CN105752971A - Nano-graphene material special for drug carrier and preparing method - Google Patents
Nano-graphene material special for drug carrier and preparing method Download PDFInfo
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- CN105752971A CN105752971A CN201610189834.0A CN201610189834A CN105752971A CN 105752971 A CN105752971 A CN 105752971A CN 201610189834 A CN201610189834 A CN 201610189834A CN 105752971 A CN105752971 A CN 105752971A
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
Abstract
The invention relates to a nano-graphene material special for a drug carrier and a preparing method thereof.The method comprises the steps that crystalline flake graphene is oxidized through an HUMMMERS method so that graphene oxide can be obtained, the graphene oxide is subjected to micromechanical ultrasonic peeling so that single-layer nano-graphene oxide can be obtained; then, fatty alcohol-polyoxyethylene ether is used for modifying the single-layer nano-graphene oxide, modified graphene oxide is obtained, the water solubility and dispersity of the modified graphene oxide are improved, and cyanate ester modifying amphiphilic polymers are used for reducing the modified graphene oxide into graphene; finally, the nano-graphene material with superior water solubility and physiological stability is obtained.The obtained reduction graphene is good in water solubility, wide in stable dispersion solvent range, good in biocompatibility, good in physiological stability and capable of meeting the application requirements in the field of drug carriers.According to the method, the technology is simple, price is low, reduction degree is controllable, functionalized graphemes with different reduction degrees and dispersities can be acquired, and the application range of graphene is expanded in the field of drug carriers.
Description
Technical field
The present invention relates to pharmaceutical carrier technical field, be specifically related to a kind of pharmaceutical carrier special-purpose nanometer grapheme material and preparation method.
Background technology
Develop new and effective delivery system, to improve the therapeutic profile of medicine and curative effect is one of encountered key issue of modern medicine.The progress of nano science and nanotechnology so that new nano material is synthesized, has promoted the development of many novel drugs induction systems.
The discovery of Graphene in recent years causes people increases research concern day by day, explores the application in medicine conveying of this new material.Graphene is the monolayer bi-dimensional cellular shape lattice structure that carbon atom SP2 hydridization is piled into, and since 2004 are found, it has caused the huge interest of whole scientific circles.Chemical constitution and geometry due to its uniqueness, Graphene has outstanding physicochemical properties, at biomedicine field, it is being widely applied in scope is providing infusive opportunity as a kind of new biomaterial Graphene and complex thereof, including a new generation's biosensor, drug conveying carrier, cell and bio-imaging probe.Owing to Graphene has monoatomic layer structure, its specific surface area is very big, is highly suitable as pharmaceutical carrier.The preparation method of Graphene mainly has compound between graphite layers approach, graphite oxide reduction approach, micromechanics to peel off approach, deposition growing approach etc..
Graphite intercalation complex (GICs) is a kind of with natural flake graphite for raw material, that graphite is formed after inserting the atom of some non-carbonaceous, molecule, ion even atomic group between layers a kind of new lamellar compound.Plasma etching technology is widely used in the manufacture fields such as microelectronics, micro-optic, micromechanics.The etched line of plasma etching can reach Nano grade, and the pattern etched can be as accurate as nanometer.It is in the successful Application of microelectronic, makes research worker thirst for utilizing its etching to separate Graphene.Chemical vapour deposition technique (Chemicalvapordeposition) is the method that most widely used a kind of heavy industrialization prepares semiconductor film material.Its production technology is very perfect, also becomes research worker and prepares an approach of Graphene.Although the above method can obtain the good Graphene of quality, but can not prepare Graphene in high volume, and oxidation-reduction method is prepared a large amount of single-layer graphene for people and is provided possibility, and this method is with low cost.The method for oxidation that graphite is conventional mainly has 3 kinds: Standenmaier method, Brodie method, Hummers method, its process is to make crystalline flake graphite fully oxidized with strong oxidizers such as concentrated hydrochloric acid, concentrated nitric acid and excessive potassium chlorate, there is substantial amounts of oxy radical at oxidized graphite flake interlayer and edge, graphite oxide processes through suitable ultrasonic wave concussion and is very easily dispersed into uniform single-layer graphene oxide solution in aqueous solution or organic solvent, and graphene oxide is by obtaining graphene solution after the reducing agent reduction such as hydrazine hydrate.
