CN105732916A - Organic-inorganic hybrid microsphere particles, and preparation and application thereof - Google Patents
Organic-inorganic hybrid microsphere particles, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to the field of polymer material and analysis, and relates to organic-inorganic hybrid core-shell-structured microsphere particles, and a preparation and an application thereof. According to the invention, inorganic silica gel particles are adopted as cores, and are modified with a silanization agent; with a thiol-ene click chemistry technology, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and methylene diacrylamide are wrapped on the surfaces of the cores, such that the organic-inorganic hybrid core-shell-structured nano/micro particles with smooth surface and with hydrophilic functional groups such as hydroxyl group, sulfonic acid group, amide and the like are formed. According to the invention, the hydrophilic functional groups such as hydroxyl group, sulfonic acid group, amide and the like are introduced to the surface of the material through the thiol-ene method, such that the defects of complicated steps and low reaction efficiency of a traditional post-modification method are solved, and a polymer three-dimensional-structured hydrophilic layer is formed. Better advantage is shown when the particles are used in hydrophilic chromatography. The microsphere particles can be used in hydrophilic interaction chromatography for separating and enriching glycopeptide, and have good practical value and application prospect in the fields of separation analysis and sugar proteomics.
Description
Technical field
The present invention relates to organic inorganic hybridization microsphere particle and preparation thereof and application, the organic inorganic hybridization nucleocapsid structure microsphere particle of the functional groups such as specifically a kind of end is with hydroxyl, sulfonic acid, amide.
Background technology
Highly polar compound (such as oligosaccharide, glucosides, glycopeptide etc.) plays an important role in medicine and organism, and therefore, it separates to analyze and is increasingly becoming the focus that everybody pays close attention to.But, the currently used reversed-phase high-performance liquid chromatography of high efficient separation technology the most widely (RP-HPLC) is very weak for the reservation of highly polar compound.Hydrophilic interaction liquid chromatograph (HILIC) is as a kind of chromatographic technique (Strege, M.A.etal, Anal.Chem.2000,72,4629-4633 for separating highly polar compound;Wang, X.D.etal, J.Chromatogr.A, 2005,1083,58-62) it is widely developed in recent years, especially amide-type, hydroxy kind, saccharide etc. (Guo, Y.etal, J.Chromatogr.A, 2005,1074,71-80;Irgum, K.etal, J.Sep.Sci., 2006,29,1784-1821) fixing separate be enriched with polar molecule and glycopeptide in there is significant advantage.
But, these process for fixation generally modify a kind of functionalization group, and require that comparatively strict (such as anhydrous solvent, the reaction temperature etc. compared with the high) preparation process of reaction condition is many, and reaction efficiency is low, requires the reaction for intersecting between functional group.It is, thus, sought for a kind of reaction condition is gentle, the new method that selectivity height reaction condition is compatible with water environment.The feature that click chemistry has reaction yield height, functional group is stable and reactivity is high.Guo, Z.etal, Chem.Commun., 2007,2,491 2493 report a kind of hydrophilic fixing phase modifying maltose at silicon ball surface, and the maltose containing azido group is fixed to silicon ball surface by " click chemistry " method by the method, it is effectively increased the fixing rate of maltose, significantly improve its separating power to polar substances, but this technology belongs to the azide of metal catalytic and the reaction of alkynyl and the hydroxyl only modifying saccharide of this material.
Summary of the invention
For above deficiency, the present invention provides a kind of mercaptan-alkene clicking chemistry to prepare surface simultaneous with hydroxyl, the hydrophilic microsphere particle of functionalization of amide and sulfonic acid group, the method has reaction condition gentleness, the feature that selectivity height reaction condition is compatible with water environment, the product grain shape obtained is regular, and monodispersity is good, can be used for the separation and concentration to nucleoside and glycopeptide under hydrophilic interaction Liquid Chromatography mode.
For achieving the above object, the technical solution used in the present invention is:
Step one: by silica gel particle, add in reaction vessel containing the silylating reagent of thiol group, reaction dissolvent toluene etc., ultrasonic 1 minute, the reagent added and silica gel particle is made to be uniformly dispersed in solvent, flask connects condensing tube, adding magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan, is heated to reflux 6~30h, afterwards stopped reaction, is cooled to room temperature.Use the high speed centrifuge centrifugation of 3000~10000rad/min afterwards, remove supernatant, use toluene, methanol, acetone filtering and washing successively, repeat filtering and washing 3 times, vacuum drying 24 hours in 50 DEG C of vacuum drying ovens.
