CN106824139A - It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle - Google Patents
It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle Download PDFInfo
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Abstract
A kind of to stablize overall column preparation method of the Pickering emulsions as filler based on nano-particle, it is related to analysis detection and nanometer technique field, and in particular to a kind of preparation method of integral post.Filler hydrophilic and hydrophobic the invention aims to solve existing integral post is different, it is impossible to while the problem of the different molecule of separation and concentration hydrophilic and hydrophobic.Method：First, nano-particle stabilization Pickering emulsions are prepared；2nd, integral post pretreatment；3rd, filling Pickering emulsions in integral post；4th, integral post wash-out；Obtain the integral post as filler based on nano-particle stabilization Pickering emulsions.The inventive method has the advantages that quick, efficient, convenient, low cost, environment-friendly, while can largely prepare and reuse.The present invention can obtain it is a kind of based on nano-particle stabilization Pickering emulsions as filler overall column preparation method.
Description
Technical field
The present invention relates to analyze detection and nanometer technique field, and in particular to a kind of preparation method of integral post.
Background technology
Integral post, as a kind of separation and concentration packed column, is to develop very fast a kind of new chromatographic column in recent years,
Possess separative efficiency high, good biocompatibility, permeability is good, the advantages of technology of preparing is simple, be widely used in efficient liquid phase
In the analytical instrument such as chromatogram, micro-nano high performance liquid chromatography, capillary electric chromatogram.At present, the integral post of preparation is by its synthesis material
The attribute of material can be divided into two major classes：Organic polymer is filled and inorganic material filling.Preparation method is relatively single, two class integral posts
Respectively there are advantage and disadvantage, give full play to the superiority of different materials.And two kinds of Monolithic Columns hydrophilic and hydrophobics are different, and it is right
When separation and concentration hydrophilic and hydrophobic different molecular, two kinds of Monolithic Columns seem that performance is single, so prepare hydrophilic and hydrophobic having
Anisotropic material is particularly important.
Pickering emulsions refer to the emulsion using micro Nano material stabilization, and this emulsion is that name is Pickering
After researcher has carried out systematic research to the emulsion of solids stabilization, hereafter researchers are solids stabilization
Emulsion is referred to as Pickering microemulsions.The material of special construction, such as Janus knots can be prepared using emulsion two-way system
Material of structure etc. is that surface has different hydrophilic and hydrophobics.And the integral post for utilizing Pickering emulsion technologies to fill, can prepare
Go out anisotropy entirety column material, so as to improve the separation and enrichment to sample.So far, will not also
The report of the integral post of Pickering emulsions filling, therefore, carry out the preparation work of the integral post of Pickering emulsions filling
And the application of material is by with important academic significance and realistic meaning.
The content of the invention
Filler hydrophilic and hydrophobic the invention aims to solve existing integral post is different, it is impossible to while separation and concentration
The problem of the different molecule of hydrophilic and hydrophobic, and provide it is a kind of based on nano-particle stabilization Pickering emulsions as the whole of filler
Scapus preparation method.
It is a kind of based on nano-particle stabilization Pickering emulsions as filler overall column preparation method, specifically by with
What lower step was completed：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 10min~60min, add after water phase vortex mixed 1min again
~10min, obtains nano-particle stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be (5 μ L~30 μ L):1mL；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is (2 μ L~8 μ L):1mL；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:(0.3mL~5mL)；
Water phase and the volume ratio of oil phase described in step one are (0.1~10):100；
Nano material described in step one is in tubular nanometer material, lamella nano material and nano spherical particle
Plant or wherein several mixtures；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 10min~30min each to capillary with acetone, then by the acetone soln of γ-MAPS that volume fraction is 10%~50%
It is injected into capillary, the two ends of capillary is sealed with silica gel plug, then is placed in heating in the baking oven that temperature is 40 DEG C~70 DEG C
8h~14h, then the silica gel plug at capillary two ends is opened, acetone is reused to capillary douche 10min~30min, reuse nitrogen
Gas dries up capillary, obtains pretreated integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 50%~98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1~0.5mLmin-1Flow velocity be injected into pretreated integral post, then by the two ends silicon of capillary
Plug is sealed, and obtains populated integral post；Populated integral post is put into the baking oven that temperature is 30 DEG C~200 DEG C and is solidified
1h~48h；The integral post for being solidified；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 account for capillary volume 90%~
100%；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min~60min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.42~0.67.
