CN109382076A - A kind of preparation and its application method of combined nano Magnetic Isolation medium - Google Patents
A kind of preparation and its application method of combined nano Magnetic Isolation medium Download PDFInfo
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Abstract
A kind of preparation and its application method of combined nano Magnetic Isolation medium, the method that disposable concentration and separation is carried out for the component in complex system with opposed polarity feature using the combination of a variety of different characteristic nano-magnetic separating mediums.It will be modified with porous or non-porous structure magnetic Nano material matrix, be prepared into the nano-magnetic separating medium of different characteristic.By different types of separation material be combined into it is new there is special selective hybrid separation medium, make it that there is high adsorptive selectivity and adsorption capacity to different target component.The nano-magnetic separating medium for having adsorbed target components is separated with complex sample matrix by magnetic separation technique, and develops Qualitative and quantitative analysis through thermal desorption GC/MS.It is an advantage of the invention that it is highly selective, be efficiently enriched with target compound, sample pretreating method is convenient, efficient, and the stability of method is good, effective and rapid ground adjusting method with adapt to particular types target components in different component sample method develop.
Description
Technical field
The present invention relates to the sample pretreatments and technical field of chromatographic analysis in analytical chemistry, are a kind of group specifically
Close the preparation and its application method of nano-magnetic separating medium.
Background technique
Analysis method development for specific structure volatile component in complex system, there are many technologies for choosing
It selects, these technologies include extraction, absorption etc..Simultaneously for characteristic components such as a variety of different structures, polarity in complex sample matrix
The Sample Pretreatment Technique of concentration and separation is always the hot spot direction of analytical chemist research.
In recent years, the application of magnetic Nano separation material receives significant attention in the numerous areas such as biology, environment, and
It is successfully applied in complex biological matrix toxic contaminant trace species in the research of protein, metabolic components etc. and environment
Analysis method establish.Magnetic nano-particle passes through surface modification appropriate, can combining target molecule with high selectivity, solving
The quick separating of object detects and the Selective Separation context of detection of high specific has advantage.Using different groups to base
Matter is modified, available to have different selective different types of separating mediums, and may be implemented to specific structure
The selective enrichment of target components separates.After the completion of enrichment, the paramagnetism based on magnetic substrate can be easily by material from base
Carry out Magneto separate and cleaning in matter, it is easy to operate, analysis is quick, ultrahigh in efficiency.
In order to realize specific separation purpose, sometimes, the modification of single group can not reach requirement, it usually needs to base
Matter surface carries out special modification mode, it is also possible to need the surface bond or the different types of modification of coating in same matrix
Agent can play the influence of different clastotypes or difference intermolecular interaction.Mixed chromatogram stationary phase use is
Another method that separation selectivity is adjusted.The three-in-one Solid Phase Extraction needle of SUPELCO company production, not by three kinds
Connatural extraction stationary phase is also secured to the surface of extraction needle, and the same of the target components such as opposed polarity, structure may be implemented
When obtain, enrichment for volatile component in the complex matrices such as milk, coffee and analysis method development are achieved and are imitated well
Fruit, and be widely used.However, this method fixes three kinds of stationary phases according to specific ratio, not only stationary phase
Type is strictly limited, and ratio is also fixed, and limits its flexibility for being used for method development.
