CN105801914A - Functional graphene composite material modified with polypeptide and preparing method thereof - Google Patents

Functional graphene composite material modified with polypeptide and preparing method thereof Download PDF

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CN105801914A
CN105801914A CN201610152498.2A CN201610152498A CN105801914A CN 105801914 A CN105801914 A CN 105801914A CN 201610152498 A CN201610152498 A CN 201610152498A CN 105801914 A CN105801914 A CN 105801914A
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graphene
polypeptide
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石玲英
李航
冉蓉
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Sichuan University
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Abstract

The invention discloses a novel method for preparing a functional graphene material modified with a polypeptide.The prepared functional graphene has potential application value in the biological field due to high biocompatibility and large specific surface area.Graphene modified with the polypeptide is obtained with the graft to method, and a novel idea and method are provided for application of graphene in the biological field.The polypeptide obtained through NCA polymerization triggered by an amine initiator is made to react with graphene subjected to acylating chlorination, so that the graphene material modified with the polypeptide is obtained.The method is suitable for all occasions where graphene is modified with a polypeptide obtained through NCA ring opening polymerization to obtain a corresponding functional composite material.Besides, functional graphene composite nanogel can be prepared through combination of the graphene modified with the polypeptide and the polypeptide.

Description

Graphene composite material that functional poly is peptide modified and preparation method thereof
Technical field
The preparation method that the present invention relates to a kind of poly-polypeptide functionalization graphene composite.
Background technology
Graphene (Graphene) is the two dimensional crystal of the only one layer of carbon atom thickness being stripped out from graphite material.Wherein, carbon atom is arranged in cellular two dimensional surface in the way of sp2 hydridization.From 2004, since physicist A.K.Geim and the K.S.Novoselov of University of Manchester adopts the method for simple mechanical stripping to isolate the Graphene of monolithic layer from highly directional graphite, the physicochemical property of its excellence is subject to the extensive concern Novoselov of scientist, K.S., etal.science, 2004.306 (5696): p.666-669.Graphene is to have now been found that almost fully transparent, the thinnest, a kind of novel nano material that maximum intensity, electrical and thermal conductivity performance are the strongest.
Due to reasons such as the chemical inertness of Graphene and its bad dispersibility in water, organic solvent, it is difficult to processing with process, limit the application of Graphene.So far, the preparation method of Graphene has (1) mechanical stripping method (2) chemical vapour deposition technique (3) chemistry redox method repeatedly.Three kinds of methods of Integrated comparative, wherein chemistry redox method is through big quantity research in recent years, has been able to production efficient, low cost and prepares high-quality Graphene.Graphene oxide (Grapheneoxide), the intermediate product in the production of chemistry redox method, its lamellar structure is essentially identical with Graphene, but graphene oxide lamella surface and edge thereof contain many oxygen-containing functional groups.The modified of Graphene that exist for of these oxygen-containing functional groups provides probability and has widened its application at Material Field.The method of the polymer modification of Graphene mainly has two kinds of methods of graftto and graftingfrom.Wherein graftto is Graphene or graphite oxide alkene reaction that the polymer containing function end group of synthesis passes through the reactions such as esterification, amidatioon and click chemistry and functionalization.This kind of method can control the structure of polymer, and modified middle at Graphene applies wider Layek, R.K.andA.K.Nandi.Polymer, 2013, and 54 (19): p.5087-5103..
Poly-polypeptide is to be synthesized homopolymer or copolymer as initiator by ring-opening polymerisation (NCA) using little molecule organic amine by one or more aminoacid or amino acid derivativges.Because it has good biocompatibility, biodegradability, in biomedical and field of tissue engineering technology, there is important potential using value.And the activated amino of polymer ends band obtained, this makes poly-polypeptide be provided with the feature of further functionalization.
Present stage, can be used for the macromolecular material of biomedical engineering field and can be counted on one's fingers, e.g., polylactic acid (PLLA), Polyethylene Glycol (PEO) etc..Therefore, the Graphene application at biomedical sector of functionalization is limited.
Summary of the invention
Biocompatibility and bigger specific surface area that Graphene is good make it have potential application at biological field.In the application, obtain, by the method for graftto, the Graphene that poly-polypeptide is modified.Provide a kind of new thinking and method for Graphene in the application of biological field: the Graphene that the NCA caused by amine initiator is polymerized poly-polypeptide and the chloride obtained reacts, obtain the grapheme material that poly-polypeptide is modified.
