extracting solution is added into the Chinese herbal medicine sample after smashing by S1., extraction salt is then added and is extracted；S2. adsorbent and magnetic nano-particle are added thereto, by the absorptive collection supernatant of externally-applied magnetic field, filters up to liquid to be checked.Pre-treating method of the present invention carries out separation detection to perfluorochemical in Chinese herbal medicine in conjunction with chromatography, it is easy to operate, quickly, for the traditional Chinese medicinal material samples of matrix complexity, clean-up effect is good, improves accuracy, sensitivity, the repeatability of subsequent detection, meets fast and accurately testing requirements, it is satisfactory to apply to result in the detection of actual sample, therefore there is good practical application value.
Description
Technical field
The invention belongs to technical field of analytical chemistry, are related to the remaining detection of perfluorochemical more particularly to a kind of detection
The sample-pretreating method of perfluorochemical residual quantity in Chinese herbal medicine.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without should
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Perfluorochemical (PFCs) typically refers to all hydrogen atoms in chemical structural formula to be had by one kind that fluorine atom replaces
Machine compound, can long-term existence in the environment, mainly include perfluorocarboxylic acid and perfluorinated sulfonic acid two major classes compound.Perfluor chemical combination
Object has the characteristic of hydrophobic oleophobic, and chemistry, biological stability are higher, is difficult to degrade in the environment under natural conditions, and can
As being delivered in living organism for food chain is enriched with.Perfluorochemical can generate toxicity and influence to a variety of organs, be one
Kind can endanger environment and the chronicity pollutant of the mankind, it has organ toxicity, genotoxicity, carcinogenicity, immunotoxicity, mind
It through a variety of physiological actions such as toxicity and endocrine disruption, brings and seriously threatens to human health, increasingly obtain both domestic and external extensive
Concern and attention.
In recent years, demand of the countries in the world to natural drug is growing, and especially pays close attention to particularly with green medicine.In and
Herbal medicine is the rarity of our Chinese nation, possesses thousands of years long histories.However the matter occurred in Chinese herbal medicine production process
Amount safety problem constrains the development of China's Chinese medicine cause.Wherein, perfluorochemical residue problem is particularly subject to pay close attention in recent years.
Pre-treating method common for perfluorochemical mainly includes liquid-liquid extraction, ultrasonic extraction, Soxhlet extraction, accelerates solvent at present
Extraction, Solid Phase Extraction, ion pair extraction and alkali digestion etc. can also perform the derivatization technical treatment to perfluorochemical sometimes, but
Not yet form a set of unified pre-treating method regulation.It is reported that the error of detection and analysis nearly 50% is from sample
Pretreatment process, therefore, the reasonable efficient Sample Pretreatment Technique of selection are that realization is quick, accurately detect perfluorochemical
Basis and guarantee.However, the generally existing pre-treatment program of the above method is more complex or clean-up effect is poor, error is larger, cost
The defects of higher, poor universality, it is therefore necessary to establish a kind of pair of Chinese herbal medicine perfluorochemical testing cost it is low, it is quick, efficient,
The good sample-pretreating method of high sensitivity, selectivity.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides a kind of sample for detecting perfluorochemical residual quantity in Chinese herbal medicine
Product pre-treating method, especially a kind of one-step method sample-pretreating method for detecting perfluorochemical residual quantity in Chinese herbal medicine, i.e.,
The extraction and purification of target compound are realized in single stepping, this method is simple, efficient, time saving and energy saving, at low cost, can be effective
Meet quickly, it is accurate, sensitively detect needs, therefore there is good practical application value.
One of the objects of the present invention is to provide a kind of sample pre-treatments of perfluorochemical residual quantity in detection Chinese herbal medicine
Method.
The second object of the present invention is to provide the above method answering in perfluorochemical in chromatography detection Chinese herbal medicine
With.
To achieve the above object, the present invention relates to following technical schemes:
The first aspect of the invention provides a kind of sample pre-treatments side for detecting perfluorochemical residual quantity in Chinese herbal medicine
Method, which comprises
S1. acetonitrile extracting solution is added into the Chinese herbal medicine sample after smashing, extraction salt is then added and is extracted；
S2. adsorbent and magnetic nano-particle are added thereto, by the absorptive collection supernatant of externally-applied magnetic field, filtering is
Obtain liquid to be checked.