Although graphene oxide can be dispersed in water, but it is difficult to be dispersed in the solution such as PBS containing ion.In addition, Graphene after graphene oxide reduction is the two dimensional crystal combined by benzene hexatomic ring, chemical stability is high, the inert state in its surface, interaction with other media (such as solvent etc.) is more weak, and has stronger Van der Waals force between graphene film and sheet so that it is easily produce reunite and be insoluble in water, this causes the application at biomedicine field of great difficulty, particularly Graphene to research and the application further of Graphene.Graphene in biomedicine field application generally requires and uses in physiological environment.
Existing technique generally adopts the reagent redox graphenes such as hydrazine hydrate, vitamin C, protein, galactose, glucose, but in reduction process, exhibiting high surface functional group is reduced, cause that material is reunited, it is difficult to disperse in the solution, limit the extensive use of reduced graphene, although there being numerous researcher to develop a lot of method to improve the solution dispersion of reduced graphene at present, but mostly there is complex process, poor controllability, high in cost of production problem in these methods.
For above-mentioned technological deficiency, the invention provides a kind of pharmaceutical carrier special-purpose nanometer grapheme material and preparation method, for improving water solublity and the physiological stability of nano-graphene.
Summary of the invention
It is desirable to provide a kind of pharmaceutical carrier special-purpose nanometer grapheme material and preparation method, its technique is simple, reduction degree is controlled, and the reduced graphene water solublity of preparation is good, can stable dispersion solvent wide ranges, physiological stability good, thus overcoming deficiency of the prior art.The present invention protects the nano-graphene material being prepared gained by preparation method of the present invention further.
For realizing the purpose of foregoing invention, present invention employs following technical scheme:
First by crystalline flake graphite after HUMMMERS method aoxidizes, obtain graphite oxide, the nanoscale Graphene obtaining monolayer is peeled off then through micromachined ultrasonic, then utilize fatty alcohol-polyoxyethylene ether that it is modified, obtain modified graphene oxide, to increase its water solublity and dispersibility, at the amphiphilic polymers utilizing cyanate to modify, modified graphene oxide is reduced to Graphene, finally gives the nano-graphene with excellent water dissolubility and physiological stability.
Further, specific embodiment of the invention step is:
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium strong oxidizer, water-bath 30-40 DEG C, intermittent stirring is stopped reaction after 4-12 hour, it is subsequently added a certain amount of water, make system be warming up to 60～80 DEG C, and keep 30～60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 4～5, obtain graphite oxide mother solution；Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=10～30: 3～6: 1～2: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 4-8 hour, supersonic frequency is 250-400Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution is added under mechanical stirring, after reacting 4-8h at 70-100 DEG C, filtering, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water, at 40-80 DEG C, vacuum drying 24-72h obtains modified graphene oxide solution；Fatty alcohol-polyoxyethylene ether is a kind of nonionic surfactant, and the present invention is introduced into graphene oxide, improves graphene oxide dispersibility in solion with the synergism of reducing agent and other conditions.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, react 0.1-120h at 50-200oC, then will separate in solid product reaction mixture, and fully wash with organic solvent, it is thus achieved that target product.In reduction process, adopt the amphiphilic polymers that cyanate is modified as reducing agent, it is possible to be prevented effectively from exhibiting high surface functional group and be reduced, thus the water solublity of enhancing modified Graphene and physiological stability.
Strong oxdiative acid described in step (1) is concentrated sulphuric acid or perchloric acid, and described is potassium permanganate or potassium hyperchlorate containing potassium strong oxidizer.
The ultrasonic disperse time described in step (2) is preferably 5-7 hour, and more preferably 6 hours, supersonic frequency was preferably 300-350Hz.