Multifunction magnetic nanometer separating medium preparation and its separating, analyzing in detection field application be used as analysisization
One of the research hotspot in field, needs to combine a variety of functional groups on the same nano particle, brings very big difficulty to preparation
Degree.In order to separate a variety of different structures simultaneously with the target components of property in primary pretreatment separation, knot of the present invention
The theory for closing spectra unmixing separation is built into newly using by a variety of mix with different selective magnetic Nano separating mediums
The method with target selectivity separating medium, the either type of separating medium, or the ratio being added can be convenient
Ground is adjusted, and greatlys improve the flexibility of its application.By Magneto separate, volatile component is carried out in conjunction with thermal desorption, GC/MS technology
Analysis method development have broad application prospects and commercial value.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparations of combined nano Magnetic Isolation medium
And its application method.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of method of the preparation of combined nano Magnetic Isolation medium, it is characterised in that: will have magnetism
Nano material matrix carries out the modification of functional group, is prepared into the nano-magnetic separating medium of different characteristic, by the modified base of selectivity
Different types of separation material of group is combined into hybrid separation medium, comprising the following steps:
(1) preparation of magnetic nanoparticle matrix: using superparamag-netic iron oxide as the core of matrix, with solvent-thermal method
Superparamag-netic iron oxide is prepared, further in the coated porous silica shell in its surface, obtains Fe3O4@SiO2It receives
Rice material；
(2) the pre- modification of stromal surface: synthesis Fe3O4@SiO2- MPS obtains the magnetic Nano material of surface bond double bond
Fe3O4@SiO2- MPS further synthesizes Fe3O4@SiO2-PGMA；
(3 preparations are for separating the functional magnetic for the magnetic Nano material that selective enrichment separates in complex biological sample
Nanometer separating medium；
(4) preparation of composite magnetic nanometer separating medium: a variety of magnetic Nano separating mediums are directly mixed, can be obtained
With different selective nanometer separating mediums.
Magnetic Nano matrix described in step (1) has magnetic kernel, and the porous silica layer of core surface cladding,
The size of nano material is 100nm-2000nm, and the pore diameter range on surface is 1nm-100nm.
The property modifying functional group includes: nonpolar C18, C8, benzene homologue, graphene；Moderately polar cyano, terpene
Alkenes molecule, acrylamide；Polar group sulfonic group, carboxylic acid, alkaloid, amide and metallorganic；Selective modified group
It include: one of cyclodextrin, macrocyclic antibiotic, protein, cellulose and natural products or a variety of terpenes, flavonoids object
Matter.
The magnetic Nano of at least three kinds of above identical or different classes in the preparation of step (4) composite magnetic nanometer separating medium
Separating medium combines in proportion, and new nanometer separating medium is constituted after mixing.Combined method 1: uniform combination, each separation are situated between
Matter is mixed according to identical weight percent；Combined method 2: non-homogeneous combination, each separating medium is according to different
Weight percent is mixed, such as the first 10%-50%, second of 20%-40%, the third 10%-0%.
The present invention also provides a kind of application methods of combined nano Magnetic Isolation medium, it is characterised in that: passes through magnetic point
The nano-magnetic separating medium for having adsorbed target components is separated with complex sample matrix from technology, and further combined with heat
Desorption GC/MS carries out qualitative and quantitative analysis, and steps are as follows for specifically used method:
(1) Magneto separate operates: magnetic Nano material is weighed according to the volume ratio of 1:1 to 1:1000, after being washed with sample solution
It is scattered in sample solution, is made into 60mg mL-1Homogeneous solution, and be directly thrown into sample solution, stir 1min-100min,
It is adsorbed using magnet and carries out Magneto separate and cleaning operation, wherein sample solution are as follows: ACN-H2O-TFA, 88/11.9/0.1, v/v/
v。
(2) thermal desorption operates: the separating medium for having adsorbed target compound by above-mentioned steps (1) is directly placed in
Thermal desorption is carried out in thermal desorption pipe,
(3) GC/MS is analyzed: qualitative and quantitative point of the sample component further progress GC/MS that above-mentioned steps (2) are desorbed
Analysis, obtains the information of target components.
Separation material and method of the invention is waved suitable for natural products, body fluid, environmental sample class complex sample matrix
The separation analysis of hair property component, particularly suitable for the analysis of essence, fragrance, volatile oil.
Compared with prior art, the positive effect of the present invention is:
(1) the combined nano Magnetic Isolation medium prepared by, preparation method is simple, cost is relatively low, stationary phase stable structure；
(2) combined nano Magnetic Isolation medium had both had the features such as high pressure resistant silicon ball matrix, large specific surface area, while can
For Magneto separate, it is convenient to operate；Meanwhile mixed proportion can be adjusted arbitrarily, selective control has huge space；
(3) combined nano Magnetic Isolation medium is the mixture of same matrix difference modified form Magnetic Isolation medium,
Both part having the same in characteristic, it is also different and different because of binding groups.But it has abandoned " three-in-one " extraction
The type of needle class adsorbent not only stationary phase is strictly limited, and ratio also fixed defect significantly improves its side
The flexibility of method development.