Principle of the invention and advantage：
First, the nano-particle stabilization Pickering emulsions that prepared by the present invention are the materials of Janus structures, and this material has
Different hydrophilic and hydrophobics, because two kinds of nano-particles of the Pickering emulsions for stablizing can be hydrophilic with one of which, separately
A kind of is hydrophobic, so the material that thus prepared by Pickering emulsions is also with dual character, referred to as Janus structures,
I.e. a part is hydrophilic, and a part is hydrophobic；
2nd, the present invention prepares filler of the nano-particle stabilization Pickering emulsions as entire capillary, obtains a kind of new
The integral post of the Nanoparticle Modified of type, it can be used for SPME, it is also possible to for micro-nano liquid-phase chromatographic column；It is this
Pickering emulsions using nano-particle stabilization are domestic initiations as the filling method of capillary column, are not reported so far；
What the 3rd, prepared by the present invention is had adjustable based on nano-particle stabilization Pickering emulsions as the integral post of filler
The pore structure of control, with good biocompatibility；Collection is extracted, purified, being enriched in one, and can be realized with various analytical instrument
Offline/on-line coupling；Present invention utilization Pickering emulsion technologies of preparing, the integral post of the 3-D solid structure of synthesizing new,
Successfully prepare with anisotropic overall column material, enrich the preparation method of integral post, expand the species of integral post,
For the development of chromatogram micro separation technique lays the foundation, with important academic significance and realistic meaning；
4th, the present invention is successfully made using new Pickering emulsions technology of preparing combination and the multiple advantage of integral post
It is standby that there is anisotropic overall column material, i.e. nano-particle stabilization Pickering emulsion capillary columns, and to sample
In close and distant property, or the material such as the different molecule of polarity, protein detection provide it is quick, efficiently, it is convenient, simple separate it is new
Material, is very suitable for the analysis of glucocorticoids material in cosmetic sample, is separated and the micro- extraction of solid phase in hormonal substance
The field of taking has great application potential；
5th, the inventive method has the advantages that quick, efficient, convenient, low cost, environment-friendly, while can largely prepare
And reuse.
The present invention can obtain it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post preparation side
Method.
Brief description of the drawings：
Fig. 1 is the cutting as the integral post of filler based on nano-particle stabilization Pickering emulsions prepared by embodiment seven
Surface scan electron microscope；
Fig. 2 is chromatogram, and A is the chromatographic curve of direct liquid phase-mass spectral analysis in Fig. 2, and B is to be prepared by embodiment seven
Liquid phase-the mass spectral analysis determined after overall column extracting, parsing based on nano-particle stabilization Pickering emulsions as filler
Chromatographic curve, 3 is dexamethasone chromatographic peak, and 4 is betamethasone chromatographic peak；
Fig. 3 is chromatogram, and A is the chromatographic curve of direct liquid phase-mass spectral analysis in Fig. 3, and B is to be prepared by embodiment seven
Liquid phase-the mass spectral analysis determined after overall column extracting, parsing based on nano-particle stabilization Pickering emulsions as filler
Chromatographic curve, 1 is prednisolone, and 2 is cortisone.
Specific embodiment：
With reference to specific embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Specific embodiment one：Present embodiment is a kind of nano-particle stabilization Pickering emulsions that are based on as filler
Overall column preparation method, what the method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 10min~60min, add after water phase vortex mixed 1min again
~10min, obtains nano-particle stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be (5 μ L~30 μ L):1mL；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is (2 μ L~8 μ L):1mL；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:(0.3mL~5mL)；
Water phase and the volume ratio of oil phase described in step one are (0.1~10):100；
Nano material described in step one is in tubular nanometer material, lamella nano material and nano spherical particle
Plant or wherein several mixtures；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 10min~30min each to capillary with acetone, then by the acetone soln of γ-MAPS that volume fraction is 10%~50%
It is injected into capillary, the two ends of capillary is sealed with silica gel plug, then is placed in heating in the baking oven that temperature is 40 DEG C~70 DEG C
8h~14h, then the silica gel plug at capillary two ends is opened, acetone is reused to capillary douche 10min~30min, reuse nitrogen
Gas dries up capillary, obtains pretreated integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 50%~98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1~0.5mLmin-1Flow velocity be injected into pretreated integral post, then by the two ends silicon of capillary
Plug is sealed, and obtains populated integral post；Populated integral post is put into the baking oven that temperature is 30 DEG C~200 DEG C and is solidified
1h~48h；The integral post for being solidified；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 account for capillary volume 90%~
100%；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min~60min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.42~0.67.
