CN107474254A - The preparation and application of organic-inorganic hydrophilic hybrid integral material - Google Patents
The preparation and application of organic-inorganic hydrophilic hybrid integral material Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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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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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Abstract
The present invention relates to a kind of method for preparing hydrophily hybrid integral material based on sulfydryl-alkene clicking chemistry reaction, the polyhedral oligomeric sesquialter silane reagent after modification, sulfhydryl compound, initiator and pore-foaming agent are specifically mixed into simultaneously ultrasonic dissolution, then generation sulfydryl in situ-alkene clicking chemistry reaction can prepare organic-inorganic hydrophilic hybrid integral material under ultraviolet light.Porous hybrid integral material microstructure is homogeneous regular, and duct is more orderly, there is good application in chromatographic isolation.Described preparation method have the advantages that it is easy to operate it is quick, reaction speed is fast, it can in addition contain select different function monomers and pore-foaming agent system according to different application requirements, a series of porous hybrid integral materials with different physics and chemical property are prepared.
Description
Technical field
Parent is prepared based on light-initiated sulfydryl-alkene clicking chemistry rapid reaction the present invention relates to a kind of
Water-based organic-inorganic hybridization porous monolithic material and its preparation method and application, specifically will be through
Eight vinyl sesquialter silane after the modification of 1- thioglycerols, sulfhydryl compound and light trigger are causing
Ultrasonic dissolution in the solvent of hole, reacted using light-initiated sulfydryl-alkene clicking chemistry
(photoinduced thiol-ene click polymerization reaction) is formed in situ hydrophilic
Organic-the inorganic hybridization porous monolithic material of property.By adjusting the concentration of monomer and the ratio of pore-foaming agent
Example, you can be prepared into the porous hybrid integral material with different surfaces property and function.
Background technology
Since 20th century, the nineties integral post occurred, integral material is as a kind of novel porous
Micro- separating medium is of great interest in Analyze ＆ separate field.With traditional packed column
Compare, capillary monolithic column be easily achieved it is quick prepare and quick separating, have concurrently stable performance,
The advantages that being easy to modification and good permeability, and when analyzing complex sample, the antipollution of integral post
Ability will be significantly stronger than packed column.Because it shows good performance in work is analyzed in separation,
The forth generation chromatography separation media being described as after polysaccharide, crosslinking and coated, single dispersing,
It is widely used in the fields such as materia medica, environmental science and life science.Based on integral material matrix
The difference of property, capillary monolithic column are broadly divided into three classes, i.e. Organic Polymer Monolithic Columns, nothing
Machine integral post and organic-inorganic hybridization integral post.First, organic whole post has preparation process
Simply, good biocompatibility, the advantages that pH scope of applications are wide and selectable monomeric species are relative
It is abundant, it can also be modified or derived in stromal surface.But, organic whole post there is also
Specific surface area is smaller, poor to the separating property of micromolecular compound, in organic phase flow easily
In swelling the problems such as.By comparison, the high mechanical strength of inorganic integral post, solvent tolerance is good,
But prepare cumbersome, also need the processing of further subsequent derivation just to can apply to chromatographic isolation.
The advantages of organic-inorganic hybridization integral post combines both to a certain extent, from 2000
After year Hayes and Malik prepares hydridization integral post using sol-gal process first, hydridization is whole
Scapus is paid close attention to by more and more chromatogram workers, has been widely used in minute yardstick point at present
Matrix from analysis, SPME and immobilized enzyme reactor etc..By years of researches and
Development, have developed a variety of preparation methods, wherein mainly include colloidal sol-gel method,
One kettle way and some other polymerization etc..But it is whole to prepare inorganic-organic hybrid containing silicon substrate
Body material still will pass through multiple steps, and easily influenceed by PH, on repeatability is prepared
Deficiency limits its development, thus develop more quickness and high efficiency hybrid integral material preparation method be
It is necessary.
