CN107321313B - A kind of Surface porous core-shell structure silica gel microball and its preparation method and application - Google Patents

A kind of Surface porous core-shell structure silica gel microball and its preparation method and application Download PDF

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CN107321313B
CN107321313B CN201610841658.4A CN201610841658A CN107321313B CN 107321313 B CN107321313 B CN 107321313B CN 201610841658 A CN201610841658 A CN 201610841658A CN 107321313 B CN107321313 B CN 107321313B
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silica gel
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CN107321313A (en
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冯钰锜
余琼卫
胡艺凡
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Wuhan University WHU
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Abstract

The invention discloses a kind of preparation method of Surface porous core-shell structure silica gel microball and its chromatographic isolation applications, and the present invention is first by H2SiF6The nano silicon oxide of hydrolysis is deposited in spherical silica gel surface, form the silicon ball of the Surface porous coreshell type structure containing certain pore size, the modification for carrying out different function group on its surface again is respectively applied to the separation analysis of the macromolecular compounds such as protein, polypeptide and a variety of different small molecule compounds.The prices of raw materials that this method uses are cheap, preparation method is simple, preparation time is short, method is controllable, can prepare the porous shell of different pore size different-thickness, and prepared stationary phase can be widely applied in the separation analysis of macromolecular compound and the quick separating analysis of small molecule compound.

Description

A kind of Surface porous core-shell structure silica gel microball and its preparation method and application
Technical field
The present invention relates to a kind of Surface porous core-shell structure silica gel microball and preparation method thereof and its chromatographic isolation application, Belong to analytical chemistry field.
Background technique
In recent years, the core-shell structure chromatographic stationary phases being made of the shell of solid core and porous surface are widely used in high stream In fast low-pressure chromatography system.Since the shell of solid core porous surface is capable of increasing the size of solid core, column pressure is reduced, simultaneously Since porous sheathing material increases the specific surface area of core, so that chromatographic column volume containing the sample is improved, such as 2.2 μm of core-shell structure silica gel (G.Guiochon and F.Gritti, Journal of is formed by the porous shell of 0.5 μ m-thick and 1.7 μm of core Chromatography A, 2011,1218,1915-1938.), column effect identical with 2 μm of particle, while column pressure can be generated Again close to the column pressure of the chromatographic column for the Silica microparticle packings for having loaded 3 μm.Thus, the lesser pore volume energy of core-shell structure Longitudinal diffusion (the B item i.e. in Van Deemter equation) enough is reduced, meanwhile, shorter diffusion path can reduce resistance to mass tranfer, To reduce C item in Van Deemter equation, thus to the macromolecular compound such as protein being difficult to using chromatographic isolation with The large biological molecules compound such as polypeptide has preferable separating effect.
Van Deemter equation: H=A+B/u+Cu
Core in core-shell structure and shell can be different material or the different structure composition of identical material, as schemed institute Show, Fig. 1 is the schematic diagram of several different core-shell structure particles, and center can be an individual ball (Fig. 1 (A)) either The zoarium (Fig. 1 (B)) of several beads；Core-shell structure may be containing a hollow shell and the one bead (Fig. 1 in centre (C)), or as a yolk-eggshell structure (Fig. 1 (C))；Shell structure can be pantostrat (Fig. 1 (C) and Fig. 1 (H)), Some smaller balls are adsorbed onto one big core surface (Fig. 1 (D) and Fig. 1 (E)) or core is to synthesize (Fig. 1 by the aggregation of a group small nut (F))(X.L.Zhang,H.Y.Niu,W.H.Li,Y.L.Shi and Y.Q.Cai,Chemical Communications, 2011,47,4454-4456.).More complicated core-shell structure is embedded into some smaller beads inside shell (Fig. 1 (G)) (X.Y.Lai,J.Li,B.A.Korgel,Z.H.Dong,Z.M.Li,F.B.Su,J.A.Du and D.Wang,Angewandte Chemie-International Edition, 2011,50,2738-2741.) (Fig. 1 (I)) is either formed by multilayered shell (R.J.Gui, A.Wan and H.Jin, Analyst, 2013,138,5956-5964.), these cores and shell are all non-porous by one Core and porous shell composition, the material of core-shell structure is widely used in chromatographic isolation, wherein filling out using most matrix Material is silica gel.The core-shell structure of different pore size size can be used for separating different size of analyte, when the aperture of core-shell material Between 8-10nm, suitable for small molecule compound separation (J.J.DeStefano, S.A.Schuster, J.M.Lawhorn and J.J.Kirkland, Journal of Chromatography A, 2012,1258,76-83.), hole The bigger filler of diameter can be used for separating the molecular compound of bigger relative molecular mass.If aperture 16nm is for isolated polypeptide and small Molecule protein (Mw < 15KDa) (J.J.Kirkland, F.A.Truszkowski, C.H.Dilks and G.S.Engel, Journal of Chromatography A,2000,890,3-13.)；The porous material of more large aperture can such as aperture 40nm To allow macromolecular (Mw < 500KDa) compound that can unlimitedly enter stationary phase, to obtain preferable separating effect.
