CN108129612A - The preparation of phosphoric acid functionalized multistage pore canal hybrid integral material and material and application - Google Patents
The preparation of phosphoric acid functionalized multistage pore canal hybrid integral material and material and application Download PDFInfo
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- CN108129612A CN108129612A CN201611087904.8A CN201611087904A CN108129612A CN 108129612 A CN108129612 A CN 108129612A CN 201611087904 A CN201611087904 A CN 201611087904A CN 108129612 A CN108129612 A CN 108129612A
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The present invention relates to a kind of methods for the multi-stage porous hybrid integral material that phosphorous acid functionalization is prepared using degradable polymer as template, by polyhedral oligomeric sesquialter silane reagent, phosphoric acid function monomer, degradable polymer, initiator, and organic solvent mixes and ultrasonic dissolution, then free radicals copolymerization reaction is occurred using mode of heating, then be not involved in by degrading under acid condition the degradable polymer of copolyreaction to prepare the hybrid integral material with multi-stage artery structure of phosphoric acid functionalized.Prepared hybrid integral material has micropore, mesoporous and macropore simultaneously, not only with larger specific surface area, but also has the characteristics that mass transfer velocity is fast, good application prospect is shown in sample pre-treatments.The preparation method has many advantages, such as easy to operate quick, in addition it can the function monomer and degradable polymer according to different application requirement addition different ratios, prepares the multi-stage porous hybrid integral material with different physics and chemical property.
Description
Technical field
The present invention relates to a kind of multi-stage porous hydridization that phosphoric acid functionalized is used to prepare based on addition degradable polymer is whole
The method of material, specifically by polyhedral oligomeric sesquialter silane reagent, phosphoric acid function monomer, degradable polymer, initiator, with
And solvent mixes and ultrasonic dissolution, is then copolymerized by heating, then is not involved in reacting by degrading under acid condition
Polymer, you can prepare the multi-stage porous hybrid integral material of phosphoric acid functionalized.The hydridization of phosphoric acid functionalized multi-stage porous is whole
Material has micropore, mesoporous and macropore simultaneously, not only with larger specific surface area, but also has the characteristics that mass transfer velocity is fast, in sample
Good application prospect is shown in product pre-treatment.The preparation method has many advantages, such as easy to operate quick, in addition may be used also
With the function monomer and degradable polymer according to different application requirement addition different ratios, prepare a series of with difference
The multi-stage porous hybrid integral material of the phosphoric acid functionalized of physics and chemical property.
Background technology
Nearly ten years, multilevel hole material has become the emphasis of scientific research, not only achieves huge progress, but also still
So in fast development.This material contains infiltration pore structure and continuous matrix structure simultaneously.Various pore structure can
Can combine micropore (<2nm), mesoporous (2-50nm) and macropore (>50nm).Such multiple pore structure is according to the combination of pore size
Assign the unique property of material.Wherein, micropore and mesoporous presence can make material have very big specific surface area, provide more
Activated centre, and the presence of macropore can accelerate mass transfer rate in application process.In short, multilevel hole material has low back pressure
And the features such as high osmosis, had a wide range of applications in catalysis, separation, optics, the energy and life science.
According to the constituent of material, multilevel hole material can be divided into multi-stage porous metal material, multi-stage porous inorganic non-metallic
Material and multi-stage porous high molecular material.Wherein, multi-stage porous high molecular material is based on polymer monomer, is assembled by being crosslinked
Form pore structure.This kind of material has both porous material and high molecular advantage, such as high-specific surface area and good porosity, adds
Work is simple etc..It, can be with since certain multi-stage porous high molecular materials have the characteristics that good biocompatibility and hypotoxicity
For encapsulated drug, and control release in vivo；Stent is can also be used as biomolecule and cell is fixed.Separately
Outside, such as phenolic resin, polystyrene high molecular material, other than as foraminous die plate or common carbon materials material precursor.
Protein phosphorylation and dephosphorylation almost adjust the whole process of vital movement, the proliferation including cell, hair
Educate and break up, nervous activity, contraction of muscle, metabolism, tumour occur etc..As tree species for bio-energy source in Mass accuracy and is swept
The raising of speed and the appearance of new peptide fragment fragmentation technology and the development of relevant bioinformatics are retouched, mass-spectrometric technique is
One of technology most supported as phosphorylating protein analysis.But it is highly desirable before carrying out Mass Spectrometric Identification from highly complex
Biological sample in specifically separation and enriched phosphorus acidizing protein and phosphated peptide section.Up to the present, it detaches and is enriched with
The most common means of phosphated peptide section are immobilized metal affinity chromatography (Immobilized Metal Affinity
Chromatography,IMAC).IMAC technologies are by phosphate group in positively charged metal ion and phosphated peptide section
Separation and the enriching phosphated peptide section of chelation and ionic interaction and specificity.