Click chemistry (click chemistry) has been widely used big in Macroscopic single crystal, dendroid
The field such as molecule preparation and surface modification.Wherein, sulfydryl-alkene clicking chemistry reaction need not
It is transition metal-catalyzed, so that it may to be rapidly completed under the conditions of free radical or nucleophilic catalysis.At present, adopt
The report of integral material is prepared with click chemistry also increasingly to be increased, such as the integral post successfully prepared
Also it is widely used in from simple small molecule to the pretreatment of large biological molecule and complex sample and color
Spectrum separation.The it is proposed of sulfydryl-alkene clicking chemistry reaction opens for the preparation of hybrid integral material
New approaches.Because the light initiating polymerizing reaction containing alkenyl monomer and mercapto monomers is in air and inertia
React same rapid in gas, therefore the reaction there can be preferable physical property to quick preparation
Hybrid integral material.
In recent years, with the development of the subjects such as proteomics, environmental science, pharmaceutical chemistry,
Strong supplement of the hydrophilic Interaction Chromatography (HILIC) as reversed-phase liquid chromatography (RPLC), by
To extensive concern and pay attention to.Relative with RPLC, HILIC uses the flowing of high content organic solvent
Relatively strong polar compound and ionic compound, which include polypeptide, poisonous substance, natural products etc., to be had
Suitable reservation and separating property.Between different types of hydrophilic stationary phase separation selectivity and should
Also differed greatly with scope, therefore the research to novel hydrophilic interaction chromatography material is established to promoting
Rapidly and efficiently method for separating and analyzing important in inhibiting.
The content of the invention
It is whole based on sulfydryl-alkene clicking chemistry reaction preparation hydrophily hydridization the invention provides one kind
The method of body material.Specifically by the function monomer containing sulfydryl, eight containing unsaturated double-bond
After vinyl sesquialter silane, porogenic solvents and light trigger mix ultrasound uniformly, ultraviolet light is utilized
The sulfydryl of initiation-alkene clicking chemistry reaction prepares organic-inorganic hybrid integral material.
The technical solution adopted by the present invention is：
By through 1- thioglycerols modification after the eight vinyl sesquialter silane containing unsaturated double-bond,
Function monomer and light trigger containing sulfydryl are dissolved in porogenic solvents, and ultrasonic mixing is uniformly simultaneously
After removing dissolved oxygen, it is overall to prepare organic-inorganic porous hydridization using sulfydryl-alkene click-reaction
Material, and according to different demands, by adjusting monomer concentration and pore-foaming agent ratio, can make
It is standby go out organic-inorganic porous hybrid integral material of different nature.
Organic-inorganic porous hybrid integral material prepared by the present invention can be applied to chromatogram point
Analysis, be particularly suitable for use in capillary liquid chromatography and liquid chromatogram-mass spectrometry, separation object point
Wei not four kinds of polar compounds, phenyl amines micromolecular compound, antibiotic and complex sample.Knot
Fruit is shown in that the lower four kinds of compounds of hydrophilic pattern reach baseline separation and peak shape is symmetrical, while
In LC-MS, this material can realize the separation and identification of composition in complex sample.
Beneficial effects of the present invention and advantage are:
This method clicks on polymerisation (photoinduced using light-initiated sulfydryl-alkene
Thiol-ene click polymerization reaction), in order to avoid dissolved oxygen produces shadow to reaction
Ring, reaction needs to be ultrasonically treated mixed liquor progress deoxygenation before starting.In order to improve eight vinyl times
The dissolubility of half silane, it is modified by adding a certain proportion of 1- thioglycerols.Have
The formation of machine-inorganic hybridization porous monolithic material only needs to react under ultraviolet lighting, and
And its aperture and pore structure can add crosslinking agent and function monomer concentration and change by changing
The compositions of porogenic solvents or content are regulated and controled.
Hybrid integral material prepared by the present invention has more homogeneous regular loose structure, fits
Analyzed in chromatographic isolation.Liquid chromatogram is investigated result and shown, hybridization porous monolithic material surface tool
There is hydrophilic nmature, centering compound shows typical positive retention mechanism.
Porous organic-inorganic hybrid integral material prepared by the present invention has that permeability is good, color
It is good to compose separating capacity, functionalized modification method is easy, while versatility is stronger, can use other
Sulfydryl function monomer is raw material.
Brief description of the drawings
Fig. 1 is the eight vinyl sesquialter silane after the modification of 1- thioglycerols
MADLI-TOF-MS phenograms.
Fig. 2 be capillary hydridization integral post scanning electron microscope (SEM) photograph (a be 1000 times, b 10000
Times).
