CN106745007B - A kind of multi-stage porous mesoporous organosilicon ball and preparation method thereof - Google Patents
A kind of multi-stage porous mesoporous organosilicon ball and preparation method thereof Download PDFInfo
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- CN106745007B CN106745007B CN201611038009.7A CN201611038009A CN106745007B CN 106745007 B CN106745007 B CN 106745007B CN 201611038009 A CN201611038009 A CN 201611038009A CN 106745007 B CN106745007 B CN 106745007B
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 39
- 229910052710 silicon Inorganic materials 0.000 claims description 39
- 239000010703 silicon Substances 0.000 claims description 39
- 239000004094 surface-active agent Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001282 organosilanes Chemical class 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 5
- 229960003067 cystine Drugs 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 45
- 239000003814 drug Substances 0.000 description 21
- 239000002585 base Substances 0.000 description 18
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229940079593 drug Drugs 0.000 description 14
- 229910052814 silicon oxide Inorganic materials 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000011799 hole material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 108020004459 Small interfering RNA Proteins 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical compound Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- JNYIQRMXGCWKOU-UHFFFAOYSA-M sodium methanol chloride Chemical compound [Na+].[Cl-].OC JNYIQRMXGCWKOU-UHFFFAOYSA-M 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229960002918 doxorubicin hydrochloride Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229940126586 small molecule drug Drugs 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention relates to a kind of multi-stage porous mesoporous organosilicon balls and preparation method thereof, more particularly to a kind of multi-stage porous mesoporous silica nano-particle, the nano SiO 2 particle is while having the hierarchical porous structure of large aperture and small-bore, including mesoporous silica spheres and the dendritic shell of organosilicon for being wrapped in the mesoporous silica spheres surface, the mesoporous pore size of the mesoporous silica spheres is in 3nm hereinafter, the mesoporous pore size of the dendritic shell of the organosilicon is 4~9nm.The multi-stage porous mesoporous silica particles good dispersion of the present invention, specific surface area height, large pore volume, pore-size distribution is uniform adjustable.
Description
Technical field
The invention belongs to micropore/mesopore/macropore molecular sieve technical field of nano material, and it is mesoporous organic to be related to a kind of multi-stage porous
Silicon ball and preparation method thereof.
Background technology
It is provided according to International Union of Pure and Applied Chemistry (IUPAC), the material with pore structure is divided into poromerics
(aperture is less than 2nm), mesoporous material (aperture is between 2nm and 50nm) and large pore material (aperture is more than 50nm).Since
The mesoporous SiO of MCM-41 types in 19922Molecular sieve synthesized by the scientist of Mobil companies since (Nature 1992,359,
(6397), 710-712.), mesoporous SiO2Material due to high specific surface area, big Kong Rong, uniform pore passage structure,
The fields such as chemical industry catalysis, medicine, nanometer biotechnology show wide application prospect.In the mesoporous SiO of various patterns2Material
In, spherical mesoporous SiO2Wide application prospect is shown in field of nano biotechnology.Especially macro-pore SiO2Nano-particle,
It is one of carrier most with practical value, can be widely applied to catalysis, absorption, separation and the targeting of drug and the fields such as transport.
Multistage mesoporous SiO2Nano particle has the following advantages：(1) mesoporous lamella has high specific surface area, big Kong Rong and uniform
Pore-size distribution；(2) big hollow parts have high substance loading, can support drug, DNA and various catalyst etc.；(3)
Easily modified surface silanol group is easy to integrate other function inorganic nano-particles or organic molecule, obtains multi-functional miscellaneous
Change compound.
However, organic SiO that current synthesis technology obtains2Though the aperture of nano particle is big, big point can be loaded simultaneously
Son and small-molecule drug are in duct, such as siRNA, DNA and doxorubicin hydrochloride, but be different drug in same duct by
It can be interfered with each other in charge effect, can not effectively play respective effect.Therefore, developing new synthesis technology is had
The SiO of hierarchical porous structure2, make it while there is large aperture (aperture>5nm) and small-bore, further by different ducts
Modification realizes that the classification to different pharmaceutical loads, classification release, to realize classification treatment.It is actually used in doctor in mesoporous organosilicon
Medicine field has great importance.
