CN107099046A - A kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers - Google Patents
A kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers Download PDFInfo
- Publication number
- CN107099046A CN107099046A CN201710274918.9A CN201710274918A CN107099046A CN 107099046 A CN107099046 A CN 107099046A CN 201710274918 A CN201710274918 A CN 201710274918A CN 107099046 A CN107099046 A CN 107099046A
- Authority
- CN
- China
- Prior art keywords
- fibroin
- biomimetic mineralization
- silk
- hydroxyl group
- phenolic hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Cosmetics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers, carboxylic acid containing vinyl and phenolic hydroxyl group is first grafted in fibroin macromolecular by carbodiimide (EDC) and N HOSu NHSs (NHS), again by horseradish peroxidase enzyme catalytic modified fibroin and acrylic monomers graft copolymerization, fibroin base biomimetic mineralization material is prepared.Comprise the following steps that：(1) preparation of silk fibroin protein solution；(2) carboxylic acid of the EDC/NHS methods grafting containing vinyl and phenolic hydroxyl group；(3) horseradish peroxidase enzyme catalytic fibroin and acrylic graft copolymer；(4) shaping of fibroin membrane material；(5) prepared by fibroin base biomimetic mineralization material.With triggering fibroin compared with acrylic monomers graft copolymerization using conventional methods such as chemical method or Ultraviolet irradiation methods, the enzymatic fibroin that the present invention is addressed and acrylic graft copolymer efficiency high, treatment conditions relax, and the fibroin base biomimetic mineralization material property of preparation is excellent.
Description
Technical field
The present invention relates to a kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers, it is characterized in that
First be grafted the carboxylic acid containing vinyl and phenolic hydroxyl group in fibroin macromolecular, then by horseradish peroxidase enzyme catalytic modified fibroin with
Acrylic monomers graft copolymerization, prepares fibroin base biomimetic mineralization material, belongs to field of textile biotechnology.
Background technology
Fibroin albumen is the main component of silk, is made up of 18 kinds of amino acid, wherein most aminoacetic acid relatively low for polarity
With alanine segment, remaining is then mainly made up of polar amino acid residues.Fibroin albumen has good biocompatibility and ring
Border friendly, the regrown material processed with fibroin albumen has the features such as nontoxic, nonirritant, hygroscopicity is excellent.Fibroin fiber
After calcium salt or the processing of lithium salts and its alcoholic solution, dissolving and partial hydrolysis occur for fibroin albumen macromolecular, and desalination is removed by dialysis
Ion, can obtain silk fibroin protein solution.The performance of fibroin base biomaterial has larger correlation with its molecular weight.Molecular weight compared with
Big fibroin albumen can dramatically increase the mechanical property of material, but because elecrtonegativity carboxyl-content is less, the silk in biomimetic mineralization
Element declines to calcium ion complexing power, have impact on the formation of hydroxyapatite and the preparation of fibroin base biomimetic mineralization material.Therewith
Compare, carboxyl-content is more in the less fibroin molecule of molecular weight, stronger to calcium ion complexing power in biomimetic mineralization, is conducive to
The synthos structures such as hydroxyapatite are formed, biomimetic mineralization effect are lifted, it, which has the disadvantage that fibroin molecular weight is too low, can influence silk
The mechanical property of plain base regrown material.Research shows, fibroin albumen and propylene are triggered using persulfate or ultraviolet light irradiation etc.
Sour graft copolymerization, or directly polyacrylic acid and fibroin albumen are blended, it can increase the elecrtonegativity on fibroin sill surface, and then
The biomimetic mineralization effect of fibroin albumen can be improved.