Fig. 3 is the capillary liquid chromatography separation figure of capillary hydridization integral post.
Fig. 4 is that the van Deemter of capillary hydridization integral post scheme.
Fig. 5 is the mechanical strength of capillary hydridization integral post.
Fig. 6 is the reaction equation for preparing hybridization porous monolithic material.
Embodiment
One group of embodiment is provided, technical scheme is described, but is not restricted to
Within the scope of this Parameter Conditions, for those skilled in the art, it still can be to reality
Apply the technical scheme described in example to modify, or which part technical characteristic is equal
Replace, within the spirit and principles of the invention, any modification for being made, equivalent substitution,
Improve etc., it should be included in the scope of the protection.
Embodiment 1
Preparation process is as follows：
1) the vinyl silsesquioxanes of 300mg eight are added into UV transparent centrifuge tube；
2) 107.9mg 1- thioglycerols are added into the UV transparent centrifuge tube of step 1)；
3) 10mL tetrahydrofurans are added into the UV transparent centrifuge tube of step 1)；
4) 20 μ L light trigger 2,2- diformazans are added into the UV transparent centrifuge tube of step 1)
Epoxide-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
5) mixed system that will be obtained after step 4) is ultrasonic at normal temperatures, makes it completely molten
Solution forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
6) mixed solution for obtaining step 5) is sealed in UV transparent vial；
7) the UV transparent vial that mixed solution is encapsulate in step 6) is placed under uviol lamp
React 20min；
8) the product at reduced pressure evaporation of solvent for obtaining step 7) UV transparent vial；
9) product that step 8) obtains is added into UV transparent centrifuge tube；
10) 12mg dithiothreitol (DTT)s are added into the UV transparent centrifuge tube of step 9)；
11) 130 μ L tetrahydrofurans and 5 μ L are added into the UV transparent centrifuge tube of step 10)
Lauryl alcohol is as pore-foaming agent；
12) 1 μ L light triggers 2,2- bis- is added into the UV transparent centrifuge tube of step 11)
Methoxyl group-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
13) mixed system that will be obtained after step 12) is ultrasonic at normal temperatures, makes its complete
Dissolving forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
14) mixed solution for obtaining step 13) is sealed in UV transparent centrifuge tube；
15) reactor that mixed solution is encapsulate in step 14) is placed under uviol lamp and reacts 5
min；
16) product that at least 3 step 15) reactors obtain is washed with methanol, by pore-foaming agent
And unreacted or it is uncombined on material go out, it is hybridization porous whole to obtain organic-inorganic hydrophilic
Body material.
The preparation process of embodiment 2 is as follows：
1) the vinyl silsesquioxanes of 300mg eight are added into UV transparent centrifuge tube；
2) 161.8mg 1- thioglycerols are added into the UV transparent centrifuge tube of step 1)；
3) 10mL tetrahydrofurans are added into the UV transparent centrifuge tube of step 1)；
4) 20 μ L light trigger 2,2- diformazans are added into the UV transparent centrifuge tube of step 1)
Epoxide-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
5) mixed system that will be obtained after step 4) is ultrasonic at normal temperatures, makes it completely molten
Solution forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
6) mixed solution for obtaining step 5) is sealed in UV transparent vial；
7) the UV transparent vial that mixed solution is encapsulate in step 6) is placed under uviol lamp
React 20min；
8) the product at reduced pressure evaporation of solvent for obtaining step 7) UV transparent vial；
9) product that step 8) obtains is added into UV transparent centrifuge tube；
10) 12mg dithiothreitol (DTT)s are added into the UV transparent centrifuge tube of step 9)；
11) 130 μ L tetrahydrofurans and 5 μ L are added into the UV transparent centrifuge tube of step 10)
Lauryl alcohol is as pore-foaming agent；
12) 1 μ L light triggers 2,2- bis- is added into the UV transparent centrifuge tube of step 11)
Methoxyl group-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
13) mixed system that will be obtained after step 12) is ultrasonic at normal temperatures, makes its complete
Dissolving forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
14) the μ L of pre-polymerization liquid 1 obtained in step 13) are incorporated into syringe and passed through in advance
Cross 75 μm (internal diameters) of 3- (trimethoxy first silicon substrate) propyl methacrylate activation process
UV transparent capillary in, sealed with postcapillary both ends with silica gel, then will be equipped with residue
The UV transparent centrifugation seal of tube of mixed liquor；
15) the UV transparent capillary in step 14) and UV transparent centrifuge tube are placed in purple
Under outer lamp (λ=365nm), 10min is reacted, the mixing liquid in UV transparent centrifuge tube becomes
Into the solid of white.