However, traditional multi-stage porous nano material is mainly dendritic organic high molecular polymer, it by covalent bond or
Electrostatic Absorption carrying medicament.It as traditional medical nano material, the advantage is that, good biocompatibility and degradable.And
Its shortcoming is that each dendritic high molecular polymer can only generally load a kind of drug, and lasting realizing controlled-release difficult to realize
It puts, these disadvantages significantly limit its application as multilevel hole material.On the other hand, mesoporous silicon oxide is as a kind of nothing
The advantages that airborne body has large specific surface area, and duct is uniform, and surface is easy to carry out functional modification, but mesoporous silicon oxide is made
For inorganic material in vivo it is not degradable be always its Important Problems to be solved in Biology Applications.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of multi-stage porous mesoporous silicon dioxide nanos
Grain, to realize that the classification load of macromolecular and small-molecule substance provides good carrier.
Here, the present invention provides a kind of multi-stage porous mesoporous silica nano-particle, the nano SiO 2 particle is
There is the hierarchical porous structure of large aperture and small-bore simultaneously, including mesoporous silica spheres and be wrapped in the mesoporous silicon oxide
The dendritic shell of organosilicon of ball surface, the mesoporous pore sizes of the mesoporous silica spheres is in 3nm hereinafter, it is preferred that 2~3 nanometers of (examples
Such as, about 2.5nm), the mesoporous pore size of the dendritic shell of organosilicon is 4~9nm.
The present invention further generates the dendritic shell of organosilicon on the surface of mesoporous silica spheres, is to have to obtain skeleton
Machine inorganic hybrid structure at the same have large aperture and small-bore hierarchical porous structure multi-stage porous mesoporous silicon dioxide nano
Grain.Due to the SiO of the present invention2Nano particle is while having the hierarchical porous structure of large aperture and small-bore, therefore can be to not
Substance with size carries out classification load, especially in field of medicaments, can carry out classification load to various sizes of drug,
Classification release is supported to provide material for classification treatment.Simultaneously as organic-inorganic hybrid nanometer particle is generally based on
Inorganic material carries out the modification of organic chemistry, specific function and purpose may be implemented, compared to the dioxy as inorganic material
SiClx nano particle, organic inorganic hybridization SiO of the invention2The degradability enhancing of nano particle in vivo, and cystine linkage
Incorporation make its have under tumor microenvironment stress degradation effect, make the drug for being supported on shell be more easy to release in tumor microenvironment
It puts.SiO of the organo-functional group (PEI) in the present invention2Modification on nano pore also significantly improves the efficiency of gene load.
Field of medicaments clinically realizes that application increases possibility for silica.
In the present invention, a diameter of 50~200nm of the nano SiO 2 particle, preferably 50~100nm.The dioxy
The specific surface area of SiClx nano particle is 400 ± 100m20.6 ± 0.3cm of/g, Kong Rongwei3/g。
In the present invention, the mesoporous silica spheres are solid core/mesoporous shell structure, a diameter of 30~80nm.
The present invention also provides a kind of method preparing above-mentioned multi-stage porous mesoporous silica nano-particle, the method includes
Following steps：
1) mesoporous silica spheres of small-bore are synthesized using surfactant as directed agents using sol-gal process；
2) it is 1.3~2 that volume ratio is added in the reaction system of step 1)：1 organosilane precursor and silicon source B, in 90
~100 DEG C (such as 95 DEG C) carry out hydro-thermal reaction, so that the surface of the mesoporous silica spheres is grown large aperture organosilicon dendritic
Shell, to obtain the multi-stage porous mesoporous silica nano-particle.
The present invention uses sol-gal processSurfactant is added to be oriented to the aperture of method synthesis solid core/mesoporous shell
The mesoporous SiO of diameter2Ball, the SiO2The particle size of ball can be adjusted by controlling the dosage of base catalyst (TEA), herein
On the basis of organosilane precursor and silicon source is added, so that its surface is grown the dendritic shell of large aperture organosilicon, product is washed, extraction
After removing surfactant, the mesoporous SiO of the multi-stage porous for having good dispersion, size tunable, aperture controllable is obtained2Nanometer
Grain, internal is the SiO of small-bore2Ball, outside package large aperture organic silicon sphere shell.It can be according to the organosilicon forerunner of addition
The dosage of body and/or reaction time reasonably control the size of the dendritic shell mesoporous pore size.It can be according to the organic of addition
The dosage and/or reaction time of silicon precursor and silicon source B adjust the thickness of the dendritic shell, to obtain different-grain diameter
Multi-stage porous mesoporous silica nano-particle.
