CN104499093A - Preparation method of dipeptide derivative Fmoc-FF self-assembly fiber by graphene oxide regulation - Google Patents
Preparation method of dipeptide derivative Fmoc-FF self-assembly fiber by graphene oxide regulation Download PDFInfo
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Abstract
The invention relates to a preparation method of a dipeptide derivative Fmoc-FF self-assembly fiber by graphene oxide regulation. The method includes the steps of: preparing GO; dissolving the GO in deionized water to obtain a GO solution; adding and dissolving a dipeptide derivative Fmoc-FF into HFIP to obtain a Fmoc-FF solution; rapidly dropwise adding the Fmoc-FF solution into the GO solution or adding the GO solution to the Fmoc-FF solution, oscillating and mixing to obtain a mixed system of Fmoc-FF and GO; and well mixing, immediately absorbing and dropwise adding the mixed solution onto a clean silica sheet, and drying respectively at room temperature and 60 DEG C. The method provided by the invention has simple, convenient for operation and obvious in effect; the preparation technology of the used GO is mature, has high yield, and realizes good biocompatibility; and the prepared Fmoc-FF / GO composite has wide potential application in biological materials and super capacitor.
Description
Technical field
The invention belongs to dipeptidase derivant Fmoc-FF field, particularly the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control.
Background technology
Polypeptide relates to the bioactivator of various cell function in organism, is the compounds between protein and amino acid, by multiple according to specifically putting in order and being linked together by peptide bond and formed.Self-assembling polypeptide refers to that the class formation formed by non-covalent interaction spontaneous combination between amino acid residue is under proper condition clear and definite, construction of stable, the molecule aggregate with certain physicochemical property or supramolecular structure.Because polypeptide to be formed by peptide linkage according to certain putting in order by several amino acids, segment upper amino acid residue has different chemical constitutions, polypeptide can utilize the hydrogen bond action between hydrogen bond action between its peptide bond and amino acid residue, electrostatic interaction, hydrophobicity effect and pi-pi accumulation effect etc. effectively realize molecular self-assembling, form nanofiber network, nanometer rods, Nano microsphere, and nanotube etc.In addition, polypeptide relates to the bioactivator of various cell function in organism, has extraordinary degradability, biocompatibility, and polypeptide is human body regulation and control activity, carries out the important substance of metabolism.Therefore, the self assembly of polypeptide in recent years becomes the study hotspot in the field such as materialogy and biomedicine gradually.Utilize the various functional materials of self-assembling polypeptide technique construction also in the fields such as drug controlled release, tissue engineering bracket material and biomineralization, to present distinctive advantage, have huge application prospect.
Up to the present, people study the more polypeptide with self assembly ability and mainly contain cationic polypeptide, Amphiphilic peptide, ring type polypeptide, aroma type polypeptide etc.Except natural polypeptides, people are also studying some Prof. Du Yucang and manually modified polypeptide, such as, and the polypeptide that dendritic macromole is modified, the polypeptide of the polypeptide that organic long-chain is modified and specific functional groups structural modification.Wherein, the polypeptide modified with 9-fluorenylmethyloxycarbonyl (Fmoc-) has shown good flexibility and application prospect in self assembly field in recent years; be subject to people's attention (9-fluorenylmethyloxycarbonyl (Fmoc-) in artificial synthetic polypeptide process through being often used as amino protecting group, the intermediate as oligopeptides building-up process).And, since the self assembly ability that Late Cambrian Fmoc-FF in 2005 is good, cause numerous researchers' interest.Someone have studied the self assembly performance of the various oligopeptides that Fmoc-modifies again in succession, comprise Fmoc-FRGD, Fmoc-GF, Fmoc-FGDF, Fmoc-FP, Fmoc-FS etc., found that, compare the self-assembly of oligopeptides, the self-assembling polypeptide material modified through Fmoc-has fine biocompatibility equally, and self-assembly form is abundanter.But merely utilize Fmoc-oligopeptides to carry out self assembly and still can not meet the demand of people for special material, therefore, also need to utilize the assembling of better material to Fmoc-oligopeptides to regulate and control.
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbit composition hexangle type is the flat film of honeycomb lattice arrangement, is the two-dimensional material only having a carbon atom thickness, by Andre Geim and Konstantin Novoselov Late Cambrian.Graphene is also the thinnest, the hardest, the material that resistivity is minimum that find of the mankind so far, and its application in electronic device, supercomputer, solar cell, photon sensor etc. is also launching gradually.Along with going deep into of research, it is found that, the Graphene (GO) of oxidation state is due to the existence of the group such as carbonyl, hydroxyl, there is better activity, therefore, the research of Graphene, graphene oxide is more and more abundanter, no matter be its preparation method, dispersion or carry out compound with other materials.