Further, in the step S1,
Extracting salt is that anhydrous magnesium sulfate and sodium chloride mixing form, and the mass ratio of the anhydrous magnesium sulfate and sodium chloride is 1
~2:0.4~0.8 (preferably 1:0.4)；
The step S1 method particularly includes:
Uniform Chinese herbal medicine sample powder will be smashed and add water, stood, acetonitrile extracting solution and extraction of ocean eddies is added, is then added
Extraction salt carries out vortex processing, is centrifuged to obtain supernatant；
Further, the mass volume ratio of Chinese herbal medicine sample, water, acetonitrile extracting solution and extraction salt is 1~2g:1~2mL:5
~10mL:1.4~2.8g (preferably 1g:1mL:5mL:1.4g)；
In the step S2,
Adsorbent is the mixture of ketjenblack EC GCB and N- propyl ethylenediamine PSA, the ketjenblack EC and N- propyl
The mass ratio of ethylenediamine is 1~3:2~4；
The magnetic nano-particle is Fe3O4Magnetic nano-particle, size controlling are 10~20nm, it is preferred to use chemistry is altogether
The precipitation method are prepared.
Specific preparation method includes: after being added to the water iron chloride and frerrous chloride and being completely dissolved, to be slowly added to ammonium hydroxide liter
Temperature is reacted, and obtains Fe after purified3O4Magnetic nano-particle.
Wherein, molar ratio 1:1~3 (preferably 1:2) of frerrous chloride and iron chloride；
Reaction condition are as follows: 75~85 DEG C of reaction temperature (preferably 80 DEG C), reaction time are 2~4h (preferably 3h)；Instead
Answer the control of temperature and time that Fe is prepared to final3O4The pattern influence of magnetic nano-particle is very big, and then influences its absorption
Purification process finally has an impact the perfluorochemical rate of recovery.
The purification step includes: during the magnetic nano-particle that will be prepared first is cleaned to pH with deionized water and reaches
Property, after with ethyl alcohol clean then carry out (40~50 DEG C) dryings of low temperature.
The Fe3O4The mass ratio of magnetic nano-particle and adsorbent is 1~2:3~7；
The Fe3O4The mass ratio of magnetic nano-particle and Chinese herbal medicine is 0.02~0.04:1~2；
It is described to be filtered into 0.22 μm of filter membrane.
The second aspect of the invention provides the above method answering in perfluorochemical in chromatography detection Chinese herbal medicine
With.
Wherein, the chromatography is preferably liquid chromatography tandem mass spectrometry.
The application specifically: detect liquid to be checked using Liquid Chromatography-Tandem Mass Spectrometry, actual conditions control are as follows:
Liquid phase chromatogram condition: chromatographic column: AcclaimTM C18 (2.1 × 150mm, 3 μm)；Column temperature: 40 DEG C；Flow velocity:
0.4mL/min；Sample volume: 10 μ L；Mobile phase: A is 5mM ammonium acetate buffer, and B is methanol, and gradient elution, elution program is such as
Under: the volume fraction of B phase maintains 10% from initial time to 1min, when rising to 40%, 12min in 0.5min, the body of B phase
Fraction rises to 95%, continue 1min, so that B phase volume fraction is down to 10% in 0.1min, in total analysis time be
17min。
Mass Spectrometry Conditions are as follows: electron spray ion mode (ESI-), multiple-reaction monitoring (MRM)；Gas curtain gas (CUR), atomization gas
(GS1) and auxiliary gas (GS2) pressure is respectively 0.28,0.38 and 0.41MPa；Ion source temperature (TEM): 650 DEG C；Ion source electricity
Press (IS): -4500V.
Since hydrogen atoms most in perfluorochemical structural formula are replaced fluorine atom, the perfluorochemical surveyed is all
It is carboxylic acid and sulfonate, therefore pH value has large effect for its separation analysis.In order to keep perfluorochemical maximum
The deprotonation of limit ground, the present invention is in liquid chromatogram separation process using the side that a certain amount of ammonium acetate is added in mobile phase
Method, while by using gradient elution mode, the deprotonation ability of perfluorochemical not only can be improved, while also can be reduced
The phenomenon that peak trails in chromatogram improves peak shape；In analyte detection process, perfluorochemical is deprotonation in ionization,
So being scanned using negative particle mode to it.
Wherein, the Chinese herbal medicine is fructus lycii, honeysuckle or American Ginseng, preferably honeysuckle.
