CN108455566A - The silicon dioxide nano composite material and its preparation method and application of fullerene insertion - Google Patents

The silicon dioxide nano composite material and its preparation method and application of fullerene insertion Download PDF

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CN108455566A
CN108455566A CN201810216455.5A CN201810216455A CN108455566A CN 108455566 A CN108455566 A CN 108455566A CN 201810216455 A CN201810216455 A CN 201810216455A CN 108455566 A CN108455566 A CN 108455566A
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fullerene
silicon dioxide
composite material
nano composite
dioxide nano
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杨天赦
高惠
赵强
刘淑娟
黄维
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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Nanjing Post and Telecommunication University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/0002General or multifunctional contrast agents, e.g. chelated agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51Nanocapsules; Nanoparticles
    • A61K9/5107Excipients; Inactive ingredients
    • A61K9/5115Inorganic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract

The invention belongs to nano material preparation technologies and special material technical field, and in particular to a kind of mesoporous silicon dioxide nano composite material and preparation method of fullerene insertion and application.The Reverse Microemulsion System being made of hexamethylene, Triton X-100 (TritonX 100), n-hexyl alcohol and aqueous solution is specifically first built, later by C70Fullerene is encapsulated in the silica nano material being embedded in get fullerene in the core of Nano particles of silicon dioxide.Preparation method is simple, raw material sources are abundant, applied widely.And the nano particle diameter of preparation is small, specific surface area is high, load capacity is high, good biocompatibility.

