CN104387446B - A kind of graphene dispersion agent and the preparation method of graphene dispersing solution - Google Patents
A kind of graphene dispersion agent and the preparation method of graphene dispersing solution Download PDFInfo
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Abstract
The present invention relates to dispersant technical field, more particularly to a kind of graphene dispersion agent and the preparation method of graphene dispersing solution, the present invention has designed and developed the Amphiphilic peptide molecule of Gemini structures, and realizes Graphene stable dispersion in aqueous as dispersant using the molecule.Graphene dispersion dispersant of the present invention is polypeptide dispersant, is made up of native amino acid residues completely, has the advantages that high-biocompatibility, is conducive to developing application of the graphene dispersion system in biomedical sector；Polypeptide dispersant institute is electrically charged to change and change with solution ph, and obtained graphene dispersion system has pH responses, it is possible to use the dispersion behavior of pH change regulation Graphenes, for preparing intelligent nano drug-carrying and control delivery；Meanwhile, dispersion disclosed by the invention is the complex of a kind of polypeptide nano assembly and graphene film Rotating fields, can be used for preparing nano composite material.
Description
Technical field
The present invention relates to dispersant technical field, more particularly to a kind of graphene dispersion agent and the preparation of graphene dispersing solution
Method.
Background technology
Graphene has the properties such as excellent electricity, mechanics, optics and calorifics, is widely used in electronic component, energy
The fields such as amount storage, catalysis, bio-sensing.Graphene film interlayer has stronger Van der Waals force, very easy to assemble, and makes it
Water and conventional organic solvent are insoluble in, the performance of Graphene performance in practical application is largely effected on.Therefore, in order to give full play to
Its advantageous property, it is it in various fields research and the important bar of application to prepare homogeneous, high stability graphene dispersion system
Part.
At present, " oxidation-modification-reduction-dispersion " method is a kind of indirect method for preparing graphene dispersing solution, i.e., first to stone
Ink carries out Strong oxdiative treatment, obtains surface and edge and possesses the graphene oxide of the groups such as substantial amounts of hydroxyl, carboxyl, epoxy
(GO), these functional groups make GO easily be reacted with other reagents, obtain modified graphene oxide, and then it is carried out again
Reduction obtains hydrophilic grapheme modified, with good dispersion in aqueous.But used in these methods strong
The material of corrosivity, strong oxidizing property, needs significant care in and operating process high to equipment requirement, and the Graphene for obtaining its
Crystal structure is also extremely imperfect, with the presence of a large amount of defects, has considerable influence to its electricity, calorifics, biology performance etc., limits
Its research and application in association area.
A kind of method for directly preparing graphene dispersing solution is that graphite or expanded graphite are applied directly into certain organic solvent
Or in aqueous surfactant solution, certain density single or multiple lift graphite is prepared by ultrasonic wave, heating or the effect of air-flow
Alkene solution.Solvent molecule or surfactant molecule are adsorbed in graphenic surface by pi-pi accumulation and hydrophobic effect etc., by quiet
Electric repulsion or intermolecular force, realize effective dispersion of Graphene, and then are material assembling and property based on Graphene
Research provides convenient.The solvent of document report has dimethylformamide (DMF), N- methyl-pyrrolidons (NMP), polyethylene pyrrole
Pyrrolidone (PVP), o-dichlorohenzene, acetonitrile, chloroform etc., surfactant have neopelex (SDBS), cholic acid
(SDC), cetyl trimethylammonium bromide (CTAB), Tween 80, triton X-100 etc..The liquid phase Direct dispersion method system of Graphene
Standby process is not related to chemical change, with low cost, simple to operate, high quality, but there is also single-layer graphene
Yield is not high, lamella is reunited seriously, need to further slough the defects such as stabilizer.Wherein：Aqueous surfactant solution low cost, behaviour
Make easy, but the graphene dispersing solution concentration for obtaining is relatively low；Organic solvent can obtain the graphene dispersing solution of higher concentration,
But high cost, and its boiling point is higher, is difficult to remove, and is unfavorable for further applying for Graphene.
