阅读说明：本技术 一种多巴胺改性角蛋白复合膜的制备方法 (A kind of preparation method of the modified keratin composite membrane of dopamine ) 是由 尹国强 王喜倩 郭清兵 陈文杰 于 2019-09-09 设计创作，主要内容包括：本发明涉及一种多巴胺改性角蛋白制备复合膜的方法,涉及农产生物质功能化领域,包括以下的步骤：(1)通过物理、化学、生物法从羽毛中提取角蛋白,(2)将角蛋白溶于三羟甲基氨基化合物溶液,搅拌溶解,得到角蛋白-三羟甲基氨基化合物溶液,(3)将多巴胺加入角蛋白-三羟甲基氨基化合物溶液中,搅拌溶解,得到多巴胺改性角蛋白溶液。(4)将聚乙烯醇等高分子聚合物溶液加入角蛋白-三羟甲基氨基化合物溶液中,搅拌溶解,得到角蛋白复合溶液。(5)待角蛋白复合溶液冷却,通过浇铸、静电纺丝等方法即得多巴胺改性角蛋白复合膜。本发明所制备的多巴胺改性角蛋白复合膜,一方面可以为废弃鸡羽毛的回收利用提供一种可能性,另一方面可以制备一种可以应用于医用伤口敷料等领域的复合膜。(The present invention relates to the methods that a kind of modified keratin of dopamine prepares composite membrane, it is related to agricultural production biomass functionalization field, include the following steps: that (1) extracts keratin by physics, chemistry, bioanalysis from feather, (2) keratin is dissolved in trihydroxy methyl amino-compound solution, stirring and dissolving, obtains keratin-trihydroxy methyl amino-compound solution, and (3) dopamine is added in keratin-trihydroxy methyl amino-compound solution, stirring and dissolving obtains the modified keratin solution of dopamine.(4) macromolecule polymer solutions such as polyvinyl alcohol are added in keratin-trihydroxy methyl amino-compound solution, stirring and dissolving obtains keratin composite solution.(5) cooling to keratin composite solution, by the methods of casting, electrostatic spinning up to the modified keratin composite membrane of dopamine.Dopamine prepared by the present invention is modified keratin composite membrane, on the one hand can provide a kind of possibility to discard the recycling of chicken feather, on the other hand can prepare a kind of composite membrane that can be applied to the fields such as medical wound dressing.)

1. a kind of preparation method of the modified keratin composite membrane of dopamine, it is characterised in that include the following steps:

(1) keratin is extracted from feather by physics, chemistry, bioanalysis；

(2) keratin is dissolved in trihydroxy methyl amino-compound solution, stirring and dissolving obtains keratin-trihydroxy methyl amination Polymer solution；

(3) dopamine is added in keratin-trihydroxy methyl amino-compound solution, stirring and dissolving, obtains the modified angle of dopamine Protein solution；

(4) macromolecule polymer solutions such as polyvinyl alcohol are added in keratin-trihydroxy methyl amino-compound solution, are stirred molten Solution, obtains keratin composite solution；

(5) cooling to keratin composite solution, it is compound up to the modified keratin of dopamine by the methods of casting, electrostatic spinning Film.

2. a kind of preparation method of the modified keratin composite nano-fiber membrane of dopamine according to claim 1, feature It is, chicken, duck, the goose feather etc. that step (1) feather is discarded from the market of farm produce clean repeatedly through alcohol, dish washing liquid etc., Petroleum ether degreasing processing.

3. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, which is characterized in that described It is 2~5% trihydroxy methyl amino-compound aqueous solutions that step (2), which dissolves keratin,.

4. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, (2) three hydroxyl of step Methylamino compound includes trishydroxymethylaminomethane, trihydroxy methyl aminoethane, trihydroxy methyl aminopropane etc..

5. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, which is characterized in that described (hydrochloric acid) dopamine is added in keratin solution step (3), stirs 10 ~ 20h in 30 ~ 60 DEG C of thermostat water baths, prepares DOPA Amine-keratin composite solution.

6. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, which is characterized in that described Step (4) can also select the high molecular polymers such as polyethylene oxide, pla-pcl other than polyvinyl alcohol.

7. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, which is characterized in that described Step (4) poly-vinyl alcohol solution mass fraction is 10~14%.

8. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, which is characterized in that described The solid masses content of step (5) composite solution is 8~12%.

9. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, which is characterized in that described Step (5) film build method has casting, electrostatic spinning film forming etc..

10. a kind of preparation method of the modified keratin composite membrane of dopamine according to claim 1, the step (5) is such as Casting film is cast at room temperature, and the mold equipped with composite solution is placed in 30 ~ 60 DEG C of baking ovens, and freeze-day with constant temperature 5 ~ Keratin-composite membrane of polyvinyl alcohol 10h modified to get dopamine；If electrostatic spinning form a film, by the composite spinning liquid of preparation into Row electrostatic spinning, and nano wire is received with aluminium foil etc., keratin composite nano-fiber membrane is obtained after continuous spinning；Wherein electrostatic Spinning technology parameter are as follows: voltage 18~35k V receives 8~12cm of distance, and spinning rate is 0.5~1.0ml/h, spinneret orifice Internal diameter be 0.3~0.6mm, 25~40 DEG C of spinning temperature, spinning humidity 45~65%.