Step 2: in flask, load onto condensing tube, add reaction dissolvent, silica gel particle after the silylation modification obtained in step one, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid, methylene diacrylamide, initiator etc. are added in beaker, ultrasonic 1 minute so that the reagent of addition and grain dissolution are uniformly dispersed in solution, logical nitrogen 15 minutes afterwards, adding magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan and is uniformly slowly heated, and is warming up to 60~140 DEG C in 30min.Maintain and react 4-48 hour under 60~80 DEG C of conditions, stopped reaction, it is cooled to room temperature.Use the high speed centrifuge centrifugation of 3000~10000rad/min afterwards, remove supernatant, add reaction dissolvent and wash three times, vacuum drying 24 hours in 50 DEG C of vacuum drying ovens.
In step one, described silylating reagent is the silylating reagent containing sulfydryl.Containing silica gel particle, in the solution of silylating reagent, it is 0.05~1mol/L that silica gel particle accounts for the total mole number concentration of 0.01~0.2wt% monomer of gross mass, and surplus is reaction dissolvent.Microsphere particle after modification, its particle diameter is 100nm~10 μm.
In step 2, described initiator selects azo-initiator.Reaction solution is water, acetonitrile, methanol, toluene, N,N-dimethylformamide or its mixture.In solution containing 3-allyloxy-2-hydroxyl-1-propane sulfonic acid, methylene diacrylamide and initiator, the total mole number concentration of monomer is 0.05~0.4mol/L, and initiator accounts for the 0.5~10% of monomer gross mass, and surplus is reaction dissolvent.The organic inorganic hybridization microsphere particle prepared, its particle diameter is 100nm~10 μm.
The present invention passes through mercaptan-alkene method at material surface and introduces the hydrophilic functional groups such as hydroxyl, sulfonic group, amide groups, not only overcome tradition post-decoration method complex steps, shortcoming that reaction efficiency is low, and making the microsphere surface of the nucleocapsid structure formed have the polymer chain of three dimensional structure, this structure can improve the hydrophilic chromatographic ability of material.The microsphere particle of the present invention can as the fixing phase of a kind of novel hydrophilic action chromatography, and be used for conforming to the principle of simplicity to separate or enrichment nucleoside, glycopeptide in monocyte sample mixture or complex sample.
Present invention have the advantage that
1. preparation method of the present invention, the method adopting sulfydryl-alkene clicking chemistry so that prepare reaction condition gentleness, response speed is fast, and reaction efficiency is high, and resulting materials repeatability is high.
2. organic inorganic hybridization nucleocapsid structure microsphere particle outer layer is formed by sulfydryl-alkene clicking chemistry method, the particle size distribution making nucleocapsid structure microsphere particle of the present invention is narrower, particle diameter single dispersing, and surface contains the hydrophilic functional groups such as substantial amounts of hydroxyl, amide, sulfonic acid simultaneously.
3. the boric acid functionalization nucleocapsid structure microsphere prepared by the present invention is owing to containing substantial amounts of various hydrophilic radical simultaneously, therefore, can as the fixing phase of a kind of novel hydrophilic action chromatography, and it is used for conforming to the principle of simplicity monocyte sample mixture or complex sample separate or enrichment nucleoside, glycopeptide, opens up and prepare microsphere particle at the new opplication separating analysis field by sulfydryl-alkene clicking chemistry method.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the polymer microballoon of preparation in embodiment 1
Fig. 2 uses the polymer microballoon prepared in embodiment 1 as the fixing separation chromatography figure for nucleoside.
Detailed description of the invention
Adopt specific embodiment that technical scheme is described further below.
Embodiment 1
1. the preparation of single dispersing nucleocapsid structure polymer nano-particle
In the round-bottomed flask of 150mL, add 80mL toluene, add the silica gel particle that 6g particle diameter is 5 μm, the 3-mercaptopropyltriethoxysilane of 3g, ultrasonic 1 minute so that the reagent of addition and evengranular dispersion in the solution, connect condensing tube on flask, adding magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan, is heated to reflux 6h, afterwards stopped reaction, is cooled to room temperature.Use the centrifugation of high speed centrifuge 10000rad/min afterwards, remove supernatant, use toluene, acetone, methanol, acetone filtering and washing successively, repeat filtering and washing and wash three times 3 times, vacuum drying 24 hours in 50 DEG C of vacuum drying ovens, obtains the silica gel particle of the silylating reagent modified.