Horseradish peroxidase (HRP) has very strong catalytic activity, with hydrogen peroxide (H2O2) it is oxidant, acetylacetone,2,4-pentanedione
(ACAC) for acrylic acid (AA) polymerization in the system of initiator, can be catalyzed, polyacrylic acid (PAA) is formed.In addition, fibroin albumen
(SF) in contain a number of tyrosine residue, HRP can also catalytic tyrosine phenolic hydroxyl group produce Phenoxy radical, trigger silk
Element and acrylic graft copolymer, form fibroin/acrylic acid composite (SF-g-PAA), and this is the fibroin grafting third based on enzyme process
Olefin(e) acid is modified processing there is provided possible.By HRP enzymic catalytic reactions, more elecrtonegativity carboxylic acid group can be introduced on fibroin surface
To the complexing of calcium ion in group, enhancing biomimetic mineralization, the biomimetic mineralization effect of fibroin albumen is lifted.On the other hand, although
HRP can be catalyzed tyrosine residue in fibroin and produce Phenoxy radical, trigger and carry out graft copolymerization with acrylic monomers, but due to silk
Accessibility is relatively low in tyrosine residue negligible amounts or enzymatic reaction on fibroin, difficult with the efficient graft copolymerization of acrylic monomers,
So that the carboxyl quantity increase on fibroin surface is less after reaction, the preparation of fibroin base biomimetic mineralization material have impact on.
To solve this problem, the present invention carries out fibroin albumen modification, the first step using two step method first：By in fibroin egg
White surface introduces vinyl and more phenolic hydroxyl groups, improves the enzymic catalytic reaction of fibroin, specific practice is by carbodiimide
(EDC) and n-hydroxysuccinimide (NHS), by the carboxylic acid graft containing vinyl and phenolic hydroxyl group to fibroin albumen, with fibroin
Molecule formation amido link；Second step：The vinyl introduced with horseradish peroxidase enzyme catalytic fibroin albumen surface, is produced freely
Base, and occur graft copolymerization with the acrylic monomers of addition；During this, horseradish peroxidase is also catalyzed in fibroin simultaneously
The phenolic hydroxyl group that tyrosine residue and fibroin surface are introduced, produces more active Phenoxy radical, can be also grafted with acrylic monomers
The grafting rate and hydroxy-acid group number of acrylic acid, improve the biomimetic mineralization performance of fibroin albumen on copolymerization, increase fibroin albumen.Fibroin
Albumen is modified through above-mentioned two step method, then carries out fibroin membrane shaping, finally carries out fibroin base biomimetic mineralization material and prepares.
The content of the invention
The technical problems to be solved by the invention are to provide one kind and prepare the bionical ore deposit of fibroin base by grafting vinyl monomers
Change the method for material, it is intended to by fibroin and acrylic graft copolymer, increase elecrtonegativity carboxyl quantity in fibroin albumen, improve silk
The biomimetic mineralization effect of element.
In order to solve the above technical problems, the technical solution adopted by the present invention：Fibroin modification first is carried out by EDC and NHS, will
Carboxylic acid graft containing vinyl and phenolic hydroxyl group improves the reactivity of fibroin albumen in fibroin macromolecular；Again by horseradish peroxide
Compound enzymatic modified fibroin and acrylic monomers graft copolymerization, prepare fibroin base biomimetic mineralization material, concrete technology and step
It is as follows：
(1) preparation of silk fibroin protein solution：With the silk after lithium bromide or calcium chloride dissolving degumming, fibroin albumen is prepared molten
Liquid；
Handling process prescription and condition：In the ethanol solution that silk after degumming is added to lithium bromide or calcium chloride,
