CN105732916B - A kind of organic inorganic hybridization microsphere particle and its preparation and application - Google Patents
A kind of organic inorganic hybridization microsphere particle and its preparation and application Download PDFInfo
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- CN105732916B CN105732916B CN201410748234.4A CN201410748234A CN105732916B CN 105732916 B CN105732916 B CN 105732916B CN 201410748234 A CN201410748234 A CN 201410748234A CN 105732916 B CN105732916 B CN 105732916B
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Abstract
The invention belongs to polymeric material and analysis technical field, is related to microsphere particle and its preparation and the application of a kind of organic inorganic hybridization core shell structure.Using inorganic silica gel particle as core, afterwards by modifying upper silylating reagent, then the propane sulfonic acid of 3 allyloxy, 2 hydroxyl 1 and methylene diacrylamide are wrapped up on core surface by the click chemistry technology of thiol-ene, formation surface is smooth and carries hydroxyl, the core shell structure nano/micron particle of the organic inorganic hybridization of the hydrophily functional group such as sulfonic group, acid amides.The present invention introduces hydroxyl in material surface by thiol-ene method, sulfonic group, the hydrophily functional group such as acid amides, not only overcome traditional post-decoration method complex steps, the shortcomings that reaction efficiency is low but also form the hydrophilic layer of polymer three-dimensional structure, there is more preferable advantage as hydrophilic chromatographic.The microsphere particle of the present invention is used for separation and concentration glycopeptide available for hydrophilic Interaction Chromatography, has preferable practical value and application prospect in the field such as separation analysis and glycoproteomics.
Description
Technical field
The present invention relates to organic inorganic hybridization microsphere particle and its preparation and application, specifically a kind of end carries hydroxyl
The organic inorganic hybridization core shell structure microsphere particle of the functional groups such as base, sulfonic acid, acid amides.
Background technology
Highly polar compound (such as oligosaccharides, glucosides, glycopeptide etc.) plays an important role in medicine and organism, therefore,
It separates analysis and is increasingly becoming everybody focus of attention.But current most popular high efficient separation technology reversed phase high performance liquid
Reservation of the phase chromatogram (RP-HPLC) for highly polar compound is very weak.Hydrophilic interaction liquid chromatogram (HILIC) is used for as one kind
Separate chromatographic technique (Strege, the M.A.et al, Anal.Chem.2000,72,4629-4633 of highly polar compound；Wang,
X.D.et al, J.Chromatogr.A, 2005,1083,58-62) it is widely developed in recent years, especially amide-type,
Hydroxy kind, carbohydrate etc. (Guo, Y.et al, J.Chromatogr.A, 2005,1074,71-80；Irgum, K.et al,
J.Sep.Sci., 2006,29,1784-1821) stationary phase has significant excellent in terms of separating with enrichment polar molecule and glycopeptide
Gesture.
However, these process for fixation generally modify a kind of functionalization group, and require reaction condition more it is strict (such as
Anhydrous solvent, compared with high reaction temperature etc.) preparation process is more, and reaction efficiency is low, and the reaction to intersect is required between functional group.
It is, thus, sought for a kind of reaction condition is gentle, the high reaction condition of the selectivity new method compatible with water environment.Click chemistry has
There is the characteristics of reaction yield is high, functional group is stable and reactivity is high.Guo,Z.et al,Chem.Commun.,2007,
2491-2493 report a kind of hydrophilic stationary phase in silicon ball surface modification maltose, and this method passes through " click chemistry " method
Maltose containing azido group is fixed to silicon ball surface, the fixation rate of maltose is effectively increased, significantly improves it
To the separating capacity of polar substances, but the technology belongs to the reaction of the azide and alkynyl of metal catalytic, and the material
Only modify the hydroxyl of carbohydrate.
The content of the invention
The deficiency for more than, the present invention provide a kind of mercaptan-alkene clicking chemistry and prepare surface simultaneous with hydroxyl, acid amides and
The hydrophilic microsphere particle of functionalization of sulfonic acid group, this method have that reaction condition is gentle, the high reaction condition of selectivity and water environment
The characteristics of compatible, obtained product grain shape is regular, and monodispersity is good, available for right under hydrophilic interaction Liquid Chromatography mode
The separation and concentration of nucleosides and glycopeptide.
To achieve the above object, the technical solution adopted by the present invention is：
Step 1：Silica gel particle, the silylating reagent containing thiol group, reaction dissolvent toluene etc. are added into reaction vessel
In, ultrasound 1 minute so that the reagent and silica gel particle of addition are uniformly dispersed in solvent, and condenser pipe is connect on flask, is added
Enter magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan, it is heated to reflux 6~
30h, stop reaction afterwards, be cooled to room temperature.3000~10000rad/min of supercentrifuge centrifugation is used afterwards,
Supernatant is removed, successively using toluene, methanol, acetone filtering and washing, repeats filtering and washing 3 times, it is true in 50 DEG C of vacuum drying chambers
Sky is dried 24 hours.