Recent years, Graphene and its derivative in biomedical sector, including the preparation of biological component, medical diagnosis on disease,
The application of bio-imaging and drug delivery oncotherapy etc. is paid attention to by numerous scientists, is ground as nano biological medical domain
The focus studied carefully.And in current graphene dispersion system, the graphene dispersing solution based on organic solvent (DMF, NMP, PVP etc.) by
Living things system is not used in the bio-toxicity of organic solvent；Although can be obtained as dispersant by the use of conventional surfactants
The aqueous solution of graphene dispersion, but by the biocompatibility of surfactant for being utilized is general all poor, also day of one's doom
Its application in biomedical sector is made.Therefore, the Biology Applications of Graphene are carried out, in the urgent need to bio-compatible high
Property graphene dispersion agent and aqueous dispersion system design, exploitation, this is also an important class in the research of current Graphene
Topic.Further, if resulting graphene dispersion system has the response to specific external condition (such as pH value, temperature)
Property, will be provided powerful support for for the exploitation of intelligent nano material and pharmaceutical carrier etc. is provided.
The content of the invention
In order to solve problems of the prior art, the present invention proposes a kind of graphene dispersion agent and graphene dispersion
The preparation method of liquid.
The present invention is adopted the technical scheme that：
A kind of graphene dispersion agent, the structure of the dispersant is：
The preparation method of graphene dispersion agent as described above, specific step is as follows：
1) Fmoc solid-phase synthesis synthesis polypeptides are used
Obtain crude product；
2) reacted reaction solution is transferred in revolving bottle, the rotary evaporation in vacuo under the conditions of 35 DEG C, removes DCM, TFA
Deng residual liquid；The liquid after rotary evaporation is added dropwise in the 7-8 times of ice ether of raffinate volume with dropper, is stood to produce and is sunk
Behind shallow lake, 10min is centrifuged under the conditions of 9000rpm, 4 DEG C with high speed freezing centrifuge, repeatedly ether precipitation, is centrifuged 5-6 times；Remove
Supernatant liquor, retains precipitation, and after treating that ether is evaporated completely in fume hood, to ultra-pure water is added in precipitation, ultrasound shakes up, and is put into refrigerator
Middle pre-freeze 1h, reuses -60 DEG C of freeze-drying 24h of freeze dryer, that is, the product for being purified seals -20 DEG C of preservations.
3) by step 2) polypeptide that obtains is dissolved in the mixed solution of DCM/DMF (volume ratio 1/1), is passed through oxygen 24 small
When；
4) by step 3) after reaction solution be transferred in revolving bottle, the rotary evaporation in vacuo under the conditions of 35 DEG C, remove DCM/
The residual liquids such as DMF；
5) liquid after rotary evaporation is added dropwise in the 7-8 times of ice ether of volume with dropper, is stood after producing precipitation,
10min is centrifuged under the conditions of 9000rpm, 4 DEG C with high speed freezing centrifuge, repeatedly ether precipitation, is centrifuged 5-6 times；Remove upper strata
Clear liquid, retains precipitation, and after treating that ether is evaporated completely in fume hood, in precipitation plus ultra-pure water, ultrasound shakes up, and is put into pre- in refrigerator
Freeze 1h, reuse -60 DEG C of freeze-drying 24h of freeze dryer, that is, the dispersant for being purified seals -20 DEG C of preservations.
A kind of preparation method of Graphene, has used dispersant as described above, and specific preparation method is as follows：
The described dispersant of 5 weight portions and the graphite powder of 25 weight portions are weighed respectively, add the water of 10 weight portions, regulation
PH to 6-7, concussion is well mixed, is put into ultrasound in ultrasonic machine, and water temperature must not during ultrasonic time is at least 24h, and ultrasonic procedure
Higher than 70 DEG C；After the completion of ultrasound, polypeptide/graphene mixed liquor is centrifuged；Centrifugal rotational speed 500rpm-8000rpm, centrifugation
10min-30min；After the completion of centrifugation, isolated supernatant is Graphene.
Preferably, the method for the ultrasonic procedure is：Power 100W, ultrasound stops after 4 hours, after 12 hours, then ultrasound
4 hours, then stop 12 hours, be so recycled to ultrasonic time and add and be 24 hours.