Then 50~80 DEG C of stirrings are dialysed 24~48 hours to dissolving with deionized water, and it is 10~40g/L silk fibroin solutions that concentration, which is made,；
(2) carboxylic acid of the EDC/NHS methods grafting containing vinyl and phenolic hydroxyl group：In the silk fibroin solution of step (1) add EDC,
NHS, the carboxylic acid processing containing vinyl and phenolic hydroxyl group, introduce vinyl and phenolic hydroxyl group on fibroin；
Handling process prescription and condition：EDC 1~10g/L of 1~10g/L, NHS, the carboxylic acid containing vinyl and phenolic hydroxyl group
0.2~5g/L, 20~30 DEG C of temperature, pH 4.5~7,0.5~24 hour processing time；
(3) horseradish peroxidase enzyme catalytic fibroin and acrylic graft copolymer：In the silk fibroin solution of step (2), addition
Horseradish peroxidase, acetylacetone,2,4-pentanedione and acrylic acid, add hydrogen peroxide under nitrogen protection, promote fibroin with it is acrylic acid-grafted common
It is poly-；
Handling process prescription and condition：2~20U/mL of horseradish peroxidase, 5~10g/L of acetylacetone,2,4-pentanedione, hydrogen peroxide 5~
20g/L, 5~25g/L of acrylic acid, 20~45 DEG C of temperature, pH 6.0~8.0,0.5~15 hour processing time；
(4) shaping of fibroin membrane material：Step (3) reacted silk fibroin solution is freezed under the conditions of -50 DEG C~-20 DEG C
Drying and forming-film；Then fibroin membrane is impregnated 0.25~1 hour in 50~80% ethanol solutions, in 30 DEG C of drying after washing；
(5) prepared by fibroin base biomimetic mineralization material：Fibroin membrane after step (4) processing is immersed in 10~50mmol/L chlorinations
In calcium solution, handled 0.5~24 hour at 37 DEG C, carry out pre-calcification；Then fibroin membrane is immersed in 1.5 times of SBF analogue bodies again
In liquid, a simulated body fluid is changed in biomimetic mineralization 1~7 day under the conditions of 37 DEG C during which daily；Finally cleaned with deionized water,
It is freeze-dried again under the conditions of -50~-20 DEG C, obtains fibroin base biomimetic mineralization material.
A kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers, it is described to contain vinyl and phenol hydroxyl
The carboxylic acid of base includes caffeic acid, forulic acid, chlorogenic acid；The horseradish peroxidase derives from animal, plant or microorganism.
The present invention, in carboxylic acid of the fibroin albumen surface grafting containing vinyl and phenolic hydroxyl group, is added by means of EDC/NHS methods
Acrylic monomers, by horseradish peroxidase enzyme catalytic fibroin and acrylic graft copolymer, prepares fibroin base biomimetic mineralization material.
With triggering fibroin compared with vinyl monomer graft copolymerization using the conventional method such as chemical method or Ultraviolet irradiation method, the present invention have with
Lower advantage：
(1) graft copolymerization efficiency high, introduces vinyl and phenolic hydroxyl group using EDC/NHS methods on fibroin, improves horseradish
Catalyzed Synthesis By Peroxidase fibroin carries out the efficiency of graft copolymerization with acrylic acid；
(2) ferment treatment condition relaxes, under low temperature and near-neutral sulfite deinking, is grafted altogether by means of horseradish peroxidase enzyme catalytic
It is poly-, have the advantages that energy consumption is low, handling process is safe, it is to avoid chemical method or Ultraviolet irradiation method graft copolymerization are also easy to produce fibroin change
The defects such as property；
(3) biomimetic mineralization material property is excellent, addresses method catalysis fibroin grafted propylene acid with the present invention, adds to calcium
Ion complexation ability, enhances fibroin biomimetic mineralization effect；EDC/NHS processing can also promote crosslinking between fibroin albumen macromolecular,
Also the mechanical property of fibroin base biomimetic mineralization material is improved.