Invention content
The present invention relates to a kind of multi-stage porous hydridization entirety materials that phosphorous acid functionalization is prepared using degradable polymer as template
The method of material, specifically first by polyhedral oligomeric sesquialter silane reagent, phosphoric acid function monomer, degradable polymer, initiator,
And organic solvent mixes and ultrasonic dissolution, free radicals copolymerization reaction then occurs using mode of heating, then pass through acid condition
Lower degrade is not involved in the degradable polymer of copolyreaction, you can for preparing phosphoric acid functionalized has the miscellaneous of multi-stage artery structure
Change integral material.
The technical solution adopted by the present invention is：
By the eight vinyl sesquialter silane containing multiple double bonds, containing there are one phosphoric acid function monomer, the degradable polies of double bond
It closes object and thermal initiator dissolving in a solvent, is transferred in ampoule bottle after ultrasonic mixing is uniform, and after removing dissolved oxygen, by adding
Heat occurs Raolical polymerizable and prepares integral material, then hydrolyzes degradable polymer in acid condition, you can prepare
Phosphoric acid functionalized has the hybrid integral material of multi-stage artery structure, and according to different demands, by adjust monomer concentration and
Degradable polymer concentration can prepare the multi-stage porous hybrid integral material of phosphoric acid functionalized of different nature.
The multi-stage porous hybrid integral material of phosphoric acid functionalized prepared by the present invention, not only with 1 μm or so of macropore, but also tool
There are the mesoporous and micropore of below 10nm, and specific surface area may be up to 500m2/g.Due to containing phosphonic functional groups in material, pass through
Chelated mineral titanium ion can be prepared into the multi-stage porous hybrid integral material of Titanium ion chelating affinity chromatography, before sample
Reason has a good application prospect, and is particularly suitable in micromolecular compound and biological sample of the absorption with phosphonic functional groups
Phosphoeptide is enriched with.
1) eight vinyl silsesquioxanes of 75-200mg are added in into the ampoule bottle that volume is 5mL or 10mL；
2) 10-100mg vinyl phosphonic acids are added in into the ampoule bottle of step 1)；
3) 0-70mg polycaprolactones are added in into the ampoule bottle of step 1)；
4) 0.5-5.0mL tetrahydrofurans are added in into the ampoule bottle of step 1)；
5) 12-40mg thermal initiator azodiisobutyronitriles are added in into the ampoule bottle of step 1)；
6) it is the mixed system obtained after step 5) is ultrasonic at normal temperatures, make it completely dissolved that form homogeneous transparent molten
Liquid, to remove the dissolved oxygen in mixed system；
7) ampoule bottle that mixed solution is housed in step 6) is put into liquid nitrogen (temperature is -193 DEG C or so), makes mixing molten
Liquid is frozen into solid；
8) ampoule bottle in step 7) is vacuumized, to remove the oxygen in bottle；
9) ampoule bottle in step 8) is sealed；
10) ampoule bottle sealed in step 9) is put into 50-70 DEG C of water-bath, reaction 12-48h, in ampoule bottle
Polymerisation occurs for mixing liquid, becomes solid；
11) to tetrahydrofuran washing by soaking 3-5 times of the solid in ampoule bottle, some of them are had neither part nor lot in the substances of reaction
Cleaning, obtains integral material；
12) integral material that step 11) obtains is put into vial, and adds in 1-2mol/L hydrochloric acid；
13) vial in step 12) is sealed, and is put into 48-96h in 60-80 DEG C of water-bath, it can with complete hydrolysis
Degradation polymer；
14) above-mentioned integral material is rinsed with methanol, to remove demineralizing acid and hydrolysate, you can obtain the more of phosphoric acid functionalized
Grade hole hybrid integral material.
15) integral material obtained by step 14) is put into centrifuge tube, adds in the sulfuric acid of 30-50mL 0.1-0.3g/mL
Titanium aqueous solution vibrates 24-48h.