Wherein, step 1) includes：According to 200：1~8 mass ratio mixes surfactant, base catalyst in water,
It is stirred under the conditions of 90~100 DEG C (such as 95 DEG C), silicon source A is added, react 40~60 minutes synthesizing mesoporous silicon dioxide balls,
In, the volume ratio of the silicon source A and the base catalyst is 100~1：8.
Preferably, the mass ratio of the gross mass and water of the surfactant and base catalyst is 1：9.
Preferably, the volume ratio of the silicon source B and base catalyst described in step 1) is 100：1~8.
Preferably, the surfactant is hexadecyltrimethylammonium chloride or cetyl trimethylammonium bromide.
Preferably, the base catalyst is triethylamine, trimethylamine or pyridine.
Preferably, the silicon source A and/or silicon source B is selected from methyl orthosilicate, ethyl orthosilicate (TEOS), positive silicic acid
At least one of propyl ester, butyl silicate.
In the preparation method of the present invention, the organosilane precursor is the organosilane precursor containing cystine linkage, preferably double-
[3- (triethoxysilicane) propyl] tetrasulfide.
Preferably, in step 2), the hydro-thermal reaction time is 4~8 hours.
Preferably, step 2) is repeated more than once.By the step of repeatedly generating organosilicon dendritic shell, can also obtain
The nano SiO 2 particle simultaneously with a variety of (two or more) different apertures, to reach diversified aperture demand.This
Outside, in step 2), the multi-stage porous mesoporous silica nano-particle can be obtained after washing, extracting.It is described to extract
Conventional acidic alcohol extraction or sodium chloride methanol extraction can be used in journey, and for removing surfactant, extraction time can be with
For 6-12h.
Preparation is simple by the present invention, high, at low cost, efficient without any pollution, yield, obtained multi-stage porous
Mesoporous SiO2Particle dispersion is good, specific surface area is high, large pore volume, pore-size distribution is uniform adjustable, is conducive to various sizes of drug
And nano particle wherein efficiently support, be great application prospect drug, gene, biological enzyme and catalyst carrier it
One, it shows wide application prospect in the fields such as drug delivery and chemical industry catalysis, especially for needs while cladding and passes
Defeated big molecule and small molecule, such as siRNA and DOX have unique advantage.
Description of the drawings
Fig. 1 is the mesoporous SiO with multi-stage porous that the embodiment of the present invention 1 obtains2The transmission electron microscope picture of nano particle；
Fig. 2 is the mesoporous SiO with multi-stage porous that the embodiment of the present invention 1 obtains2The scanning electron microscope (SEM) photograph of nano particle；
Fig. 3 is the mesoporous SiO with multi-stage porous that the embodiment of the present invention 2 obtains2The transmission electron microscope picture of nano particle；
Fig. 4 is the mesoporous SiO with multi-stage porous that the embodiment of the present invention 2 obtains2The scanning electron microscope (SEM) photograph of nano particle；
Fig. 5 a are the SiO with multi-stage porous that the embodiment of the present invention 1 obtains2The N of nano particle2Adsorption-desorption isothermal is bent
Line；
Fig. 5 b are the SiO with multi-stage porous that the embodiment of the present invention 1 obtains2The graph of pore diameter distribution of nano particle；
Fig. 6 a are the SiO with multi-stage porous that the embodiment of the present invention 2 obtains2The N of nano particle2Adsorption-desorption isothermal is bent
Line；
Fig. 6 b are the SiO with multi-stage porous that the embodiment of the present invention 2 obtains2The graph of pore diameter distribution of nano particle；
Fig. 7 is the transmission of the mesoporous silica nano-particle with hierarchical porous structure obtained in the embodiment of the present invention 3
Electron microscope；
Fig. 8 is the transmission of the mesoporous silica nano-particle with hierarchical porous structure obtained in the embodiment of the present invention 4
Electron microscope；
Fig. 9 is the transmission of the mesoporous silica nano-particle with hierarchical porous structure obtained in the embodiment of the present invention 5
Electron microscope；
Figure 10 is the transmission of the mesoporous silica nano-particle with hierarchical porous structure obtained in the embodiment of the present invention 6
Electron microscope；
Figure 11 is the transmission of the mesoporous silica nano-particle with hierarchical porous structure obtained in the embodiment of the present invention 7
Electron microscope；
Figure 12 is the process flow diagram of the preparation method of the present invention.