Described poly-polypeptide is the copolymer being polymerized poly-polypeptide homopolymer and the multiple poly-polypeptide obtained by NCA, and initiator is amine initiator.
The preparation method of the grapheme material that a kind of poly-polypeptide of the present invention is modified comprises the following steps:
One, the preparation of graphene oxide: weigh the graphite powder of 3 parts by ratio of weight and the number of copies, the potassium permanganate of the sodium nitrate of 1.5 parts and 9 parts.By volume number weighs the pure water of the concentrated sulphuric acid of the 98% of 7 parts, the hydrogen peroxide of 1 part and 14 parts again.Graphite powder, sodium nitrate and concentrated sulphuric acid are stirred at 0 ~ 5 DEG C 0.5h so that three's mix homogeneously.Then, the potassium permanganate of 9 parts is added slowly in mixed liquor at 0 ~ 5 DEG C.Reaction 1h.3h is reacted afterwards when 35 DEG C.After end, the pure water of 14 parts are slowly added in mixed liquor, are warmed up to 95 ~ 98 DEG C of reaction 0.5h.Finally the solution obtained is diluted with substantial amounts of pure water, add the hydrogen peroxide of 1 part.Dialysing one week, after ultrasonic 1h, be centrifuged and obtain supernatant under 6000 ~ 8000rmp, vacuum drying obtains graphene oxide.
Two, the preparation of poly-polypeptide: we prefer that the polyglutamic acid benzyl fat poly-polypeptide as reaction.(1) synthesis of monomer Pidolidone γ-benzyl ester-N-carboxylic acid anhydrides (BLG-NCA): weigh the γ benzyl-Pidolidone of 3 parts, 1.32 parts of triphosgenes by mole portion rate.By volume number weighs the anhydrous ethyl acetate of 1 part and the anhydrous n-hexane of 1 part.At nitrogen environment, it is warming up to ethyl acetate and backflow occurs, add the triphosgene reaction 4 ~ 5h of 1.32 parts.Obtain settled solution, add the normal hexane of 1 part, the static 10 ~ 12h of refrigerator.Sucking filtration.Ethyl acetate/normal hexane recrystallization obtains monomer.(2) synthesis of poly-polypeptide: weigh a certain proportion of amine initiator and monomer by molfraction.By volume number weighs the dry DMF of 5 parts.React 3 ~ 5 days under a nitrogen atmosphere.Precipitating three times in methanol, vacuum drying obtains poly-polypeptide.
Three, the preparation of chloride Graphene: weigh the graphene oxide of 1 part by weight.By volume number weighs the thionyl chloride of 20 parts and the dry DMF of 1 part.The graphene oxide of 1 part is dispersed in the dry DMF of 1 part by the method for use ultrasonic agitation, adds the thionyl chloride of 20 parts.The back flow reaction 24h when 70 DEG C.It is centrifuged when 6000 ~ 8000rmp by dry DMF, washs the Graphene obtaining chloride for three times.
Four, the system of the grapheme material that poly-polypeptide is modified: weigh the Graphene of the chloride of 1 part and the poly-polypeptide of 20 parts by weight.By volume number weighs the dry DMF of 25 parts and the anhydrous triethylamine of 1 part.First, in 0 ~ 5 DEG C of mixed solution that the anhydrous triethylamine of 1 part is joined chloride Graphene, 25 parts of dry DMF and poly-polypeptide, stir.Then under 50 DEG C of conditions, react 24h.Finally it is centrifuged under 6000 ~ 8000rmp with DMF, washs the Graphene obtaining poly-polypeptide functionalization for three times.
The present invention is obtained by reacting, by the poly-polypeptide that the Graphene of chloride and end group are amido, the grapheme material that poly-polypeptide is modified, provides feasible method and thinking for grapheme material in the application of biological field.
Accompanying drawing explanation
Fig. 1: the full spectrogram of XPS of graphene oxide.
Fig. 2: the C1sXPS spectrogram of graphene oxide.
Fig. 3: the TEM figure of graphene oxide.
Fig. 4: the XRD figure of graphene oxide.
Fig. 5: the FT-IR figure of graphene oxide.
Fig. 6: the AFM figure of graphene oxide.
The nuclear-magnetism H spectrogram of Fig. 7: Pidolidone γ-benzyl ester-N-carboxylic acid anhydride monomer.
Fig. 8: the GPC figure of the poly-polypeptide in embodiment one.
Fig. 9: the nuclear-magnetism H spectrogram of the poly-polypeptide in embodiment one.