16) above-mentioned integral material is rinsed with deionized water, to remove the metal titanium ion not chelated, you can obtain to answer
For the multi-stage porous hybrid integral material of Titanium ion chelating affinity chromatography.
This method using thermal initiation Raolical polymerizable (thermal induced free radical
Polymerization reaction), the radical polymerization that thermal initiator generates in a heated condition, so instead
It needs to freeze before should starting, carries out vacuumizing deoxygenation.
This method quickly prepares the multi-stage porous hydridization entirety material of phosphoric acid functionalized using the method for thermal initiation free radical polymerization
Material.Degradable polymer is not involved in reacting in the course of the polymerization process, then passes through hydrolyzed under acidic conditions degradable polymer, you can
Obtain multi-stage porous hybrid integral material.The aperture of prepared porous integral material and pore structure can be by changing function monomer
The composition of ratio and degradable polymer is regulated and controled.
The hybrid integral material with multi-stage artery structure of phosphoric acid functionalized prepared by the present invention has enriching rate
Soon, it the features such as large amount of adsorption, has a good application prospect in sample pre-treatments.Phosphoric acid work(is shown to small molecule absorption result
The multi-stage porous hybrid integral material of energyization may be up to 62.8mg/g to carrying phosphonic functional groups adsorptive capacity of small molecules into high, and in 60min
It is interior to reach adsorption equilibrium.The mass spectrometry results of enrichment acid peptide show prepared phosphoric acid functionalized in biological sample
Multi-stage porous hybrid integral material can also be applied to the separation and concentration of trace samplings.
Prepared hybrid integral material has micropore, mesoporous and macropore simultaneously, not only with larger specific surface area, but also tool
There is the features such as mass transfer velocity is fast, good application prospect is shown in sample pre-treatments.The preparation method has operation
The advantages that easy and quick, in addition it can the function monomer and degradable poly according to different application requirement addition different ratios
Object is closed, prepares a series of multi-stage porous hybrid integral materials with different physics and chemical property.
Description of the drawings
Fig. 1 is the signal that phosphoric acid functionalized multi-stage porous hybrid integral material is prepared based on thermal initiation Raolical polymerizable
Figure.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of phosphoric acid functionalized multi-stage porous hybrid integral material.Wherein a, b are embodiment 1
The SEM of the hybrid integral material column of preparation；C, d are that (a, c are 5000 times to the SEM of hybrid integral material for preparing of embodiment 2, c, d
It it is 10000 times).
Fig. 3 is phosphoric acid functionalized multi-stage porous hybrid integral material to the adsorption dynamics adsorption kinetics figure (a) of 5- phosphonic acids pyridoxals and quiet
State absorption figure (b).Wherein (■) is phosphoric acid functionalized multi-stage porous hybrid integral material prepared by embodiment 1, and (zero) is embodiment 2
The phosphoric acid functionalized multi-stage porous hybrid integral material of preparation.
Fig. 4 is that phosphoric acid functionalized multi-stage porous hybrid integral material prepared by embodiment 1 is endogenous in human serum applied to being enriched with
Property phosphoeptide MALDI TOF-MS analysis collection of illustrative plates.
Specific embodiment
Embodiment 1
Preparation process is as follows：
1) eight vinyl silsesquioxanes of 75mg are added in into the ampoule bottle that volume is 5mL；
2) 20mg vinyl phosphonic acids are added in into the ampoule bottle of step 1)；
3) 0mg polycaprolactones are added in into the ampoule bottle of step 1)；
4) 12mg initiator azodiisobutyronitriles are added in into the ampoule bottle of step 1)；
5) 1.0mL tetrahydrofurans are added in into the ampoule bottle of step 1)；
6) it is the mixed system obtained after step 5) is ultrasonic at normal temperatures, make it completely dissolved that form homogeneous transparent molten
Liquid, to remove the dissolved oxygen in mixed system；
7) ampoule bottle that mixed solution is housed in step 6) is put into liquid nitrogen, mixed solution is made to be frozen into solid；
8) ampoule bottle in step 7) is vacuumized, to remove the oxygen in bottle；
9) ampoule bottle in step 8) is sealed；
10) ampoule bottle sealed in step 9) is put into 60 DEG C of water-baths, reacted for 24 hours, the mixing liquid in ampoule bottle
Polymerisation occurs, becomes solid；
11) to the tetrahydrofuran washing by soaking 3 times of the solid in ampoule bottle, the substances that some of them are had neither part nor lot in reaction are clear
It washes, obtains integral material；
12) integral material that step 11) obtains is put into vial, and adds in hydrochloric acid；
13) vial in step 12) is sealed, and is put into 72h in 70 DEG C of water-baths, with the degradable polymerization of complete hydrolysis
Object；
14) above-mentioned integral material is rinsed with methanol, to remove demineralizing acid and hydrolysate, you can obtain the more of phosphoric acid functionalized
Grade hole hybrid integral material.