Embodiment
Using EDC/NHS activation systems, be grafted the carboxylic acid containing vinyl on fibroin, recycle horseradish peroxidase/
Hydrogen peroxide/acetylacetone,2,4-pentanedione system catalysis fibroin and acrylic graft copolymer, prepare fibroin base biomimetic mineralization material, specific embodiment
It is as follows：
Embodiment 1
Fibroin base biomimetic mineralization material is prepared in the method that the present invention is addressed, concrete technology step is as follows：
(1) preparation of silk fibroin protein solution：In the ethanol solution that silk after degumming is added to lithium bromide or calcium chloride,
In 70 DEG C of stirrings to dissolving, then dialysed 24 hours with deionized water, 20g/L silk fibroin protein solutions are made；
(2) carboxylic acid of the EDC/NHS methods grafting containing vinyl and phenolic hydroxyl group：In the silk fibroin solution of step (1) add EDC,
NHS and coffee acid treatment, wherein EDC 3g/L, NHS 2g/L, caffeic acid 2g/L, 25 DEG C of temperature, pH 5.5, processing time 12 is small
When；
(3) horseradish peroxidase enzyme catalytic fibroin and acrylic graft copolymer：In the silk fibroin solution of step (2), addition
Horseradish peroxidase, acetylacetone,2,4-pentanedione and acrylic acid, add hydrogen peroxide under nitrogen protection, promote fibroin with it is acrylic acid-grafted common
It is poly-；Wherein horseradish peroxidase 5.5U/mL, acetylacetone,2,4-pentanedione 5g/L, hydrogen peroxide 6g/L, acrylic acid 10g/L, 30 DEG C of temperature, pH
7.0,8 hours processing times；
(4) shaping of fibroin membrane material：Step (3) reacted solution is freeze-dried film forming at -50 DEG C；Then by silk
Plain membrane material impregnates 0.5 hour in 70% ethanol solution, in 30 DEG C of drying after washing；
(5) prepared by fibroin base biomimetic mineralization material：Fibroin membrane after step (4) processing is immersed in 20mmol/L calcium chloride molten
In liquid, handled 6 hours at 37 DEG C, carry out pre-calcification；Then fibroin membrane is immersed in 1.5 times of SBF simulated body fluids again, at 37 DEG C
Under the conditions of biomimetic mineralization 6 days, a simulated body fluid is during which changed daily；Finally cleaned with deionized water, under the conditions of -50 DEG C again
Secondary freeze-drying, obtains fibroin base biomimetic mineralization material.
Sample 1：Through step (1), (4), (5) processing, handled without step (2), (3)；
Sample 2：Handle, handled without step (2) through step (1), (3), (4) and (5)；
Sample 3：Handled through step (1), (2), (3), (4) and (5)；
After above-mentioned PROCESS FOR TREATMENT, the surface calcium of sample 1, phosphorus content are respectively 13.5% and 9.8%, and modulus of elasticity is
8.3MPa；The surface calcium of sample 2, phosphorus content are respectively 15.1% and 11.6%, and modulus of elasticity is 9.0MPa；The surface calcium of sample 3, phosphorus
Content is respectively 18.9% and 14.2%, and modulus of elasticity is 12.1MPa.
Embodiment 2
Fibroin base biomimetic mineralization material is prepared in the method that the present invention is addressed, concrete technology step is as follows：
(1) preparation of silk fibroin protein solution：In the ethanol solution that silk after degumming is added to lithium bromide or calcium chloride,
In 70 DEG C of stirrings to dissolving, then dialysed 36 hours with deionized water, 25g/L silk fibroin protein solutions are made；
(2) carboxylic acid of the EDC/NHS methods grafting containing vinyl and phenolic hydroxyl group：In the silk fibroin solution of step (1) add EDC,
NHS and asafoetide acid treatment, wherein EDC 5g/L, NHS 4g/L, forulic acid 4g/L, 25 DEG C of temperature, pH 5.75, processing time 18
Hour；
(3) horseradish peroxidase enzyme catalytic fibroin and acrylic graft copolymer：In the silk fibroin solution of step (2), addition
Horseradish peroxidase, acetylacetone,2,4-pentanedione and acrylic acid, add hydrogen peroxide under nitrogen protection, promote fibroin with it is acrylic acid-grafted common
It is poly-；Wherein horseradish peroxidase 10U/mL, acetylacetone,2,4-pentanedione 6g/L, hydrogen peroxide 7.5g/L, acrylic acid 15g/L, 30 DEG C of temperature, pH
7.5,12 hours processing times；
(4) shaping of fibroin membrane material：Step (3) reacted solution is freeze-dried film forming at -50 DEG C；Then by silk
Plain membrane material impregnates 1 hour in 75% ethanol solution, in 30 DEG C of drying after washing；
(5) prepared by fibroin base biomimetic mineralization material：Fibroin membrane after step (4) processing is immersed in 40mmol/L calcium chloride molten
In liquid, handled 24 hours at 37 DEG C, carry out pre-calcification；Then fibroin membrane is immersed in 1.5 times of SBF simulated body fluids again, 37
Biomimetic mineralization 7 days under the conditions of DEG C, during which change a simulated body fluid daily；Finally cleaned with deionized water, under the conditions of -50 DEG C
It is freeze-dried again, obtains fibroin base biomimetic mineralization material.