The silica gel material of most of core-shell structure is prepared using the method for LBL self-assembly (LBL), especially present city Silica gel (G.Guiochon and F.Gritti, the Journal of Chromatography for the core-shell structure being commercialized in A,2011,1218,1915-1938.).This method utilizes electrostatic interaction (or hydrogen bond action, covalent bond, the model between positive and negative charge De Huali etc.) it is assembled into multilayer, method particularly includes: silica gel core adsorbs one layer of electropolymer (such as negatively charged silica gel first Positively charged polymer can be adsorbed), the electropolymer of excess surface is washed with water, and the nuclear material of this package infiltrates again In the nanoparticles solution that there is opposite charges with electropolymer, to adsorb one layer of shell again.This process is alternately heavy It is immersed in the suspension of charged polymer solution and nano particle again, the shell (G.Guiochon until forming required thickness and F.Gritti,Journal of Chromatography A,2011,1218,1915-1938.)；Finally by the grain of formation Son forms the porous material of nucleocapsid using the organic polymer on high-temperature calcination removal surface.But this preparation method time is long, Poor reproducibility, thus need to find out it is a kind of prepare simple, method is controllable, the method that reproducibility preferably prepares hud typed material.
Summary of the invention
In order to overcome technical problem existing in the prior art, the present invention provides a kind of easy to operate, widely used table The preparation method of the porous nucleocapsid stationary phase in face and the method that above-mentioned Surface porous core-shell structure silica gel microball is modified, First H will be accumulated on silica gel microball surface2SiF6The nano oxidized silicon particle of hydrolysis forms hud typed material, then in the nucleocapsid material Expect that surface carries out functional modification, available a variety of different chromatographic stationary phases.
Technical solution provided by the present invention is specific as follows:
A kind of Surface porous core-shell structure silica gel microball has core-shell structure, the spherical silica gel for being 2~5 μm with partial size For core, porous shell-like structure is formed by as shell using the silica gel nano particle that spherical silica gel surface is accumulated, core is combined closely with shell, Shell with a thickness of 100-700nm, pore diameter range 15-120nm.
A kind of preparation method of Surface porous core-shell structure silica gel microball, comprising the following steps: by partial size be 2~5 μm Spherical silica gel be added 10 parts by volume 35wt% H2SiF6In aqueous solution, 2~16h is stirred, wherein spherical silica gel and H2SiF6 The amount ratio of aqueous solution is 1g:1mL；Then 5 parts by volume water and 6 parts by volume 0.1molL are sequentially added-1H3BO3Aqueous solution mixes It closes uniform；Mixed solution is first stood into 1h in vacuum environment, then in 40 DEG C of constant-temperature table oscillation 12~for 24 hours, then will Mixed solution after reaction is filtered with sintered filter funnel, and the solid filtered out is dried at 120 DEG C, then drying product is placed in Muffle In furnace, 200 DEG C are warming up to the rate of 140 DEG C/min, 2h is kept, obtains Surface porous core-shell structure silica gel microball, i.e., SiO2@SiO2。
A method of above-mentioned Surface porous core-shell structure silica gel microball is modified, comprising the following steps: by table Face porous type core-shell structure silica gel microball is placed in reaction kettle, and 8 parts by volume silane coupling agents and 200 parts by volume are added without water beetle Benzene reacts 12h at 130 DEG C, is filtered after being cooled to room temperature, and is then successively washed with first benzene ﹑ acetone, methanol, 45 DEG C of bakings It does to get the Surface porous core-shell structure silica gel microball of surface modification silane coupling agent is arrived.
The silane coupling agent is that the silane such as octadecyl trimethoxysilane or TSL 8330 are even Join agent.
A kind of Surface porous core-shell structure silica gel microball of surface modification silane coupling agent, is prepared by the above method It arrives.
The Surface porous core-shell structure silica gel microball of above-mentioned surface modification silane coupling agent for protein separation or The separation of polypeptide.
Surface porous core-shell structure silica gel microball the answering as chromatographic stationary phases of above-mentioned surface modification silane coupling agent With.
The present invention has the following advantages and beneficial effects:
1. preparation method of the present invention is simple, preparation time is short, and method controllably (can prepare different pore size different-thickness Porous shell), favorable reproducibility.
2. hud typed silica gel application performance prepared by the present invention is good, it can be used for the large biological molecules chemical combination such as protein, polypeptide The separation of object and the flash chromatography separation of many kinds of substance.
