CN1392097A - Silicon amide shell nano particle material and its preparing process - Google Patents

Silicon amide shell nano particle material and its preparing process Download PDF

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Publication number
CN1392097A
CN1392097A CN 02114157 CN02114157A CN1392097A CN 1392097 A CN1392097 A CN 1392097A CN 02114157 CN02114157 CN 02114157 CN 02114157 A CN02114157 A CN 02114157A CN 1392097 A CN1392097 A CN 1392097A
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nano particle
silicon
particle material
shell nano
silicon amide
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CN 02114157
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CN1173884C (en
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王柯敏
何晓晓
李杜
谭蔚泓
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Hunan University
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Hunan University
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Abstract

The said particle material has netted SiO2 moleculae shell layer in the surface crosslinked with amino chain hydrocarbon compound and special biochemical, acoustic, optical, electrical, thermal and magnetic functional kernel material inside the shell layer. Its preparation process includes the technological steps of: dispersing water and surfactant in oil phase to form water-in-oil microemulsion; adding biochemical, acoustic, optical, electrical, thermal and magnetic functional kernel material while adding silanizing reagent into the microemulsion; and adding catalyst for synchronous silane hydrolysis to produce aminated silicon shell nano particle material. The nano particle is easy to prepare, exhibits positive dynamic potential in neutral liquid and has physical and chemical stability and is easy to modify.