Sample 4：Through step (1), (4), (5) processing, handled without step (2), (3)；
Sample 5：Handle, handled without step (2) through step (1), (3), (4) and (5)；
Sample 6：Handled through step (1), (2), (3), (4) and (5)；
After above-mentioned PROCESS FOR TREATMENT, the surface calcium of sample 4, phosphorus content are respectively 12.1% and 10.1%, and modulus of elasticity is
9.5MPa；The surface calcium of sample 5, phosphorus content are respectively 14.7% and 11.6%, and modulus of elasticity is 10.9MPa；The surface calcium of sample 6,
Phosphorus content is respectively 19.7% and 15.2%, and modulus of elasticity is 15.6MPa.
By to embodiment data analysis：With without fibroin graft modification, directly carry out fibroin film preparation and biomimetic mineralization
Material (sample 1, sample 4) compare, fibroin base biomimetic mineralization material (sample 3, the sample prepared in the method addressed of the present invention
6) modulus of elasticity substantially increases, and material surface calcium and phosphorus content are higher, shows to obtain preferable remineralization efficacy.With without step
(2) obtained fibroin base biomimetic mineralization material after the processing of EDC/NHS methods, directly progress enzymatic fibroin and acrylic graft copolymer
(sample 2, sample 5) is compared, fibroin base biomimetic mineralization material (sample 3, sample 6) elasticity prepared by the method addressed with the present invention
Modulus increase is more, and mechanical property is significantly improved, and biomimetic mineralization effect is more preferable.As can be seen here, the method addressed with the present invention
Preparing fibroin base biomimetic mineralization material has preferable performance.
Although the present invention is disclosed as above with preferred embodiment, it is not limited to the present invention, any to be familiar with this skill
The people of art, without departing from the spirit and scope of the present invention, can do various changes and modification, therefore the protection model of the present invention
Enclose being defined of being defined by claims.
Claims (2)
1. a kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers, it is characterized in that first sub- by carbon two
Amine (EDC) and n-hydroxysuccinimide (NHS) carry out fibroin modification, by the carboxylic acid graft containing vinyl and phenolic hydroxyl group to fibroin
In macromolecular, the reactivity of fibroin albumen is improved；Connect again by horseradish peroxidase enzyme catalytic modified fibroin and acrylic monomers
Branch copolymerization, prepares fibroin base biomimetic mineralization material, concrete technology is as follows with step：
(1) preparation of silk fibroin protein solution：With the silk after lithium bromide or calcium chloride dissolving degumming, silk fibroin protein solution is prepared；
Handling process prescription and condition：In the ethanol solution that silk after degumming is added to lithium bromide or calcium chloride, 50~
Then 80 DEG C of stirrings are dialysed 24~48 hours to dissolving with deionized water, and it is 10~40g/L silk fibroin solutions that concentration, which is made,；
(2) carboxylic acid of the EDC/NHS methods grafting containing vinyl and phenolic hydroxyl group：In the silk fibroin solution of step (1) add EDC, NHS,
Carboxylic acid processing containing vinyl and phenolic hydroxyl group, introduces vinyl and phenolic hydroxyl group on fibroin；
Handling process prescription and condition：EDC 1~10g/L of 1~10g/L, NHS, the carboxylic acid 0.2 containing vinyl and phenolic hydroxyl group~
5g/L, 20~30 DEG C of temperature, pH 4.5~7,0.5~24 hour processing time；
(3) horseradish peroxidase enzyme catalytic fibroin and acrylic graft copolymer：In the silk fibroin solution of step (2), horseradish is added
Peroxidase, acetylacetone,2,4-pentanedione and acrylic acid, add hydrogen peroxide under nitrogen protection, promote fibroin and acrylic graft copolymer；
Handling process prescription and condition：2~20U/mL of horseradish peroxidase, 5~10g/L of acetylacetone,2,4-pentanedione, 5~20g/ of hydrogen peroxide
L, 5~25g/L of acrylic acid, 20~45 DEG C of temperature, pH 6.0~8.0,0.5~15 hour processing time；
(4) shaping of fibroin membrane material：Step (3) reacted silk fibroin solution is freeze-dried under the conditions of -50 DEG C~-20 DEG C
Film forming；Then fibroin membrane is impregnated 0.25~1 hour in 50~80% ethanol solutions, in 30 DEG C of drying after washing；
(5) prepared by fibroin base biomimetic mineralization material：Fibroin membrane after step (4) processing is immersed in 10~50mmol/L calcium chloride molten
In liquid, handled 0.5~24 hour at 37 DEG C, carry out pre-calcification；Then fibroin membrane is immersed in 1.5 times of SBF simulated body fluids again,
Biomimetic mineralization 1~7 day under the conditions of 37 DEG C, during which changes a simulated body fluid daily；Finally cleaned with deionized water, -50
It is freeze-dried again under the conditions of~-20 DEG C, obtains fibroin base biomimetic mineralization material.