In the round-bottomed flask of 100mL, load onto condensing tube, add reaction dissolvent water-ethanol mixed solution (volume ratio is 2:1) 50mL, add 1000mg and modify the silica gel particle of silanization, 200mg3-allyloxy-2-hydroxyl-1-propane sulfonic acid (PSAS), the acid of 600mg methylene diacrylamide, ultrasonic 1 minute of 100mg azodiisobutyronitrile (AIBN), make add reagent and grain dissolution formed dispersed in a solvent, logical nitrogen 15 minutes afterwards, adding magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan and is uniformly slowly heated, and is warming up to 75 DEG C in 30min.Maintain and react 12 hours under 75 DEG C of conditions, stopped reaction, it is cooled to room temperature, the centrifugation of high speed centrifuge 10000rad/min is used after obtaining microsphere particle silica (MBAAm-co-PSAS), remove supernatant, add reaction solution to wash three times, vacuum drying 24 hours in 50 DEG C of vacuum drying ovens.
2. the sign of polymer microballoon particle
Being scanned through Electronic Speculum test, result is as shown in Figure 1.
3. polymer microballoon can be used for the separation of nucleoside
Micro polymer ball particle is used to be used for loading 2.1 × 50mm chromatographic column, for the separation analysis of nucleoside.As in figure 2 it is shown, (1) thymidine, (2) uridnine, (3) adenosine, (4) cytidine, (5) guanosine.Nucleoside 5 kinds different obtains good separation.Chromatographic condition is:
Chromatographic column: 2.1 × 50mm;Mobile phase: A, 20mMNH4HCO3Aqueous solution, pH4;B, acetonitrile;Isocratic condition: 0-5min, 15%A;Flow velocity: 0.25mL/min;Column temperature: 25 DEG C;Detection wavelength: 254nm..
Embodiment 2
1. the preparation of single dispersing nucleocapsid structure polymer nano-particle
In the round-bottomed flask of 150mL, add 60mL toluene, add the silica gel particle that 3g particle diameter is 5 μm, the 3-mercaptopropyltriethoxysilane of 3g, ultrasonic 1 minute so that the reagent of addition and evengranular dispersion in the solution, connect condensing tube on flask, adding magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan, is heated to reflux 6h, afterwards stopped reaction, is cooled to room temperature.Use the centrifugation of high speed centrifuge 10000rad/min afterwards, remove supernatant, use toluene, acetone, methanol, acetone filtering and washing successively, repeat filtering and washing and wash three times 3 times, vacuum drying 24 hours in 50 DEG C of vacuum drying ovens, obtains the silica gel particle of the silylating reagent modified.
In the round-bottomed flask of 100mL, load onto condensing tube, add reaction dissolvent water-ethanol mixed solution (volume ratio is 2:1) 80mL, add 1200mg and modify the silica gel particle of silanization, 600mg3-allyloxy-2-hydroxyl-1-propane sulfonic acid (PSAS), the acid of 300mg methylene diacrylamide, ultrasonic 1 minute of 100mg azodiisobutyronitrile (AIBN), make add reagent and grain dissolution formed dispersed in a solvent, logical nitrogen 15 minutes afterwards, adding magnetic stir bar, magnetic stir bar keeps 300rad/min speed.Reaction unit is placed in oil bath pan and is uniformly slowly heated, and is warming up to 75 DEG C in 30min.Maintain and react 12 hours under 75 DEG C of conditions, stopped reaction, it is cooled to room temperature, the centrifugation of high speed centrifuge 10000rad/min is used after obtaining microsphere particle silica (MBAAm-co-PSAS), remove supernatant, add reaction solution to wash three times, vacuum drying 24 hours in 50 DEG C of vacuum drying ovens.
Other are with embodiment 1.
Claims (10)
1. an organic inorganic hybridization microsphere particle, it is characterised in that:
Described organic inorganic hybridization nucleocapsid structure microsphere particle, first with silica gel particle for core, afterwards by modifying upper silylating reagent, the click chemistry technology then passing through mercaptan-alkene (thiol-ene) wraps up 3-allyloxy-2-hydroxyl-1-propane sulfonic acid and methylene diacrylamide on core surface, forms the polymer beads of smooth surface and the nucleocapsid structure with hydrophilic functional group.
2. the hybrid microspheres granule described in claim 1, it is characterised in that: described nuclear particle is silica gel particle, and its silica gel microball particle diameter is between 100nm~10 μm.
3. the hybrid microspheres granule described in claim 1, it is characterised in that: its selected silylating reagent is the silylating reagent with thiol group.
4. the hybrid microspheres granule described in claim 1, it is characterized in that: the surface of shell is with hydroxyl, sulfonic group, one or two or more kinds hydrophilic functional group in amide etc., its 3-allyloxy-2-hydroxyl-1-propane sulfonic acid mass fraction scope in shell is 5%~95%.
5. the polymer microballoon described in claim 1, it is characterised in that:
Described hybrid microspheres granule is the microsphere particle of single dispersing organic-inorganic nucleocapsid structure, and size scope is 100nm~10 μm.