(4) combined nano Magnetic Isolation medium is waved suitable for the complex samples matrix such as natural products, body fluid, environmental sample
The separation analysis of hair property component, develops particularly suitable for the analysis method of essence, fragrance, volatile oil.
Detailed description of the invention
Fig. 1 is a kind of for separating the magnetic Nano material of selective glycopeptide concentration and separation in complex biological sample；
Fig. 2 is a kind of magnetic Nano material for selective phosphoeptide concentration and separation；
Specific embodiment
A kind of preparation of combined nano Magnetic Isolation medium of the present invention presented below and its specific embodiment party of application method
Formula.
Implementation column one
1. the preparation of magnetic nanoparticle matrix:
Magnetic nano particle matrix can be obtained using the method directly purchased or voluntarily prepared.General preparation
Method is to prepare core of the superparamag-netic iron oxide as its matrix first, further in the coated porous silica in its surface
Shell.
Superparamag-netic iron oxide is prepared with solvent-thermal method, 100mL ethylene glycol is measured and is placed in 250mL three-necked flask,
2.7g Iron(III) chloride hexahydrate is added, after ultrasonic 10min, is added 7.2g anhydrous sodium acetate, after mechanical stirring 30min, will mix
Good homogenate is transferred to the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reacts 8h in 200 DEG C of baking ovens.Later, in extraneous magnetic
Under the auxiliary of field, is washed respectively with ethyl alcohol and pure water and collect magnetic Nano matrix Fe3O4, 60 DEG C are dried overnight, and obtain magnetic oxygen
Change iron nano-particle.
Weigh the above-mentioned Fe of 150mg3O4Even particulate dispersion is in 160mL ethyl alcohol, the mixed solution of 40mL water and 2mL ammonium hydroxide
In, 1.5mL TEOS is added dropwise in ultrasonic 30min, at room temperature 8 h of mechanical stirring.Magneto separate successively cleans number with second alcohol and water
Secondary, 60 DEG C are dried overnight, and obtain the Fe of coated silica layer3O4@SiO2Nano material.
2. the pre- modification of stromal surface:
(1)Fe3O4@SiO2The synthesis of-MPS
Take the above-mentioned Fe of 300mg3O4@SiO2Nano material is dispersed in the mixed liquor containing 40mL ethyl alcohol and 10mL water, is added
1.5mL concentrated ammonia liquor, ultrasonic disperse are uniformly placed in 60 DEG C of oil baths, and 800 μ L 3- (trimethoxy first silicon substrate) methyl is added dropwise
Acrylate, stirring is for 24 hours.After reaction, under magnet auxiliary, product for several times, obtains surface key through ethyl alcohol and pure water
Close the magnetic Nano material Fe of double bond3O4@SiO2-MPS。
(2)Fe3O4@SiO2The synthesis of-PGMA
Weigh 60mg Fe3O4@SiO2- MPS ultrasonic disperse is in 40mL acetonitrile.140 μ L methyl are separately added into solution
Glycidyl acrylate, 150mg N, N- methylene bisacrylamide, 8mg azodiisobutyronitrile after ultrasonic disperse, are placed in oil bath
90 DEG C of reaction 1.5h in pot.Magneto separate is cleaned with second alcohol and water after washing, and obtains the magnetic Nano material of polymer P GMA package
Fe3O4@SiO2@PGMA.Later, polymer epoxide epoxy group group open loop is made by ethylenediamine, obtains a large amount of amido modified magnetic
Ball.Magneto separate is cleaned several times with second alcohol and water, and product drying is stand-by.