Specific implementation mode
It is further illustrated the present invention below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The present invention provides a kind of multi-stage porous mesoporous silica nano-particle, the SiO2Nano particle has macropore simultaneously
The hierarchical porous structure of diameter and small-bore, skeleton are organic-inorganic hybrid structure, the SiO2The mesoporous pore size of nano particle be 2.5~
9nm.In addition, preparing the SiO the present invention also provides a kind of2The method of nano particle first passes through sol-gel method and surface is added to live
Property agent be oriented to method synthesize high degree of dispersion, the solid core of uniform particle diameter/mesoporous shell SiO2Ball；Again by the way that organic silicon source synthesis is added
Second layer dendritic morphology obtains multistage mesoporous organosilicon.The synthetic method of the present invention is simple and practicable, without any pollution, yield it is high,
At low cost, efficient, easily industrialized production；Biography of the mesoporous organosilicon structure of obtained multi-stage porous in macromolecular drug
Before the fields such as the loading of defeated, DNA and siRNA and transmission, catalysis, microreactor, absorption, separation, chromatography have a wide range of applications
Scape.
Figure 12 schematically shows the process flow chart of the preparation method of the present invention, as shown in Figure 12, preparation side of the invention
Method for example including：Sol-gel process and surfactant are oriented to the SiO of method synthesis size tunable2Nano particle；Hydrothermal condition
Under, silicon source and organic silicon source presoma cohydrolysis and copolycondensation form the adjustable dendritic shell of thickness；After product separation (such as
With second alcohol and water) it washs repeatedly；(such as with extracted under 75 degrees Celsius of acidic alcohol) removes surfactant, and washing is produced
Object.Hereinafter, illustrating the method for preparing the multi-stage porous mesoporous silica nano-particle.
First, using traditional sol-gelMethod, using surfactant as directed agents, synthesis is monodispersed
The SiO of solid core/mesoporous shell2Particle (SiO2Ball).Specifically, surfactant, base catalyst, water are mixed according to a certain percentage
Even, constant temperature, is then added silicon source A and is reacted, you can obtain the SiO of solid core/mesoporous shell under hydrothermal conditions2Ball.
Hexadecyltrimethylammonium chloride (CTAC) or cetyl trimethylammonium bromide may be used in surfactant
(CTAB)。
Triethylamine (TEA), trimethylamine (TMA) or pyridine may be used in base catalyst.It, can be by controlling alkali in the present invention
The dosage of catalyst is to gained SiO2The particle size of ball is adjusted.The mass ratio of surfactant and base catalyst is 200：
It is adjustable in (1-8) range.The mass ratio of surfactant and base catalyst is 200：When in (1-8) range, have grain size adjustable
The advantages of.In addition, the ratio of surfactant and base catalyst and water can be the gross mass of surfactant and base catalyst：
Water=1：9.Mixed surfactant, base catalyst, water sequence be not particularly limited, can be by surfactant, base catalysis
Agent directly mixes in water, surfactant, base catalyst can also be mixed and made into aqueous solution with water respectively and then by two
Kind aqueous solution mixing.In this case, the ratio of surfactant and base catalyst and water can be surfactant：Water, alkali
Catalyst：Water is respectively 1：9、1：9, such as surfactant and TEA are pressed (1 with water respectively：9) ratio mixing prepares A liquid
With B liquid, then by A liquid and B liquid with 200：The ratio mixing of (1-8).
Silicon source A can be selected from methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate.The addition of silicon source A
It can be 1.2~10 times of base catalyst volume.
In addition, the temperature of hydrothermal condition can be at 90~100 DEG C (such as 95 DEG C).The time reacted after silicon source A is added can
With in 40-60min.