Description

Silicon amide shell nano particle material and preparation technology's method thereof
Technical field: the present invention relates to field of nanometer material technology, relate in particular to improvement and preparation technology's method thereof of the silica-based nanometer material structure that is used for biology, medical science.
Background technology: contemporary medical science, biology have been deep into molecular level, to biomacromolecule or its segment is separated efficiently, enrichment, extraction, reprinting etc. have become the technical issues that need to address day by day urgently, adopt nanotechnology might bring new breakthrough; And the nano particle of existing other kinds or is not used because of physicochemical property is unstable, or because of produce difficulty, the raw material costliness is difficult to popularization; And nano SiO 2 particle, on the one hand with its excellent network molecular structure, widely physical and chemical stability, produce easily and raw material advantage cheap and easy to get relatively, cause expert's concern; But then, existing nano SiO 2 particle surface tissue is single, electrokinetic potential in neutral solution is a negative value, do not possess required biochemical characteristic and be difficult to follow-up modification, so biomacromolecule and segment thereof are separated, operating aspect such as enrichment, extraction, reprinting is restricted, in molecular biosciences/medical science, can not be used widely.
Summary of the invention: at the above-mentioned contradiction of prior art, one of technical problem to be solved by this invention is to provide a kind of cheap and easy to manufacture, in neutral solution, be on the occasion of electrokinetic potential, not only had a physical and chemical stability but also be easy to the silicon amide shell nano particle material of finishing;
Two of technical problem to be solved by this invention is preparation technology's methods that a kind of above-mentioned silicon amide shell nano particle material will be provided.
For this reason, technical solution of the present invention is a kind of silicon amide shell nano particle material, its particle surface is the silicon-dioxide network molecular structure, it is characterized in that: described silicon-dioxide network molecule is submitted and is associated with amino chain hydrocarbon compound, and the silicon-dioxide network molecule forms shell.
Described amino chain hydrocarbon compound has end of the chain amino.
Described amino chain hydrocarbon compound with end of the chain amino is one or the polyamine alkyl, and the carbon value of alkyl is C 3~C 10
In pH neutral normal temperature medium, the electrokinetic potential of described silicon amide shell nano particle material is higher than 10mv.
Described silicon-dioxide network molecule shell contains functional inner nuclear materials such as silicon-dioxide inner nuclear material or special biochemistry, sound, light, electricity, heat, magnetic as dyestuff, fluorescent substance, magnetic substance, quantum dot, metal, medicine etc.
A kind of preparation technology's method of described silicon amide shell nano particle material, comprise the steps: A) in oil phase, add entry and tensio-active agent and disperse to form water-in-oil microemulsion, B) add biochemistry, sound, light,, heat, functional inner nuclear material such as magnetic and silylating reagent are gone in the microemulsion, C) add catalyzer and go into to carry out in the microemulsion silane hydrolysis reaction generation nano SiO 2 particle, D) add aminosilane reagent nano SiO 2 particle is carried out finishing, it is characterized in that: at described step B) add two or more different silylating reagents simultaneously, and wherein the molecule of at least a silylating reagent has amino chain hydrocarbon structure; At described step C) in the hydrolysis reaction, the synchronous hydrolysis reaction of various silylating reagents generates silicon amide shell nano particle, thus cancellation step D).
Described silylating reagent is two kinds, and one is the silicic acid organic ester, preferred tetraethoxy; Its two be alkylamine for organoalkoxysilane, preferred N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane.
The present invention has following advantage.
Nano particle of the present invention, in acidity and neutral medium, the silica sphere of uncrosslinked amino still keeps materialization stability widely, and crosslinked amino at particle surface occurs protonated, produce clean positive electricity effectively, in pH neutral normal temperature medium, the electrokinetic potential of described silicon amide shell nano particle material is up to 35mv, thereby can be easily and electronegative DNA, biomacromolecules such as RNA form " nano particle-DNA " by electrostatic interaction, mixtures such as " nano particle-RNA ", nano particle and DNA, the binding ability of biomacromolecules such as RNA is very strong, and the bonded biomacromolecule had obvious provide protection, for biomacromolecule is separated, enrichment, extract, condition has been created in reprinting;
The amino of nano grain surface has reactive behavior, be easy to direct or indirect and other biological macromole active group reaction by the chemical cross-linking agent of tool double-functional group, modify each other realizing, reach certain biochemistry operation or testing goal then as structure biological nano transmitter etc.;
Nano particle forms shell structure, can enrich functional kernels such as biochemistry, sound, light, electricity, heat, magnetic in shell inside, and these functional kernels are externally under the exciting of particular field, can implement specific function as: orientation movement, excite monochromatic light, specific change or reaction etc., thereby realize the biochemistry operation of expection efficiently or detect;
Adopt the multiple amino chain hydrocarbon silylating reagent that has, in the microcapsule that water-in-oil forms, directly prepare silicon amide shell nano particle with method with one-step hydrolysis, raw material is easy to get, step is simply direct, one step generated amido modified nano SiO 2 particle, had reduced reactions steps, and main is the difficulty that has overcome follow-up modification, promoted product specification, improve preparation efficiency, reduced production cost, easy to utilize;