3. the preparation of functional magnetic nanometer separating medium:
Take the above-mentioned magnetic Nano material Fe of 50mg3O4@SiO2@PGMA-NH2 is scattered in the ultrapure water of 70mL, 70 DEG C of oil
In bath, 500 μ L tetrachloro alloy aqueous acids (20mg mL-1), product washed several times with water is added dropwise.It is scattered in 80mL water, adds
Enter excessive L-cysteine, is stirred overnight at room temperature.Gained final product, Fe3O4@SiO2@PGMA@Au-L-cys.It washs for several times,
It is dried in 50 DEG C of baking ovens to get to the magnetic Nano material for separating in complex biological sample selective glycopeptide concentration and separation
Material.Referring to Fig. 1
4. the preparation of composite magnetic nanometer separating medium:
A variety of magnetic Nano separating mediums are directly mixed, can be obtained with different selective new separating mediums.
It is combined, is constituted after mixing new in proportion using the magnetic Nano separating medium of at least three kinds of above identical or different classes
Nanometer separating medium.Combined method 1: uniform combination, each separating medium are mixed according to identical weight percent；
Combined method 2: non-homogeneous combination, each separating medium are mixed according to different weight percent, such as the first
10%-50%；Second of 20%-40% etc..
5. the application method of composite magnetic nanometer separating medium:
(1) Magneto separate operates:
Suitable magnetic Nano material is weighed, after sample solution (ACN-H2O-TFA, 88/11.9/0.1, v/v/v) washing
It is scattered in sample solution, is made into 60mg mL-1Homogeneous solution.And sample is directly thrown into according to the volume ratio of 1:1 to 1:1000
In product solution, 1min-100min is stirred；It is adsorbed using magnet and carries out Magneto separate and cleaning operation.
(2) thermal desorption operates:
The separating medium for having adsorbed target compound is directly placed in thermal desorption pipe and carries out thermal desorption, typical conditions
Are as follows: Tube parsing, using Splitless injecting samples mode, thermal desorption pipe is in 280 DEG C of parsing 5min；Trap parsing, using not being diverted into
Original mold formula, sample enter cold-trap after level-one parses, and condenser temperature is -20 DEG C, enriched sample, subsequent Trap parsing, from -20
DEG C 280 DEG C are warming up to maximum heating rate, keep 5min, transmission line temperature is 200 DEG C between makings and thermal desorption.
(3) GC/MS is analyzed:
By the sample component further progress GC/MS qualitative and quantitative analysis of desorption, the relevant information of target components is obtained.
The present embodiment GC-MS analysis condition: middle polarity capillary chromatographic column, column length 50m；Column temperature retains at 57 DEG C
2min is warming up to 260 DEG C of holding 20min with the rate of 4 DEG C/min, and carrier gas is helium, and flow velocity 1.0ml/min, injection port is not
Shunt mode, injector temperature are 250 DEG C；Electron impact ion source be the source EI, 230 DEG C of ion source temperature, level four bars temperature 150
DEG C, ionization energy 70eV, using scan type collection data, scanning range 29-420amu.
Embodiment two
1) superparamag-netic iron oxide is prepared with solvent-thermal method, measures 100mL ethylene glycol and is placed in 250mL three-necked flask
In, 2.7g Iron(III) chloride hexahydrate is added, after ultrasonic 10min, is added 7.2g anhydrous sodium acetate, after mechanical stirring 30min, will mix
The homogenate got togather is transferred to the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), reacts 8h in 200 DEG C of baking ovens.Later, in the external world
Under the auxiliary in magnetic field, is washed respectively with ethyl alcohol and pure water and collect magnetic Nano matrix Fe3O4, 60 DEG C are dried overnight, and obtain magnetism
Ferric oxide nanometer particle.
2) the above-mentioned Fe of 150mg is weighed3O4Even particulate dispersion is in 160mL ethyl alcohol, the mixed solution of 40mL water and 2mL ammonium hydroxide
In, 1.5mL TEOS is added dropwise, at room temperature mechanical stirring 8h in ultrasonic 30min.Magneto separate successively cleans number with second alcohol and water
Secondary, 60 DEG C are dried overnight, and obtain the Fe of coated silica layer3O4@SiO2Nano material.