Fatty alcohol-polyoxyethylene ether described in step (3), it is preferred to aliphatic alcohol polyethenoxy (7) ether, aliphatic alcohol polyethenoxy (9) ether, aliphatic alcohol polyethenoxy (10) ether.The concentration (by weight) of described fatty alcohol-polyoxyethylene ether aqueous solution is 35-40%, more preferably 37-38%, and the best is 38%.Described graphene oxide water solution and fatty alcohol-polyoxyethylene ether aqueous solution ratio can be 20: 1,15: 1,10: 1,5: 1,2: 1,1: 1,1: 2,1: 5,1: 10,1: 15,1: 20.More preferably 1: 5,1: 10,1: 20, further it is preferably 1: 10.Reaction temperature can be 20-95 DEG C, is optimized for 80-90 DEG C further, and the best is 88 DEG C.Vacuum drying temperature can be 40-70 DEG C, more preferably 50-60 DEG C, and the best is 55 DEG C.The vacuum drying time can be 24h, 30h, 36h, 42h, 48h, 54h, 60 more preferably 42h, 48h, 54h, and the best is 48h.
The amphiphilic polymers of the diisocyanate modification described in step (4) and the mass ratio 1000:1 1:1000 of graphene oxide, it is preferably 100:1-1:100, described diisocyanate be selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide carbanil, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and PPDI, but it is not limited to this.Described amphiphilic polymers is selected from Polyethylene Glycol, monomethyl Polyethylene Glycol, tween, Triton, F-68, paraoctyl phenol polyoxyethylene ether, Span and polyethenoxy ether, but is not limited to this.The amphiphilic polymers that described diisocyanate is modified is the product after above-mentioned amphiphilic polymers and di-isocyanate reaction.Described organic solvent is selected from DMF, DMSO and NMP, but is not limited to this.
Compared with prior art, advantages of the present invention is as follows:
(1) the reduced graphene water solublity obtained is good, can stable dispersion solvent wide ranges, good biocompatibility, physiological stability is good, can meet the application requirement in pharmaceutical carrier field；
(2) technique is simple, cheap, reduction degree is controlled, can obtain the functionalization graphene of different reduction degree and dispersibility, expand the Graphene range of application in pharmaceutical carrier field.
Specific implementation method
Embodiment 1
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium permanganate, water-bath 30 DEG C, intermittent stirring is stopped reaction after 4 hours, it is subsequently added a certain amount of water, make system be warming up to 80 DEG C, and keep 60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 4～5, obtain graphite oxide mother solution.Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=25: 3: 2: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 6 hours, supersonic frequency is 250Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) adding the aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 4h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 80 DEG C, at 40 DEG C, vacuum drying 72h obtains modified graphene oxide solution.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, 120h is reacted at 180oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
Embodiment 2
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium permanganate, water-bath 40 DEG C, intermittent stirring is stopped reaction after 8 hours, it is subsequently added a certain amount of water, make system be warming up to 60 DEG C, and keep 60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 5, obtain graphite oxide mother solution.Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=10: 3: 1: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 8 hours, supersonic frequency is 300Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) adding the aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 4h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 100 DEG C, at 80 DEG C, vacuum drying 24h obtains modified graphene oxide solution.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, 100h is reacted at 120oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
Embodiment 3
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium hyperchlorate, water-bath 30 DEG C, intermittent stirring is stopped reaction after 12 hours, it is subsequently added a certain amount of water, make system be warming up to 80 DEG C, and keep 60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 4～5, obtain graphite oxide mother solution.Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=30: 6: 2: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 6 hours, supersonic frequency is 250Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) adding the aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 6h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 40 DEG C, at 80 DEG C, vacuum drying 48h obtains modified graphene oxide solution.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, 80h is reacted at 50oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
Embodiment 4
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium permanganate, water-bath 30 DEG C, intermittent stirring is stopped reaction after 12 hours, it is subsequently added a certain amount of water, make system be warming up to 80 DEG C, and keep 60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 5, obtain graphite oxide mother solution.Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=20: 4: 2: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 6 hours, supersonic frequency is 350Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) adding the aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 7h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 70 DEG C, at 60 DEG C, vacuum drying 72h obtains modified graphene oxide solution.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, 120h is reacted at 180oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
Embodiment 5
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium hyperchlorate, water-bath 40 DEG C, intermittent stirring is stopped reaction after 10 hours, it is subsequently added a certain amount of water, make system be warming up to 80 DEG C, and keep 60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 5, obtain graphite oxide mother solution.Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=15: 6: 2: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 6 hours, supersonic frequency is 250Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) adding the aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 8h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 100 DEG C, at 40 DEG C, vacuum drying 72h obtains modified graphene oxide solution.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, 80h is reacted at 100oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
Embodiment 6
(1) take crystalline flake graphite, be subsequently adding a certain amount of concentrated sulphuric acid, mixing, adding a certain amount of potassium permanganate, water-bath 40 DEG C, intermittent stirring is stopped reaction after 8 hours, it is subsequently added a certain amount of water, make system be warming up to 80 DEG C, and keep 60 minutes, add hydrogen peroxide, stirring, various ions in washing removal system, until pH value reaches 4, obtain graphite oxide mother solution.Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=15: 3: 2: 1.