2. according to the method described in claim 1, it is characterised in that the carboxylic acid containing vinyl and phenolic hydroxyl group include caffeic acid,
Forulic acid, chlorogenic acid；The horseradish peroxidase derives from animal, plant or microorganism.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710274918.9A CN107099046B (en) | 2017-04-25 | 2017-04-25 | Method for preparing fibroin-based biomimetic mineralized material by grafting vinyl monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710274918.9A CN107099046B (en) | 2017-04-25 | 2017-04-25 | Method for preparing fibroin-based biomimetic mineralized material by grafting vinyl monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107099046A true CN107099046A (en) | 2017-08-29 |
| CN107099046B CN107099046B (en) | 2020-03-06 |
Family
ID=59657560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710274918.9A Active CN107099046B (en) | 2017-04-25 | 2017-04-25 | Method for preparing fibroin-based biomimetic mineralized material by grafting vinyl monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107099046B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623759A (en) * | 2018-04-13 | 2018-10-09 | 江南大学 | A method of fibroin base water-absorbent material is prepared based on coupling and enzymatic graft copolymerization |
| CN109281166A (en) * | 2018-09-17 | 2019-01-29 | 江南大学 | A kind of protein fibre antibiotic finishing method based on enzymatic graft copolymerization |
| CN113005766A (en) * | 2021-03-29 | 2021-06-22 | 江南大学 | Processing method of fiber product with cool feeling |
| CN113005781A (en) * | 2021-03-29 | 2021-06-22 | 江南大学 | Conductive fabric processing method based on cascade catalytic graft polymerization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819707A (en) * | 2014-02-19 | 2014-05-28 | 江南大学 | Preparation method of enzymatic grafting based antioxidant silk fibroin membrane |
| CN105088540A (en) * | 2015-09-25 | 2015-11-25 | 江南大学 | Method for preparing nano fibroin material on basis of tyrosinase/polyphenol medium |
| KR20160035917A (en) * | 2014-09-24 | 2016-04-01 | 한림대학교 산학협력단 | Fabrication method of 3D porous silk fibroin scaffolds for tissue and bone regeneration |
| CN105924596A (en) * | 2016-07-11 | 2016-09-07 | 江南大学 | Method for preparing silk-fibroin-based water-absorbing material by grafting vinyl monomer |
-
2017
- 2017-04-25 CN CN201710274918.9A patent/CN107099046B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819707A (en) * | 2014-02-19 | 2014-05-28 | 江南大学 | Preparation method of enzymatic grafting based antioxidant silk fibroin membrane |
| KR20160035917A (en) * | 2014-09-24 | 2016-04-01 | 한림대학교 산학협력단 | Fabrication method of 3D porous silk fibroin scaffolds for tissue and bone regeneration |
| CN105088540A (en) * | 2015-09-25 | 2015-11-25 | 江南大学 | Method for preparing nano fibroin material on basis of tyrosinase/polyphenol medium |
| CN105924596A (en) * | 2016-07-11 | 2016-09-07 | 江南大学 | Method for preparing silk-fibroin-based water-absorbing material by grafting vinyl monomer |
Non-Patent Citations (2)
| Title |
|---|
| 李荣: "改性丝素蛋白仿生诱导丝素蛋白/羟基磷灰石合成", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
| 马新兰等: "丝素蛋白/聚丙烯酸共混膜仿生合成羟基磷灰石", 《化学世界》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623759A (en) * | 2018-04-13 | 2018-10-09 | 江南大学 | A method of fibroin base water-absorbent material is prepared based on coupling and enzymatic graft copolymerization |
| CN108623759B (en) * | 2018-04-13 | 2019-10-25 | 江南大学 | A method of fibroin base water-absorbent material is prepared based on coupling and enzymatic graft copolymerization |
| CN109281166A (en) * | 2018-09-17 | 2019-01-29 | 江南大学 | A kind of protein fibre antibiotic finishing method based on enzymatic graft copolymerization |
