CN100457617C - Hollow silicon gel nano powder material and its preparation method - Google Patents
Hollow silicon gel nano powder material and its preparation method Download PDFInfo
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- CN100457617C CN100457617C CNB2007100667405A CN200710066740A CN100457617C CN 100457617 C CN100457617 C CN 100457617C CN B2007100667405 A CNB2007100667405 A CN B2007100667405A CN 200710066740 A CN200710066740 A CN 200710066740A CN 100457617 C CN100457617 C CN 100457617C
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Abstract
The invention discloses a nanometer ball powder material of hollow silicon gel, which comprises the following steps: blending long-chained organic molecule, ammonia and inorganic salt with alkaline metal ion into deionized water; stirring to form clear solution; adding alcohol solution with silicon source; stirring; proceeding ultrasonic cavitation disposal; filtering; washing; drying; obtaining the product with through-out pore path on the case and inner wall surface of case decorated by organic molecule.
Description
Technical field
The present invention relates to a kind of hollow silicon gel nano powder material and preparation method thereof, belong to the inorganic porous material field.
Background technology
Recent years, the actual application value of silicon nano material and the concrete manifestation in application more and more are subject to people's attention, wherein mesoporous and hollow type silicon nano material is because its particular structure and physicochemical property and satisfactory stability all have good application potential in nanoelectronic element, catalysis and wastewater treatment; Moreover, silicon-dioxide and silicon gel also have good biocompatibility, and the silicon that slowly discharges in physiological environment is necessary a kind of trace element during skeleton is grown, so hollow silica and silicon gel micro-ball also have application potential widely in biological medicine such as fixing, the encapsulation of enzyme, medicine, protein, DNA etc. or sustained release and biological technical field.
German Mark think of-Planck colloid in 1998 and Interface Study the investigator on Science, reported with the polystyrene sub-micron ball to be that hard template prepares hollow silica microsphere (F.Caruso, et al.Science, 1998 first; 282:1111-1114).Since then, people have carried out extensive studies to synthetic, the microstructure sign of hollow silica or silicon gel micro-ball.People such as M.Chen (Adv.Mater., 2006; 18:801-806) prepare the complex microsphere template by vinylbenzene, azo isobutyronitrile and polyvinylpyrrolidone addition polymerization, use ammonia-catalyzed teos hydrolysis and polymeric simultaneously, decompose the complex microsphere template again, the synthetic single disperse, hollow silicon gel micro-ball of success must calcination process not removed template.Thisly realized a step preparation hollow silicon gel micro-ball, in one-step synthesis, decomposed fully and residue in hollow microsphere inside but this microsphere template is still difficult through improved hard template method.People (Adv.Mater., 2001 such as K.J.C.van Bommel; 13:1472-1476.) utilize poly-(L-Methionin) under the hydrophobic amine regulation and control, to form the submicron micella, by the micellar surface amine molecule positively chargedly induce the silicon-oxygen network cohesion behind the teos hydrolysis and form silicon gel shell, obtain hollow silicon gel micro-ball.This method technology is simple, and still a large amount of poly-(L-Methionins) and hydrophobic amine are still sealed up for safekeeping in hollow ball in conjunction with the micella that forms and be difficult to be got rid of, and its using value is restricted.In addition, people such as M.Fujiwara (Chem.Mater., 2004; 22:5420-5426) with the water glass be the silicon source, with inorganic ammonium salts such as ammonium chlorides is catalyzer, adopt water/oil/water three-phase emulsion method one step preparation hollow silicon gel micro-ball, need not to remove the kernel template, technology is simpler, and can original position encapsulate biomacromolecule (J.Biomed.Mater.Res.Part A., 2007 such as albumin (BSA) and double-stranded DNA; DOI:10.1002/jbm.a.31021).But the duct yardstick inside and outside this microballoon shell connects is too small, and the strong basicity of water is destroyed BSA and double-stranded DNA structure/conformation easily, and guest molecule original position encapsulation rate is low and be difficult to release, and the using value of this method is not high.People such as H.P.Lin (Chem.Mater., 1998; 10:3772-3776) silicon-oxygen network of having reported tensio-active agent and teos hydrolysis in oil-in-water microemulsion forms the mesoporous lamella structure in the self-assembly of microemulsion interface, and removes tensio-active agent through calcination process.Although this microemulsion method technology is simple, hollow microsphere shell mesopore orbit is parallel with weft direction, and guest molecule is difficult to inside and outside transmission.Recently, Chinese patent CN1792788A discloses a kind of cosurfactant and collaborative auxiliary synthetic silicon dioxide hollow sphere preparation methods of hexagonal phase penetrating mesopore orbit that has of tensio-active agent of adopting.Also adopt roasting to remove the polymer organic molecule in this method, but the shell duct only can be for the micromolecular inside and outside transmission of object, medicine big to volume, that molecular structure is complicated and encapsulation and the release of biomacromolecule are restricted.In addition, Chinese patent CN1539733A, CN1730389A and CN1816493 disclose preparation respectively and have had the method for the silica nanosphere of meso-hole structure, but only there is mesopore orbit in the silica nanosphere granule interior of these method preparations, there is not continuity hollow structure on a large scale, and all need high-temperature roasting to remove organic surface active agent, complex process among the preparation technology.