The principle and advantage of present embodiment：
First, the nano-particle stabilization Pickering emulsions that prepared by present embodiment are the material of Janus structures, this material
With different hydrophilic and hydrophobics, because can be hydrophilic with one of which for two kinds of nano-particles of the Pickering emulsions of stabilization
, another kind is hydrophobic, so the material that thus prepared by Pickering emulsions is also with dual character, referred to as Janus
Structure, i.e. a part are hydrophilic, and a part is hydrophobic；
2nd, present embodiment prepares nano-particle stabilization Pickering emulsions as the filler of entire capillary, obtains one
The integral post of new Nanoparticle Modified is planted, it can be used for SPME, it is also possible to for micro-nano liquid-phase chromatographic column；
This Pickering emulsions using nano-particle stabilization are domestic initiations as the filling method of capillary column, and so far there are no reports
Road；
What the 3rd, prepared by present embodiment is had based on nano-particle stabilization Pickering emulsions as the integral post of filler
Regulatable pore structure, with good biocompatibility；Collection is extracted, purified, being enriched in one, and can be with various analytical instrument
Realize offline/on-line coupling；Present embodiment utilizes Pickering emulsion technologies of preparing, the 3-D solid structure of synthesizing new
Integral post, successfully prepare with anisotropic overall column material, enrich the preparation method of integral post, expand overall
The species of post, is that the development of chromatogram micro separation technique lays the foundation, with important academic significance and realistic meaning；
4th, present embodiment combined using new Pickering emulsions technology of preparing and integral post multiple advantage, into
Prepared by work(have anisotropic overall column material, i.e. nano-particle stabilization Pickering emulsion capillary columns, and right
Close and distant property in sample, or the material such as the different molecule of polarity, protein detection provide it is quick, efficiently, convenient, simple point
From new material, it is very suitable for the analysis of glucocorticoids material in cosmetic sample, is separated and solid phase in hormonal substance
Micro-extraction field has great application potential；
5th, present embodiment method has the advantages that quick, efficient, convenient, low cost, environment-friendly, while can be a large amount of
Prepare and reuse.
Present embodiment can obtain it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post prepare
Method.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Ultrasound described in step one
Scattered power is 30W~80W.Other steps are identical with specific embodiment one.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference is：Institute in step one
The rotating speed of the vortex mixed stated is 500r/min~3000r/min.Other steps are identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Institute in step 4
The deionized water stated is 1 with the volume ratio of absolute ethyl alcohol with deionized water in the mixed liquor of absolute ethyl alcohol:1.Other steps and tool
Body implementation method one to three is identical.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Institute in step one
The polyelectrolyte stated is the alkyl dimethyl ammonium chloride of polydiene base third, polyethyleneimine, PAH.Other steps and tool
Body implementation method one to four is identical.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Institute in step one
The lamella nano material stated is modified graphene or molybdenum disulfide nano sheet；Tubular nanometer material described in step one is modified
CNT or titania nanotube；Nano spherical particle described in step one is MODIFIED Fe3O4, silica, titanium dioxide
Titanium, ceria or zirconium oxide.Other steps are identical with specific embodiment one to five.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Described is modified
Graphene is prepared according to the following steps：
Added to 40mg graphene oxides and 40mL distilled water, ultrasonic disperse 5min after mixing is added in round-bottomed flask
0.270g FeCl3·6H2O and 0.528g ascorbic acid, then ultrasonic disperse 15min, add 10mL hydrazine hydrates, then under agitation
With temperature to be flowed back at 50 DEG C, until solution blackening, obtains mixed liquor；The high pressure that mixed liquor is transferred into stainless steel polytetrafluoro is anti-
Taken out in answering kettle, then after reacting 8h, then natural cooling at 180 DEG C, then carry out Magneto separate, obtain product, use deionized water
Product is washed in neutrality, then 1h~12h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified graphene.Other steps and tool
Body implementation method one to six is identical.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Described is modified
CNT is prepared according to the following steps：
0.2g CNTs are added to 50mL concentration for 3.0mol L-1HNO3In solution, then in the case where temperature is for 60 DEG C
Ultrasonic disperse 15min, obtains reactant；Reactant is cleaned using deionized water 3 times, then be vacuum dried 1h in the case where temperature is for 60 DEG C
~12h, obtains modified carbon nano-tube；Described CNT is SWCN or multi-walled carbon nano-tubes.Other steps with
Specific embodiment one to seven is identical.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Described is modified
Fe3O4Prepare according to the following steps：
By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol, and magnetic agitation obtains yellow transparent solution, is subsequently adding
0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation 20min obtain mixed liquor；Mixed liquor is transferred into stainless steel to gather