6. the preparation method of the arbitrary described polymer microballoon of claim 1-5, it is characterised in that:
1) process of silylation modification silica gel particle: the silica gel particle after activation is dispersed in toluene, ultrasonic, adding the silylating reagent with thiol group, the mass ratio that addition is silica gel particle and silylating reagent is 1:0.05 to 1:1, is stirred at reflux 6-30h;
Use toluene, methanol, acetone filtering and washing afterwards successively, repeat filtering and washing 2~5 times, to constant weight in vacuum drying oven;
2) prepared by the shell of polymer particles: the silylation modification silica gel particle obtained, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid, methylene diacrylamide, initiator are mixed in reaction dissolvent system, reacts 4-48 hour at 60-80 DEG C;It is centrifugally separating to obtain the nucleocapsid structure microsphere of organic inorganic hybridization, uses unreacting substance in reaction dissolvent washing microsphere to cleaning, to repeat filtering and washing 2~5 times, to constant weight in vacuum drying oven afterwards successively.
7. the preparation method described in claim 6, it is characterized in that: form nucleocapsid period, adding the mol ratio that monoene class function monomer is 3-allyloxy-2-hydroxyl-1-propane sulfonic acid and methylene diacrylamide in system is 0.1:1 to 1:0.1, and both the total mole number concentration in system is 0.05-0.4mol/L;
Forming nucleocapsid period, silica gel nuclear particle adds quality and the monomer total mass ratio forming shell is 1:0.1 to 1:10.
8. the preparation method described in claim 6, forming nucleocapsid period, described initiator is azo-initiator, including one or both in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline hydrochloride and combination of the above, add total amount and account for the 0.5~10% of the monomer gross mass forming shell.
9. the preparation method described in claim 6, is forming nucleocapsid period, and its solvent used is a kind of in methanol, ethanol, toluene, propanol, DMF, water or two kinds and solution mixed above.
10. polymer microballoon described in claim 1 can as the fixing phase of a kind of novel hydrophilic action chromatography, and be used for separating from biological sample or enrichment glycopeptide, glycoprotein.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106807341A (en) * | 2015-12-01 | 2017-06-09 | 中国科学院大连化学物理研究所 | The silica matrix hydrophilic Interaction Chromatography fixing 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 |
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CN112111066A (en) * | 2020-08-18 | 2020-12-22 | 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 |
CN112844258A (en) * | 2019-11-27 | 2021-05-28 | 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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102112191A (en) * | 2008-07-30 | 2011-06-29 | 默克专利股份公司 | Graft copolymers for ion exchange chromatography |
CN103304732A (en) * | 2012-03-14 | 2013-09-18 | 中国科学院大连化学物理研究所 | Monodisperse core-shell structure polymer nano particle as well as preparation and application thereof |
CN103877955A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Amide monolithic column for enriching glycopeptide based on hydrophilic interaction mechanism and preparation and application method thereof |
CN104072678A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Polymer microsphere, preparation and applications thereof |
-
2014
- 2014-12-09 CN CN201410748234.4A patent/CN105732916B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102112191A (en) * | 2008-07-30 | 2011-06-29 | 默克专利股份公司 | Graft copolymers for ion exchange chromatography |
CN103304732A (en) * | 2012-03-14 | 2013-09-18 | 中国科学院大连化学物理研究所 | Monodisperse core-shell structure polymer nano particle as well as preparation and application thereof |
CN103877955A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Amide monolithic column for enriching glycopeptide based on hydrophilic interaction mechanism and preparation and application method thereof |
CN104072678A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Polymer microsphere, preparation and applications thereof |
Non-Patent Citations (3)
Title |
---|
YONG GUO等: "Retention behavior of small polar compounds on polar stationary phases in hydrophilic interaction chromatography", 《JOURNAL OF CHROMATOGRAPHY A》 * |
ZHIMOU GUO等: ""Click saccharides":novel separation materials for hydrophilic interaction liquid chromatography", 《CHEMICAL COMMUNICATIONS》 * |
杨帆等: "基于巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱用于糖蛋白的选择性富集", 《色谱》 * |
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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 |
CN109851960A (en) * | 2019-02-19 | 2019-06-07 | 广东烯王科技有限公司 | A kind of compound PTFE material of white graphite alkene and preparation method thereof |
CN109880353A (en) * | 2019-02-19 | 2019-06-14 | 广东烯王科技有限公司 | A kind of white graphite alkene composite polyamide material, film and preparation method thereof |
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CN112844258A (en) * | 2019-11-27 | 2021-05-28 | 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 |
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 |
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