15) integral material obtained by step 14) is put into 50mL centrifuge tubes, adds in the titanium sulfate water of 40mL 0.1g/mL
Solution, oscillation is for 24 hours.
16) above-mentioned integral material is rinsed with deionized water, to remove the titanium ion not chelated, you can be applied to
The multi-stage porous hybrid integral material of Titanium ion chelating affinity chromatography.
Embodiment 2
Preparation process is as follows：
1) eight vinyl silsesquioxanes of 75mg are added in into the ampoule bottle that volume is 5mL；
2) 20mg vinyl phosphonic acids are added in into the ampoule bottle of step 1)；
3) 25mg polycaprolactones are added in into the ampoule bottle of step 1)；
4) 12mg initiator azodiisobutyronitriles are added in into the ampoule bottle of step 1)；
5) 1.0mL tetrahydrofurans are added in into the ampoule bottle of step 1)；
6) it is the mixed system obtained after step 5) is ultrasonic at normal temperatures, make it completely dissolved that form homogeneous transparent molten
Liquid, to remove the dissolved oxygen in mixed system；
7) ampoule bottle that mixed solution is housed in step 6) is put into liquid nitrogen, mixed solution is made to be frozen into solid；
8) ampoule bottle in step 7) is vacuumized, to remove the oxygen in bottle；
9) ampoule bottle in step 8) is sealed；
10) ampoule bottle sealed in step 9) is put into 60 DEG C of water-baths, reacted for 24 hours, the mixing liquid in ampoule bottle
Polymerisation occurs, becomes solid；
11) to the tetrahydrofuran washing by soaking 3 times of the solid in ampoule bottle, the substances that some of them are had neither part nor lot in reaction are clear
It washes, obtains integral material；
12) integral material that step 11) obtains is put into vial, and adds in hydrochloric acid；
13) vial in step 12) is sealed, and is put into 72h in 70 DEG C of water-baths, with the degradable polymerization of complete hydrolysis
Object；
14) above-mentioned integral material is rinsed with methanol, to remove demineralizing acid and hydrolysate, you can obtain the more of phosphoric acid functionalized
Grade hole hybrid integral material.
15) integral material obtained by step 14) is put into 50mL centrifuge tubes, adds in the titanium sulfate water of 40mL 0.1g/mL
Solution, oscillation is for 24 hours.
16) above-mentioned integral material is rinsed with deionized water, to remove the titanium ion not chelated, you can be applied to
The multi-stage porous hybrid integral material of Titanium ion chelating affinity chromatography.
Scanning electron microscope (SEM) photograph such as Fig. 2 (c, d) of integral material prepared by embodiment 2, is clear that in integral material and deposits
In macropore, and scanning electron microscope (SEM) photograph such as Fig. 2 (a, b) of integral material prepared by embodiment is then without macropore.By phosphoric acid functionalized
Absorption of the multi-stage porous hybrid integral material (Examples 1 and 2) applied to 5- phosphonic acids pyridoxals, experimental result such as Fig. 3.As a result table
It is bright to contain eurypyloue multi-stage porous hybrid integral material (embodiment 2) rate of adsorption faster, it is flat that absorption can be reached in 60min
Weighing apparatus, adsorption capacity may be up to 62.8mg/g.Experiment condition：5- phosphonic acids pyridoxals solution is acetonitrile/water (50/50, v/v) solution,
Ultraviolet detection wavelength is 295nm.Multi-stage porous hybrid integral material (embodiment 2) is applied to endogenous phosphoeptide in enrichment human serum
MADLI TOF-MS mass spectral analyses figures as shown in figure 4, result show can be by being effectively enriched with and mass spectral analysis can detect
4 endogenous phosphoeptides into human serum.These results have absolutely proved multi-stage porous hybrid integral material in complex biological sample
There are certain practical application potentiality in product.