Detailed description of the invention
Fig. 1 is the schematic diagram of different types of core-shell structure；Wherein, Fig. 1 (A) indicates that core is the nucleocapsid of an individual ball Structure, Fig. 1 (B) indicate that core is the fit core-shell structure of several beads；Fig. 1 (C) is indicated containing a hollow shell in Between a bead yolk-eggshell core-shell structure；Fig. 1 (D) and Fig. 1 (E) indicates that some smaller balls are adsorbed onto one big core table The core-shell structure in face, Fig. 1 (F) indicate that core and shell are assembled the core-shell structure synthesized by a group small nut, and Fig. 1 (G) expression will be some Smaller bead is embedded into the complicated core-shell structure inside shell, and Fig. 1 (H) indicates the core-shell structure of hollow core and continuous shell, Fig. 1 (I) indicates the core-shell structure with multilayered shell.
Fig. 2 is that partial size is 5 μm of spherical silica gels and vibrates thickness of the shell prepared for 24 hours in 40 DEG C of constant-temperature table to be 0.48 μm SiO2@SiO2Scanning electron microscope (SEM) figure；Wherein, it is SEM of 5 μm of spherical silica gels at 10,000 times of amplification that Fig. 2 (a), which is partial size, Figure；Fig. 2 (b) is that partial size is the SEM figure that 5 μm of spherical silica gels amplify 50,000 times；Fig. 2 (c) is the SiO that thickness of the shell is 0.48 μm2@ SiO2Amplify 10,000 times of SEM figure；Fig. 2 (d) is the SiO that thickness of the shell is 0.48 μm2@SiO2Amplify 50,000 times of SEM figure.
Fig. 3 is the SiO that partial size is 5 μm of spherical silica gels and prepared thickness of the shell is 0.48 μm2@SiO2Transmission electron microscope (TEM) spectrogram；Wherein, it is the TEM figure that 5 μm of spherical silica gels amplify 50,000 times that Fig. 3 (a), which is partial size,；Fig. 3 (b) is that thickness of the shell is 0.48 μm SiO2@SiO2Amplify 50,000 times of TEM figure.
Fig. 4 is that octadecyl is bonded SiO2@SiO2Separate the chromatographic fractionation figure of 5 kinds of protein mixtures.
Fig. 5 is that octadecyl is bonded SiO2@SiO2The enzymatic hydrolysis for separating the bovine serum albumin (BSA) of trypsin digestion is looked for Spectrum separation figure.
Specific embodiment
Following embodiment does not limit in any way in order to make those of ordinary skill in the art be more clearly understood that the present invention The system present invention.If following percentage is without specified otherwise, expression percent by volume.
Embodiment 1
The spherical silica gel that 10g partial size is 5 μm is added to 10mL 35wt%H2SiF6In aqueous solution, 2h is stirred；Then according to Secondary addition 5mL water and 6mL 0.1molL-1H3BO3Solution is uniformly mixed；Mixed solution is first stood into 1h in vacuum environment, It vibrates in 40 DEG C of shaking table for 24 hours, then filters the mixed solution after reaction with sintered filter funnel again, the solid filtered out exists Dried at 120 DEG C, then by drying product be placed in Muffle furnace, rise to 200 DEG C with the rate of 140 DEG C/min, and keep 2h to get To Surface porous core-shell structure silica gel microball, i.e. SiO2@SiO2；
Then the Surface porous nucleocapsid silica gel of preparation is placed in reaction kettle, adds 8mL octadecyl Silane and 20mL dry toluene react 12h at a temperature of 130 DEG C, cooling, filter, and the solid filtered out successively uses Jia Ben ﹑ third Ketone, methanol washing, 45 DEG C are dried for standby to get octadecyl bonding SiO is arrived2@SiO2。
Embodiment 2
The spherical silica gel that 10g partial size is 5 μm is added to 10mL 35wt%H2SiF6In aqueous solution, 16h is stirred；Then according to Secondary addition 5mL water and 6mL 0.1molL-1H3BO3Solution is uniformly mixed；Mixed solution is first stood into 1h in vacuum environment, 12h is vibrated in 40 DEG C of shaking table again, then filters the mixed solution after reaction with sintered filter funnel, the solid filtered out exists Dried at 120 DEG C, then by drying product be placed in Muffle furnace, rise to 200 DEG C with the rate of 140 DEG C/min, and keep 2h to get To Surface porous core-shell structure silica gel microball, i.e. SiO2@SiO2；
Then the Surface porous nucleocapsid silica gel of preparation is placed in reaction kettle, adds 8mL aminopropyl trimethoxy Silane and 20mL dry toluene react 12h at a temperature of 130 DEG C, cooling, filter, and the solid filtered out successively uses Jia Ben ﹑ third Ketone, methanol washing, 45 DEG C are dried for standby to get amino bonded SiO is arrived2@SiO2。
Embodiment 3
Octadecyl is bonded SiO2@SiO2It is loaded in the liquid-phase chromatographic column of 50mm × 4.6mm (i.d.), then by it For 5 kinds of reference polypeptide sample mixtures (CRGRGRGR-594.73kDa, SPVLAEDPSEGEE-1269.21kDa, CFRGL- 594.73, CFRGLRGFRG-1381.61, Angitotensin II -1046.18) chromatographic isolation, obtained good separation Effect.