The beneficial effects of the invention are as follows：
In current graphene dispersion system, the graphene dispersing solution based on organic solvent is due to the biology poison of organic solvent
Property and be not used to living things system；Although the water-soluble of graphene dispersion can be obtained as dispersant by the use of conventional surfactants
Liquid, but by the biocompatibility of the surfactant for being utilized is general all poor, it is also greatly limit in biomedicine
The application in field.And, above two graphene dispersion system does not possess the response of condition to external world, is unfavorable for intelligent sound
The exploitation of answering property nano material and pharmaceutical carrier etc..The present invention has designed and developed the Amphiphilic peptide molecule of Gemini structures, and
Graphene stable dispersion in aqueous is realized as dispersant using the molecule.
The acquisition of graphene dispersing solution of the present invention：
1) deposition and film preparation of the Graphene in the surface of solids are conducive to.
2) dispersant of disclosure of the invention is polypeptide dispersant, is made up of native amino acid residues completely, with Gao Sheng
The advantage of thing compatibility, is conducive to developing application of the graphene dispersion system in biomedical sector.
3) polypeptide dispersant institute is electrically charged changes and change with solution ph, and obtained graphene dispersion system has
PH responses, it is possible to use the dispersion behavior of pH change regulation Graphenes, for preparing intelligent nano drug-carrying and control delivery.
4) the polypeptide dispersant itself can be assembled into nanofibre-like structure, therefore dispersions obtained system is a kind of polypeptide
The complex of Nanoscale assemblies and graphene film Rotating fields, can be used for preparing nano composite material.
Brief description of the drawings
The present invention has drawings described below：
Fig. 1 is by the I after 1000rpm centrifugal treatings 30 minutes3C-CI3Scattered graphene aqueous solution photo；
Fig. 2 is by the I after 1000rpm centrifugal treatings 30 minutes3C-CI3The ultraviolet-visible of scattered graphene aqueous solution
Spectrum；
Fig. 3 crosses I of the 1000rpm centrifugal treatings after 30 minutes3C-CI3The transmission electron microscope picture of scattered graphene aqueous solution
Wherein, Fig. 3 (a)：Staining counter, Fig. 3 (b)：Cryo-TEM；
Fig. 4 I3C-CI3Photo of the scattered graphene aqueous solution under different pH.
Specific embodiment
Embodiment 1：
I3The preparation of C：
Design synthesis C-terminal contains the single-chain polypeptide molecules I of cysteine residues3C, its structure is：
Its synthetic method is synthesizing the I of 0.25mM3(it is biochemical that following all reagents used are purchased from gill as a example by C molecules
(Shanghai))：
1) Wang-resin resins 0.439g is weighed；Compound concentration for 0.2mol/L 50mL Fmoc-Ile-OH (A) and
The amino acid DMF solution of 25mL Fmoc-Cys (Trt)-OH (C), weighs A respectively:2.456g；C:1.661g, is sufficiently stirred for molten
Solution；
2) following synthetic agents are prepared：1. activator：0.45mol/L, takes HBTU 17.07g and HOBt 6.08g and is dissolved in
In 100mLDMF；2. alkali is activated：2mol/L, takes the DMF mixing of the diisopropylethylamine (DIEA) and 32.6mL of 17.4mL；3. take off
Protective agent：The HOBt of the piperidines of volume ratio 20% and 0.1mol/L is dissolved in DMF, is taken piperidinyl-1 00mL, 6.756g HOBt and is dissolved in
In 400mL DMF；4. acetylation reagent：0.5mol/L acetic anhydrides, 0.125mol/L DIEA and 0.015mol/L HOBt are dissolved in
DMF solution in be configured to, take 3mL acetic anhydrides, DIEA 0.244g, HOBt 0.031g are dissolved in 12mLDMF solution；5. crack
Agent：TFA: TIS: Water=95: 2.5: 2.5 (volume ratios), prepare 15mL solution.
3) using the Liberty microwave Peptide synthesizer application Fmoc solid-phase synthesis synthesis polypeptides of CEM companies, obtain still
The uncracked polypeptide crude product for being connected with resin；
4) reaction solution is transferred in revolving bottle after the completion of reacting, the rotary evaporation in vacuo under the conditions of 35 DEG C, removing DCM,
The residual liquids such as TFA.The liquid after rotary evaporation is added dropwise in the 7-8 times of ice ether of raffinate volume with dropper, is stood and is produced
After raw precipitation, 10min is centrifuged under the conditions of 9000rpm, 4 DEG C with high speed freezing centrifuge, repeatedly ether precipitation, is centrifuged 5-6 times.
Supernatant liquor is removed, retains precipitation, after treating that ether is evaporated completely in fume hood, to ultra-pure water is added in precipitation, ultrasound shakes up, is put into
Pre-freeze 1h in refrigerator, reuses -60 DEG C of freeze-drying 24h of freeze dryer or so, that is, the product for being purified seals -20 DEG C of preservations.
Embodiment 2：
Single-chain polypeptide molecules prepared by connection embodiment 1 obtain peptide molecule, and flow is as follows：
Specifically synthetic method is：
1) I is weighed3C monomer molecule, is dissolved in the mixed solution of DCM/DMF (volume ratio 1/1), molten in above-mentioned mixing
Pure O is passed through in liquid2Gas 24 hours；
2) reaction solution is transferred in revolving bottle, the rotary evaporation in vacuo under the conditions of 35 DEG C, removes the residual solutions such as DCM/DMF
Body.The liquid after rotary evaporation is added dropwise in the 7-8 times of ice ether of raffinate volume with dropper, is stood after producing precipitation, used
High speed freezing centrifuge is centrifuged 10min under the conditions of 9000rpm, 4 DEG C, repeatedly ether precipitation, is centrifuged 5-6 times.Remove upper strata clear
Liquid, retains precipitation, and after treating that ether is evaporated completely in fume hood, to ultra-pure water is added in precipitation, ultrasound shakes up, and is put into pre-freeze in refrigerator
1h, reuses -60 DEG C of freeze-drying 24h of freeze dryer or so, that is, the product for being purified seals -20 DEG C of preservations.
Embodiment 3：
The preparation of graphene dispersing solution：
Graphite flake is purchased from Qingdao Jin Peng graphite Co., Ltd, standby into graphite powder using porcelain mortar grinder.Choose clean
Reagent bottle, weigh respectively 5mg embodiments preparation peptide molecule and 25mg graphite powders, add 10ml water, regulation pH to 6-7,
Concussion is well mixed, and sealed membrane is put into ultrasound in ultrasonic machine after sealing.
Ultrasonic method：Power 100W, ultrasound stops after 4 hours, after 12 hours then ultrasonic 4 hours, then stops 12 small
When, so it is recycled to ultrasonic time and adds and be 24 hours.Maintained water temperature in ultrasonic procedure between 30 DEG C to 70 DEG C, water temperature exceedes
The water that changes on the rocks is answered at 70 DEG C reduces temperature.After the completion of ultrasound, polypeptide/graphene mixed liquor is centrifuged.Centrifugal rotational speed
1000rpm, is centrifuged 30 minutes.After the completion of centrifugation, isolated supernatant is graphene dispersing solution.
Centrifugation can remove not fully dissociation and scattered graphite particle, obtain the dispersion liquid rich in graphene sheet layer, knot
Fruit, without the generation for precipitating, there is substantial amounts of graphite as shown in figure 1, dispersion liquid is presented the aterrimus of stable homogeneous in explanation system
Alkene lamella is present.
The scattered Graphene system of polypeptide is characterized, ultraviolet-visible spectrum (Fig. 2) is presented a spy at 268nm
Spectral peak is levied, illustrates to contain graphene film Rotating fields in solution.
There is depositing for substantial amounts of graphene sheet layer and polypeptide nano fiber in transmission electron microscope Electronic Speculum result (Fig. 3) display solution
.
I3C-CI3Peptide molecule contains carboxyl (- COOH), and its ionization changes and changes with pH, causes its static electrification lotus number
Purpose changes, and this causes I3C-CI3/ graphene dispersing solution has pH responses, as shown in figure 4, working as pH<When 5, system produces heavy
Form sediment, Graphene is separated out, and when pH >=5, system can be with stable existence, and graphene dispersion is good.