16) mixed liquor rinsed with methanol in UV transparent capillary, by pore-foaming agent therein and
Some materials for having neither part nor lot in reaction, which are gone out, is prepared into capillary organic-inorganic hybridization monolithic column,
White solid in UV transparent centrifuge tube is then obtained for 3 times with methanol washing by soaking organic
Integral material.The scanning electron microscope (SEM) photograph of capillary organic-inorganic hybridization monolithic column is shown in Fig. 2, step 8)
The MALDI-TOF-MS mass spectrograms of eight vinyl silsesquioxanes after obtained modification are shown in Fig. 1,
Capillary liquid chromatography separation figure is shown in Fig. 3, the van Deemter figures of capillary organic whole post
See Fig. 4, the mechanical strength of capillary organic-inorganic hybridization monolithic column is shown in Fig. 5, prepare it is organic-
The anti-schematic diagram of inorganic hybridization porous monolithic material is shown in Fig. 6.
Fig. 1 is the MALDI-TOF-MS mass spectrograms of eight vinyl silsesquioxanes after modification,
Mass Spectrometry Conditions are：Molecular weight ranges are 700to 1600Da, wavelength 355nm, detect mould
Formula is linear positive ion mode.The of poor quality of 108Da exactly corresponds to 1- thioglycerols in figure
Molecular weight.
Fig. 3 is toluene, DMF, formamide, thiocarbamide in capillary hybrid inorganic-organic entirety
The capillary liquid chromatography separation figure of post.Chromatographic condition is capillary column (20cm × 75 μm
I.d.), mobile phase is acetonitrile/water (95/5, v/v), and flow velocity is 200 μ L/min (before shunting).Color
Peak in spectrogram is followed successively by (1) toluene, (2) DMF, (3) formamide, (4) thiocarbamide.Appearance is suitable
Sequence grows from weak to strong appearance by hydrophily, is typical normal-phase chromatography retention mechanism.
Fig. 4 is that benzene homologues are schemed in the van Deemter of capillary organic whole post.Chromatographic condition
For capillary column (20cm × 75 μm i.d.), mobile phase is acetonitrile/water (95/5, v/v), flow velocity
For 40-250 μ L/min (before shunting)
From embodiment and accompanying drawing, this method preparation process is simple, and the reaction time is short, made
Standby hydrophily hydridization integral post pattern is homogeneous, and mechanical strength is good, for Separation of Neutral and pole
Property small molecule, there is good separating effect, the advantages that high post effect.Meanwhile by adjusting sulfydryl work(
Energy monomer and eight vinyl silsesquioxane reaction ratios, can prepare a series of different physics
With the hybrid integral material of chemical property, applied to capillary liquid chromatography difference clastotype.
Claims (9)
1. the preparation method of organic-inorganic hydrophilic hybrid integral material, it is characterised in that：
In the presence of photoinitiators, by eight vinyl silsesquioxane (Polyhedral
Oligomeric vinylsilsesquioxane, vinylPOSS) and 1- thioglycerols
(1-Thioglycerol) is dissolved in tetrahydrofuran, through UV illumination after ultrasonic dissolution,
Generation sulfydryl-alkene clicking chemistry reaction, the rotated evaporimeter of product are used as preparation after removing solvent
The presoma of integral material；Presoma further with dithiothreitol (DTT)
(DL-Dithiothreitol, DTT), pore-foaming agent and light trigger mixing and ultrasonic dissolution,
Then sulfydryl-alkene clicking chemistry reaction (thiol-ene occurs under ultra violet lamp
Polymerization click reaction), porous organic-inorganic hybridization is prepared
Integral material.
2. preparation method according to claim 1, it is characterised in that：
The pore-foaming agent is tetrahydrofuran (Tetrahydrofuran, THF) and lauryl alcohol
The mixing of (Dodecyl alcohol)；
The light trigger is 2,2- dimethoxy-phenylfs acetophenone (DMPA).