Summary of the invention
Technical problem to be solved by this invention is to provide the method that dipeptidase derivant Fmoc-FF self assembly fiber is prepared in the regulation and control of a kind of graphene oxide, and the method is simple, easy to operate, successful; The GO technology of preparing used is ripe, and output is high, and Biocompatibility is good; The Fmoc-FF/GO composite of preparation has potential application widely in biomaterial, ultracapacitor etc.
The method of dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control of the present invention, comprising:
(1) GO is prepared; Be dissolved in deionized water by ultrasonic for GO, by the suspension GO of the large lamella of centrifugal removing, obtain GO solution; Dipeptidase derivant Fmoc-FF (nine fluorenylmethyloxycarbonyl-two phenylalanines, are purchased from Bachem company of Switzerland) is joined in HFIP, dissolves, obtain Fmoc-FF solution;
(2) added by Fmoc-FF solution and join in Fmoc-FF solution in GO solution or by GO solution, concussion, mixing, obtains the mixed system of Fmoc-FF and GO; Mixed system is added drop-wise on silica thin slice, dry under room temperature or 60 DEG C of environment, obtain dipeptidase derivant Fmoc-FF self assembly fiber.
In described step (1), the technique of preparation GO is specially:
Prepare GO by the Hummers method improved, method is as follows:
A. pre-oxidation
1. 12 ~ 18g K is taken
2s
2o
8with 12 ~ 18g P
2o
5join in 500ml round-bottomed flask successively,
2. round-bottomed flask is put into 80 DEG C of water-baths,
3. measure 70 ~ 80ml sulfuric acid and join round-bottomed flask,
4. stir 20 ~ 30min, become clear to solution,
5. under safeguard procedures, 20g Graphene is added to round-bottomed flask,
6. under 80 DEG C of conditions, 4.5h is stirred,
7. take out round-bottomed flask, natural cooling number minute, then black mixture joined the conical flask of 2L,
8. add deionized water, by volume constant volume to 2L, and collect solid product by Vacuum filtration device,
And with the continuous drip washing solid product of deionized water, check pH value 9., until pH value is to about 5,
10. product drying is spent the night.
B. be oxidized
1. in 2L conical flask, 740 ~ 760ml sulfuric acid is added,
2. stir in frozen water, until temperature arrives 5 DEG C,
3. the Graphene of pre-oxidation is joined in flask, and is stirred to powder and disperses completely,
4. in flask, 100g KMnO is added
4,
5. flask is transferred in the water-bath of 35 DEG C, and keeps 3h to stir,
6. flask is transferred in ice-water bath, under stirring, cools the temperature to about 10 DEG C,
7. in 3h, slowly add 1L deionized water, the incipient stage is especially a small amount of at a slow speed
8. mixed liquor is on average assigned in the conical flask of another 2L, and with deionized water by solution dilution in each flask to 2L,
9. ring slowly adds 40 ~ 45ml H in each flask under agitation
2o
2, and leave standstill 30min,
10. close stirring, shift out bar magnet, hold over night.
C. sour purifying
1. slowly supernatant is leached,
2. with hydrophilic polytetrafluoroethylmicroporous membrane filtration remaining mixture, solid product is collected,
3. be the hydrochloric acid of 100ml:1L and the solution drip washing of deionized water by proportioning, purified product, and the bottom of collecting product is constantly stirred with glass bar, repeat 6 cycles, each cycle 1 ~ 2h,
4. after drip washing completes, by product drying 1 ~ 2h, collection desciccate is kept at and fills P
2o
5drying wherein, stay standby rear use.
Ultrasonic time in described step (1) is 5-15min, and power-frequency is 40KHz.
Centrifugation rate in described step (1) is 3000rpm, and centrifugation time is 10min.
GO solution concentration in described step (1) is 0.01 ~ 0.03wt%.
The proportioning of Fmoc-FF and HFIP in described step (1) is 6 ~ 12mg:120 μ l.
GO solution in described step (2) and the volume ratio of Fmoc-FF solution are 2ml:40-60 μ l.
Concussion mode in described step (2) is the concussion of whirlpool concussion instrument, and the concussion time is 30 ~ 60s, and rotating speed is 2000rpm/min.
The present invention has good pliability in view of graphene oxide sheet layer material, and be rich in carbonyl, hydroxyl, carboxyl isoreactivity functional group, can form a large amount of avtive spot, energy and Fmoc-FF polypeptide form the π-π interaction equimolecular intermolecular forces between hydrogen bond, Van der Waals force and class phenyl ring.By changing action condition, the self assembly situation of regulation and control Fmoc-FF in Graphene dicyandiamide solution, obtain the self-assembling polypeptide material of combining form different from Graphene, simultaneously by the mechanical performance of Graphene excellence, outstanding chemical property and good biocompatibility, improve intensity and the conductive characteristic thereof of self-assembling polypeptide material, expand its application in biomaterial and ultracapacitor.