Description

The silicon dioxide nano composite material and its preparation method and application of fullerene insertion
Technical field
The invention belongs to nano material preparation technologies and special material technical field, and in particular to a kind of C70Fullerene is embedded in The preparation method and application of the nanocomposite of silica.
Background technology
Fullerene be it is a kind of it is novel contain carbon nanomaterial, because its unique structure and physicochemical properties biology, medicine, Superconduction, optics and catalysis etc. are multi-field extremely wide application prospect.Meanwhile fullerene and its derivative are with anti-oxidant Activity, cytoprotection, antibacterial activity, antivirus action, carrier band drug and oncotherapy isoreactivity, therefore, in biology and Medical domain is widely used.But fullerene itself is difficult to be directly dissolved in biological friendly medium, and it is remaining in preparation process Organic solvent easily causes bio-toxicity, it usually needs it is living further to improve its biology that suitable chemical modification is carried out to it Property.
Improving the water-soluble method of fullerene mainly has following 3 kinds:(1) ultrasound prepares fullerene water colloidal sol;(2) it prepares rich Strangle the water-soluble inclusion complex of alkene;(3) in Fullerene Carbon cage surface-bonded water soluble group, fullerene synthesis derivative.Currently, compared with Good solution is to add multiple highly polar groups, such as-OH ,-COOH and-NH on Fullerene Carbon cage surface2Deng synthesis Assign fullerene new physicochemical properties while water-soluble preferable fullerene derivate.But the chemistry in fullerene is repaiied Decorations reaction in easily formed add derivative, it is difficult to accomplish selectivity synthesis, this be after isolate and purify cause it is larger It is difficult.Therefore, it is necessary to seek a kind of simple effective method to improve the water solubility of fullerene.
Silica is widely distributed, has good biocompatibility.Metaporous silicon dioxide material is a kind of with high ratio The controllable novel inorganic biomaterial of surface area, big pore capacities, morphology and size, mesopore silicon dioxide nano material have had both Jie The double grading of Porous materials and nano material has very high chemical stability, biocompatibility, synthesis convenient and at low cost The features such as honest and clean, in addition to other than traditional mesoporous material application field, in other field such as biological medicine and genetic engineering etc. Also show great application prospect.
The present invention is by reverse microemulsion process by fullerene (C70) center of meso-porous titanium dioxide silicon matrix is embedded in form water The good nanocomposite of dissolubility.The nanocomposite has meso-hole structure, large specific surface area, biocompatibility Good and stability is high.
Invention content
It is an object of the invention to solve deficiency in the prior art, the mesoporous silicon oxide of fullerene insertion is provided Nanocomposite.The nanocomposite is by reverse microemulsion process by fullerene (C70) it is encapsulated in silica nanometer Formation is prepared in the core of particle.Obtained nanocomposite has good biocompatibility, is a good carrier Platform has a good application prospect in fields such as drug delivery, cell imaging, living imagings, and can be used in cancer and swell Tumor therapy field.
The specific technical solution of the present invention is as described below:
A kind of C70The preparation method of the mesoporous silicon dioxide nano composite material of fullerene insertion, specifically includes following step Suddenly:
(1) surfactant, cosurfactant, hexamethylene, deionized water are mixed with certain volume ratio, Form reverse micro emulsion;
(2) by C70Fullerene is dissolved in toluene solution and is added in above-mentioned reverse micro emulsion, adds hydroxide later Ammonium and tetraethoxysilane, react 40-50h at room temperature;
(3) ethyl alcohol is added to stop reacting, products therefrom ethyl alcohol centrifuge washing is three times to obtain the two of fullerene insertion Aoxidize silicon nano material.
Further, the surfactant in the step of above-mentioned preparation method (1) is Triton X-100 (Triton X-100), cosurfactant are n-hexyl alcohol, and surfactant, cosurfactant, hexamethylene, deionized water Volume ratio be 5: 2.5:50:1;
Further, the C in the step of above-mentioned preparation method (2)70Fullerene structure formula is as follows:
Further, the grain size of the mesoporous silicon dioxide nano composite material of the fullerene insertion is about 50-70nm.
Further, the mesoporous silicon dioxide nano composite material of fullerene insertion of the present invention can be applied to drug In the treatment of transmission, cell imaging, living imaging, cancer and tumour.
The invention has the advantages that:
1, the silicon dioxide nano composite material grain size of fullerene insertion of the present invention is small, specific surface is high, load capacity Greatly, good biocompatibility;
2, the preparation method of the nanocomposite is simple, abundant raw material, it is applied widely, can be used for industrial metaplasia Production;
3, the nanocomposite is a good carrier platform, can be applied not only to drug delivery, cell imaging, The fields such as living imaging also highlight preferable effect in the treatment of cancer and tumour.
Description of the drawings
Fig. 1 is the scanning electron of the silicon dioxide nano composite material of the fullerene insertion prepared in the embodiment of the present invention 2 Microscope figure;
Fig. 2 is the transmitted electron of the silicon dioxide nano composite material of the fullerene insertion prepared in the embodiment of the present invention 2 Microscope figure;
Fig. 3 is that the dynamic optical of the silicon dioxide nano composite material of the fullerene insertion prepared in the embodiment of the present invention 2 dissipates Penetrate figure.
Specific implementation mode
The content that following embodiment further illustrates the present invention, but should not be construed as limiting the invention.Without departing substantially from In the case of essence of the present invention, to changing and replacing made by the method for the present invention, step or condition, the model of the present invention is belonged to It encloses.
Embodiment 1
(1) by 1ml Triton X-100,0.5ml n-hexyl alcohols, 10ml hexamethylenes and 0.2ml deionized waters mix To form reverse micro emulsion;
(2) and then by 4mg C70Fullerene is dissolved in toluene solution and is added in above-mentioned solution, is slowly added later Ammonium hydroxide and tetraethoxysilane, react 48h at room temperature;
(3) the last 2ml ethyl alcohol that is added in the sample is to stop reacting, and products therefrom is with ethyl alcohol centrifuge washing three times to obtain The silica nano material of fullerene insertion.
Embodiment 2:The property of the silica nano material of fullerene insertion provided in this embodiment in order to better understand Can, it is characterized by following test:
Nanotopography and grain size test
Silica (the i.e. C of fullerene insertion70S) pattern of nanocomposite and particle diameter distribution test
Fig. 1 is silica (the i.e. C of fullerene provided by the invention insertion70S) scanning electron of nanocomposite is aobvious Micro mirror figure.
Specifically testing procedure is:The sample solution of 20 a concentration of 0.2mg/ml of μ l is taken to drop on silicon chip, after sample drying Carry out pattern test.Silica (the i.e. C of fullerene insertion70S) grain size of nano-particle is 50-70nm, from Fig. 1 scanning electrons Microscope graphical results can be seen that the uniform particle diameter of nano-particle provided by the invention, favorable dispersibility;
Fig. 2 is silica (the i.e. C of fullerene provided by the invention insertion70S) transmitted electron of nanocomposite is aobvious Micro mirror figure.
Specifically testing procedure is:The sample solution of 20 a concentration of 0.2mg/ml of μ l is taken to drop on copper mesh, after sample drying Carry out pattern test.Silica (the i.e. C of fullerene insertion70S) grain size of nano-particle is 50-70nm, aobvious from transmitted electron Micro mirror graphical results can be seen that the material is a nucleocapsid, and core is fullerene, and outside is Metaporous silicon dioxide material, And the uniform particle diameter of nano-particle provided by the invention, show that result is consistent with scanning electron microscope diagram;
Fig. 3 is silica (the i.e. C of fullerene provided by the invention insertion70S) the dynamic light scattering of nanocomposite Figure.
Specifically testing procedure is:It takes the sample solution of 20 a concentration of 0.2mg/ml of μ l in plastic cuvette, measures fowler Silica (the i.e. C of alkene insertion70S) the particle diameter distribution of nano-particle, the result shown from figure three can be seen that the present invention and carried The nano particle diameter narrow distribution range of confession, the display result one with scanning electron microscope diagram and transmission electron microscope figure It causes.