3. preparation method according to claim 1, it is characterised in that：The ultrasound is molten
The time of solution is 5-10min；The wavelength of the uviol lamp is 360-370nm；Light application time
5-10min。
4. according to the preparation method described in claim 1,2 or 3, it is characterised in that：Its mistake
Journey is as follows,
1) eight vinyl silsesquioxanes are added into UV transparent centrifuge tube；
2) 1- thioglycerols are added into the UV transparent centrifuge tube of step 1)；
3) tetrahydrofuran is added into the UV transparent centrifuge tube of step 1)；
4) added into the UV transparent centrifuge tube of step 1) light trigger 2,2- dimethoxys-
Phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
5) mixed system that will be obtained after step 4) is ultrasonic at normal temperatures, makes it completely molten
Solution forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
6) mixed solution for obtaining step 5) is sealed in UV transparent vial；
7) the UV transparent vial that mixed solution is encapsulate in step 6) is placed under uviol lamp
Reaction；
8) the product at reduced pressure evaporation of solvent for obtaining step 7)；
9) product that step 8) obtains is added into UV transparent centrifuge tube；
10) dithiothreitol (DTT) is added into the UV transparent centrifuge tube of step 9)；
11) tetrahydrofuran and lauryl alcohol conduct are added into the UV transparent centrifuge tube of step 10)
Pore-foaming agent；
12) light trigger 2,2- dimethoxies are added into the UV transparent centrifuge tube of step 11)
Base-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone, DMPA)；
13) mixed system that will be obtained after step 12) is ultrasonic at normal temperatures, makes its complete
Dissolving forms homogeneous transparent solution, to remove the dissolved oxygen in mixed system；
14) mixed solution for obtaining step 13) is sealed in UV transparent centrifuge tube；
15) the UV transparent centrifuge tube that mixed solution is encapsulate in step 14) is placed in uviol lamp
Lower reaction, until forming solid；
16) product that at least 3 step 15) obtain is washed with methanol, it is by pore-foaming agent and not anti-
Material on should or being not associated with is gone out, and obtains Porous-Organic integral material.
5. the preparation method in step 1)-step 8) according to claim 4, its
It is characterised by：Eight vinyl silsesquioxanes：1- thioglycerols：Tetrahydrofuran：It is light-initiated
The raw material ratio of agent is 600-1000mg:200-700mg:15-30mL:2-5mg.
6. the preparation method in step 9)-step 16) according to claim 4, its
It is characterised by：Eight vinyl silsesquioxanes after the modification that step 8) obtains:Two sulphur threoses
Alcohol:Pore-foaming agent:The raw material ratio of initiator is 30mg:8-16mg:135μL:1-5μL；Institute
The volume range of tetrahydrofuran and lauryl alcohol is 8 in the porogenic solvents stated:1-26:1.
7. the preparation method according to claim 1 or 4, it is characterised in that：By step
14) mixed solution in UV transparent centrifuge tube after ultrasound is introduced into UV transparent capillary, then
Sealed, illumination reaction, methanol scrubbing step, that is, it is hydrophilic to obtain capillary organic and inorganic
Property hydridization integral post.
A kind of 8. organic-inorganic hybridization that any preparation methods of claim 1-8 obtain
Integral material.
9. porous organic-inorganic hybrid integral material is in chromatography described in claim 8
Application.
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| CN108187367A (en) * | 2018-01-05 | 2018-06-22 | 福州大学 | Sulfydryl derivatization L-PROLINE type organic-inorganic hybridization monolithic column and preparation method thereof |
| CN108452784A (en) * | 2018-04-04 | 2018-08-28 | 广西民族大学 | Catecholamine Solid Phase Extraction functional composite material and its preparation method and application |
| 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 |
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| CN108187367A (en) * | 2018-01-05 | 2018-06-22 | 福州大学 | Sulfydryl derivatization L-PROLINE type organic-inorganic hybridization monolithic column and preparation method thereof |
| CN108452784A (en) * | 2018-04-04 | 2018-08-28 | 广西民族大学 | Catecholamine Solid Phase Extraction functional composite material and its preparation method and application |
| CN108452784B (en) * | 2018-04-04 | 2021-01-26 | 广西民族大学 | Catecholamine solid phase extraction functional composite material, preparation method and application thereof |
| 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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