| CN109281166B (en) * | 2018-09-17 | 2020-10-27 | 江南大学 | Protein fiber antibacterial finishing method based on enzymatic graft copolymerization |
| CN113005766A (en) * | 2021-03-29 | 2021-06-22 | 江南大学 | Processing method of fiber product with cool feeling |
| CN113005781A (en) * | 2021-03-29 | 2021-06-22 | 江南大学 | Conductive fabric processing method based on cascade catalytic graft polymerization |
| CN113005766B (en) * | 2021-03-29 | 2022-02-01 | 江南大学 | Processing method of fiber product with cool feeling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107099046B (en) | 2020-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107099046A (en) | A kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers | |
| CN105924596B (en) | A kind of method that fibroin base absorbent material is prepared by grafting vinyl monomers | |
| CN105064045B (en) | Method for carrying out enzymatic fibroin functional modification based on grafted polypeptide | |
| CN103421201B (en) | A kind of antibacterial silk fibroin membrane by biological enzyme preparation method | |
| CN105734981B (en) | A kind of method that laccase TEMPO methods carry out the wrinkle resistant antibiotic finish of real silk fabric | |
| CN102888027B (en) | Bacterial cellulose/collagen-chitosan composite material and preparation method thereof | |
| CN105801771B (en) | A kind of method that fibroin base composite absorbent material is prepared based on enzymatic graft copolymerization | |
| CA3127968C (en) | Amphoteric biomass-based hyperbranched adsorption material to multiple heavy metal ions and preparation method and use thereof | |
| Kuwabara et al. | Water‐absorbing characteristics of acrylic acid‐grafted carboxymethyl cellulose synthesized by photografting | |
| CN103526554B (en) | A kind of enzymatic grafting lysozyme carries out the method for real silk antibiotic finish | |
| CN110982092B (en) | Method for temporarily repairing high molecular material based on kinetic stability of enzymatic reaction regulation and control | |
| Zhang et al. | Improving properties of silk sericin membranes via enzymatic oxidation with laccase and TEMPO | |
| CN105131308B (en) | The method that a kind of laccase/tert-butyl hydroperoxide catalysis prepares wooden hydrogel | |
| CN105218842B (en) | A kind of method that enzyme process prepares fibroin/elastin laminin composite film material | |
| CN106977671B (en) | A method of silk gum membrane material is prepared based on Enzymatic grafting vinyl monomer | |
| CN110642357B (en) | Flocculating agent for microalgae capture and preparation method and application thereof | |
| CN109281166B (en) | Protein fiber antibacterial finishing method based on enzymatic graft copolymerization | |
| CN103667239B (en) | A kind of method of enzymatic silk fibroin immobilized catalase | |
| CN107033366B (en) | A method of fibroin biomimetic mineralization is carried out based on enzymatic grafting/phosphorylation | |
| CN107050511A (en) | A kind of biological enzyme fibroin albumen/calcium phosphate composite materials preparation method | |
| CN108517028B (en) | Method for preparing sericin membrane material based on enzymatic graft copolymerization | |
| CN108642023B (en) | Laccase composite modification method and application thereof | |
| Godjevargova | Radiation grafting of AMPSA and DMAEM onto membranes of acrylonitrile copolymer and polyamide for immobilization of glucose oxidase | |
| CN110591168A (en) | Method for preparing hyaluronic acid-based conductive film material by enzyme method | |
| CN108623759A (en) | A method of fibroin base water-absorbent material is prepared based on coupling and enzymatic graft copolymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |