CN107033366B - A method of fibroin biomimetic mineralization is carried out based on enzymatic grafting/phosphorylation - Google Patents
A method of fibroin biomimetic mineralization is carried out based on enzymatic grafting/phosphorylation Download PDFInfo
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Abstract
本发明公开了一种基于酶促接枝/磷酸化进行丝素仿生矿化的方法，属于纺织生物技术领域。旨在实现在温和条件下以漆酶催化丝素接枝壳寡糖，促进蛋白分子间交联，同时结合己糖激酶催化壳寡糖磷酸化，改善丝素的仿生矿化效果。具体步骤如下：(1)丝素蛋白溶液制备；(2)漆酶催化丝素接枝壳寡糖；(3)己糖激酶催化壳寡糖磷酸化；(4)改性丝素蛋白膜成型；(5)丝素蛋白膜仿生矿化。通过本发明不仅赋予丝素蛋白较好的诱导仿生矿化效果，且制备的丝素蛋白矿化膜有较好的力学性能。与传统化学法交联接枝相比，酶催化丝素蛋白与壳寡糖接枝及催化磷酸化效率高，反应条件缓和，丝素蛋白膜矿化效果好。The invention discloses a method for biomimetic mineralization of silk fibroin based on enzymatic grafting/phosphorylation, and belongs to the field of textile biotechnology. The purpose is to realize the grafting of chitosan oligosaccharide catalyzed by laccase under mild conditions to promote the cross-linking of protein molecules, and at the same time, combined with hexokinase to catalyze the phosphorylation of chitosan oligosaccharide to improve the biomimetic mineralization effect of silk fibroin. The specific steps are as follows: (1) Preparation of silk fibroin solution; (2) Grafting of chitosan oligosaccharide catalyzed by laccase; (3) Phosphorylation of chitosan oligosaccharide catalyzed by hexokinase; (4) Formation of modified silk fibroin membrane ; (5) Silk fibroin membrane biomimetic mineralization. The invention not only imparts a better effect of inducing biomimetic mineralization to the silk fibroin, but also the prepared silk fibroin mineralization film has better mechanical properties. Compared with the traditional chemical cross-linking grafting, the enzymatically catalyzed grafting of silk fibroin and chitosan oligosaccharide and catalytic phosphorylation has high efficiency, mild reaction conditions, and good silk fibroin membrane mineralization effect.
Description
Technical field
The present invention relates to a kind of methods for carrying out fibroin biomimetic mineralization based on enzymatic grafting/phosphorylation, it is characterized in that first borrowing
Help Laccase Catalyzed oxidation fibroin to react with amino-containing chitosan oligosaccharide, then chitosan oligosaccharide phosphorylation is catalyzed with hexokinase, it is most laggard
Row fibroin membrane biomimetic mineralization, belongs to field of textile biotechnology.
Background technique
Fibroin fiber derives from the mulberry silk after degumming, has graceful gloss, good hygroscopicity and good mechanical performance etc. all
More advantages are comparatively ideal textile fiber materials.At the same time, fibroin albumen itself is nontoxic, nonirritant, has low immunogene
Property and good biocompatibility, are a kind of biomaterial for medical purpose of function admirable, can be applied to include self-bone grafting timbering material
Various aspects inside.
The performance of regenerated silk material has biggish correlation with its molecular weight and structure composition.Fibroin fiber through calcium salt,
After lithium salts and its alcoholic solution dissolution, dissolution and partial hydrolysis occur for fibroin albumen, and it is molten to obtain fibroin after dialysis removes salt ion
Liquid can be used for preparing the fibroin timbering material of different purposes.Silk fibroin solution middle-molecular-weihydroxyethyl wider distribution is general, wherein low molecular weight silk
Plain molecule will affect the mechanical property of timbering material, therefore need to be promoted to be crosslinked between silk fibroin molecular by means of crosslinking agent etc..It examines
Considering fibroin albumen polar groups is carboxyl, amino and hydroxyl, usually by glutaraldehyde, carbodiimides (EDC) and N- hydroxyl
The chemical reagent such as base succinimide (NHS), make covalent cross-linking between fibroin macromolecular.Such method is increasing material mechanical performance
While, there is also certain deficiencies, as being also easy to produce chemical noxious substance residual in glutaraldehyde cross-linking reaction；EDC/NHS crosslinking
Carboxyl quantity is reduced in fibroin afterwards, is declined to the complexing power of calcium ion, declines the biomimetic mineralization performance of fibroin albumen etc..