In tetrafluoro inner bag reactor, then 8h is reacted in the case where temperature is for 200 DEG C, after room temperature to be cooled, by gained black product centrifugation,
Reuse washes of absolute alcohol 3 times, then make to be washed with deionized water 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, be modified
Fe3O4.Other steps are identical with specific embodiment one to eight.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：Institute in step one
The silane stated is octadecyl trimethoxysilane, positive last of the ten Heavenly stems dimethyl methyl oxosilane, (3- mercaptopropyis) trimethoxy silane, urea
Propyl-triethoxysilicane or N- (β-aminoethyl-γ-aminopropyl) methyl dimethoxysilane；Described solvent is hexane, the last of the ten Heavenly stems
Alkane, heptane or toluene.Other steps are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 10 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 4 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 0.1:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified carbon nano-tube；Described nano material
Middle MODIFIED Fe3O4It is 1 with the mass ratio of modified carbon nano-tube:9；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified carbon nano-tube is prepared according to the following steps：0.2g CNTs are added into 50mL concentration is
3.0mol L-1HNO3In solution, then the ultrasonic disperse 15min in the case where temperature is for 60 DEG C, obtain reactant；It is clear using deionized water
Wash reactant 3 times, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified carbon nano-tube；Described CNT is single wall
CNT；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 40% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 90% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 18h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 90% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.42。
Embodiment two：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 10 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 2 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 0.2:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified carbon nano-tube；Described nano material
Middle MODIFIED Fe3O4It is 1 with the mass ratio of modified carbon nano-tube:9；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified carbon nano-tube is prepared according to the following steps：0.2g CNTs are added into 50mL concentration is
3.0mol L-1HNO3In solution, then the ultrasonic disperse 15min in the case where temperature is for 60 DEG C, obtain reactant；It is clear using deionized water
Wash reactant 3 times, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified carbon nano-tube；Described CNT is single wall
CNT；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 50% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 97% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 20h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 95% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.52。
Embodiment three：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 20 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 3 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 0.5:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified carbon nano-tube；Described nano material
Middle MODIFIED Fe3O4It is 1 with the mass ratio of modified carbon nano-tube:9；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified carbon nano-tube is prepared according to the following steps：0.2g CNTs are added into 50mL concentration is
3.0mol L-1HNO3In solution, then the ultrasonic disperse 15min in the case where temperature is for 60 DEG C, obtain reactant；It is clear using deionized water
Wash reactant 3 times, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified carbon nano-tube；Described CNT is single wall
CNT；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 50% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 24h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 98% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.48。
Example IV：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 10 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 3 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 1:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified carbon nano-tube；Described nano material
Middle MODIFIED Fe3O4It is 1 with the mass ratio of modified carbon nano-tube:7；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified carbon nano-tube is prepared according to the following steps：0.2g CNTs are added into 50mL concentration is
3.0mol L-1HNO3In solution, then the ultrasonic disperse 15min in the case where temperature is for 60 DEG C, obtain reactant；It is clear using deionized water
Wash reactant 3 times, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified carbon nano-tube；Described CNT is single wall
CNT；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 50% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 48h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 99% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.53。
Embodiment five：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 10 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 4 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 1:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified graphene；In described nano material
MODIFIED Fe3O4It is 1 with the mass ratio of modified graphene:0.01；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified graphene is prepared according to the following steps：
Added to 40mg graphene oxides and 40mL distilled water, ultrasonic disperse 5min after mixing is added in round-bottomed flask
0.270g FeCl3·6H2O and 0.528g ascorbic acid, then ultrasonic disperse 15min, add 10mL hydrazine hydrates, then under agitation
With temperature to be flowed back at 50 DEG C, until solution blackening, obtains mixed liquor；The high pressure that mixed liquor is transferred into stainless steel polytetrafluoro is anti-