Figure 10: the poly-polypeptide modified graphene in embodiment one, the poly-polypeptide modified graphene in embodiment two and graphene oxide scatter diagram in toluene.
Figure 11: the FT-IR of the poly-polypeptide modified graphene in embodiment one and graphene oxide schemes.
Figure 12: the TGA figure of poly-polypeptide modified graphene in embodiment one, graphene oxide and poly-polypeptide.
Figure 13: the full spectrogram of the poly-polypeptide modified graphene XPS in embodiment one.
Figure 14: the C1sXPS spectrogram of the poly-polypeptide modified graphene in embodiment one.
Figure 15: the GPC figure of the poly-polypeptide in embodiment two.
Figure 16: the nuclear-magnetism H spectrogram of the poly-polypeptide in embodiment two.
Figure 17: the FT-IR of the poly-polypeptide modified graphene in embodiment two and graphene oxide schemes.
Figure 18: the TGA figure of poly-polypeptide modified graphene in embodiment two, graphene oxide and poly-polypeptide.
Figure 19: the full spectrogram of the poly-polypeptide modified graphene XPS in embodiment two.
Figure 20: the C1sXPS spectrogram of the poly-polypeptide modified graphene in embodiment two.
Figure 21: gel photograph that poly-polypeptide modified graphene and poly-polypeptide are compounded to form and transmission electron microscope photo.
Detailed description of the invention
Following by specific embodiment, the present invention will be described in detail with accompanying drawing, but is not limited to poly-polypeptide used.
Graphene oxide adopts the synthesis of Hummers method, concretely comprises the following steps: weigh the graphite of 3g and the sodium nitrate of 1.5g, joins in the concentrated sulphuric acid of 98% of 70ml, stirs 0.5h, make three's mix homogeneously at 0 ~ 5 DEG C.Then, at 0 ~ 5 DEG C, the potassium permanganate of 9g is added slowly in mixed liquor.Reaction 1h.Reaction temperature is being risen to 35 DEG C, is reacting 3h.The pure water of 140ml is slowly added to after terminating by reaction, and reacts 0.5h at 95 ~ 98 DEG C.Obtain jonquilleous dispersion liquid.Dilute with lot of pure water, the hydrogen peroxide of the 30% of addition 10ml.After dialysing one week, take out ultrasonic 1h.Being centrifuged under 6000 ~ 8000rmp and obtain supernatant, vacuum drying obtains graphene oxide.The relevant test result such as XPS, FT-IR, TEM, XRD and AFM that characterizes shows: the successful synthesis of graphene oxide.
The constituent content of graphene oxide in table 1, XPS result
Sample C(atom%) O(atom%) C:O
GO 72.99 27.01 2.70
Table can be seen that and pure graphite-phase ratio, the increase of the content of oxygen element, illustrate that the oxygen-containing functional group successful, substantial amounts of of oxidizing process is present on the lamella of Graphene.
Fig. 1 is the full spectrogram of XPS of graphene oxide, is belonging respectively to C and O at the peak of 284.0eV and 532eV, and the oxidation success of graphite is described.
Fig. 2 is the XPS spectrum figure of the C1s of graphene oxide, occurs in that the peak of C-C, C-O, C=O and O-C=O in 284.5,286.5,287.5 and 288.5eV, illustrates to exist on graphene oxide lamella a large amount of oxygen-containing functional group.
Fig. 3 is the TEM figure of graphene oxide, it can be seen that graphene oxide is well stripped into monolithic layer, and surface of graphene oxide is more smooth.
Fig. 4 is the XRD figure of graphene oxide, it can be seen that occur in that diffraction maximum at 10.00 °, show that interlamellar spacing is 0.88nm according to Bragg equation.
Fig. 5 is the FT-IR figure of graphene oxide, it can be seen that 3430cm-1、1721cm-1、1628cm-1With 1107cm-1The vibration peak of peak respectively corresponding O-H, C=O, C=C and C-O key, the successful oxidizing process of graphite is described.
Fig. 6 is the AFM figure of graphene oxide, and recording Graphene thickness is about 1nm, close with XRD result, illustrates that graphite is successfully peeled off into the graphene oxide of monolithic layer.
The synthesis of BLG-NCA monomer: take 7.119g(0.03mol) the anhydrous ethyl acetate with 125ml of γ benzyl-Pidolidone, in a nitrogen environment, heating is to 79 ~ 82 DEG C, and backflow occurs in ethyl acetate, add the triphosgene of 3.9171g (0.0132mol), react 4 ~ 5h.Standing, add the anhydrous n-hexane of 125ml, refrigerator stands 10 ~ 12h.Sucking filtration, recrystallization obtain monomer.