As an example, synthesising mesoporous SiO2The process of ball for example including：Surfactant and TEA are pressed with water respectively
(1：9) ratio mixing prepares A liquid and B liquid, then by A liquid and B liquid with 200：The ratio mixing of (1-8), 95 degrees Celsius of hydro-thermals
Constant temperature stirring a period of time (such as 5min)；Then the silicon source A that volume is 1.2~10 times of the TEA volumes is added, reacts 1h,
It can be obtained the SiO of solid core/mesoporous shell2Ball.
The SiO of the mesoporous shell of solid core-of gained in the present invention2The grain size of ball is adjustable within the scope of 30-80nm.The grain size model
Enclose interior mesoporous SiO2Ball has the advantages of orderly and continuously adjustable large specific surface area, Kong Ronggao, aperture, morphology controllable.Pass through
The amount for controlling base catalyst, can adjust the SiO of the mesoporous shell of solid core-2The grain size of ball.The SiO of the mesoporous shell of solid core-2Jie of ball
Hole aperture is in 3nm hereinafter, it is preferred that 2~3 nanometers, for example, about 2.5nm.
Then, organosilane precursor and silicon source B is added, using hydrothermal condition by organosilane precursor and silicon source B cohydrolysis,
Copolycondensation, in the SiO of the mesoporous shell structure of the solid core-2Ball surface generates dendritic shell, to generate simultaneously have large aperture with
The hierarchical porous structure of small-bore.The temperature of hydrothermal condition can be at 90~100 DEG C (such as 95 DEG C).
The present invention use the organosilane precursor containing cystine linkage, such as double-[3- (triethoxysilicane) propyl] tetrasulfide,
Double-[γ-(triethoxysilicane)-propyl]-disulphide, disulfide bond under reproducibility environment (for example, tumor microenvironment) are easy
Fracture, keeps shell more degradable, the drug loaded is easier to be released in the incorporation of shell.
Silicon source B is selected from methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate.In the present invention, silicon source A with
Silicon source B can select same silicon source, can also select different silicon sources.
It, can be mesoporous to dendritic shell according to the dosage of the organosilane precursor of addition and/or reaction time in the present invention
The size in aperture is reasonably controlled.The volume ratio of organosilane precursor and silicon source B are 1.3~2：It is adjustable in 1 range.It is organic
The volume ratio of silicon precursor and silicon source B are 1.3~2：When 1, have the advantages that dendritic generation is clear, shell pattern is uniform.In addition,
The volume ratio of the silicon source B and base catalyst when synthesizing mesoporous silicon dioxide ball can be 100：1~8.
During generating the dendritic shell of organosilicon, reaction time of hydro-thermal reaction is according to the SiO of the mesoporous shell of solid core-2
The particle size of ball needs to select optimum reacting time, and the reaction time is too short or too long is all unable to get ideal product.This hair
In bright, the hydro-thermal reaction time for generating the dendritic shell of organosilicon can be at 4~8 hours.For example, being the solid of 30nm for grain size
The silica spheres of the mesoporous shell of core-, reaction time 4h-8h, preferably time are 4h, and gained nano SiO 2 particle grain size is about
For 70nm.And between when reacted at 4~8 hours, preferable dendritic effect can be obtained.
The step of can repeating the generation organosilicon dendritic shell, with obtain while having it is a variety of it is (two or more) no
The nano SiO 2 particle in same aperture.
The present invention can also include the last handling process of product.Specifically, final products therefrom, institute are reacted in centrifugation, collection
After product is washed successively, extraction removes surfactant, obtaining having multi-stage porous, (inside is the SiO of small-bore2Ball, outside
Portion wrap up large aperture organic silicon sphere shell) structure mesoporous silicon oxide.
As an example, such as multiple with ethyl alcohol and water washing, conventional acidic alcohol (example may be used in extraction process
Such as 75 DEG C) extraction or sodium chloride methanol extraction, for removing surfactant, extraction time is generally 6-12h (3 times).