The present invention combines nano particle dexterously with molecular biosciences/medical science, for the breakthrough of molecular biosciences/medical science provides brand-new opportunity, has wide market outlook and social benefit.
Description of drawings: now in conjunction with the accompanying drawings the present invention is explained.
Fig. 1 is the structural representation of silicon amide shell nano particle of the present invention.
Fig. 2 comprises the electrokinetic potential that various nano particle of the present invention is compared and the graphic representation of pH value.
Fig. 3 is the transmission electron microscope photo of the silicon amide core-shell nanoparticles of silicon-dioxide kernel.
Fig. 4 is Ru (BPY) 3The transmission electron microscope photo of the silicon amide core-shell nanoparticles of fluorescence kernel.
As shown in Figure 1: silicon amide shell nano particle material, its particle surface are silica network molecular structure shell 2, submit at silica network molecule shell 2 that to be associated with carbon value be C3~C 10Two Unit's amine alkyl; Silica network molecule shell 2 includes inner nuclear material 1 and comprises: silica or spy The functional inner nuclear materials such as different biochemistry, sound, light, electricity, heat, magnetic are such as dyestuff, fluorescent material, magnetic Property material, quantum dot, metal, medicine etc.; And crosslinked end of the chain amino is directly or indirectly on the shell 2 With 3 reactions of large biological molecule active group, realize the shell modification;
As shown in Figure 2: the pH automatic Titration that adopts Malvern Zetasizer 3000HS analyzer to form System measures respectively silicon amide core-shell nanoparticles 4, ferroferric oxide gel nano particle 5, simple The moving electricity under different pH such as silica magnetic nano particle 6, simple nano SiO 2 particle 7 The position namely at first is suspended in various nano particles and begins to measure zeta potential value in the ultra-pure water, and then progressively With the pH value of the sodium hydroxide solution regulating system of the hydrochloric acid solution of 0.1mol/L, 0.25mol/L, and The point-to-point measurement electrokinetic potential, measurement shows: in the normal temperature medium of pH neutrality, the silicon amide shell type nanometer Particle 4 (comprising: magnetic, fluorescence etc.) surface amino proton can effectively produce clean positive electricity, And electrokinetic potential is higher than 35mv, only when pH is higher than isoelectric point about 9.6, amino the apparent matter of going takes place Sonization, electrokinetic potential reach null value and negative trend; Comparatively speaking, ferroferric oxide gel nano particle 5, the electrokinetic potential of simple silica magnetic nano particle 6, simple nano SiO 2 particle 7 etc. early In 7 sour environment, just present negative value at pH, all than silicon amide shell nano particle 4 Correlated performance far short of what is expected.
Embodiment:
Embodiment one, the silicon amide core-shell nanoparticles of preparation silicon-dioxide kernel:
A) in the oil phase of hexanaphthene/n-hexyl alcohol, add entry and TritonX100 and dispersion formation water-in-oil microemulsion, B) adding tetraethoxy and N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane synchronously goes in the microemulsion, C) adding catalyst ammonia water goes in the microemulsion, reacted 24 hours, finish hydrolysis reaction synchronously, the silicon amide shell nano particle material of generation shown in Fig. 1,3, from Fig. 3 electromicroscopic photograph as seen: even, the good dispersity of nano particle size.
Embodiment two, the silicon amide core-shell nanoparticles of preparation magnetic kernel:
A) in the oil phase of hexanaphthene/n-hexyl alcohol, add entry and TritonX100 and dispersion formation water-in-oil microemulsion, B) add Fe 3O 4Colloidal solution is gone in the microemulsion, and add tetraethoxy synchronously and N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane is gone in the microemulsion, and C) add catalyst ammonia water and go in the microemulsion, reacted 24 hours, finish hydrolysis reaction synchronously, generate the silicon amide shell nano-particle material of magnetic kernel.
Embodiment three, preparation fluorescence kernel (one of) the silicon amide core-shell nanoparticles:
A) in the oil phase of hexanaphthene/n-hexyl alcohol, add entry and TritonX100 and dispersion formation water-in-oil microemulsion, B) adding water soluble fluorescence dye-bipyridyl ruthenium title complex Ru (BPY) 3Go in the microemulsion, and add tetraethoxy synchronously and N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane is gone in the microemulsion, C) adding catalyst ammonia water goes in the microemulsion, reacted 24 hours, finish hydrolysis reaction synchronously, generate silicon amide shell nano-particle material, from Fig. 4 electromicroscopic photograph as seen: even, the good dispersity of nano particle size as the fluorescence kernel of Fig. 4.
Embodiment four, the silicon amide core-shell nanoparticles of preparation fluorescence kernel (two):
A) in the oil phase of hexanaphthene/n-hexyl alcohol, add entry and TritonX100 and dispersion formation water-in-oil microemulsion, B) adding water soluble fluorescence dye-fluorescein isothiocyanate (FITC) is gone in the microemulsion, and add tetraethoxy synchronously and N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane is gone in the microemulsion, C) adding catalyst ammonia water goes in the microemulsion, reacted 24 hours, finish hydrolysis reaction synchronously, generate the silicon amide shell nano-particle material of another kind of fluorescence kernel.
Embodiment five, the silicon amide core-shell nanoparticles of preparation fluorescence kernel (three):
A) in the oil phase of hexanaphthene/n-hexyl alcohol, add entry and TritonX100 and dispersion formation water-in-oil microemulsion, B) adding water soluble fluorescence dye-rhodamine isothiocyanate is gone in the microemulsion, and add tetraethoxy synchronously and N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane is gone in the microemulsion, C) adding catalyst ammonia water goes in the microemulsion, reacted 24 hours, finish hydrolysis reaction synchronously, generate the silicon amide shell nano-particle material of another kind of fluorescence kernel.