Step 2：In flask, condenser pipe is loaded onto, reaction dissolvent is added, after the silylation modification obtained in step 1
Silica gel particle, 3- allyloxy -2- hydroxyl -1- propane sulfonic acid, methylene diacrylamide, initiator etc. add in beaker, ultrasound 1
Minute so that the reagent and grain dissolution of addition are uniformly dispersed in solution, lead to nitrogen afterwards 15 minutes, are added magnetic force and are stirred
Son is mixed, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan and is uniformly slowly heated, in 30min
It is warming up to 60~140 DEG C.4-48 hours are reacted under the conditions of maintaining 60~80 DEG C, stops reaction, is cooled to room temperature.Afterwards using height
Fast 3000~10000rad/min of centrifuge centrifugation, supernatant is removed, add reaction dissolvent and wash three times, 50 DEG C of vacuum
Vacuum drying 24 hours in drying box.
In step 1, described silylating reagent is the silylating reagent containing sulfydryl.Contain silica gel particle, silanization
In the solution of reagent, the total mole number concentration that silica gel particle accounts for 0.01~0.2wt% monomers of gross mass is 0.05~1mol/L,
Surplus is reaction dissolvent.Microsphere particle after modification, its particle diameter are 100nm~10 μm.
In step 2, described initiator selects azo-initiator.Reaction solution is water, acetonitrile, methanol, toluene, N,
Dinethylformamide or its mixture.Containing 3- allyloxy -2- hydroxyl -1- propane sulfonic acid, methylene diacrylamide and draw
In the solution for sending out agent, the total mole number concentration of monomer is 0.05~0.4mol/L, initiator account for monomer gross mass 0.5~
10%, surplus is reaction dissolvent.The organic inorganic hybridization microsphere particle prepared, its particle diameter are 100nm~10 μm.
The present invention introduces the hydrophilic sexual function bases such as hydroxyl, sulfonic group, amide groups in material surface by mercaptan-alkene method
Group, not only overcome traditional post-decoration method complex steps, the shortcomings that reaction efficiency is low, and the core shell structure for be formed
Microsphere surface has the polymer chain of three-dimensional structure, and the structure can improve the hydrophilic chromatographic ability of material.The microballoon of the present invention
Particle can be used as a kind of novel hydrophilic action chromatography stationary phase, and in conform to the principle of simplicity monocyte sample mixture or complex sample
Separation or enrichment nucleosides, glycopeptide.
The invention has the advantages that：
1. preparation method of the present invention, using the method for sulfydryl-alkene clicking chemistry so that it is gentle to prepare reaction condition,
Reaction speed is fast, and reaction efficiency is high, and resulting materials reappearance is high.
2. organic inorganic hybridization core shell structure microsphere particle outer layer is formed by sulfydryl-alkene clicking chemistry method so that this
The particle diameter distribution of invention core shell structure microsphere particle is narrower, particle diameter single dispersing, and surface simultaneously containing substantial amounts of hydroxyl, acid amides,
The hydrophily functional group such as sulfonic acid.
3. by boric acid functionalization core shell structure microballoon prepared by the present invention due to simultaneously containing substantial amounts of various hydrophilies
Group, therefore, a kind of novel hydrophilic action chromatography stationary phase can be used as, and for conform to the principle of simplicity monocyte sample mixture or complicated sample
Nucleosides, glycopeptide are separated or be enriched with product, open up and microsphere particle is prepared in separation analysis field by sulfydryl-alkene clicking chemistry method
New opplication.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the polymer microballoon prepared in embodiment 1
Fig. 2 is that the polymer microballoon prepared using in embodiment 1 is used for the separation chromatography figure of nucleosides as stationary phase.
Embodiment
Technical scheme is described further using specific embodiment below.
Embodiment 1
1. the preparation of single dispersing core shell structure polymer nano-particle
In 150mL round-bottomed flask, 80mL toluene is added, adds the silica gel particle that 6g particle diameters are 5 μm, 3g 3- mercaptos third
Ethyl triethoxy silicane alkane, ultrasound 1 minute so that the reagent of addition and it is evengranular it is scattered in the solution, connect on flask
Condenser pipe, adds magnetic stir bar, and magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan, heating
Flow back 6h, stops reaction afterwards, is cooled to room temperature.Supercentrifuge 10000rad/min centrifugation is used afterwards, is gone
Except supernatant, successively using toluene, acetone, methanol, acetone filtering and washing, repeat filtering and washing and wash three times for 3 times, 50 DEG C of vacuum are done
Vacuum drying 24 hours, the silica gel particle for the silylating reagent modified in dry case.