Under the regulation and control of graphene oxide, dipeptidase derivant Fmoc-FF can be self-assembled into according to the control of the addition sequence of Graphene and temperature the structure come in every shape at silica surface, the difference of front and back and addition sequence is added on the impact of Fmoc-FF self-assembled material performance by contrast Graphene, overall merit Graphene is on the impact of Fmoc-FF self assembly, according to the difference of self-assembled material, its using value in biomaterial, ultracapacitor etc. can be studied further, therefore there is important significance of scientific research and using value.
beneficial effect
(1) the present invention relates to method simple, easy and simple to handle, successful;
(2) graphene oxide of the present invention's use, there is excellent mechanical performance, outstanding chemical property and good biocompatibility, by controlled condition parameter, prepare the composite of different combining form, for polypeptide provides reference in the application in the field such as biomaterial and ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the structural formula of Fmoc-FF;
Fig. 2 is transmission electron microscope (TEM) photo of GO;
Fig. 3 be Fmoc-FF be subject to Graphene regulate and control before and after at room temperature and 60 DEG C at the ESEM structure chart of silica surface self-assembled material; Under wherein a and b represents respectively and does not add Graphene situation, Fmoc-FF at room temperature and 60 DEG C at the self-assembled structures figure of silica surface; After c and d represents graphene solution is added Fmoc-FF solution, Fmoc-FF at room temperature and 60 DEG C at the self-assembled structures figure of silica surface; After e and f represents Fmoc-FF solution is added graphene solution, Fmoc-FF at room temperature and 60 DEG C at the self-assembled structures figure of silica surface.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) prepare GO by Hummers method, method is as follows:
A. pre-oxidation
1. 12 ~ 18g K is taken
2s
2o
8with 12 ~ 18g P
2o
5join in 500ml round-bottomed flask successively,
2. round-bottomed flask is put into 80 DEG C of water-baths,
3. measure 70 ~ 80ml sulfuric acid and join round-bottomed flask,
4. stir 20 ~ 30min, become clear to solution,
5. under safeguard procedures, 20g Graphene is added to round-bottomed flask,
6. under 80 DEG C of conditions, 4.5h is stirred,
7. take out round-bottomed flask, natural cooling number minute, then black mixture joined the conical flask of 2L,
8. add deionized water, by volume constant volume to 2L, and collect solid product by Vacuum filtration device,
And with the continuous drip washing solid product of deionized water, check pH value 9., until pH value is to about 5,
10. product drying is spent the night.
B. be oxidized
1. in 2L conical flask, 740 ~ 760ml sulfuric acid is added,
2. stir in frozen water, until temperature arrives 5 DEG C,
3. the Graphene of pre-oxidation is joined in flask, and is stirred to powder and disperses completely,
4. in flask, 100g KMnO is added
4,
5. flask is transferred in the water-bath of 35 DEG C, and keeps 3h to stir,
6. flask is transferred in ice-water bath, under stirring, cools the temperature to about 10 DEG C,
7. in 3h, slowly add 1L deionized water, the incipient stage is especially a small amount of at a slow speed
8. mixed liquor is on average assigned in the conical flask of another 2L, and with deionized water by solution dilution in each flask to 2L,
9. ring slowly adds 40 ~ 45ml H in each flask under agitation
2o
2, and leave standstill 30min,
10. close stirring, shift out bar magnet, hold over night.
C. sour purifying
1. slowly supernatant is leached,
2. with hydrophilic polytetrafluoroethylmicroporous membrane filtration remaining mixture, solid product is collected,
3. be the hydrochloric acid of 100ml:1L and the solution drip washing of deionized water by proportioning, purified product, and the bottom of collecting product is constantly stirred with glass bar, repeat 6 cycles, each cycle 1 ~ 2h,
4. after drip washing completes, by product drying 1 ~ 2h, collection desciccate is kept at and fills P
2o
5drying wherein, stay standby rear use.(2) GO is dissolved in deionized water by Ultrasound Instrument, and ultrasonic time is 5min, and power-frequency is 40KHz, removes large lamella suspension GO by centrifugal process (3000rpm, 10min), obtains the GO solution that concentration is 0.01wt%;
(3) Fmoc-FF solution is prepared; Taking Fmoc-FF joins in HFIP, and dissolve, obtain Fmoc-FF solution, wherein the proportioning of Fmoc-FF and HFIP is 50mg:1ml;
(4) Fmoc-FF solution is added drop-wise to rapidly in GO solution, and concussion (concussion of whirlpool concussion instrument, the concussion time is 30s, rotating speed is 2000rpm/min), mixing, obtains GO/Fmoc-FF mixed system, wherein the volume ratio 20 μ l of Fmoc-FF solution and GO; 1ml;
(5) draw above-mentioned solution before system gelation to be mixed to be immediately added drop-wise on clean silica glass dish, drier under respectively sample being positioned over room temperature and 60 DEG C of environment.