With the development of biotechnology, become research heat increasingly by the crosslinking of biological enzyme catalyst fibroin and graft modification
Point.Compared with traditional chemical cross-linking method, enzyme modification is with efficient, single-minded, action condition is mild, advantages of environment protection.Paint
Enzyme is a kind of oxidizing ferment with catalytic oxidation activity, can hydroxyl on tyrosine and serine in catalysis oxidation fibroin, formed anti-
The stronger quinones active group of answering property or aldehyde radical, can cause fibroin albumen self-crosslinking by further reacting with amino in fibroin,
It can be with the amino-containing functional macromolecule covalence graft of external source.In addition, hexokinase is the phosphorylase of hexose, three can be catalyzed
γ-phosphate group in adenosine phosphate (ATP) is transferred to the position C6 of glucose or chitosan oligosaccharide, makes C6 dis.It is above-mentioned
The specificity of laccase and hexokinase provides new method with functional modification to be crosslinked based on the fibroin albumen of enzyme process.
The hydroxyl for aoxidizing tyrosine and serine residue in fibroin molecule in the present invention by Laccase Catalyzed, generates reactivity
Stronger quinones active group and aldehyde radical, and reacted with amino in chitosan oligosaccharide, realize chitosan oligosaccharide in fibroin surface grafting；It is basic herein
On, then with C6 dis in hexokinase catalysis chitooligose monomer, form the modified fibroin albumen of phosphorous acid group.Pass through
The method, not only formed with chitosan oligosaccharide be connection silk fibroin molecular between be crosslinked, increase fibroin molecular weight；And pass through hexose
Kinase catalytic chitosan oligosaccharide phosphorylation introduces more elecrtonegativity phosphate group on fibroin surface, also improves the bionical mine of fibroin
Change performance, so that fibroin membrane is obtained better biomimetic mineralization effect in SBF simulated body fluid or calcium ion-phosphate solution, favorably
In the building of fibroin base bionic bone matrix timbering material.
Summary of the invention
The purpose of the present invention is intended to provide a kind of method for carrying out fibroin biomimetic mineralization based on enzymatic grafting/phosphorylation, makes
Can chitosan oligosaccharide be grafted with the present invention by enzymatic and promote to be crosslinked between silk fibroin molecular, desmoenzyme is urged under mild reaction conditions
Change chitosan oligosaccharide phosphorylation, improves the biomimetic mineralization effect of fibroin albumen.
Technical solution of the present invention: a method of fibroin biomimetic mineralization, feature are carried out based on enzymatic grafting/phosphorylation
It is to first pass through tyrosine and serine residue in Laccase Catalyzed oxidation fibroin albumen, chitosan oligosaccharide is grafted on fibroin molecule, then
By di on hexokinase catalysis chitosan oligosaccharide, improve the biomimetic mineralization effect of fibroin albumen, concrete technology and step
It is as follows:
(1) prepared by silk fibroin protein solution: with the mulberry silk after lithium bromide or calcium chloride dissolution degumming, preparing silk fibroin solution；
Treatment process prescription and condition: the mulberry silk after degumming being added in the aqueous solution of lithium bromide or calcium chloride,
After 60~80 DEG C of dissolutions, to filter after dialyse 8~36 hours in deionized water, it is 10~40g/L silk fibroin solution that concentration, which is made,；
(2) Laccase Catalyzed fibroin is grafted chitosan oligosaccharide: laccase and shell being added in step (1) treated silk fibroin protein solution
Oligosaccharides processing；
Treatment process prescription and condition: 1~10U/mL of laccase, 0.5~5g/L of chitosan oligosaccharide, 20~60 DEG C for the treatment of temperature, pH
Range 4.0~7.0 is handled the time 2~24 hours；Then to dialyse 8~36 hours in deionized water, it is few to remove unreacted shell
The modified fibroin solution that concentration is 20~40g/L is made in sugar；
(3) hexokinase is catalyzed chitosan oligosaccharide phosphorylation: hexose being added in step (2) treated modified fibroin solution and swashs
Enzyme and atriphos processing；
Treatment process prescription and condition: Hexokinase 1~15U/mL, 0.5~10g/L of atriphos, cyclic adenosine monophosphate 0
~5g/L, 20~40 DEG C for the treatment of temperature, pH range 6.0~8.0 is handled the time 2~24 hours；Then to dialyse in deionized water
8~24 hours, the modified fibroin solution that concentration is 20~40g/L is made；
(4) modified fibroin protein film forms: the solution after taking step (3) to react, vacuum is cold under the conditions of -50~-20 DEG C
Freeze drying and forming-film；Then the fibroin membrane material is impregnated 0.25~1 hour in 50~80% ethanol solutions, is dried at 30 DEG C；
(5) fibroin protein film biomimetic mineralization: by step (4), treated that fibroin membrane is immersed in 1.5 times of SBF simulated body fluids
In, during which the biomimetic mineralization 1~7 day under the conditions of 37 DEG C replaces a simulated body fluid daily；With deionization after biomimetic mineralization
Water cleaning, obtains mineralising fibroin membrane after 30 DEG C of drying.
A method of fibroin biomimetic mineralization being carried out based on enzymatic grafting/phosphorylation, the laccase derives from animal, plant
Or microorganism；The hexokinase derives from animal, plant or microorganism.
Beneficial consequence of the invention
The present invention is grafted using Laccase Catalyzed chitosan oligosaccharide and fibroin albumen, is catalyzed chitosan oligosaccharide phosphorylation in conjunction with hexokinase,
Assign the preferable biomimetic mineralization effect of fibroin albumen.Compared with conventional chemical methods cross-linked graft, the invention has the following advantages that
(1) enzymic catalytic reaction is high-efficient, generates quinones active group and aldehyde radical using Laccase Catalyzed fibroin albumen, then with contain ammonia
The chitosan oligosaccharide of base is grafted, and has the advantages that specificity is strong and reaction efficiency is high；
(2) graft reaction condition mitigate, under low temperature near-neutral sulfite deinking realize fibroin albumen enzymatic grafting chitosan oligosaccharide and
Phosphorylation be easy to cause residual crosslinker or reaction condition dramatic impact silk fibroin material performance etc. to ask when avoiding chemical finishing
Topic；
(3) fibroin albumen remineralization efficacy is good, and constructing by enzyme process with chitosan oligosaccharide is the fibroin intermolecular cross-linking connected, passes through
It is catalyzed chitosan oligosaccharide phosphorylation, increases to calcium ion complexing power, enhances the biomimetic mineralization effect of fibroin albumen.
Specific embodiment
Chitosan oligosaccharide containing amino is grafted using laccase enzymatic oxidation fibroin, is catalyzed chitosan oligosaccharide phosphorylation in conjunction with hexokinase,
The specific embodiment for improving the biomimetic mineralization effect of fibroin albumen is as follows:
Embodiment 1
Fibroin enzymatic grafting/phosphorylation and fibroin protein film biomimetic mineralization are carried out in the method that the present invention addresses；
(1) silk fibroin solution prepare: the mulberry silk after degumming is added in lithium-bromide solution, 70 DEG C dissolution after with go from
Sub- water filters after dialysing 24 hours, and it is 20g/L silk fibroin solution that concentration, which is made,；
(2) Laccase Catalyzed fibroin is grafted chitosan oligosaccharide: laccase and shell being added in step (1) treated silk fibroin protein solution
Oligosaccharides processing, wherein laccase 5.5U/mL, chitosan oligosaccharide 2.4g/L, are handled the time 12 hours by 45 DEG C for the treatment of temperature, pH 5.5；Then
To dialyse 24 hours in deionized water, unreacted chitosan oligosaccharide is removed, the modified fibroin solution that concentration is 25g/L is made；
(3) hexokinase is catalyzed chitosan oligosaccharide phosphorylation: hexose being added in step (2) treated modified fibroin solution and swashs
Enzyme and atriphos processing, wherein Hexokinase 2 .5U/mL, atriphos 2.5g/L, cyclic adenosine monophosphate 1g/L, processing are warm
30 DEG C, pH 7.0 of degree is handled the time 8 hours；Then to dialyse 20 hours in deionized water, the modification that concentration is 25g/L is made
Silk fibroin solution；
(4) modified fibroin protein film forms: the solution after taking step (3) to react, vacuum freeze drying under the conditions of -50 DEG C
Film forming；Then the fibroin membrane material is impregnated 0.6 hour in 75% ethanol solution, is dried at 30 DEG C；
(5) fibroin protein film biomimetic mineralization: fibroin membrane after step (4) processing is immersed in 1.5 times of SBF simulated body fluids,
The biomimetic mineralization 6 days under the conditions of 37 DEG C, during which replaces a simulated body fluid daily；It is clear with deionized water after biomimetic mineralization
It washes, obtains mineralising fibroin membrane after 30 DEG C of drying.
Sample 1: only being handled through step (1), (4) and (5), is handled without step (2) and (3)；
Sample 2: it is only handled through step (1), (2), (4) and (5)；It is handled without step (3)；
Sample 3: it is handled through step (1), (2), (3), (4) and (5)；
After above-mentioned process, 1 surface calcium of sample, phosphorus content are respectively 12.1% and 7.2%, and elasticity modulus is
10.2MPa；2 surface calcium of sample, phosphorus content are respectively 11.9% and 7.5%, elasticity modulus 12.5MPa；2 surface calcium of sample,
Phosphorus content is respectively 15.0% and 11.1%, elasticity modulus 12.8MPa.
Embodiment 2
Fibroin enzymatic grafting/phosphorylation and fibroin protein film biomimetic mineralization are carried out in the method that the present invention addresses；
(1) silk fibroin solution prepare: the mulberry silk after degumming is added in lithium-bromide solution system, 72 DEG C dissolution after with
Deionized water dialysis filters after 20 hours, and it is 25g/L silk fibroin solution that concentration, which is made,；
(2) Laccase Catalyzed fibroin is grafted chitosan oligosaccharide: laccase and shell being added in step (1) treated silk fibroin protein solution
Oligosaccharides processing, wherein laccase 7.5U/mL, chitosan oligosaccharide 3.0g/L, temperature 45 C, pH 5.5 are handled the time 8 hours；Then to go
It dialyses 20 hours in ionized water, removes unreacted chitosan oligosaccharide, the modified fibroin solution that concentration is 20g/L is made；
(3) hexokinase is catalyzed chitosan oligosaccharide phosphorylation: hexose being added in step (2) treated modified fibroin solution and swashs
Enzyme and atriphos are handled, wherein hexokinase 6U/mL, atriphos 9g/L, cyclic adenosine monophosphate 1g/L, and 25 DEG C of temperature,
PH 7.5 is handled the time 8 hours；Then to dialyse 20 hours in deionized water, it is 20g/L modified fibroin solution that concentration, which is made,；
(4) modified fibroin protein film forms: the solution after taking step (3) to react, vacuum freeze drying under the conditions of -50 DEG C
Film forming；Then the fibroin membrane material is impregnated 0.5 hour in 70% ethanol solution, is dried at 30 DEG C；
(5) fibroin protein film biomimetic mineralization: fibroin membrane after step (4) processing is immersed in 1.5 times of SBF simulated body fluids,
The biomimetic mineralization 7 days under the conditions of 37 DEG C, during which replaces a simulated body fluid daily；It is clear with deionized water after biomimetic mineralization
It washes, obtains mineralising fibroin membrane after 30 DEG C of drying.
Sample 4: only being handled through step (1), (4) and (5), is handled without step (2) and (3)；
Sample 5: it is only handled through step (1), (2), (4) and (5)；It is handled without step (3)；
Sample 6: it is handled through step (1), (2), (3), (4) and (5)；
After above-mentioned process, 4 surface calcium of sample, phosphorus content are respectively 12.0% and 8.7%, and elasticity modulus is
9.4MPa；5 surface calcium of sample, phosphorus content are respectively 11.2% and 8.8%, elasticity modulus 11.9MPa；6 surface calcium of sample, phosphorus
Content is respectively 15.4% and 11.6%, elasticity modulus 12.3MPa.