The above method of the present invention is oriented to method and organosilane precursor in hydro-thermal using sol-gal process and surfactant
Under the conditions of synthesize controllable with good dispersion, size tunable, aperture with silicon source cohydrolysis, the combination of copolycondensation growth
The mesoporous SiO of multi-stage porous2Ball, consisting of SiO2With organic matter (such as organic matter containing cystine linkage).It can be by adjusting organosilicon
The amount of presoma and silicon source can adjust dendritic shell thickness, obtain the multi-stage porous mesoporous silicon oxide of different-grain diameter.For example,
The amount of organosilane precursor and silicon source is more, and dendritic shell thickness is bigger.Further, it is also possible to by adjusting be added organic silicon source it
The time of hydro-thermal reaction afterwards adjusts dendritic shell thickness, obtains the multi-stage porous mesoporous silicon oxide of different-grain diameter.For example, water
The thermal response time is longer, and dendritic shell thickness is bigger.In the present invention, the mesoporous SiO of multi-stage porous2The diameter of ball is in 50-200nm ranges
Interior adjustable, outer layer mesoporous pore size is adjustable within the scope of 5-9nm.
The present invention has expanded application of the mesoporous silicon oxide in fields such as medicine, catalysis.It, can especially in field of medicaments
To carry out classification load to various sizes of drug, classification release is supported to provide material for classification treatment.It is two simultaneously
Silica, which is clinically realized to apply, increases possibility.
Advantages of the present invention：
Preparation is simple by the present invention, high, at low cost, efficient without any pollution, yield, obtained multi-stage porous
Mesoporous SiO2Particle dispersion is good, specific surface area is high, large pore volume, pore-size distribution is uniform adjustable, is conducive to various sizes of drug
And nano particle efficiently supporting wherein, also, compared to the nano SiO 2 particle as inorganic material, the present invention
Organic inorganic hybridization SiO2Drug loading can be better achieved in nano particle, and its degradation property in vivo obtains
Reinforce, is one of drug, gene, biological enzyme and catalyst carrier of great application prospect, be catalyzed in drug delivery and chemical industry etc.
Field shows wide application prospect, especially for needs while coating and transmitting big molecule and small molecule, such as
SiRNA and DOX etc. has unique advantage.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.Multistage prepared by following embodiments and comparative example
The mesoporous SiO in hole2The Kong Rong and specific surface area of structural material respectively according to Barrett-Joyner-Halenda (BJH) and
Brunauer-Emmett-Teller (BET) method calculates, and pore-size distribution is according to the sides Barrett-Joyner-Halenda (BJH)
Method calculates.
Embodiment 1
45mL deionized waters and 5gCTAC are mixed, A liquid is denoted as.9mL deionized waters and 1gTEA mixing, are denoted as B liquid.It takes
20gA liquid and the mixing of 0.8gB liquid, constant temperature stirs 5min under conditions of 95 DEG C；Rapidly join 1mL ethyl orthosilicates, magnetic stirring
1h；By 1mL ethyl orthosilicates and 2mL it is bis--[3- (triethoxysilicane) propyl] tetrasulfide (BTES) after evenly mixing, it is rapid plus
Enter above-mentioned solution, magnetic stirring 4h obtains the mesoporous SiO of multi-stage porous after product centrifugation2Ball.It is washed twice with ethyl alcohol, acidic alcohol
Under the conditions of the extraction removing surfactants of 6h (3 times), washed twice with ethyl alcohol, deionized water washed once, and obtain high degree of dispersion
The mesoporous SiO with multi-stage porous2Particle.
The SiO obtained in the present embodiment2The transmission electron microscope picture of particle is as shown in Figure 1, the grain of particle as can be seen from Figure
Diameter is 60nm, has regular spherical morphology, the dispersibility of uniform grain size and height.Wherein shell has macroporous structure (hole
Diameter is about 6nm), inside is the silica ball portion with small-bore (2.5nm).Its scanning electron microscope (SEM) photograph is as shown in Fig. 2, can
Intuitively to show the dispersibility of regular dendritic spherical morphology and height.