Advantageous effects of the invention:
(1) in a kind of detection Chinese herbal medicine proposed by the invention perfluorochemical residual quantity sample-pretreating method, will
Salt and adsorbent etc. are added sequentially, and centrifugation step is saved in centre, not only simplify processing method, and save cleanser dosage, are obtained
To good clean-up effect, while the Fe being added3O4Magnetic nano-particle is adsorbed under the action of an external magnetic field, avoid from
Heart step keeps processing method quicker.
(2) in a kind of detection Chinese herbal medicine of the invention perfluorochemical residual quantity sample-pretreating method, with chromatography knot
It closes and separation detection is carried out to perfluorochemical in Chinese herbal medicine, it is easy to operate, quickly, for the traditional Chinese medicinal material samples of matrix complexity, only
Change works well, and improves accuracy, sensitivity, the repeatability of subsequent detection, meets fast and accurately testing requirements, applies to
Result is satisfactory in the detection of actual sample, therefore has good practical application value.
Specific embodiment
It is noted that following detailed description is all illustrative, 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.
As previously mentioned, generally existing pre-treatment program is more complex in the prior art in the detection process of perfluorochemical,
Or the defects of clean-up effect is poor, and error is larger, higher cost, poor universality.
In view of this, in the specific embodiment of the present invention, it is residual to provide perfluorochemical in a kind of detection Chinese herbal medicine
The sample-pretreating method of allowance, specific steps are as follows:
(1) it prepares: the medicinal pulverizer of medium-height grass is uniformly crushed；
(2) it extracts: weighing step (1) smashed sample, be placed in centrifuge tube, deionized water is added, stand, second is added
Then nitrile extracting solution and extraction of ocean eddies are added anhydrous magnesium sulfate and sodium chloride and are vortexed；
(3) it purifies: rapidly joining ketjenblack EC GCB, N- propyl ethylenediamine PSA and Fe3O4Magnetic nano-particle is vortexed,
By the absorptive collection supernatant of externally-applied magnetic field, cross 0.22 μm of filter membrane to get.
In still another embodiment of the invention, the specific processing method of the step (2) are as follows: weigh 1.0~2.0g powder
Broken sample is placed in 15mL centrifuge tube, and 1.0~2.0mL deionized water is added, and stands 5~10min, and 5~10mL acetonitrile is added and mentions
It takes liquid and the 1~2min that is vortexed is extracted, 1.0~2.0g anhydrous magnesium sulfate and 0.4~0.8g sodium chloride is then added and it is vortexed 1~
2min。
In still another embodiment of the invention, Chinese herbal medicine and the solid-liquid ratio of deionized water are 1:1~2 in step (2).
In still another embodiment of the invention, in step (2) solid-liquid ratio of Chinese herbal medicine and acetonitrile extracting solution be 1:5~
10。
In still another embodiment of the invention, the specific processing method of the step (3) are as follows: rapidly join 20~60mg
Ketjenblack EC GCB, 40~80mg N- propyl ethylenediamine PSA and 20~40mg Fe3O4Magnetic nano-particle, vortex 1~
2min, by the absorptive collection supernatant of externally-applied magnetic field, cross 0.22 μm of filter membrane to get.
In still another embodiment of the invention, a kind of sample for detecting perfluorochemical residual quantity in Chinese herbal medicine is provided
Pre-treating method, comprising the following steps:
(1) it prepares: the medicinal pulverizer of medium-height grass is uniformly crushed；
(2) it weighs 1.0g and crushes sample, be placed in 15mL centrifuge tube, 1.0mL deionized water is added, stand 10min, be added
8mL acetonitrile extracting solution and the 1min that is vortexed extraction, are then added 1.0g anhydrous magnesium sulfate and 0.4g sodium chloride and the 1min that is vortexed.
(3) it purifies: rapidly joining 40mg ketjenblack EC GCB, 60mg N- propyl ethylenediamine PSA and 40mgFe3O4It is magnetic
Nanoparticle, vortex 2min cross 0.22 μm of filter membrane by the absorptive collection supernatant of externally-applied magnetic field, wait and enter liquid chromatogram
Tandem mass spectrometer measurement；
Wherein, the Fe3O4The preparation method of magnetic nano-particle, the method are as follows: weigh 5.4110g iron chloride
(FeCl3·6H2O 100mL deionized water) is dissolved in 250mL round-bottomed flask, adds 1.9889g frerrous chloride (FeCl2·
4H2O), magnetic agitation is allowed to dissolve.120mL ammonium hydroxide (NH is added dropwise dropwise in 30min3·H2O), magnetic agitation is kept for 80 DEG C
Oil bath 3h.The magnetic nano-particle being prepared first cleans 5-6 times with deionized water and reaches neutral to pH, after with ethyl alcohol clean two
Secondary be put into 45 DEG C of vacuum ovens is drying to obtain.