Find that according to relevant patented technology and bibliographical information existing hollow silica or silicon gel micro-ball and technology of preparing thereof can't realize: (1) carries out the good organic molecule in-situ modification of biocompatibility to the ball inner wall surface; (2) the convenient outward transmission of the large and small intramolecularly of guest species; (3) avoid the unfriendly reagent of environment for use.In actual applications, different guest species are because of its chemical constitution, structure/conformation and qualitative difference, for avoiding structure that guest species (such as biomacromolecules such as enzyme, protein, somatomedin, genomic medicine) causes because of interface/surface and solvent, strong basicity or byproduct of reaction interaction and active damaged in hollow microsphere is synthetic, need in synthetic hollow microsphere, encapsulate and manage with sustained release.Therefore, press for exploration (1) on forming with the organism highly compatible, (2) the ball inner wall surface is modified so that the assembling of specific guest molecule by functional group (as amino, carboxyl or hydroxyl etc.), (3) shell holes road yardstick can satisfy large and small intramolecularly and transmits outward, (4) the big character such as (being that granularity is low, hollow parts is big) of specific surface area/or hollow silica or the silicon gel nano and the technology of preparing thereof of function is to satisfy in biological medicine and Application in Biotechnology requirement.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, mild condition, and dispersiveness and good biocompatibility, the large and small intramolecularly of object transmit powder body material of hollow silicon gel nano easily and preparation method thereof outward.
Hollow silicon gel nano powder material of the present invention is to be the hollow ball nano particle of shell with the silicon gel, it is characterized in that having on the shell the inside and outside duct that connects, the shell inner wall surface is modified by organic molecule, its component comprises inorganic components and organic molecule, inorganic components represents that with oxide form the weight percentage content of each composition is:
Organic molecule 0.01～10%; The said components sum is 100%, and CaO and SrO are not 0 simultaneously.
The grain diameter of hollow silicon gel nano powder of the present invention is generally 50～800 nanometers.
The preparation method of hollow silicon gel nano powder material of the present invention may further comprise the steps:
1) be 1: 1～20: 100～500 to be mixed in the deionized water in molar ratio with organic molecule, alkaline including earth metal ionic inorganic salt and ammoniacal liquor, alkaline including earth metal ionic volumetric molar concentration be 0.05～10 mmole/liter, this mixing solutions 5～60 ℃ of following continuously stirring, is formed settled solution;
2) the silicon source is joined in the absolute alcohol reagent, the mole number ratio of ammoniacal liquor is 1: 5～100 in the mole number in silicon source and the step 1), and the volume ratio of deionized water is 10: 1～8 in absolute alcohol reagent and the step 1), and continuously stirring forms settled solution;
3) stir down, step 2) settled solution join in the settled solution of step 1) ultrasonic and ageing 5～60 minutes;
4) the ageing liquid with step 3) carries out filtering separation, after handling with deionized water dispersion and ultrasonic cavitation, filters drying.
Among the present invention, said alkaline including earth metal ionic inorganic salt can be Ca (CH
3COO)
2, Ca (NO
3)
24H
2O, CaCl
2, Sr (CH
3COO)
2, Sr (NO
3)
24H
2O and SrCl
2In a kind of or its mixture.
Above-mentioned organic molecule can be a kind of or its mixture in gelatin, type i collagen albumen, sodium polyacrylate, polyacrylic acid potassium, poly-aspartic-acid sodium, poly-aspartic-acid potassium, polyepoxy sodium succinate and the poly-epoxy succinic acid potassium.Said absolute alcohol reagent is a kind of or its mixture in dehydrated alcohol and the anhydrous isopropyl alcohol.Said silicon source is a kind of or its mixture in methyl silicate and the tetraethoxy.
The present invention can control the thickness of silicon gel nano shell by changing ultrasonic cavitation and digestion time.