Embodiment 2
45mL deionized waters and 5gCTAC are mixed, A liquid is denoted as.9mL deionized waters and 1gTEA mixing, are denoted as B liquid.It takes
20gA liquid and the mixing of 0.8gB liquid, constant temperature stirs 5min under conditions of 95 DEG C；Rapidly join 1mL ethyl orthosilicates, magnetic stirring
1h；By 1mL ethyl orthosilicates and 1.3mL it is bis--[3- (triethoxysilicane) propyl] tetrasulfide (BTES) after evenly mixing, rapidly
Above-mentioned solution, magnetic stirring 4h is added；Then by 1mL ethyl orthosilicates and 2mL it is bis--[3- (triethoxysilicane) propyl] four vulcanize
Object (BTES) uniformly mixes, and is rapidly added above-mentioned solution, continues magnetic stirring 4h.The mesoporous SiO of multi-stage porous is obtained after product centrifugation2
Ball.Washed twice with ethyl alcohol, the removing surfactants of 6h (3 times) extracted under the conditions of acidic alcohol, are washed twice with ethyl alcohol, go from
Sub- water washing is primary, obtains the mesoporous SiO with multi-stage porous of high degree of dispersion2Particle.
The SiO obtained in the present embodiment2The transmission electron microscope picture of particle is as shown in figure 3, the grain of particle as can be seen from Figure
Diameter is 100nm, has regular spherical morphology, the dispersibility of uniform grain size and height.Wherein shell has macroporous structure (hole
Diameter is about 8nm), central hole structure (6nm), inside is the silica ball portion with small-bore (2.5nm).Its scanning electron microscope
Figure is as shown in figure 4, the dispersibility of regular dendritic spherical morphology and height can intuitively be shown.
Fig. 5 a, 5b are the SiO with multi-stage porous that embodiment 1 obtains2The N of ball2Adsorption-desorption isothermal curve and aperture point
Butut.The result shows that material has high 400 ± 100m of specific surface area2/ g and hole hold 0.6 ± 0.3cm3/g.Aperture is shown as
The multi-stage porous of 2.5nm and 6nm.
Fig. 6 a, 6b are the SiO with multi-stage porous that embodiment 2 obtains2The N of ball2Adsorption-desorption isothermal curve and aperture point
Butut.The result shows that material has high 400 ± 50m of specific surface area2/ g and hole hold 0.4 ± 0.2cm3The apertures /g are shown as
The multi-stage porous of 2.5nm, 6nm and 8nm.
Embodiment 3
Solid core/mesoporous shell SiO is first obtained according to the synthesis technology of embodiment 12Ball.Then 1ml ethyl orthosilicates are added
With 1.3mL it is bis--after evenly mixing, above-mentioned solution, magnetic stirring is added in [3- (triethoxysilicane) propyl] tetrasulfide (BTES)
4h.Subsequent processing is the same as embodiment 1.
Embodiment 4
Solid core/mesoporous shell SiO is first obtained according to the synthesis technology of embodiment 12Ball.Then 1ml ethyl orthosilicates are added
With 1.6mL it is bis--after evenly mixing, above-mentioned solution, magnetic stirring is added in [3- (triethoxysilicane) propyl] tetrasulfide (BTES)
4h.Subsequent processing is the same as embodiment 1.
Embodiment 5
Solid core/mesoporous shell SiO is first obtained according to the synthesis technology of embodiment 12Ball.Then the positive silicic acid second of 0.3ml is added
Ester and 1.3mL it is bis--after evenly mixing, above-mentioned solution is added, magnetism is stirred in [3- (triethoxysilicane) propyl] tetrasulfide (BTES)
Mix 4h.Subsequent processing is the same as embodiment 1.
The mesoporous silicon oxide with hierarchical porous structure obtained in above-described embodiment 3,4,5 corresponds to transmission electron microscope picture respectively
7,8,9.It can be seen from the figure that obtained product is the different multi-stage porous mesoporous silicon oxide of dendritic shell thickness, wherein in fact
It is 65nm to apply example 3, and embodiment 4 is 70nm, and embodiment 5 is 60nm, therefore it is known that can be by adjusting TEOS's and BTES
Amount can adjust dendritic shell thickness, obtain the multi-stage porous mesoporous silicon oxide of different-grain diameter.
Embodiment 6
Solid core/mesoporous shell SiO is first obtained according to the synthesis technology of embodiment 12Ball.Then 1ml ethyl orthosilicates are added
With 2mL it is bis--after evenly mixing, above-mentioned solution, magnetic stirring 8h is added in [3- (triethoxysilicane) propyl] tetrasulfide (BTES).