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 6 hours, supersonic frequency is 350Hz, obtains the graphite oxide colloid that suspension stability is good.
(3) adding the aqueous solution of fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 4h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 100 DEG C, at 40 DEG C, vacuum drying 72h obtains modified graphene oxide solution.
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in machine solvent, 80h is reacted at 120oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
The method of reducing of disclosure and announcement graphene oxide, can pass through to use for reference disclosure.Although the pharmaceutical carrier special-purpose nanometer graphene preparation method of the present invention has passed through preferred embodiment and is described, but method described herein substantially can be changed by those skilled in the art in without departing from present invention, spirit and scope, more specifically, all similar replacements and change apparent to those skilled in the art, they are considered as including in present invention spirit, scope and content.
Claims (10)
1. a pharmaceutical carrier special-purpose nanometer grapheme material preparation method, it is characterised in that comprise the steps:
(1) take crystalline flake graphite, add concentrated sulphuric acid and potassium strong oxidizer, after heating in water bath for reaction, add hydrogen peroxide, stirring, the various ions in washing removal system, until pH value reaches 4～5, obtain graphite oxide mother solution；Mass ratio between each reactant is Strong oxdiative acid: containing potassium strong oxidizer: hydrogen peroxide: graphite=10～30: 3～6: 1～2: 1;
(2) graphite oxide that step (1) obtains being dispersed in a certain amount of deionized water for ultrasonic disperse 4-8 hour, supersonic frequency is 250-400Hz, obtains the graphite oxide colloid that suspension stability is good;
(3) adding fatty alcohol-polyoxyethylene ether aqueous solution under mechanical stirring, after reacting 4-8h, filter, wash respectively repeatedly with the dehydrated alcohol of heat and deionized water at 70-100 DEG C, at 40-80 DEG C, vacuum drying 24-72h obtains modified graphene oxide solution;
(4) amphiphilic polymers and the modified graphene oxide modified by cyanate are miscible in organic solvent, 0.1-120h is reacted at 50-200oC, then solid product reaction mixture will be separated, and fully wash with organic solvent, it is thus achieved that pharmaceutical carrier special-purpose nanometer grapheme material.
2. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 1, it is characterised in that the Strong oxdiative acid described in step (1) is concentrated sulphuric acid or perchloric acid, described is potassium permanganate or potassium hyperchlorate containing potassium strong oxidizer.
3. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 1, it is characterised in that the ultrasonic disperse time described in step (2) is preferably 5-7 hour, and more preferably 6 hours, supersonic frequency was preferably 300-350Hz.
4. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 1, it is characterized in that the fatty alcohol-polyoxyethylene ether described in step (3), it is preferably aliphatic alcohol polyethenoxy (7) ether, aliphatic alcohol polyethenoxy (9) ether, aliphatic alcohol polyethenoxy (10) ether；Its concentration (by weight) is 35-40%, more preferably 37-38%, and the best is 38%.
5. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 4, it is characterized in that described graphene oxide water solution and fatty alcohol-polyoxyethylene ether aqueous solution ratio can be 20: 1,15: 1,10: 1,5: 1,2: 1,1: 1,1: 2,1: 5,1: 10,1: 15,1: 20；More preferably 1: 5,1: 10,1: 20, further it is preferably 1: 10.
6. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 1, it is characterised in that reaction temperature can be 20-95 DEG C, is optimized for 80-90 DEG C further, and the best is 88 DEG C.
7. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 1, it is characterized in that the mass ratio 1000:1 1:1000 of the amphiphilic polymers of the diisocyanate modification described in step (4) and graphene oxide, it is preferred to 100:1-1:100.
8. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 7, it is characterised in that the amphiphilic polymers that described diisocyanate is modified is the product after above-mentioned amphiphilic polymers and di-isocyanate reaction.
9. pharmaceutical carrier special-purpose nanometer grapheme material preparation method according to claim 7, it is characterized in that described diisocyanate be selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide carbanil, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and PPDI；Described amphiphilic polymers is selected from Polyethylene Glycol, monomethyl Polyethylene Glycol, tween, Triton, F-68, paraoctyl phenol polyoxyethylene ether, Span and polyethenoxy ether.
10. a pharmaceutical carrier special-purpose nanometer grapheme material, it is characterised in that prepared the nano-graphene material of gained by claim 1-9 any one preparation method.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009114A (en) * | 2016-08-02 | 2016-10-12 | 苏州锐特捷化工制品有限公司 | Tear-resistant functional rubber material for magnetic modification and preparation method thereof |
| CN106009605A (en) * | 2016-08-01 | 2016-10-12 | 苏州锐特捷化工制品有限公司 | Graphene nano modified rubber with strong toughness and preparation process of modified rubber |
| CN106188695A (en) * | 2016-08-17 | 2016-12-07 | 常熟市瑞思知识产权服务有限公司 | A kind of for magnetic oil resistant fibre modification nanometer functional materials for building and preparation method thereof |
| CN106692975A (en) * | 2016-12-01 | 2017-05-24 | 浙江大学常州工业技术研究院 | Oxidized-graphene nano-drug carrier with targeting function and preparing method thereof |
| CN107176602A (en) * | 2017-05-18 | 2017-09-19 | 太原理工大学 | A kind of graphene oxide composite material with ordered structure and preparation method thereof |
| CN113896191A (en) * | 2020-12-31 | 2022-01-07 | 南京联智科技有限公司 | Crown-shaped modified graphene oxide load synergist and synthesis method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613098A (en) * | 2009-06-12 | 2009-12-30 | 中国科学院宁波材料技术与工程研究所 | A kind of solution phase preparation method of Graphene |
| CN102424381A (en) * | 2011-09-09 | 2012-04-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reducing method |
| KR20130015719A (en) * | 2011-08-04 | 2013-02-14 | 연세대학교 산학협력단 | A complex comprising a mesoporous silicon oxide and a graphene, and method for preparing the same |
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
-
2016
- 2016-03-30 CN CN201610189834.0A patent/CN105752971A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613098A (en) * | 2009-06-12 | 2009-12-30 | 中国科学院宁波材料技术与工程研究所 | A kind of solution phase preparation method of Graphene |
| KR20130015719A (en) * | 2011-08-04 | 2013-02-14 | 연세대학교 산학협력단 | A complex comprising a mesoporous silicon oxide and a graphene, and method for preparing the same |
| CN102424381A (en) * | 2011-09-09 | 2012-04-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide reducing method |
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009605A (en) * | 2016-08-01 | 2016-10-12 | 苏州锐特捷化工制品有限公司 | Graphene nano modified rubber with strong toughness and preparation process of modified rubber |
| CN106009114A (en) * | 2016-08-02 | 2016-10-12 | 苏州锐特捷化工制品有限公司 | Tear-resistant functional rubber material for magnetic modification and preparation method thereof |
| CN106188695A (en) * | 2016-08-17 | 2016-12-07 | 常熟市瑞思知识产权服务有限公司 | A kind of for magnetic oil resistant fibre modification nanometer functional materials for building and preparation method thereof |
| CN106692975A (en) * | 2016-12-01 | 2017-05-24 | 浙江大学常州工业技术研究院 | Oxidized-graphene nano-drug carrier with targeting function and preparing method thereof |
| CN107176602A (en) * | 2017-05-18 | 2017-09-19 | 太原理工大学 | A kind of graphene oxide composite material with ordered structure and preparation method thereof |
| CN113896191A (en) * | 2020-12-31 | 2022-01-07 | 南京联智科技有限公司 | Crown-shaped modified graphene oxide load synergist and synthesis method thereof |
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