In 100mL round-bottomed flask, condenser pipe is loaded onto, adds reaction dissolvent water-ethanol mixed solution (volume ratio 2:
1) 50mL, add the 1000mg modifications silica gel particle of silanization, 200mg 3- allyloxy -2- hydroxyl -1- propane sulfonic acid (PSAS),
600mg methylene diacrylamides acid, 100mg azodiisobutyronitriles (AIBN) ultrasound 1 minute so that the reagent and particle of addition
Dissolving formed it is dispersed lead to nitrogen 15 minutes afterwards in a solvent, add magnetic stir bar, magnetic stir bar is kept
300rad/min speed.Reaction unit is placed in oil bath pan and is uniformly slowly heated, and 75 DEG C are warming up in 30min.Maintain 75 DEG C
Under the conditions of react 12 hours, stop reaction, be cooled to room temperature, obtain making after microsphere particle silica@(MBAAm-co-PSAS)
With supercentrifuge 10000rad/min centrifugation, supernatant is removed, reaction solution is added and washes three times, 50 DEG C of vacuum are done
Vacuum drying 24 hours in dry case.
2. the sign of polymer microballoon particle
Electronic Speculum test is scanned through, as a result as shown in Figure 1.
3. polymer microballoon can be used for the separation of nucleosides
It is used to load 2.1 × 50mm chromatographic columns using polymer microballoon particle, the separation for nucleosides is analyzed.Such as Fig. 2 institutes
Show, (1) thymidine, (2) uridine, (3) adenosine, (4) cytidine, (5) guanosine.5 kinds of different nucleosides have obtained dividing well
From.Chromatographic condition is：
Chromatographic column：2.1×50mm；Mobile phase：A, 20mM NH4HCO3The aqueous solution, pH 4；B, acetonitrile；Isocratic condition：0-
5min, 15%A；Flow velocity：0.25mL/min；Column temperature：25℃；Detection wavelength：254nm..
Embodiment 2
1. the preparation of single dispersing core shell structure polymer nano-particle
In 150mL round-bottomed flask, 60mL toluene is added, adds the silica gel particle that 3g particle diameters are 5 μm, 3g 3- mercaptos third
Ethyl triethoxy silicane alkane, ultrasound 1 minute so that the reagent of addition and it is evengranular it is scattered in the solution, connect on flask
Condenser pipe, adds magnetic stir bar, and magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan, heating
Flow back 6h, stops reaction afterwards, is cooled to room temperature.Supercentrifuge 10000rad/min centrifugation is used afterwards, is gone
Except supernatant, successively using toluene, acetone, methanol, acetone filtering and washing, repeat filtering and washing and wash three times for 3 times, 50 DEG C of vacuum are done
Vacuum drying 24 hours, the silica gel particle for the silylating reagent modified in dry case.
In 100mL round-bottomed flask, condenser pipe is loaded onto, adds reaction dissolvent water-ethanol mixed solution (volume ratio 2:
1) 80mL, add the 1200mg modifications silica gel particle of silanization, 600mg 3- allyloxy -2- hydroxyl -1- propane sulfonic acid (PSAS),
300mg methylene diacrylamides acid, 100mg azodiisobutyronitriles (AIBN) ultrasound 1 minute so that the reagent and particle of addition
Dissolving formed it is dispersed lead to nitrogen 15 minutes afterwards in a solvent, add magnetic stir bar, magnetic stir bar is kept
300rad/min speed.Reaction unit is placed in oil bath pan and is uniformly slowly heated, and 75 DEG C are warming up in 30min.Maintain 75 DEG C
Under the conditions of react 12 hours, stop reaction, be cooled to room temperature, obtain making after microsphere particle silica@(MBAAm-co-PSAS)
With supercentrifuge 10000rad/min centrifugation, supernatant is removed, reaction solution is added and washes three times, 50 DEG C of vacuum are done
Vacuum drying 24 hours in dry case.
Other are the same as embodiment 1.
Claims (9)
- A kind of 1. organic inorganic hybridization microsphere particle, it is characterised in that：The organic inorganic hybridization core shell structure microsphere particle, first using silica gel particle as core, afterwards by modifying upper silanization Reagent, then wrapped up by the click chemistry technology of mercapto-alkene on core surface 3- allyloxy -2- hydroxyl -1- propane sulfonic acid with Methylene diacrylamide, forms that surface is smooth and the polymer beads of core shell structure with hydrophily functional group, selected by it Silylating reagent is the silylating reagent with thiol group.