3) the above-mentioned Fe of 300mg is taken3O4@SiO2Nano material is dispersed in the mixed liquor containing 40mL ethyl alcohol and 10mL water,
1.5mL concentrated ammonia liquor is added, ultrasonic disperse is uniformly placed in 60 DEG C of oil baths, and 800 μ L 3- (trimethoxy first silicon substrate) is added dropwise
Methacrylate, stirring is for 24 hours.After reaction, under magnet auxiliary, product for several times, obtains table through ethyl alcohol and pure water
The magnetic Nano material Fe of face bonding double bond3O4@SiO2-MPS。
4) 60mg Fe is weighed3O4@SiO2- MPS ultrasonic disperse is in 40mL acetonitrile.140 μ L first are separately added into solution
Base glycidyl acrylate, 150mg N, N- methylene bisacrylamide, 8mg azodiisobutyronitrile after ultrasonic disperse, are placed in
90 DEG C of reaction 1.5h in oil bath pan.Magneto separate is cleaned with second alcohol and water after washing, and obtains the magnetic Nano material of polymer P GMA package
Expect Fe3O4@SiO2@PGMA.Later, polymer epoxide epoxy group group open loop is made by ethylenediamine, obtains a large amount of amido modified magnetic
Ball.Magneto separate is cleaned several times with second alcohol and water, and product drying is stand-by.
5) the above-mentioned magnetic Nano material Fe of 50mg is taken3O4@SiO2@PGMA-NH2 is scattered in the ultrapure water of 70mL.Respectively
It is modified using C18, glycine betaine, obtains Fe3O4@SiO2@PGMA-C18 and Fe3O4@SiO2@PGMA- glycine betaine.
6) Fe of identical weight is weighed respectively3O4@SiO2@PGMA-NH2、Fe3O4@SiO2@PGMA-C18 and Fe3O4@
SiO2@PGMA- glycine betaine is scattered in sample solution after being washed with sample solution (ACN-H2O-TFA, 88/11.9/0.1, v/v/v),
It is made into 60mg mL-1Homogeneous solution.And sample solution is mentioned according to the water that the volume ratio of 1:800 is directly thrown into certain natural products
In, stir 5min；It is adsorbed using magnet and carries out Magneto separate and cleaning operation.
7) thermal desorption operates: Markes TD-100 thermal desorption analysis condition: Tube parsing, using Splitless injecting samples mode,
Thermal desorption pipe is in 280 DEG C of parsing 5min；Trap parsing, using Splitless injecting samples mode, sample enters cold after level-one parses
Trap, condenser temperature are -20 DEG C, enriched sample, and subsequent Trap parsing is warming up to 280 DEG C from -20 DEG C with maximum heating rate, protects
5min is held, transmission line temperature is 200 DEG C between makings and thermal desorption.
8) GC/MS is analyzed: Agilent 5973C analysis condition: column temperature is in 57 DEG C of reservation 2min, with the rate liter of 4 DEG C/min
Temperature is to 260 DEG C of holding 20min, and carrier gas is helium, and flow velocity 1.0ml/min, injection port is that shunt mode, injector temperature are not
250℃；Electron impact ion source is the source EI, 230 DEG C of ion source temperature, 150 DEG C of level four bars temperature, ionization energy 70eV, is used
Scan type collection data, scanning range 29-420amu.
Embodiment three
It is identical with embodiment one, except that in step 3 functional magnetic nanometer separating medium preparation: take 50 it is upper
State magnetic Nano material Fe3O4@SiO2@PGMA-NH2 is scattered in 80mL and contains 2,4,6- trimethylpyridine of 60mmol L-1
In ACN solution.After being passed through nitrogen 10min, 800 μ L phosphorus oxychloride are added.12h is stirred at room temperature in nitrogen protection.Resulting materials are used
Acetonitrile and water washing, 50 DEG C of magnetic Nanos obtained by drying to for dispersing the concentration and separation of selective phosphoeptide in biological sample
Material.Referring to fig. 2.