The present invention is not particularly limited the metallic cation kind, except calcium or/and the strontium, so long as divalence or trivalent metal ion stable and that help organism health all can be used for the synthetic of hollow silicon gel nano powder material in weakly alkaline solution.The long chain type biomolecules that the side chain of good biocompatibility is rich in carboxyl all can be used for the in-situ modification of hollow silicon gel nano inner wall surface.
Hollow silicon gel nano powder material of the present invention, it forms mechanism is to utilize long chain type organic molecule that the good and side chain of biocompatibility in the alkaline aqueous solution is rich in carboxyl to be changed into the character of free extension state by reeling condition at random, by stir and the ultrasonic cavitation effect under alkaline-earth metal ions and side chain carboxyl group electrostatic interaction and make the long-chain bending, form multichain around the sphere network structure of yardstick in 50～800 nanometers, silicon-oxygen network that is rich in hydroxyl and cohesion that the metallic cation that sphere adheres to is captured in the alkaline environment form silicon gel shell.
Beneficial effect of the present invention is:
Nanosphere powder particle of the present invention has the hollow microstructure, the shell inner wall surface is by the good organic molecule in-situ modification of biocompatibility, shell is the silicon gel, and in shell, store the healthy necessary inorganic metal ion calcium of a small amount of organism or/and there is the inside and outside duct that connects in strontium on the shell; The notable attribute of this particle is that the shell inner wall surface of organic molecule in-situ modification helps functional guest molecule assembling and stores, and the inside and outside transmission of the large and small molecule of object can be regulated in the inside and outside duct that connects on the shell wall.The present invention prepares all and carries out under 5～60 ℃ of temperature condition, do not relate to treatment process such as high-temperature roasting, nanoparticle structure is stable, chemical reagent environmental friendliness in the synthetic system, the chemical substance that does not have the biocompatibility difference in the nano particle, and it is simple to have technology, characteristics such as the easy regulation and control of nanometer ball particle size and shell wall thickness.The goods that utilize in-situ modification hollow silicon gel nano powder material of the present invention to make have superior safety, biocompatibility and Bioabsorbable, are expected to use in biomedical and biological technical field.
Description of drawings
Fig. 1 is a transmission electron microscope photo, wherein schemes (a) photo for the product of introducing ultrasonic cavitation, and figure (b) is the photo of hollow nano particle shell wall behind introducing ultrasonic cavitation and the ageing different time;
Fig. 2 is for introducing the product stereoscan photograph of ultrasonic cavitation;
Fig. 3 is an X ray diffracting spectrum, and figure (a) is the Small angle collection of illustrative plates, and figure (b) is the extensive angle collection of illustrative plates;
Fig. 4 is a hollow nanospheres powder composition energy spectrogram;
Fig. 5 is the thermal weight loss change curve, and wherein curve a is empty nano-powder weight-loss curve, and curve b is solid nano-powder weight-loss curve;
Fig. 6 is Fourier transform infrared spectroscopy figure, figure (a) is the product spectrogram of the sodium polyacrylate of 2.5KDa as modifier for molecular-weight average, figure (b) is the product spectrogram of the poly-aspartic-acid sodium of 5KDa as modifier for molecular-weight average, figure (c) is the product spectrogram of gelatin as modifier, and the spectrogram that dotted line is represented among each figure is represented the spectrogram of corresponding pure organic molecule;
Fig. 7 is a transmission electron microscope photo, figure (a) is the product photo of the sodium polyacrylate of 2.5KDa as modifier for molecular-weight average, figure (b) is the product photo of the sodium polyacrylate of 1000KDa as modifier for molecular-weight average, figure (c) is the product photo of the poly-aspartic-acid sodium of 5KDa as modifier for molecular-weight average, and figure (d) is the product photo of gelatin as modifier.
Embodiment
Further illustrate the present invention below in conjunction with example, but these examples do not limit the scope of the invention, all technology that realizes based on foregoing of the present invention and the material of preparation all belong to protection scope of the present invention.Embodiment agents useful for same purity all is not less than its analytical pure level purity.