Claims (7)

1, a kind of silicon amide shell nano particle material, its particle surface is the silicon-dioxide network molecular structure, it is characterized in that: described silicon-dioxide network molecule is submitted and is associated with amino chain hydrocarbon compound, and the silicon-dioxide network molecule forms shell.
2, silicon amide shell nano particle material as claimed in claim 1 is characterized in that: described amino chain hydrocarbon compound has end of the chain amino.
3, silicon amide shell nano particle material as claimed in claim 2 is characterized in that: described amino chain hydrocarbon compound with end of the chain amino is one or the polyamine alkyl, and the carbon value of alkyl is C 3~C 10
4, as arbitrary described silicon amide shell nano particle material in the claim 1,2,3, it is characterized in that: in pH neutral normal temperature medium, the electrokinetic potential of described silicon amide shell nano particle material is higher than 10mv.
5, silicon amide shell nano particle material as claimed in claim 4 is characterized in that: described silicon-dioxide network molecule shell contains functional inner nuclear materials such as silicon-dioxide inner nuclear material or special biochemistry, sound, light, electricity, heat, magnetic as dyestuff, fluorescent substance, magnetic substance, quantum dot, metal, medicine etc.
6, preparation technology's method of the described silicon amide shell nano particle material of a kind of claim 1, comprise the steps: A) in oil phase, add entry and tensio-active agent and disperse to form water-in-oil microemulsion, B) add biochemistry, sound, light,, heat, functional inner nuclear material such as magnetic and silylating reagent are gone in the microemulsion, C) add catalyzer and go into to carry out in the microemulsion silane hydrolysis reaction generation nano SiO 2 particle, D) add aminosilane reagent nano SiO 2 particle is carried out finishing, it is characterized in that: at described step B) add two or more different silylating reagents simultaneously, and wherein the molecule of at least a silylating reagent has amino chain hydrocarbon structure; At described step C) in the hydrolysis reaction, the synchronous hydrolysis reaction of various silylating reagents generates silicon amide shell nano particle, thus cancellation step D).
7, preparation technology's method of silicon amide shell nano particle material as claimed in claim 6 is characterized in that: described silylating reagent is two kinds, and one is the silicic acid organic ester, preferred tetraethoxy; Its two be alkylamine for organoalkoxysilane, preferred N-(β-aminoethyl)-γ-aminopropyl-triethoxyl silane.
CNB021141576A 2002-05-28 2002-05-28 Silicon amide shell nano particle material and its preparing process Expired - Fee Related CN1173884C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100344377C (en) * 2005-08-29 2007-10-24 中国科学院山西煤炭化学研究所 Method for preparing functional amido silicon dioxide
CN100346154C (en) * 2004-09-24 2007-10-31 湖南大学 Method for producing internal reference nano PH sensor and using for in-cell PH non-trauma monitoring
CN101906298A (en) * 2010-08-13 2010-12-08 济南大学 Surface plasma fluorescence-enhanced nano composite structure film and preparation method thereof
CN101333436B (en) * 2008-08-06 2011-03-16 湖南大学 Multi-color optic-encoding siliceous skin nano-rods and method for preparing same
CN101354968B (en) * 2008-09-16 2011-04-13 彩虹集团公司 Light anode for dye sensitization solar battery and preparation method thereof
CN102453465A (en) * 2010-10-27 2012-05-16 中国科学院大连化学物理研究所 Adhesive super-hydrophobic material and preparation method thereof
CN105482822A (en) * 2015-12-24 2016-04-13 莫婉玲 Quantum dot composite material with bi-component substrate and preparation method thereof
CN105482820A (en) * 2015-12-22 2016-04-13 莫婉玲 Quantum dot composite microsphere containing higher fatty acid and preparation method thereof
CN105542773A (en) * 2015-12-24 2016-05-04 莫婉玲 Quantum dot composite microsphere with bi-component shell layer and preparation method of quantum dot composite microsphere
CN109761240A (en) * 2019-03-19 2019-05-17 大连大学 A kind of preparation method of amination silica dioxide granule
CN115058010A (en) * 2022-05-28 2022-09-16 南昌大学 Core-shell type high-luminescence aggregation-induced-luminescence nano particle and preparation method thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100346154C (en) * 2004-09-24 2007-10-31 湖南大学 Method for producing internal reference nano PH sensor and using for in-cell PH non-trauma monitoring
CN100344377C (en) * 2005-08-29 2007-10-24 中国科学院山西煤炭化学研究所 Method for preparing functional amido silicon dioxide
CN101333436B (en) * 2008-08-06 2011-03-16 湖南大学 Multi-color optic-encoding siliceous skin nano-rods and method for preparing same
CN101354968B (en) * 2008-09-16 2011-04-13 彩虹集团公司 Light anode for dye sensitization solar battery and preparation method thereof
CN101906298B (en) * 2010-08-13 2013-02-13 济南大学 Surface plasma fluorescence-enhanced nano composite structure film and preparation method thereof
CN101906298A (en) * 2010-08-13 2010-12-08 济南大学 Surface plasma fluorescence-enhanced nano composite structure film and preparation method thereof
CN102453465A (en) * 2010-10-27 2012-05-16 中国科学院大连化学物理研究所 Adhesive super-hydrophobic material and preparation method thereof
CN102453465B (en) * 2010-10-27 2014-09-03 中国科学院大连化学物理研究所 Adhesive super-hydrophobic material and preparation method thereof
CN105482820A (en) * 2015-12-22 2016-04-13 莫婉玲 Quantum dot composite microsphere containing higher fatty acid and preparation method thereof
CN105482820B (en) * 2015-12-22 2017-12-15 泰山医学院 A kind of quantum dot complex microsphere containing higher fatty acids and preparation method thereof
CN105482822A (en) * 2015-12-24 2016-04-13 莫婉玲 Quantum dot composite material with bi-component substrate and preparation method thereof
CN105542773A (en) * 2015-12-24 2016-05-04 莫婉玲 Quantum dot composite microsphere with bi-component shell layer and preparation method of quantum dot composite microsphere
CN109761240A (en) * 2019-03-19 2019-05-17 大连大学 A kind of preparation method of amination silica dioxide granule
CN115058010A (en) * 2022-05-28 2022-09-16 南昌大学 Core-shell type high-luminescence aggregation-induced-luminescence nano particle and preparation method thereof

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