Embodiment 2
(1) GO is prepared by Hummers method, with embodiment 1;
(2) be dissolved in deionized water by Ultrasound Instrument by GO, ultrasonic time is 15min, and power-frequency is 40KHz, removes large lamella suspension GO by centrifugal process (3000rpm, 10min), obtains the GO solution that concentration is 0.03%;
(3) Fmoc-FF solution is prepared.Taking Fmoc-FF joins in HFIP, and dissolve, obtain Fmoc-FF solution, wherein the proportioning of Fmoc-FF and HFIP is 100mg:1ml;
(4) GO solution is added drop-wise to rapidly in Fmoc-FF solution, and concussion (concussion of whirlpool concussion instrument, the concussion time is 60s, rotating speed is 2000rpm/min), mixing, obtains Fmoc-FF/GO mixed system, wherein the volume ratio 30 μ l of Fmoc-FF solution and GO; 1ml;
(5) draw above-mentioned solution before system gelation to be mixed to be immediately added drop-wise on clean silica glass dish, drier under respectively sample being positioned over room temperature and 60 DEG C of environment.
Comparative example
(1) Fmoc-FF solution is prepared.Taking Fmoc-FF joins in hexafluoroisopropanol (HFIP), and dissolve, obtain Fmoc-FF solution, wherein the proportioning of Fmoc-FF and HFIP is 50mg:1ml;
(2) be added drop-wise to rapidly in deionized water by Fmoc-FF solution, concussion, mixing, obtains Fmoc-FF-deionized water system, wherein the volume ratio 10 μ l of Fmoc-FF solution and deionized water; 1ml;
(3) draw appropriate above-mentioned solution before system gelation to be mixed to be immediately added drop-wise on clean silica glass dish, drier under respectively sample being positioned over room temperature and 60 DEG C of environment.
Claims (7)
1. a method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in graphene oxide regulation and control, comprising:
(1) GO is prepared; Be dissolved in deionized water by ultrasonic for GO, by the suspension GO of the large lamella of centrifugal removing, obtain GO solution;
Dipeptidase derivant Fmoc-FF is joined in HFIP, dissolves, obtain Fmoc-FF solution;
(2) added by Fmoc-FF solution and join in Fmoc-FF solution in GO solution or by GO solution, concussion, mixing, obtains the mixed system of Fmoc-FF and GO; Mixed system is added drop-wise on silica thin slice, dry under room temperature or 60 DEG C of environment, obtain dipeptidase derivant Fmoc-FF self assembly fiber.
2. the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control according to claim 1, and it is characterized in that: the ultrasonic time in described step (1) is 5-15min, power-frequency is 40KHz.
3. the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control according to claim 1, and it is characterized in that: the centrifugation rate in described step (1) is 3000rpm, centrifugation time is 10min.
4. the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control according to claim 1, it is characterized in that: the GO solution concentration in described step (1) is 0.01 ~ 0.03wt%.
5. the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control according to claim 1, it is characterized in that: the proportioning of Fmoc-FF and HFIP in described step (1) is 6 ~ 12mg:120 μ l.
6. the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control according to claim 1, it is characterized in that: the GO solution in described step (2) and the volume ratio of Fmoc-FF solution are 2ml:40-60 μ l.
7. the method for dipeptidase derivant Fmoc-FF self assembly fiber is prepared in a kind of graphene oxide regulation and control according to claim 1, it is characterized in that: the concussion mode in described step (2) is the concussion of whirlpool concussion instrument, the concussion time is 30 ~ 60s, and rotating speed is 2000rpm/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109239345A (en) * | 2018-08-20 | 2019-01-18 | 中国科学院苏州生物医学工程技术研究所 | Prostate specific antigen detection method based on graphene complex |
| CN114062467A (en) * | 2021-09-13 | 2022-02-18 | 浙江大学 | Flexible electronic skin based on peptide self-assembly supermolecule hydrogel and preparation method thereof |
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2014
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109239345A (en) * | 2018-08-20 | 2019-01-18 | 中国科学院苏州生物医学工程技术研究所 | Prostate specific antigen detection method based on graphene complex |
| CN114062467A (en) * | 2021-09-13 | 2022-02-18 | 浙江大学 | Flexible electronic skin based on peptide self-assembly supermolecule hydrogel and preparation method thereof |
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