By analyzing embodiment data: with fibroin albumen mineralising film (sample 1, sample of not enzyme treated fibroin preparation
4) calcium phosphorus content and elasticity modulus are lower；Fibroin mineralising film (sample 2, sample prepared using the fibroin through laccase treatment as raw material
5) elasticity modulus increases, and shows that Laccase Catalyzed grafting chitosan oligosaccharide can improve silk fibroin material mechanical property；It is addressed with the present invention
Fibroin albumen mineralising film (sample 3, sample 6) elasticity modulus increase of method preparation becomes apparent from, fibroin film surface calcium and phosphorus content
Height shows there is preferable remineralization efficacy.It can be seen that enzymatic fibroin grafting chitosan oligosaccharide is carried out in the method that the present invention addresses,
The fibroin albumen mineralising film of desmoenzyme catalytic phosphatase and biomimetic mineralization, preparation has preferable performance.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (2)
1. a kind of method for carrying out fibroin biomimetic mineralization based on enzymatic grafting/phosphorylation, it is characterized in that first passing through Laccase Catalyzed oxygen
Change tyrosine residue in fibroin albumen, chitosan oligosaccharide is grafted on fibroin molecule, then by hydroxyl on hexokinase catalysis chitosan oligosaccharide
Base phosphorylation, improves the biomimetic mineralization effect of fibroin albumen, concrete technology with steps are as follows:
(1) prepared by silk fibroin protein solution: with the mulberry silk after lithium bromide or calcium chloride dissolution degumming, preparing silk fibroin solution；
Treatment process prescription and condition: the mulberry silk after degumming being added in the aqueous solution of lithium bromide or calcium chloride, 60~
After 80 DEG C of dissolutions, to filter after dialyse 8~36 hours in deionized water, it is 10~40g/L silk fibroin solution that concentration, which is made,；
(2) Laccase Catalyzed fibroin is grafted chitosan oligosaccharide: laccase and chitosan oligosaccharide being added in step (1) treated silk fibroin protein solution
Processing；
Treatment process prescription and condition: 1~10U/mL of laccase, 0.5~5g/L of chitosan oligosaccharide, 20~60 DEG C for the treatment of temperature, pH range
4.0~7.0, it handles the time 2~24 hours；Then to dialyse 8~36 hours in deionized water, unreacted chitosan oligosaccharide is removed,
The modified fibroin solution that concentration is 20~40g/L is made；
(3) hexokinase is catalyzed chitosan oligosaccharide phosphorylation: be added in step (2) treated modified fibroin solution hexokinase and
Atriphos processing；
Treatment process prescription and condition: Hexokinase 1~15U/mL, 0.5~10g/L of atriphos, cyclic adenosine monophosphate 0~
5g/L, 20~40 DEG C for the treatment of temperature, pH range 6.0~8.0 is handled the time 2~24 hours；Then to dialyse 8 in deionized water
~24 hours, the modified fibroin solution that concentration is 20~40g/L is made；
(4) modified fibroin protein film forms: the solution after taking step (3) to react, vacuum refrigeration is dry under the conditions of -50~-20 DEG C
Dry film forming；Then the fibroin membrane material is impregnated 0.25~1 hour in 50~80% ethanol solutions, is dried at 30 DEG C；
(5) fibroin protein film biomimetic mineralization: by step (4), treated that fibroin membrane is immersed in 1.5 times of SBF simulated body fluids,
During which a simulated body fluid is replaced in biomimetic mineralization 1~7 day under the conditions of 37 DEG C daily；It is clear with deionized water after biomimetic mineralization
It washes, obtains mineralising fibroin membrane after 30 DEG C of drying.
2. according to the method described in claim 1, it is characterized in that the laccase derives from animal, plant or microorganism；It is described
Hexokinase derives from animal, plant or microorganism.
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| WO2020214860A1 (en) * | 2019-04-16 | 2020-10-22 | Evolved By Nature, Inc. | Chemically linked silk fibroin coatings and methods of making and using thereof |
| CN119020993B (en) * | 2024-08-16 | 2025-09-16 | 江南大学 | Preparation method of silk suture based on enzymatic grafted chitosan oligosaccharide-protocatechuic acid |
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| CN102085391A (en) * | 2009-12-08 | 2011-06-08 | 国家纳米技术与工程研究院 | Hydroxyapatite/chitosan-silk fibroin nanocomposite and preparation method thereof |
| CN103418029A (en) * | 2013-08-29 | 2013-12-04 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation method of fibroin/chitosan composite porous scaffold |
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| CN102085391A (en) * | 2009-12-08 | 2011-06-08 | 国家纳米技术与工程研究院 | Hydroxyapatite/chitosan-silk fibroin nanocomposite and preparation method thereof |
| CN103418029A (en) * | 2013-08-29 | 2013-12-04 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation method of fibroin/chitosan composite porous scaffold |
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| "Silk Fibroin/Chitosan Conjugate Crosslinked by Tyrosinase";Gyung Don Kang等;《Macromolecular Research》;20041031;第12卷(第5期);第534-539页 |
| "丝素蛋白作为组织工程生物材料的研究进展";王宏昕等;《中国修复重建外科杂志》;20080215;第22卷(第2期);第192-195页 |
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