Fig. 7 is the nuclear-magnetism H spectrum of monomer, without assorted peak, illustrates that monomer is successfully prepared.
Embodiment 1
The synthesis step of the grapheme material of poly-polypeptide (P1) functionalization is as follows:
The synthesis of P1: take 5.9mg(0.1mmol) n-propylamine and 0.7899g(3.0mmol) BLG-NCA is dissolved in the anhydrous DMF of 5ml, react 3 ~ 5 days in a nitrogen environment, last precipitation three times in methanol, vacuum drying obtains P1.GPC and nuclear-magnetism H spectrum and characterizes the characterization of molecules of P1.Fig. 8 is that the GPC curve of P1 can show that the weight average molecular weight of P1 is 13700gmol-1, dispersion index be 1.58.Fig. 9 is the nuclear-magnetism H spectrogram of P1, is 21 by calculating the degree of polymerization of P1.Number-average molecular weight is 5800gmol-1.The polymer molecular weight information obtained is composed in Table 2. by GPC and nuclear-magnetism H
Table 2, poly-polypeptide P1 characterization of molecules
Sample Mn a gmol-1 Mw b gmol-1 PDIb DPa
P1 5800 13700 1.58 21
aCalculated by nuclear-magnetism result,bDrawn by GPC result.
Chloride graphite preparation: take the graphene oxide ultrasonic disperse of 10mg in the anhydrous DMF of 1ml.It is slowly added to the thionyl chloride of 20ml.Reflux 24h at 70 DEG C, is centrifuged when 6000 ~ 8000rmp by dry DMF, washs the Graphene obtaining chloride for three times.
The preparation of poly-polypeptide modified graphene: the Graphene of chloride taking 10mg is dissolved in the dry DMF of 50ml with the P1 of 200mg.Join in the mixed solution of chloride Graphene, dry DMF and poly-polypeptide at 0 ~ 5 DEG C of anhydrous triethylamine by 2ml part, stir.Then under 50 DEG C of conditions, react 24h.Finally it is centrifuged under 6000 ~ 8000rmp with DMF, washs the Graphene obtaining poly-polypeptide functionalization for three times.
Figure 10 is P1 modified graphene, graphene oxide and P2 modified Graphene scatter diagram in toluene, owing to π, π effect strong between Graphene causes that Graphene can not disperse in toluene, and the Graphene that P1 modifiies is due to the successful grafting of P1, the interaction between P1 and toluene molecule makes good being dispersed in toluene of Graphene that P1 is modified.
The constituent content of P1 modified graphene in table 3, XPS result
Sample C atom% O atom% N atom% C:O
GO-P1 83.14 14.36 2.5 5.79
In table 3, Graphene modified for P1 occurs in that N element, and the successful grafting of P1 is described.And the ratio of C:O compare graphene oxide increase to 5.79, illustrate that graphene oxide is reduced to Graphene in course of reaction.
Figure 11 is the FT-IR figure of Graphene modified for P1, with graphene oxide infrared compared with, at 1640cm-1Occur in that the peak of amido link, at 2920cm-1With 2850cm-1Place occurs in that the stretching vibration peak of C-H, and the successful reaction of poly-polypeptide end group amido and chloride Graphene is described, polymer graft is to graphene sheet layer.
Figure 12 is the TGA figure of poly-polypeptide modified graphene, graphene oxide and P1.It can be seen that the thermal weight loss that graphene oxide is at 100 DEG C is physical absorption and by the water of hydrogen bonded.The weightlessness of about 250 DEG C is the thermal weight loss of oxygen-containing functional group.The weightlessness of P1 is at about 300 DEG C.Graphene modified for P1 is weightless fewer at 100 DEG C, the reduction of graphene oxide in course of reaction is described, becomes hydrophobic, and Bound moisture reduces.The thermal weight loss of 250 DEG C also reduces, and also illustrates that oxygen-containing functional group is reduced in building-up process.And also occur in that thermal weight loss at 300 DEG C, for the weightlessness of grafting P1.In sum: the success of P1 is grafted on graphene sheet layer, and in course of reaction, graphene oxide is reduced into Graphene.
Figure 13 is the full spectrogram of XPS of P1 modified graphene.Compared with graphene oxide, occur in that the peak of N at 400eV, the successful grafting of P1 is described.
Figure 14 is the XPS spectrum figure of the C1s of P1 modified graphene.Compared with the C1s spectrogram of graphene oxide, occur in that the peak of C-N at 286.3eV place, the successful reaction of amido and acid chloride groups is described.And the peak area at C-C in P1 modified graphene, C-O, C=O and O-C=O peak compares graphene oxide and all reduces explanation graphene oxide and be reduced to Graphene in the preparation process of polypeptide modified graphene.
Embodiment 2
The synthesis step of the grapheme material of poly-polypeptide (P2) functionalization is as follows:
The synthesis of P2: take 5.9mg(0.1mmol) n-propylamine and 0.3950g(1.5mmol) BLG-NCA is dissolved in the anhydrous DMF of 5ml, react 3 ~ 5 days in a nitrogen environment, last precipitation three times in methanol, vacuum drying obtains P2.GPC and nuclear-magnetism H spectrum and characterizes the characterization of molecules of P2.Figure 15 is the GPC curve of P2, it can be deduced that the weight average molecular weight of P2 is 6400gmol-1, dispersion index is 1.53.Figure 16 is the nuclear-magnetism H spectrogram of P2, is 9 by calculating the degree of polymerization of P2, and number-average molecular weight is 2500gmol-1.The polymer molecular weight information obtained is composed in Table 4. by GPC and nuclear-magnetism H
Table 4, poly-polypeptide P1 characterization of molecules
Sample Mn a gmol-1 Mw b gmol-1 PDIb DPa
P2 2500 6400 1.53 9
aCalculated by nuclear-magnetism result,bDrawn by GPC result.
In the present embodiment except the synthesis of poly-polypeptide P2 is different from embodiment 1, remaining step is identical with embodiment 1.
Figure 10 is P2 modified graphene, Graphene modified for P1 and graphene oxide scatter diagram in toluene, owing to π, π effect strong between Graphene causes that Graphene can not disperse in toluene, and toluene is the good solvent of P2, Graphene modified for P2 is due to the successful grafting of P2, and the interaction between P2 and toluene molecule makes good being dispersed in toluene of Graphene that P2 is modified.
The constituent content of P2 modified graphene in table 5, XPS result
Sample C atom% O atom% N atom% C:O
GO-P2 83.86 15.34 0.80 5.47
In table 5, Graphene modified for P2 occurs in that N element, and the successful grafting of P2 is described.And the ratio of C:O compare graphene oxide increase to 5.47, illustrate that graphene oxide is reduced to Graphene in course of reaction.
Figure 17 is the FT-IR figure of Graphene modified for P2, with graphene oxide infrared compared with, at 1640cm-1Occur in that the peak of amido link, at 2920cm-1With 2850cm-1Place occurs in that the stretching vibration peak of C-H, the successful reaction of poly-polypeptide end group amido and chloride Graphene is described, and polymer graft is to graphene sheet layer.
Figure 18 is the TGA figure of poly-polypeptide modified graphene, graphene oxide and P2.It can be seen that the thermal weight loss that graphene oxide is at 100 DEG C is physical absorption and by the water of hydrogen bonded.The weightlessness of about 250 DEG C is the thermal weight loss of oxygen-containing functional group.The thermal weight loss of P2 is at about 300 DEG C.Graphene modified for P2 is weightless fewer at 100 DEG C, the reduction of graphene oxide in course of reaction is described, becomes hydrophobic, and Bound moisture reduces.The thermal weight loss of 250 DEG C also reduces, and also illustrates that oxygen-containing functional group is reduced in preparation process.And also occur in that thermal weight loss at 300 DEG C, for the weightlessness of grafting P2.In sum: the success of P2 is grafted on graphene sheet layer, and in course of reaction, graphene oxide is reduced into Graphene.
Figure 20 is the full spectrogram of XPS of P2 modified graphene.Compared with graphene oxide, occur in that the peak of N at 400eV, the successful grafting of P2 is described.
Figure 20 is the XPS spectrum figure of the C1s of P2 modified graphene.Compared with the C1s spectrogram of graphene oxide, occur in that the peak of C-N at 286.3eV place, the successful reaction of amido and acid chloride groups is described.And the peak area at C-C in P2 modified graphene, C-O, C=O and O-C=O peak compares graphene oxide and all reduces explanation graphene oxide and be reduced to Graphene in the preparation process of polypeptide modified graphene.