Taken out in answering kettle, then after reacting 8h, then natural cooling at 180 DEG C, then carry out Magneto separate, obtain product, use deionized water
Product is washed in neutrality, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified graphene；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 50% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 12h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 99% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.46。
Embodiment six：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 20 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 6 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 1:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified graphene；In described nano material
MODIFIED Fe3O4It is 1.0 with the mass ratio of modified graphene:0.05；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified graphene is prepared according to the following steps：
Added to 40mg graphene oxides and 40mL distilled water, ultrasonic disperse 5min after mixing is added in round-bottomed flask
0.270g FeCl3·6H2O and 0.528g ascorbic acid, then ultrasonic disperse 15min, add 10mL hydrazine hydrates, then under agitation
With temperature to be flowed back at 50 DEG C, until solution blackening, obtains mixed liquor；The high pressure that mixed liquor is transferred into stainless steel polytetrafluoro is anti-
Taken out in answering kettle, then after reacting 8h, then natural cooling at 180 DEG C, then carry out Magneto separate, obtain product, use deionized water
Product is washed in neutrality, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified graphene；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 50% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 18h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 99% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.43。
Embodiment seven：It is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 15min, add after water phase vortex mixed 1min again, received
Rice corpuscles stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, silane and solvent in the mixed liquor of solvent and silane
Volume ratio be 10 μ L:1mL；Described solvent is hexane；Described silane is octadecyl trimethoxysilane；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and steaming in described water phase
The volume ratio of distilled water is 4 μ L:1mL；Described polyelectrolyte is the alkyl dimethyl ammonium chloride of polydiene base third；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:1.01mL；
Water phase and the volume ratio of oil phase described in step one are 1:100；
Nano material described in step one is MODIFIED Fe3O4With the mixture of modified graphene；In described nano material
MODIFIED Fe3O4It is 1 with the mass ratio of modified graphene:0.1；
Described MODIFIED Fe3O4Prepare according to the following steps：By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol,
Magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g trisodium citrates and 4.5g anhydrous sodium acetates, magnetic agitation
20min, obtains mixed liquor；Mixed liquor is transferred in stainless steel polytetrafluoro inner bag reactor, then is reacted in the case where temperature is for 200 DEG C
8h, after room temperature to be cooled, by gained black product centrifugation, reuses washes of absolute alcohol 3 times, then uses deionized water
Wash 3 times, then vacuum is dried in the case where temperature is for 60 DEG C, obtain MODIFIED Fe3O4；
Described modified graphene is prepared according to the following steps：
Added to 40mg graphene oxides and 40mL distilled water, ultrasonic disperse 5min after mixing is added in round-bottomed flask
0.270g FeCl3·6H2O and 0.528g ascorbic acid, then ultrasonic disperse 15min, add 10mL hydrazine hydrates, then under agitation
With temperature to be flowed back at 50 DEG C, until solution blackening, obtains mixed liquor；The high pressure that mixed liquor is transferred into stainless steel polytetrafluoro is anti-
Taken out in answering kettle, then after reacting 8h, then natural cooling at 180 DEG C, then carry out Magneto separate, obtain product, use deionized water
Product is washed in neutrality, then 2h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified graphene；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water
Flushing 30min each to capillary with acetone, then the acetone soln of the γ-MAPS that volume fraction is 50% is injected into capillary
In, the two ends of capillary are sealed with silica gel plug, then be placed in 10h is heated in the baking oven that temperature is 60 DEG C, then open capillary two
The silica gel plug at end, reuses acetone to capillary douche 30min, reuses nitrogen and dries up capillary, obtains pretreated
Integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1Flow velocity be injected into pretreated integral post, then by the two ends of capillary with silica gel plug seal, obtain
Populated integral post；Populated integral post is put into the baking oven that temperature is 60 DEG C and solidifies 24h；The entirety for being solidified
Post；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 99% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Liquid wash-out 30min is closed, the integral post as filler based on nano-particle stabilization Pickering emulsions is obtained；
It is as the porosity of the integral post of filler based on nano-particle stabilization Pickering emulsions described in step 4
0.45。
Fig. 1 is the cutting as the integral post of filler based on nano-particle stabilization Pickering emulsions prepared by embodiment seven
Surface scan electron microscope；
From fig. 1, it can be seen that the Pickering emulsions of nano-particle stabilization will can be fully filled with as filler inside capillary,
Space is had no, and filler and capillary tube inner wall are combined closely, and also have no break-off.