- 2. according to the hybrid microspheres particle described in claim 1, it is characterised in that：The nuclear particle is silica gel particle, its silica gel Microspherulite diameter is between 100 nm ~ 10 μm.
- 3. according to the hybrid microspheres particle described in claim 1, it is characterised in that：The surface of shell carries hydroxyl, sulfonic group, acid amides Middle one or two or more kinds of hydrophily functional groups, wherein 3- allyloxys -2- hydroxyls -1- propane sulfonic acid mass fraction model in shell It is the % of 5 % ~ 95 to enclose.
- 4. according to the hybrid microspheres particle described in claim 1, it is characterised in that：The hybrid microspheres particle be single dispersing organic-inorganic core shell structure microsphere particle, particle size scope be 100 nm ~ 10 µm。
- A kind of 5. preparation method of any hybrid microspheres particles of claim 1-4, it is characterised in that：1）The process of silylation modification silica gel particle：Silica gel particle after activation is dispersed in toluene, ultrasound, addition carries sulphur The silylating reagent of alcohol groups, addition are that the mass ratio of silica gel particle and silylating reagent is 1:0.05 to 1:1, it is stirred at reflux 6-30 h；Filtering and washing is repeated 2 ~ 5 times using toluene, methanol, acetone filtering and washing successively afterwards, to permanent in vacuum drying chamber Weight；2）It is prepared by the shell of hybrid microspheres particle：By obtained silylation modification silica gel particle, 3- allyloxy -2- hydroxyls -1- Propane sulfonic acid, methylene diacrylamide, initiator are mixed in reaction dissolvent system, and 4-48 hours are reacted at 60-80 DEG C；Centrifugation The core shell structure microballoon of isolated organic inorganic hybridization, afterwards successively using reaction dissolvent washing microballoon in unreacting substance extremely Cleaning, repeats filtering and washing 2 ~ 5 times, to constant weight in vacuum drying chamber.
- 6. according to the preparation method described in claim 5, it is characterised in that：The shell of hybrid microspheres particle prepares period, system The mol ratio of middle addition 3- allyloxy -2- hydroxyl -1- propane sulfonic acid and methylene diacrylamide is 0.1:1 to 1:0.1, Liang Zhe Total mole number concentration in system is 0.05-0.4 mol/L；Period is prepared in the shell of hybrid microspheres particle, it is 1 that silica gel nuclear particle, which adds quality with the monomer gross mass ratio for forming shell,: 0.1 to 1:10.
- 7. according to the preparation method described in claim 5, period is prepared in the shell of hybrid microspheres particle, the initiator is even Nitrogen class initiator, including azodiisobutyronitrile, ABVN, azo-bis-isobutyrate hydrochloride, the isobutyl imidazoline of azo two One or both of hydrochloride and combination of the above, add total amount and account for the 0.5 ~ 10% of the monomer gross mass to form shell.
- 8. according to the preparation method described in claim 5, period is prepared in the shell of hybrid microspheres particle, the solvent used in it is A kind of or two kinds and solution mixed above in methanol, ethanol, toluene, propyl alcohol, N,N-dimethylformamide, water.
- 9. hybrid microspheres particle described in a kind of claim 1 is as a kind of novel hydrophilic action chromatography stationary phase, and for from Glycopeptide, glycoprotein are separated or are enriched with biological sample.
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| CN106807341B (en) * | 2015-12-01 | 2019-05-28 | 中国科学院大连化学物理研究所 | The silica matrix hydrophilic Interaction Chromatography stationary phase of polymer chain modification and its preparation and application |
| CN107296757A (en) * | 2017-06-19 | 2017-10-27 | 成都新柯力化工科技有限公司 | A kind of inorganic microbead and preparation method for beauty angle lap matter |
| CN109880353B (en) * | 2019-02-19 | 2021-07-06 | 广东烯王科技有限公司 | White graphene composite polyamide material, film and preparation method thereof |
| CN109851960B (en) * | 2019-02-19 | 2021-01-26 | 广东烯王科技有限公司 | White graphene composite PTFE material and preparation method thereof |
| CN112844258B (en) * | 2019-11-27 | 2022-09-20 | 中国科学院大连化学物理研究所 | Cysteine-modified nano core-shell silica gel material and preparation and application thereof |
| CN112111066B (en) * | 2020-08-18 | 2022-05-27 | 苏州博睿嘉晟医疗科技有限公司 | Preparation method and application of core-shell structure-based polymer microspheres for protein separation and analysis |
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