Embodiment 7
Solid core/mesoporous shell SiO is first obtained according to the synthesis technology of embodiment 12Ball.Then 1ml ethyl orthosilicates are added
With 2mL it is bis--after evenly mixing, above-mentioned solution, magnetic stirring is added in [3- (triethoxysilicane) propyl] tetrasulfide (BTES)
12h。
The mesoporous silicon oxide difference corresponding diagram 10,11 with hierarchical porous structure obtained in above-described embodiment 6,7.From figure
In as can be seen that the dendritic shell thickness of obtained multi-stage porous mesoporous silicon oxide is different, wherein embodiment 6 is 75nm, real
It is 87nm to apply example 7, therefore it is known that can adjust branch by the time of the hydro-thermal reaction after adjusting addition organic silicon source
Shape shell thickness obtains the multi-stage porous mesoporous silicon oxide of different-grain diameter.
Claims (11)
1. a kind of multi-stage porous mesoporous silica nano-particle, which is characterized in that the nano SiO 2 particle is while having
There is a hierarchical porous structure of large aperture and small-bore, including mesoporous silica spheres and is wrapped in the mesoporous silica spheres surface
The dendritic shell of organosilicon, the mesoporous pore sizes of the mesoporous silica spheres is in 3nm hereinafter, Jie of the dendritic shell of the organosilicon
Hole aperture is 4~9nm.
2. nano SiO 2 particle according to claim 1, which is characterized in that the nano SiO 2 particle it is straight
Diameter is 50~200nm, and specific surface area is 400 ± 100m20.6 ± 0.3cm of/g, Kong Rongwei3/g。
3. nano SiO 2 particle according to claim 1 or 2, which is characterized in that the mesoporous silica spheres are
Solid core/mesoporous shell structure, a diameter of 30~80nm.
4. a kind of method of the multi-stage porous mesoporous silica nano-particle prepared described in any one of claims 1 to 3, special
Sign is, the described method comprises the following steps：
1）Using sol-gal process, using surfactant as directed agents, the mesoporous silica spheres of small-bore are synthesized；
2）In step 1）Reaction system in be added volume ratio be 1.3~2：1 organosilane precursor and silicon source B, in 90~100
DEG C carry out hydro-thermal reaction, so that the surface of the mesoporous silica spheres is grown the dendritic shell of large aperture organosilicon, to obtain
State multi-stage porous mesoporous silica nano-particle.
5. according to the method described in claim 4, it is characterized in that, step 1）Including：According to 200：1~8 mass ratio is by table
Face activating agent, base catalyst mix in water, are stirred under the conditions of 90~100 DEG C, and silicon source A is added, and react 40~60 minutes and synthesize
Mesoporous silica spheres, wherein the volume ratio of the silicon source A and the base catalyst is 100：1~8.
6. according to the method described in claim 5, it is characterized in that, the silicon source B and step 1）Described in base catalyst body
Product is than being 100：1~8.
7. according to the method described in claim 5, it is characterized in that, the surfactant is hexadecyltrimethylammonium chloride
Or cetyl trimethylammonium bromide；
The base catalyst is triethylamine, trimethylamine or pyridine；
The silicon source A and/or the silicon source B are in methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate
At least one.
8. according to the method described in claim 4, it is characterized in that, the organosilane precursor is before the organosilicon containing cystine linkage
Drive body.
9. according to the method described in claim 8, it is characterized in that, the organosilane precursor is double-[3- (triethoxysilicane)
Propyl] tetrasulfide.
10. according to the method described in claim 4, it is characterized in that, step 2）In, the hydro-thermal reaction time is 4~8 hours.
11. the method according to any one of claim 4 to 10, which is characterized in that step 2）It is repeated more than once.
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| CN103663478A (en) * | 2013-11-20 | 2014-03-26 | 华东师范大学 | Preparation method of mesoporous silica spherical nano particles with dendritic pore structure |
| CN104891511A (en) * | 2015-05-25 | 2015-09-09 | 华东师范大学 | Method for synthesizing mesoporous silicon dioxide nanoparticles by using alkali-free method |
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