High Performance Liquid Chromatography/Mass Spectrometry condition：Chromatographic column used by chromatography is Shim-pack VP-ODS C18 posts
(250mm × 4.6mm, 5 μm, Shimadzu, Japan), mobile phase is by (A) 0.3% (v/v) formic acid water and (B) 0.3% (v/v)
Formic acid acetonitrile is constituted；Sample size is 5 μ L；Column temperature is 30 DEG C；Flow velocity is 1.0mL min–1；Gradient elution is used in analysis.
Cosmetic sample analyzes dexamethasone and betamethasone：Prepare mark-on blank solution sample, dexamethasone, times he
The spiked levels of meter Song are 10ng/mL.The chromatogram of the direct liquid phase-mass spectral analysis of the mark-on solution of 10ng/mL is shown in into A in Fig. 2
Curve；The mark-on solution of 10ng/mL stablizes Pickering emulsions as filler by prepared by embodiment seven based on nano-particle
Overall column extracting, parsing after the chromatographic curve of liquid phase-mass spectral analysis that determines see B curves in Fig. 2；
Fig. 2 is chromatogram, and A is the chromatographic curve of direct liquid phase-mass spectral analysis in Fig. 2, and B is to be prepared by embodiment seven
Liquid phase-the mass spectral analysis determined after overall column extracting, parsing based on nano-particle stabilization Pickering emulsions as filler
Chromatographic curve, 3 is dexamethasone chromatographic peak, and 4 is betamethasone chromatographic peak；
As can be seen from Figure 2, to identical 10ng/mL mark-on liquid, by the preparation of embodiment seven based on nano-particle stabilization
Pickering emulsions are as the dexamethasone and the chromatographic peak area of betamethasone after the integral post enrichment of filler apparently higher than not
Enriched direct injection analysis, illustrate present invention preparation stablizes Pickering emulsions as filler based on nano-particle
The advantage of integral post, it has more potential in following practical application.
Cosmetic sample analyzes prednisolone and cortisone：Prepare the blank solution sample of mark-on, prednisolone, cortisone
Spiked levels be 10ng/mL.The chromatogram of the direct liquid phase-mass spectral analysis of the mark-on solution of 10ng/mL is shown in into A curves in Fig. 3；
The mark-on solution of 10ng/mL stablizes Pickering emulsions as the whole of filler by prepared by embodiment seven based on nano-particle
The chromatographic curve of the liquid phase-mass spectral analysis determined after scapus extraction, parsing is shown in B curves in Fig. 3；
Fig. 3 is chromatogram, and A is the chromatographic curve of direct liquid phase-mass spectral analysis in Fig. 3, and B is to be prepared by embodiment seven
Liquid phase-the mass spectral analysis determined after overall column extracting, parsing based on nano-particle stabilization Pickering emulsions as filler
Chromatographic curve, 1 is prednisolone, and 2 is cortisone；
As can be seen from Figure 3, to identical 10ng/mL mark-on liquid, by the preparation of embodiment seven based on nano-particle stabilization
Pickering emulsions as filler integral post be enriched with after prednisolone and cortisone chromatographic peak area apparently higher than without
Enrichment direct injection analysis, illustrate present invention preparation stablizes Pickering emulsions as the whole of filler based on nano-particle
The advantage of scapus, it has more potential in following practical application.