Claims (4)
1. a kind of graphene dispersion agent, it is characterised in that：The structure of the dispersant is：
。
2. a kind of preparation method of graphene dispersion agent according to claim 1, it is characterised in that specific step is as follows：
1) Fmoc solid-phase synthesis synthesis polypeptides are usedObtain
Crude product；
2) reacted reaction solution is transferred in revolving bottle, the rotary evaporation in vacuo under the conditions of 35 DEG C；After rotary evaporation
Liquid is added dropwise in the 7-8 times of ice ether of raffinate volume, stand produce precipitation after, with high speed freezing centrifuge 9000rpm,
10min is centrifuged under the conditions of 4 DEG C, repeatedly ether precipitation, is centrifuged 5-6 times；Supernatant liquor is removed, retains precipitation, second is treated in fume hood
After ether is evaporated completely, to ultra-pure water is added in precipitation, ultrasound shakes up, and is put into pre-freeze 1h in refrigerator, reuses -60 DEG C of freezings of freeze dryer
24h is dried, that is, the polypeptide for being purified seals -20 DEG C of preservations；
3) by step 2) polypeptide that obtains is dissolved in volume ratio 1:In 1 DCM/DMF mixed solutions, oxygen is passed through 24 hours；
4) by step 3) after reaction solution be transferred in revolving bottle, the rotary evaporation in vacuo under the conditions of 35 DEG C removes DCM/DMF etc.
Residual liquid；
5) liquid after rotary evaporation is added dropwise in the 7-8 times of ice ether of volume with dropper, is stood after producing precipitation, with height
Fast refrigerated centrifuge is centrifuged 10min under the conditions of 9000rpm, 4 DEG C, repeatedly ether precipitation, is centrifuged 5-6 times；Remove supernatant liquor,
Retain precipitation, after treating that ether is evaporated completely, to ultra-pure water is added in precipitation, ultrasound shakes up, and is put into pre-freeze 1h in refrigerator, reuses jelly
- 60 DEG C of freeze-drying 24h of dry machine, that is, the graphene dispersion agent for being purified seals -20 DEG C of preservations.
3. a kind of preparation method of graphene dispersing solution, it is characterised in that used the graphene dispersion agent described in claim 1,
Specific preparation method is as follows：
The graphene dispersion agent and the graphite powder of 25 weight portions of 5 weight portions are weighed respectively, add the water of 10 weight portions, regulation
PH to 6-7, concussion is well mixed, is put into ultrasound in ultrasonic machine, and water temperature must not during ultrasonic time is at least 24h, and ultrasonic procedure
Higher than 70 DEG C；After the completion of ultrasound, graphene dispersion agent/graphene mixed liquor is centrifuged；Centrifugal rotational speed 500rpm-
8000rpm, is centrifuged 10min-30min；After the completion of centrifugation, isolated supernatant is graphene dispersing solution.
4. the preparation method of graphene dispersing solution according to claim 3, it is characterised in that the side of described ultrasonic procedure
Method is：Power 100W, ultrasound stops after 4 hours, after 12 hours then ultrasonic 4 hours, then stops 12 hours, is so recycled to
Ultrasonic time adds and is 24 hours.
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| CN105110318B (en) * | 2015-07-23 | 2017-11-14 | 深圳市国创新能源研究院 | A kind of graphene water paste and preparation method thereof |
| CN107934949B (en) * | 2016-10-12 | 2020-12-15 | 上海大学 | Preparation method of graphene dispersion liquid for impregnating ceramic matrix composite material |
| CN106629670A (en) * | 2016-12-14 | 2017-05-10 | 北京工业大学 | Method for dispersing carbon nano tubes by Gemini type dispersing agent |
| CN107082422A (en) * | 2017-04-28 | 2017-08-22 | 山东欧铂新材料有限公司 | A kind of process for dispersing of graphene |
| CN108559092B (en) * | 2018-03-14 | 2021-02-26 | 上海交通大学 | Carbon material dispersant, method for producing the same, and stable aqueous dispersion of carbon material containing the dispersant |
| CN109553094A (en) * | 2019-01-03 | 2019-04-02 | 深圳天元羲王材料科技有限公司 | A kind of grapheme platelet liquid phase ultrasonic dispersing method |
| CN110510606A (en) * | 2019-08-23 | 2019-11-29 | 陕西科技大学 | Degradation scrap leather bits are used as the preparation method that graphene oxide lacks lamella dispersing agent |
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| CN102778571A (en) * | 2012-08-13 | 2012-11-14 | 中国人民解放军第三军医大学第三附属医院 | Ionic liquid-graphene nanocomposite, preparation method and electrochemical immunodetection method thereof |
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