Claims (7)
1. a kind of method of the preparation of combined nano Magnetic Isolation medium, it is characterised in that: will have magnetic Nano material matrix
The modification for carrying out functional group, is prepared into the nano-magnetic separating medium of different characteristic, by the variety classes of selective modified group
Separation material be combined into hybrid separation medium, comprising the following steps:
(1) it the preparation of magnetic nanoparticle matrix: using superparamag-netic iron oxide as the core of matrix, is prepared with solvent-thermal method
Superparamag-netic iron oxide is obtained, further in the coated porous silica shell in its surface, obtains Fe3O4@SiO2Nanometer material
Material；
(2) the pre- modification of stromal surface: synthesis Fe3O4@SiO2- MPS obtains the magnetic Nano material Fe of surface bond double bond3O4@
SiO2- MPS further synthesizes Fe3O4@SiO2-PGMA；
(3 preparations are for separating the functional magnetic nanometer for the magnetic Nano material that selective enrichment separates in complex biological sample
Separating medium；
(4) preparation of composite magnetic nanometer separating medium: a variety of magnetic Nano separating mediums are directly mixed, can be obtained has
The nanometer separating medium of different selectivity.
2. a kind of preparation method of combined nano Magnetic Isolation medium as described in claim 1, it is characterised in that: step (1)
The magnetic Nano matrix have magnetic kernel, and core surface cladding porous silica layer, nano material having a size of
100nm-2000nm, the pore diameter range on surface are 0nm-100nm.
3. a kind of preparation method of combined nano Magnetic Isolation medium as described in claim 1, it is characterised in that: described changes
Property functional group includes: nonpolar C18, C8, benzene homologue, graphene；Moderately polar cyano, terpenes molecule, acryloyl
Amine；Polar group sulfonic group, carboxylic acid, alkaloid, amide and metallorganic；Selective modified group includes: cyclodextrin, big ring
One of antibiotic, protein, cellulose and natural products or a variety of terpenes, Flavonoid substances.
4. a kind of preparation method of combined nano Magnetic Isolation medium as claimed in claim 1 or 3, it is characterised in that: step
(4) in the preparation of composite magnetic nanometer separating medium the magnetic Nano separating medium of at least three kinds of identical or different classes according to identical
Weight percent mixed, obtain uniform combination composition nanometer separating medium.
5. a kind of preparation method of combined nano Magnetic Isolation medium as claimed in claim 1 or 3, it is characterised in that: step
(4) the magnetic Nano separating medium of at least three kinds of above identical or different classes is non-in the preparation of composite magnetic nanometer separating medium
Even combination, each separating medium are mixed according to different weight percent, mix to obtain ratio are as follows: the first 10%-
50%, second of 20%-40%, the third 10-80%.
6. a kind of application method of the combined nano Magnetic Isolation medium prepared with claim 1, it is characterised in that: pass through magnetic point
The nano-magnetic separating medium for having adsorbed target components is separated with complex sample matrix from technology, and further combined with heat
Desorption GC/MS carries out qualitative and quantitative analysis, and steps are as follows for specifically used method:
(1) Magneto separate operates: weighing magnetic Nano material according to the volume ratio of 1:1 to 1:1000, disperses after being washed with sample solution
In sample solution, it is made into 60mg mL-1Homogeneous solution, and be directly thrown into sample solution, stir 1min-100min, use
Magnet absorption carries out Magneto separate and cleaning operation, wherein sample solution are as follows: ACN-H2O-TFA, 88/11.9/0.1, v/v/v.
(2) thermal desorption operates: the separating medium for having adsorbed target compound by above-mentioned steps (1) being directly placed in heat and is taken off
Thermal desorption is carried out in attached pipe,
(3) GC/MS is analyzed: the sample component further progress GC/MS qualitative and quantitative analysis that above-mentioned steps (2) are desorbed obtains
To the information of target components.
7. a kind of application method of combined nano Magnetic Isolation medium as claimed in claim 6, it is characterised in that: separation material
And the separation analysis of method volatile component suitable for natural products, body fluid, environmental sample class complex sample matrix, it is especially suitable
In the analysis of essence, fragrance, volatile oil.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111330555A (en) * | 2020-03-13 | 2020-06-26 | 天津迪沃特生物电子科技有限公司 | Magnetic core-shell mesoporous silica gel material and preparation method and application thereof |
| CN111359593A (en) * | 2020-03-19 | 2020-07-03 | Tcl华星光电技术有限公司 | Magnetic solid phase extraction agent and preparation method and application thereof |
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