Claims (10)
1. it is a kind of that overall column preparation method of the Pickering emulsions as filler is stablized based on nano-particle, it is characterised in that should
What method was specifically realized by the following steps：
First, nano-particle stabilization Pickering emulsions are prepared：
Nano material is mixed with oil phase, then ultrasonic disperse 10min~60min, add after water phase again vortex mixed 1min~
10min, obtains nano-particle stabilization Pickering emulsions；
Oil phase described in step one is solvent and the mixed liquor of silane, the body of silane and solvent in the mixed liquor of solvent and silane
Product is than being (5 μ L~30 μ L):1mL；
Water described in step one is mutually distilled water and the mixed liquor of polyelectrolyte；Polyelectrolyte and distilled water in described water phase
Volume ratio be (2 μ L~8 μ L):1mL；
The quality of the nano material described in step one is 1mg with the volume ratio of oil phase:(0.3mL~5mL)；
Water phase and the volume ratio of oil phase described in step one are (0.1~10):100；
Nano material described in step one for the one kind in tubular nanometer material, lamella nano material and nano spherical particle or
Wherein several mixtures；
2nd, integral post pretreatment：
The use of acetone, concentration is successively 1molL-1NaOH solution, concentration be 1molL-1HCl solution, high purity water and third
Ketone flushing 10min~30min each to capillary, then the acetone soln of the γ-MAPS that volume fraction is 10%~50% is injected
To in capillary, by the two ends of capillary with silica gel plug seal, then be placed in the baking oven that temperature is 40 DEG C~70 DEG C heat 8h~
14h, then the silica gel plug at capillary two ends is opened, acetone is reused to capillary douche 10min~30min, reusing nitrogen will
Capillary is dried up, and obtains pretreated integral post；
The volume of the acetone soln of the γ-MAPS described in step 2 accounts for the 50%~98% of capillary volume；
3rd, filling Pickering emulsions in integral post：
Syringe is fixed on syringe pump, then will be obtained in step one nano-particle stabilization Pickering emulsions with
0.01mL·min-1~0.5mLmin-1Flow velocity be injected into pretreated integral post, then by the two ends silicon of capillary
Plug is sealed, and obtains populated integral post；Populated integral post is put into the baking oven that temperature is 30 DEG C~200 DEG C and is solidified
1h~48h；The integral post for being solidified；
The volume of the nano-particle stabilization Pickering emulsions described in step 3 accounts for the 90%~100% of capillary volume；
4th, integral post wash-out：
The silica gel plug at capillary two ends is opened, the mixed liquor of deionized water and absolute ethyl alcohol is each led into the integral post to solidification
Wash-out 30min~60min, obtains the integral post as filler based on nano-particle stabilization Pickering emulsions；
Described in step 4 is 0.42 as the porosity of the integral post of filler based on the stable Pickering emulsions of nano-particle
~0.67.
2. it is according to claim 1 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that the power of the ultrasonic disperse described in step one is 30W~80W.
3. it is according to claim 1 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that the rotating speed of the vortex mixed described in step one is 500r/min~3000r/min.
4. it is according to claim 1 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that the deionized water described in step 4 and deionized water and absolute ethyl alcohol in the mixed liquor of absolute ethyl alcohol
Volume ratio be 1:1.
5. it is according to claim 1 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that the polyelectrolyte described in step one is the alkyl dimethyl ammonium chloride of polydiene base third, polyethyleneimine, gathers
Allylamine hydrochloride.
6. it is according to claim 1 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that the lamella nano material described in step one is modified graphene or molybdenum disulfide nano sheet；Step
Tubular nanometer material described in one is modified carbon nano-tube or titania nanotube；Ball shaped nano grain described in step one
Son is MODIFIED Fe3O4, silica, titanium dioxide, ceria or zirconium oxide.
7. it is according to claim 6 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that described modified graphene is prepared according to the following steps：
Added to 40mg graphene oxides and 40mL distilled water, ultrasonic disperse 5min after mixing is added in round-bottomed flask
0.270g FeCl3·6H2O and 0.528g ascorbic acid, then ultrasonic disperse 15min, add 10mL hydrazine hydrates, then under agitation
With temperature to be flowed back at 50 DEG C, until solution blackening, obtains mixed liquor；The high pressure that mixed liquor is transferred into stainless steel polytetrafluoro is anti-
Taken out in answering kettle, then after reacting 8h, then natural cooling at 180 DEG C, then carry out Magneto separate, obtain product, use deionized water
Product is washed in neutrality, then 1h~12h is vacuum dried in the case where temperature is for 60 DEG C, obtain modified graphene.
8. it is according to claim 6 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that described modified carbon nano-tube is prepared according to the following steps：
0.2g CNTs are added to 50mL concentration for 3.0mol L-1HNO3In solution, then the ultrasound in the case where temperature is for 60 DEG C
Dispersion 15min, obtains reactant；Clean reactant 3 times using deionized water, then be vacuum dried at being 60 DEG C in temperature 1h~
12h, obtains modified carbon nano-tube；Described CNT is SWCN or multi-walled carbon nano-tubes.
9. it is according to claim 6 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that described MODIFIED Fe3O4Prepare according to the following steps：
By 1.5g FeCl3·6H2O is dissolved in 30mL ethylene glycol, and magnetic agitation obtains yellow transparent solution, is subsequently adding 0.45g
Trisodium citrate and 4.5g anhydrous sodium acetates, magnetic agitation 20min obtain mixed liquor；Mixed liquor is transferred to stainless steel polytetrafluoro
In inner bag reactor, then 8h is reacted in the case where temperature is for 200 DEG C, after room temperature to be cooled, by gained black product centrifugation, then made
With washes of absolute alcohol 3 times, then make to be washed with deionized water 3 times, then dry vacuum at being 60 DEG C in temperature, be modified
Fe3O4。
10. it is according to claim 1 it is a kind of based on nano-particle stabilization Pickering emulsions as filler integral post system
Preparation Method, it is characterised in that silane described in step one is octadecyl trimethoxysilane, positive last of the ten Heavenly stems dimethyl methyl oxosilane,
(3- mercaptopropyis) trimethoxy silane, urea propyl-triethoxysilicane or N- (β-aminoethyl-γ-aminopropyl) methyl dimethoxy oxygen
Base silane；Described solvent is hexane, decane, heptane or toluene.
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| CN109621490A (en) * | 2018-12-18 | 2019-04-16 | 辽宁大学 | Pickering lotion packed column and be based on Pickering lotion packed column separating and extracting organic matter method |
| CN110514771A (en) * | 2019-08-26 | 2019-11-29 | 首都师范大学 | Graphene oxide-molybdenum disulfide capillary electric chromatographic column and preparation method |
| CN111318265A (en) * | 2020-02-17 | 2020-06-23 | 江苏大学 | Preparation method and application of mosaic type magnetic imprinting adsorbent |
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| CN109621490A (en) * | 2018-12-18 | 2019-04-16 | 辽宁大学 | Pickering lotion packed column and be based on Pickering lotion packed column separating and extracting organic matter method |
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| CN113905982A (en) * | 2019-03-15 | 2022-01-07 | 沙特阿拉伯石油公司 | Batch synthesis of JANUS nanomaterials |
| WO2020255148A1 (en) * | 2019-06-20 | 2020-12-24 | The State Of Israel, Ministry Of Agriculture & Rural Development, Agricultural Research Organization (Aro) (Volcani Center) | Colloidosomes and porous materials by pickering emulsions |
| CN110514771A (en) * | 2019-08-26 | 2019-11-29 | 首都师范大学 | Graphene oxide-molybdenum disulfide capillary electric chromatographic column and preparation method |
| CN110514771B (en) * | 2019-08-26 | 2021-07-27 | 首都师范大学 | Graphene oxide-molybdenum disulfide capillary electrochromatography column and preparation method thereof |
| CN111318265A (en) * | 2020-02-17 | 2020-06-23 | 江苏大学 | Preparation method and application of mosaic type magnetic imprinting adsorbent |
| CN115837270A (en) * | 2022-11-03 | 2023-03-24 | 皇甫鑫 | Defluorination adsorbent, preparation method thereof and defluorination method of acidic wastewater |
| CN115837270B (en) * | 2022-11-03 | 2024-05-10 | 皇甫鑫 | Defluorination adsorbent, preparation method thereof and method for defluorination of acidic wastewater |
| CN116116390A (en) * | 2023-02-28 | 2023-05-16 | 中国石油大学(华东) | High-strength polysaccharide-inorganic nanoparticle composite monolithic column and preparation method thereof |
| CN116116390B (en) * | 2023-02-28 | 2024-01-26 | 中国石油大学(华东) | High-strength polysaccharide-inorganic nanoparticle composite monolithic column and preparation method thereof |
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