Obviously, the poly benzyl glutamate that the NCA ring-opening polymerisation caused by propylamine is obtained successfully has been grafted on graphene sheet layer, and this is the citing of the method, is not limited to the initiator that uses and poly-polypeptide monomer.The poly-polypeptide that every NCA ring-opening polymerisation caused by amido is obtained all can be applied this method and obtain the Graphene that poly-polypeptide is modified.
Poly-peptide modified Graphene has good dissolution dispersity energy in non-polar organic solvent, adopts solution blended process by by the Graphene modified and poly-polypeptide homopolymer blend, and being added with of functionalization graphene is beneficial to the gelling ability improving poly-polypeptide homopolymer.It is prepared for the functionalization graphene compound organogel of low-solid content.Figure 21 is GO-P1 (wt0.05%)/P1 (wt0.40%) gel photograph formed in toluene and transmission electron microscope photo.
The applied research that the synthetic method of this poly-polypeptide functionalization graphite and the preparation of composite gel material are leavened dough in bio-medical field at functionalization graphene has reference value.

Claims (7)

1. the preparation method of the polypeptide grafted Graphene of functional poly and composite thereof, it is characterized in that, including following step: graphene oxide is carried out chloride, improve the reactivity of graphene oxide, again the poly-polypeptide of the end strips amino obtained by ring-opening polymerisation is mixed with chloride graphene oxide and carry out amidation process and directly obtain poly-peptide modified grapheme material, the Graphene of grafting and modifying and poly-polypeptide homopolymer solution blending, form the Graphene pluralgel of low-solid content.
2. the preparation method of the polypeptide grafted Graphene of functional poly according to claim 1 and composite thereof, it is characterized in that: the preparation of chloride Graphene: weigh the graphene oxide of 1 part by weight, by volume number weighs the thionyl chloride of 20 parts and the anhydrous DMF (DMF) of 1 part;Use ultrasonic agitation method to be dispersed in 1 part of dry DMF by 1 part of graphene oxide, add 20 parts of thionyl chlorides;Back flow reaction 24h under 70 DEG C of conditions;It is centrifuged when 6000 ~ 8000rmp by dry DMF, washs and obtain chloride Graphene (acyl chloride reaction can improve follow-up amidation process activity, graphene oxide is reduced simultaneously) for three times.
3. the preparation method of the polypeptide grafted Graphene of functional poly according to claim 1 and composite thereof, it is characterised in that: poly-polypeptide can select the multiple poly-polypeptide homopolymer and copolymer that can be obtained by NCA ring-opening polymerisation;Preferred poly benzyl glutamate is as the poly-polypeptide of reaction, its preparation method: monomer is Pidolidone γ-benzyl ester-N-carboxylic acid anhydrides (BLG-NCA), a certain proportion of primary amine class initiator and monomer is weighed by molfraction, by volume number weighs the dry DMF of 5 parts, under normal temperature condition, reacting 3 ~ 5 days when nitrogen atmosphere, precipitate three times in methanol or ether, vacuum drying obtains the poly benzyl glutamate with amino.
4. the preparation method of the polypeptide grafted Graphene of functional poly according to claim 1 and composite thereof, it is characterised in that: by the poly-polypeptide grafted grapheme material of graft-to method preparation: weigh 1 part of chloride Graphene and 20 parts of poly-polypeptide by weight;By volume number weighs 25 parts of dry DMF and 1 part of anhydrous triethylamine;First, at 0 ~ 5 DEG C, anhydrous triethylamine is joined in chloride Graphene, dry DMF and poly-polypeptide mixed solution, stir, under 50 DEG C of conditions, then react 24h, finally obtain for three times gathering polypeptide functionalization graphene with DMF centrifugal, washing under 6000 ~ 8000rmp.
5. the preparation method of the polypeptide grafted Graphene of functional poly and composite thereof according to claim 1, it is characterised in that: product has good dissolution dispersity energy in toluene, the organic solvent such as dichloromethane.
6. the preparation method of the polypeptide grafted Graphene of functional poly and composite thereof according to claim 1, it is characterised in that: disperse blend method to prepare composite to functionalization graphene is blended with the dispersion of homopolymer solution by solution.
7. the preparation method of the polypeptide grafted Graphene of functional poly and composite thereof according to claim 1, it is characterized in that: the composite that according to claim 7 prepared by solution blending process gathers peptide modified Graphene at 0.05wt% and under the poly-polypeptide homopolymer mixed proportion of 0.45wt%, forms the Graphene composite gel material of low-solid content.
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