Chromatographic condition: solvent A is 0.1%TFA aqueous solution, and solvent B is acetonitrile/0.1%TFA.Eluent gradient program is (t indicates time (min), such as: t20After expression sample introduction when 20min): t0, 20%B；t20, 90%B；Flow velocity is 0.2mL/min； Sample injection volume is 20 μ L；Detection wavelength: 215nm；Column temperature: 50 DEG C.
Embodiment 4
Octadecyl is bonded SiO2@SiO2It is loaded in the liquid-phase chromatographic column of 50mm × 4.6mm (i.d.), then by it For the chromatographic isolation of 5 kinds of standard protein sample mixtures, good separating effect is obtained, as a result as shown in Figure 3.
Chromatographic condition: solvent A is 0.1%TFA aqueous solution, and solvent B is acetonitrile/0.1%TFA.Eluent gradient program is (t indicates time (min)): t0, 25%B；t15, 70%B；Flow velocity is 0.2mL/min, sample: 5 kinds of protein example (Rnase A, Cytochrome C, BSA, Myoglobin and Carbonic anhydrase)；Sample injection volume is 20 μ L；Detection wavelength: 215nm。
Embodiment 5
Octadecyl is bonded SiO2@SiO2It is loaded in the liquid-phase chromatographic column of 150mm × 2.1mm (i.d.), then will The zymolyte chromatographic isolation of its bovine serum albumin for being used for trypsin digestion (BSA), has obtained good separating effect, as a result As shown in Figure 4.
Liquid phase chromatogram condition: solvent A is 0.1%TFA aqueous solution, and solvent B is acetonitrile/0.1%TFA.Eluent gradient journey Sequence is (t indicates time (min)): t0, 10%B；t90, 90%B；t120, 10%B.Flow velocity is 0.2mL/min, sample: 3pmol BSA zymolyte；Sample injection volume is 20 μ L.
Mass Spectrometry Conditions: mass spectrograph is the MicroTOF-Q mass spectrograph of German Brooker company；Scanning of the mass spectrum mode: full scan Mode；Scanning range m/z 350-1500.
Embodiment 6
Octadecyl is bonded SiO2@SiO2It is loaded in the liquid-phase chromatographic column of 50mm × 4.6mm (i.d.), then by it For luxuriant and rich with fragrance retention analysis, it is found that the lgk of luxuriant and rich with fragrance capacity factor measure k is directly proportional to methanol content in mobile phase, show it in the color Reservation on spectrum column is based primarily upon hydrophobic effect, and its retention mechanism is different from the guarantor of the macromolecular samples compounds such as protein It stays.
Liquid phase chromatogram condition: mobile phase is respectively 90% methanol, 80% methanol, 70% methanol, 60% methanol and 50% first Alcohol；Flow velocity is 0.2mL/min；Sample injection volume is 20 μ L；Detection wavelength: 254nm.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (1)

1. a kind of preparation method for preparing Surface porous core-shell structure silica gel microball, which comprises the following steps: will The H of 10 parts by volume 35wt% is added in the spherical silica gel that partial size is 2~5 μm2SiF6In aqueous solution, 2~16h is stirred, wherein spherical Silica gel and H2SiF6The amount ratio of aqueous solution is 1g:1mL；Then 5 parts by volume water and 6 parts by volume 0.1molL are sequentially added- 1H3BO3Aqueous solution is uniformly mixed；First mixed solution is stood into 1h in vacuum environment, then is vibrated in 40 DEG C of constant-temperature table 12~for 24 hours, then the mixed solution after reaction is filtered with sintered filter funnel, the solid filtered out is dried at 120 DEG C, then will be dried Dry product is placed in Muffle furnace, is warming up to 200 DEG C with the rate of 140 DEG C/min, is kept 2h, obtain Surface porous core-shell structure Silica gel microball, i.e. SiO2@SiO2；
The Surface porous core-shell structure silica gel microball have core-shell structure, the spherical silica gel for being 2~5 μm using partial size as core, Porous shell-like structure is formed by as shell using the silica gel nano particle that spherical silica gel surface is accumulated, and core is combined closely with shell, shell With a thickness of 100-700nm, pore diameter range 15-120nm.
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