1) be 30% polyacrylic acid sodium water solution (molecular-weight average of sodium polyacrylate is 2.5KDa) in the 26.2mL deionized water, successively adding 1.0mL quality percentage composition under the magnetic agitation condition, 2.2mL ammoniacal liquor and 0.6mL volumetric molar concentration are the calcium nitrate aqueous solution of 0.5mol/L, this solution was at room temperature stirred more than 2 minutes, obtain the mixed aqueous solution of clarified polypropylene acid sodium and nitrocalcite, standby;
2) in the 70mL dehydrated alcohol, adding the 1.6mL tetraethoxy under the magnetic agitation condition, at room temperature stir 2 minutes, standby;
3) pour the clarified polypropylene acid sodium of step 1) preparation and the mixed aqueous solution of nitrocalcite into a clean there-necked flask, and insert ultrasonic cleaning machine equipment (40KHz, in water-bath 80W), open ultrasonic device, and in flask, add mechanical stirring (240rpm), then with step 2) preparation the tetraethoxy ethanolic soln join in the above-mentioned mixed solution, ultrasonic cavitation and mechanical stirring 5,12 and 20 minutes, respectively get the 30mL mixing solutions, adopt centrifugal filtration process (4000rpm) to carry out solid-liquid separation, use the deionized water ultra-sonic dispersion, washing, centrifugation again, drying is 24 hours under 60 ℃ of vacuum, the product that obtains is the nanosphere powder of hollow structure, particle size is that 50～150 nanometers (are seen Fig. 1 a, Fig. 2 a, Fig. 7 a), ultrasonic cavitation and mechanical stirring 5, the shell thickness of the product that obtained in 12 and 20 minutes is respectively 3 nanometers, 8 nanometers and 15 nanometers (seeing Fig. 1 b), there is the inside and outside duct that connects (to see Fig. 2 b on the shell, Fig. 3 a), nanometer ball is mainly the silicon gel and (sees Fig. 3 b, Fig. 4), and contain sodium polyacrylate 4.2% and (see among Fig. 5, curve (a) hollow silicon gel nano powder is weightless and curve (b) solid silicon gel nano-powder is relatively weightless, wherein solid silicon gel nano-powder is the product that obtains under any organic molecule modifier condition not adding), and hollow silicon gel nano particle outside surface polyacrylic acid sodium content is extremely low (sees Fig. 6 a).
1) be 2% polyacrylic acid sodium water solution (molecular-weight average of sodium polyacrylate is 1000KDa) in the 15.5mL deionized water, successively adding 1.5mL quality percentage composition under the magnetic agitation condition, 2.5mL ammoniacal liquor and 0.5mL volumetric molar concentration are the strontium nitrate aqueous solution of 0.5mol/L, this solution was at room temperature stirred more than 2 minutes, obtain the mixed aqueous solution of clarified polypropylene acid sodium and strontium nitrate, standby;
2) in the 78mL dehydrated alcohol, adding the 2.0mL tetraethoxy under the magnetic agitation condition, at room temperature stir 2 minutes, standby.
3) pour the clarified polypropylene acid sodium of step 1) preparation and the mixed aqueous solution of strontium nitrate into a clean there-necked flask, and insert in the water-bath of ultrasonic cleaning machine equipment, open ultrasonic device, and in flask, add mechanical stirring (300rpm), then with step 2) preparation the tetraethoxy ethanolic soln join in the above-mentioned mixed solution continuous ultrasound cavitation and mechanical stirring 20 minutes.Then, adopt centrifugal filtration process (4000rpm) to carry out solid-liquid separation, with deionized water ultra-sonic dispersion, washing, centrifugation again, drying is 24 hours under 60 ℃ of vacuum, and its product is that granularity is the hollow silicon gel nano powder (seeing Fig. 7 b) of 80～600 nanometers.
With embodiment 1, it is that the poly-aspartic-acid sodium replacement 1.0mL molecular-weight average of 5KDa is the sodium polyacrylate of 2.5KDa that difference is with the 1.2mL molecular-weight average, its product is hollow silicon gel nano (Fig. 7 c), and particle outside surface poly-aspartic-acid sodium molecule content extremely low (seeing Fig. 6 b).
Embodiment 4
With embodiment 2, difference is that replacing molecular-weight average with gelatin is the sodium polyacrylate of 1000KDa, and its product is hollow silicon gel nano powder (Fig. 7 d), and particle outside surface gelatine content extremely low (seeing Fig. 6 c).
With embodiment 2, it is that the poly-aspartic-acid sodium of 5KDa and sodium polyacrylate that the 0.5mL molecular-weight average is 2.5KDa replacement 1.5mL molecular-weight average are the sodium polyacrylate of 1000KDa that difference is with the 0.5mL molecular-weight average, to replace the 0.5mL volumetric molar concentration be the strontium nitrate aqueous solution of 0.5mol/L 0.3mL volumetric molar concentration is the strontium nitrate aqueous solution of 0.5mol/L and calcium nitrate aqueous solution that the 0.2mL volumetric molar concentration is 0.5mol/L, and its product is the hollow silicon gel nano powder.