Claims (9)

1. a kind of preparation method of the silicon dioxide nano composite material of fullerene insertion, which is characterized in that specifically include following Step:
(1) surfactant, cosurfactant, hexamethylene, deionized water are mixed with certain volume ratio, is formed Reverse micro emulsion;
(2) by C70Fullerene is dissolved in toluene solution and is added in the reverse micro emulsion, later add ammonium hydroxide and Tetraethoxysilane is reacted.
(3) ethyl alcohol is added and stops reaction, products therefrom obtains nanocomposite three times with ethyl alcohol centrifuge washing.
2. the preparation method of the silicon dioxide nano composite material of fullerene insertion as described in claim 1, which is characterized in that Surfactant described in step 1 is Triton X-100, and cosurfactant is n-hexyl alcohol, and surfactant, helps table Face activating agent, hexamethylene, deionized water volume ratio be 5:2.5:50:1.
3. the preparation method of the silicon dioxide nano composite material of fullerene insertion as described in claim 1, which is characterized in that C described in step 270Fullerene structure formula is as follows.
4. the preparation method of the silicon dioxide nano composite material of fullerene insertion as described in claim 1, which is characterized in that The reaction time being added in step 2 after ammonium hydroxide and tetraethoxysilane is 40-50h.
5. a kind of silicon dioxide nano composite material of fullerene insertion, which is characterized in that be by any one of claim 1-4 Prepared by the method.
6. the silicon dioxide nano composite material of fullerene insertion as claimed in claim 5, which is characterized in that the nanometer is multiple The grain size of condensation material is 50-70nm.
7. the silicon dioxide nano composite material of the fullerene insertion as described in any one of claim 1-5 is in drug delivery Application.
8. the silicon dioxide nano composite material of the fullerene insertion as described in any one of claim 1-5 in cell imaging and Application in living imaging.
9. the silicon dioxide nano composite material of the fullerene insertion as described in any one of claim 1-5 in treating cancer and Application in tumour.
CN201810216455.5A 2018-03-16 2018-03-16 The silicon dioxide nano composite material and its preparation method and application of fullerene insertion Pending CN108455566A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109608699A (en) * 2018-12-26 2019-04-12 哈尔滨工大泰铭科技有限公司 A kind of micro-nano compound particle and its preparation process and device
CN114948762A (en) * 2021-12-31 2022-08-30 北京福纳康生物技术有限公司 Fullerene powder material and preparation method and application thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109608699A (en) * 2018-12-26 2019-04-12 哈尔滨工大泰铭科技有限公司 A kind of micro-nano compound particle and its preparation process and device
CN114948762A (en) * 2021-12-31 2022-08-30 北京福纳康生物技术有限公司 Fullerene powder material and preparation method and application thereof

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Application publication date: 20180828