Conclusion：This method prepares phosphoric acid functionalized multi-stage porous hybrid integral material using thermal initiation Raolical polymerizable,
Its preparation process is simple, and has good concentration effect to phosphoeptide in small molecule and biological sample, and can be according to not
With needs, monomer composition is adjusted, prepares the multi-stage porous hybrid integral material of the phosphoric acid functionalized with different physical properties.
Claims (6)
1. the preparation of phosphoric acid functionalized multistage pore canal hybrid integral material, it is characterised in that：
By eight vinyl silsesquioxanes (Polyhedral oligomeric vinylsilsesquioxane,
VinylPOSS), in a solvent, by heating free radical occurs for phosphoric acid function monomer, degradable polymer and initiator dissolving
The multi-stage porous hydridization entirety material of phosphoric acid functionalized is finally prepared in polymerisation, then hydrating polymer in acid condition
Material.
2. preparation method according to claim 1, it is characterised in that：
The solvent is tetrahydrofuran (Tetrahydrofuran, THF)；
The phosphoric acid function monomer is vinyl phosphonic acid (Vinylphosphonic acid)；
The degradable polymer for polycaprolactone (Polycaprolactone, PCL, average molecular mass Mn 1,000-10,
000)；
The initiator is azodiisobutyronitrile (Azodiisobutyronitrile, AIBN).
3. preparation method according to claim 1 or 2, it is characterised in that：Its operating process is as follows,
1) eight vinyl silsesquioxanes are added in into ampoule bottle；
2) vinyl phosphonic acid is added in into the ampoule bottle of step 1)；
3) polycaprolactone is added in into the ampoule bottle of step 1)；
4) tetrahydrofuran is added in into the ampoule bottle of step 1)；
5) initiator azodiisobutyronitrile is added in into the ampoule bottle of step 1)；
6) it is the mixed system obtained after step 5) is ultrasonic at normal temperatures, it makes it completely dissolved to form homogeneous transparent solution, with
Remove the dissolved oxygen in mixed system；
7) ampoule bottle that mixed solution is housed in step 6) is put into liquid nitrogen, mixed solution is made to be frozen into solid；
8) ampoule bottle in step 7) is vacuumized, to remove the oxygen in bottle；
9) ampoule bottle in step 8) is sealed；
10) ampoule bottle sealed in step 9) is put into 50-70 DEG C of water-bath, reaction 12-48h, the mixing in ampoule bottle
Polymerisation occurs for liquid, becomes solid；
11) to tetrahydrofuran washing by soaking 3-5 times of the solid in ampoule bottle, the substances that some of them are had neither part nor lot in reaction are clear
It washes, obtains integral material；
12) integral material that step 11) obtains is put into vial, and adds in hydrochloric acid submergence integral material；
13) vial in step 12) is sealed, and is put into 48-96h in 60-80 DEG C of water-bath, it is degradable with complete hydrolysis
Polymer；
14) above-mentioned integral material is rinsed with methanol, to remove demineralizing acid and hydrolysate, you can obtain the multi-stage porous of phosphoric acid functionalized
Hybrid integral material；
15) integral material obtained by step 14) is put into centrifuge tube, adds in the titanium sulfate aqueous solution of 0.1-0.3g/mL, shake
Swing 24-48h.
16) above-mentioned integral material is rinsed with deionized water, to remove the metal titanium ion not chelated, you can be applied to
The multi-stage porous hybrid integral material of Titanium ion chelating affinity chromatography (IMAC).
4. the preparation method in step 1)-step 16) according to claim 3, it is characterised in that：The capacity of ampoule bottle is
5-10mL；The amount of eight vinyl silsesquioxanes is 75-200mg；The amount of vinyl phosphonic acid is 10-100mg；Polycaprolactone
It measures as 20-70mg；The volume of tetrahydrofuran is 0.5-5.0mL；The amount of azodiisobutyronitrile is 12-40mg；Hydrochloric acid it is a concentration of
1-2mol/L；The titanium sulfate aqueous solution of 30-50mL 0.1-02g/mL.
5. a kind of porous organic whole material that any preparation methods of claim 1-4 obtain.
6. a kind of application of the porous organic whole material during chromatography described in claim 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872383A (en) * | 2018-08-29 | 2020-03-10 | 中国科学院大连化学物理研究所 | Preparation and application of penicillamine modified hierarchical pore hybrid material |
| CN110872383B (en) * | 2018-08-29 | 2021-06-22 | 中国科学院大连化学物理研究所 | Preparation and application of penicillamine modified hierarchical pore hybrid material |
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