Claims (6)
1. hollow silicon gel nano powder material, it is to be the hollow ball nano particle of shell with the silicon gel, it is characterized in that having on the shell the inside and outside duct that connects, the shell inner wall surface is modified by organic molecule, its component comprises inorganic components and organic molecule, inorganic components represents that with oxide form the weight percentage content of each composition is:
SiO
2 80～99％；
CaO 0～3％；
SrO 0～3％；
Organic molecule 0.01～10%; The said components sum is 100%, and CaO and SrO are not 0 simultaneously, and said organic molecule is a kind of or its mixture in gelatin, type i collagen albumen, sodium polyacrylate, polyacrylic acid potassium, poly-aspartic-acid sodium, poly-aspartic-acid potassium, polyepoxy sodium succinate and the poly-epoxy succinic acid potassium.
2. hollow silicon gel nano powder material according to claim 1 is characterized in that grain diameter is 50～800 nanometers.
3. the preparation method of hollow silicon gel nano powder material according to claim 1 is characterized in that may further comprise the steps:
1) be 1: 1～20: 100～500 to be mixed in the deionized water in molar ratio with organic molecule, alkaline including earth metal ionic inorganic salt and ammoniacal liquor, alkaline including earth metal ionic volumetric molar concentration be 0.05～10 mmole/liter, with this mixing solutions 5～60 ℃ of following continuously stirring, form settled solution, said organic molecule is a kind of or its mixture in gelatin, type i collagen albumen, sodium polyacrylate, polyacrylic acid potassium, poly-aspartic-acid sodium, poly-aspartic-acid potassium, polyepoxy sodium succinate and the poly-epoxy succinic acid potassium;
2) the silicon source is joined in the absolute alcohol reagent, the mole number ratio of ammoniacal liquor is 1: 5～100 in the mole number in silicon source and the step 1), and the volume ratio of deionized water is 10: 1～8 in absolute alcohol reagent and the step 1), and continuously stirring forms settled solution;
3) stir down, step 2) settled solution join in the settled solution of step 1) ultrasonic and ageing 5～60 minutes;
4) the ageing liquid with step 3) carries out filtering separation, after handling with deionized water dispersion and ultrasonic cavitation, filters drying.
4. the preparation method of hollow silicon gel nano powder material according to claim 3 is characterized in that said alkaline including earth metal ionic inorganic salt are Ca (CH
3COO)
2, Ca (NO
3)
24H
2O, CaCl
2, Sr (CH
3COO)
2, Sr (NO
3)
24H
2O and SrCl
2In a kind of or its mixture.
5. the preparation method of hollow silicon gel nano powder material according to claim 3 is characterized in that said absolute alcohol reagent is a kind of or its mixture in dehydrated alcohol and the anhydrous isopropyl alcohol.
6. the preparation method of hollow silicon gel nano powder material according to claim 3 is characterized in that said silicon source is a kind of or its mixture in methyl silicate and the tetraethoxy.
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| TWI503279B (en) * | 2013-01-09 | 2015-10-11 | Univ Nat Cheng Kung | Silica gel composition and preparation method thereof |
| CN104138733B (en) * | 2013-05-08 | 2016-02-03 | 中国石油天然气股份有限公司 | A kind of surface has SiO 2 hollow microsphere running through macropore and preparation method thereof |
| CN104692401B (en) * | 2015-03-11 | 2017-04-12 | 江苏视客新材料股份有限公司 | Silicon dioxide composite microspheres of metal or metal oxide nanoparticles and preparation method thereof |
| CN104787769B (en) * | 2015-03-21 | 2017-10-13 | 北京化工大学 | A kind of method that silicon dioxide hollow microsphere is prepared with template |
| CN106242040B (en) * | 2016-09-13 | 2019-02-15 | 福建省建筑科学研究院 | A kind of Organic-inorganic composite water treatment ceramsite and its preparation process |
| CN107285323A (en) * | 2017-07-21 | 2017-10-24 | 南京航空航天大学 | A kind of silicon dioxide microsphere preparation method of high dispersive and size tunable |
| CN111499214B (en) * | 2020-04-24 | 2022-07-01 | 山东国瓷功能材料股份有限公司 | Hollow silicon dioxide nano dispersion liquid for high frequency, preparation method and application thereof |
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| CN1458064A (en) * | 2002-05-14 | 2003-11-26 | 中国科学院金属研究所 | Process for preparing medium porous nano silicon dioxide powder with high activity |
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