In still another embodiment of the invention, liquid phase chromatogram condition: chromatographic column: AcclaimTM C18 (2.1 ×
150mm, 3 μm)；Column temperature: 40 DEG C；Flow velocity: 0.4mL/min；Sample volume: 10 μ L；Mobile phase: A is 5mM ammonium acetate buffer, and B is
Methanol, gradient elution, elution program are as follows: the volume fraction of B phase maintains 10% from initial time to 1min, in 0.5min
When rising to 40%, 12min, the volume fraction of B phase rises to 95%, continues 1min, finally drops in 0.1min B phase volume fraction
To 10%, analysis time is 17min in total.
In still another embodiment of the invention, Mass Spectrometry Conditions are as follows: electron spray ion mode (ESI-), multiple-reaction monitoring
(MRM)；Gas curtain gas (CUR), atomization gas (GS1) and auxiliary gas (GS2) pressure are respectively 0.28,0.38 and 0.41MPa；Ion source
Temperature (TEM): 650 DEG C；Ion source voltage (IS): -4500V.
Explanation is further explained to the present invention by the following examples, but is not construed as limiting the invention.It should be understood that
These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.Actual conditions are not specified in the following example
Test method, carry out usually according to normal condition.
Embodiment 1
Preparation: fructus lycii is uniformly crushed with pulverizer.
It extracts: weighing the fructus lycii sample of 1.0g step (1) crushing, be placed in 15mL centrifuge tube, 2mL deionized water is added,
5min is stood, 8mL acetonitrile extracting solution is added and the 1min that is vortexed is extracted, 1.8g anhydrous magnesium sulfate and 0.6g sodium chloride then is added simultaneously
Vortex 60s.
Purification: 50mg ketjenblack EC GCB, 50mg N- propyl ethylenediamine PSA and 40mg Fe are rapidly joined3O4Magnetism is received
Rice corpuscles, vortex 1min cross 0.22 μm of filter membrane by the absorptive collection supernatant of externally-applied magnetic field, wait and enter liquid chromatogram string
Join mass spectrograph measurement.
Liquid phase chromatogram condition: chromatographic column: AcclaimTM C18 (2.1 × 150mm, 3 μm)；Column temperature: 40 DEG C；Flow velocity:
0.4mL/min；Sample volume: 10 μ L；Mobile phase: A is 5mM ammonium acetate buffer, and B is methanol, and gradient elution, elution program is such as
Under: the volume fraction of B phase maintains 10% from initial time to 1min, when rising to 40%, 12min in 0.5min, the body of B phase
Fraction rises to 95%, continue 1min, so that B phase volume fraction is down to 10% in 0.1min, in total analysis time be
17min。
Mass Spectrometry Conditions are as follows: electron spray ion mode (ESI-), multiple-reaction monitoring (MRM)；Gas curtain gas (CUR), atomization gas
(GS1) and auxiliary gas (GS2) pressure is respectively 0.28,0.38 and 0.41MPa；Ion source temperature (TEM): 650 DEG C；Ion source electricity
Press (IS): -4500V.Through detecting, the measurement rate of recovery to the perfluorochemical in fructus lycii is 75.46%~112.34%, relatively
Standard deviation (RSD) range is 1.92%~7.38%, betters meet the testing requirements of perfluorochemical.
Embodiment 2
Preparation: honeysuckle is uniformly crushed with pulverizer.
It extracts: weighing the honeysuckle sample of 2.0g step (1) crushing, be placed in 15mL centrifuge tube, 1mL deionization is added
Water stands 5min, and 10mL acetonitrile extracting solution is added and the 1min that is vortexed is extracted, 1.0g anhydrous magnesium sulfate and 0.4g chlorination is then added
Sodium and the 60s that is vortexed.
Purification: 60mg ketjenblack EC GCB, 60mg N- propyl ethylenediamine PSA and 40mg Fe are rapidly joined3O4Magnetism is received
Rice corpuscles, vortex 1min cross 0.22 μm of filter membrane by the absorptive collection supernatant of externally-applied magnetic field, wait and enter liquid chromatogram string
Join mass spectrograph measurement.
Liquid phase chromatogram condition: chromatographic column: AcclaimTM C18 (2.1 × 150mm, 3 μm)；Column temperature: 40 DEG C；Flow velocity:
0.4mL/min；Sample volume: 10 μ L；Mobile phase: A is 5mM ammonium acetate buffer, and B is methanol, and gradient elution, elution program is such as
Under: the volume fraction of B phase maintains 10% from initial time to 1min, when rising to 40%, 12min in 0.5min, the body of B phase
Fraction rises to 95%, continue 1min, so that B phase volume fraction is down to 10% in 0.1min, in total analysis time be
17min。
Mass Spectrometry Conditions are as follows: electron spray ion mode (ESI-), multiple-reaction monitoring (MRM)；Gas curtain gas (CUR), atomization gas
(GS1) and auxiliary gas (GS2) pressure is respectively 0.28,0.38 and 0.41MPa；Ion source temperature (TEM): 650 DEG C；Ion source electricity
Press (IS): -4500V.Through detecting, the measurement rate of recovery to the perfluorochemical in honeysuckle is 81.36%~101.96%, phase
It is 1.68%~3.64% to standard deviation (RSD) range, meets the testing requirements of perfluorochemical.
Embodiment 3
Preparation: American Ginseng is uniformly crushed with pulverizer.
It extracts: weighing the American Ginseng sample of 2.0g step (1) crushing, be placed in 15mL centrifuge tube, 2mL deionization is added
Water stands 5min, and 10mL acetonitrile extracting solution is added and the 1min that is vortexed is extracted, 1.8g anhydrous magnesium sulfate and 0.4g chlorination is then added
Sodium and the 60s that is vortexed.
Purification: 50mg ketjenblack EC GCB, 60mg N- propyl ethylenediamine PSA and 40mg Fe are rapidly joined3O4Magnetism is received
Rice corpuscles, vortex 1min cross 0.22 μm of filter membrane by the absorptive collection supernatant of externally-applied magnetic field, wait and enter liquid chromatogram string
Join mass spectrograph measurement.
Liquid phase chromatogram condition: chromatographic column: AcclaimTM C18 (2.1 × 150mm, 3 μm)；Column temperature: 40 DEG C；Flow velocity:
0.4mL/min；Sample volume: 10 μ L；Mobile phase: A is 5mM ammonium acetate buffer, and B is methanol, and gradient elution, elution program is such as
Under: the volume fraction of B phase maintains 10% from initial time to 1min, when rising to 40%, 12min in 0.5min, the body of B phase
Fraction rises to 95%, continue 1min, so that B phase volume fraction is down to 10% in 0.1min, in total analysis time be
17min。
Mass Spectrometry Conditions are as follows: electron spray ion mode (ESI-), multiple-reaction monitoring (MRM)；Gas curtain gas (CUR), atomization gas
(GS1) and auxiliary gas (GS2) pressure is respectively 0.28,0.38 and 0.41MPa；Ion source temperature (TEM): 650 DEG C；Ion source electricity
Press (IS): -4500V.Through detecting, the measurement rate of recovery to the perfluorochemical in American Ginseng is 59.92%~122.35%, phase
It is 1.05%~13.72% to standard deviation (RSD) range.
To sum up, a kind of sample-pretreating method detecting perfluorochemical residual quantity in Chinese herbal medicine of the present invention, behaviour
Make simple, quickly, for the traditional Chinese medicinal material samples of matrix complexity, clean-up effect is good, improves the accuracy, sensitive of subsequent detection
Degree, repeatability, meet fast and accurately testing requirements, it is satisfactory to apply to result in the detection of actual sample.
It should be noted that above example is only used to illustrate the technical scheme of the present invention rather than is limited.Although ginseng
It is described the invention in detail according to given example, but those skilled in the art can be as needed to this hair
Bright technical solution is modified or replaced equivalently, without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. the sample-pretreating method of perfluorochemical residual quantity in a kind of detection Chinese herbal medicine, which is characterized in that the method packet
It includes:
S1. acetonitrile extracting solution is added into the Chinese herbal medicine sample after smashing, extraction salt is then added and is extracted；
S2. adsorbent and magnetic nano-particle are added thereto, by the absorptive collection supernatant of externally-applied magnetic field, filter up to
Examine liquid.
2. a kind of sample-pretreating method as described in claim 1, which is characterized in that in the step S1,
Extracting salt is that anhydrous magnesium sulfate and sodium chloride mixing form, and the mass ratio of the anhydrous magnesium sulfate and sodium chloride is 1~2:
0.4~0.8 (preferably 1:0.4).
3. a kind of sample-pretreating method as described in claim 1, which is characterized in that the step S1 method particularly includes:
Uniform Chinese herbal medicine sample powder will be smashed and add water, stood, acetonitrile extracting solution and extraction of ocean eddies is added, extraction is then added
Salt carries out vortex processing, is centrifuged to obtain supernatant；
Preferably, Chinese herbal medicine sample, water, acetonitrile extracting solution and extraction salt mass volume ratio be 1~2g:1~2mL:5~
10mL:1.4~2.8g (more preferably 1g:1mL:5mL:1.4g).
4. a kind of sample-pretreating method described in claim 1, which is characterized in that in step S2,
Adsorbent is the mixture of ketjenblack EC GCB and N- propyl ethylenediamine PSA, the ketjenblack EC and N- propyl second two
The mass ratio of amine is 1~3:2~4.
5. a kind of sample-pretreating method as described in claim 1, which is characterized in that magnetic nano-particle Fe3O4Magnetism is received
Rice corpuscles, size controlling are 10~20nm.
6. a kind of sample-pretreating method as claimed in claim 5, which is characterized in that Fe3O4Magnetic nano-particle is specifically prepared
Method includes: to be slowly added to ammonium hydroxide heating after being added to the water iron chloride and frerrous chloride and being completely dissolved and reacted, purified
Fe is obtained afterwards3O4Magnetic nano-particle；
Preferably, molar ratio 1:1~3 (more preferably 1:2) of frerrous chloride and iron chloride；
Reaction condition are as follows: 75~85 DEG C of reaction temperature (more preferably 80 DEG C), reaction time are 2~4h (more preferably 3h)；
The purification step includes: that the magnetic nano-particle that will be prepared first is cleaned to pH with deionized water and reaches neutral, after
It is cleaned with ethyl alcohol and then carries out low temperature (preferably 40~50 DEG C) drying.
7. a kind of sample-pretreating method as described in claim 1, which is characterized in that Fe3O4Magnetic nano-particle and adsorbent
Mass ratio be 1~2:3~7；
Fe3O4The mass ratio of magnetic nano-particle and Chinese herbal medicine is 0.02~0.04:1~2.
8. application of any one of the claim 1-7 the method in chromatography detection Chinese herbal medicine in perfluorochemical.
9. application as claimed in claim 8, which is characterized in that application method specifically: liquid to be checked is used liquid chromatography tandem
Mass spectrum is detected, actual conditions control are as follows:
Liquid phase chromatogram condition: chromatographic column: AcclaimTM C18 (2.1 × 150mm, 3 μm)；Column temperature: 40 DEG C；Flow velocity: 0.4mL/
min；Sample volume: 10 μ L；Mobile phase: A is 5mM ammonium acetate buffer, and B is methanol, gradient elution, and elution program is as follows: B phase
Volume fraction maintains 10% from initial time to 1min, when rising to 40%, 12min in 0.5min, the volume fraction liter of B phase
To 95%, continues 1min, B phase volume fraction is finally made to be down to 10% in 0.1min, analysis time is 17min in total；
Mass Spectrometry Conditions are as follows: electron spray ion mode (ESI-), multiple-reaction monitoring (MRM)；Gas curtain gas (CUR), atomization gas (GS1) and
Assisting gas (GS2) pressure is respectively 0.28,0.38 and 0.41MPa；Ion source temperature (TEM): 650 DEG C；Ion source voltage
(IS): -4500V.
10. the application as described in any one of claim 1-7 the method and/or claim 8 or 9, which is characterized in that in described
Herbal medicine is fructus lycii, honeysuckle or American Ginseng, preferably honeysuckle.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111151222A (en) * | 2020-03-06 | 2020-05-15 | 福州海关技术中心 | Preparation of magnetic composite adsorption material and application of magnetic composite adsorption material in detection of multiple pesticide residues in tea |
| CN112345664A (en) * | 2020-10-26 | 2021-02-09 | 湖北省产品质量监督检验研究院 | Method for measuring residual quantity of perfluorocarboxylic acids in animal-derived food |
| CN115078607A (en) * | 2022-06-21 | 2022-09-20 | 浙江省农业科学院 | Sample pretreatment method for determining perfluorinated compounds in dairy products based on magnetic nano material one-step method |
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