Technical field

The invention belongs to the preparation field of nano fibrous membrane more particularly to a kind of systems of the modified keratin composite membrane of dopamine Preparation Method.

Background technique

China's waste eggshell white matter resource very abundant, feather keratin are exactly one of them, it with the hair of various animals, The principal modes such as feather, hoof exist, protein content 80~90%.Feather is the derivative of animal cuticle cell keratinization, according to Estimation, annual animals and poultry slaughtering is processed or feather, feather bar and its leftover bits and pieces of down products by-product are all at million tons or more, The middle overwhelming majority is thrown away in vain as rubbish.If suitable feasible technique can be established, by these discarded feather keratins Be prepared into biodegradable membrane material, on the one hand protect environment, reduce white pollution, on the other hand can be become again give up into Treasured can obtain good ecological benefits and environmental benefit while obtaining economic benefit again.It is with feather or feather keratin Raw material has prepared a variety of feather keratin films.

But it is existing there are some researches prove, since the molecular weight of keratin is lower, membrane material made of single keratin material because To be more crisp, mechanical strength is not high, so application substantially reduces.Currently, most of keratin base biomaterial often through Plasticizer is added, or poor not with natural polymer, the compound mechanical property to improve single keratin membrane of artificial macromolecule Foot.Chinese patent (CN101838466B), the invention provides a kind of preparation methods of feather keratin film, are with keratin Raw material is added the plasticizer such as ethylene glycol, sorbierite and prepares keratin membrane.Chinese patent (CN104725649A) invention is with angle egg White is raw material, and by the way that crosslinking agent KH560 is added, the plasticizer such as glycerol, ethylene glycol, propylene glycol or sorbierite prepare feather angle egg White hybridized film.Chinese patent (CN104004209A) patent provides the preparation side of a kind of keratin and pla-pcl blend film Method.Although improving the mechanical performance of keratin membrane to a certain extent, the tensile strength of membrane material, elongation at break are still Old not high, practicability is low.The invention provides a kind of PVA/ keratin high barrier is compound for Chinese patent (CN109251450A) The preparation method of film, the compound substantially improve the problem of the tensile strength deficiency of film, however the toughness of material membrane is still not Foot.

Plasticizer and high molecular polymer itself whether have toxicity with whether keratin film biocompatibility, degradable Property have an impact also be research Important Problems.Pharmaceutical grade Polyethylene alcohol is different from chemical industry rank polyvinyl alcohol, it is a kind of pole Safety macromolecule organic, it is nontoxic to the human body, it is without side-effects, have good biocompatibility, especially in medical treatment as Its aqueous gel being widely used in terms of ophthalmology, wound dressing and joint prosthesis, while in polyvinyl alcohol film medicinal Film, artificial kidney film etc. also have use.However, one side polyvinyl alcohol material inactive itself, lacks cell recognition Signal site is unfavorable for histiocytic adherency and growth.On the other hand, feather keratin-polyvinyl alcohol composite nano fiber The mechanical property of film is also insufficient.

Dopamine is endogenous organic compound, harmless, and contains more active group, can be with keratin Side-chain radical chemically reacts, while the addition of dopamine makes up lacking for the high molecular polymers inactive such as polyvinyl alcohol Point improves the affinity and and bioadhesion of Materials Cell.Dopamine can also be used as reinforcing agent, pass through covalent interaction And the noncovalent interactions such as hydrogen bond, coordinate bond are bonded with keratin-polyvinyl alcohol composite solution, to improve material Mechanical property.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of preparation methods of the modified keratin composite membrane of dopamine, originally The modified keratin composite membrane of the prepared dopamine of invention improves the mechanical property of keratin by the modifying function of dopamine, has Hope the composite membrane for being applied to the fields such as medical wound dressing.

A kind of preparation method of the modified keratin composite membrane of dopamine of the invention, comprising:^。

(1) keratin is extracted from feather by physics, chemistry, bioanalysis.

(2) keratin is dissolved in trihydroxy methyl amino-compound solution, stirring and dissolving obtains keratin-trihydroxy methyl ammonia Based compound solution.

(3) dopamine is added in keratin-trihydroxy methyl amino-compound solution, stirring and dissolving obtains dopamine and changes Property keratin solution.

(4) macromolecule polymer solutions such as polyvinyl alcohol are added in keratin-trihydroxy methyl amino-compound solution, are stirred Dissolution is mixed, keratin composite solution is obtained.

(5) cooling to keratin composite solution, it is multiple up to the modified keratin of dopamine by the methods of casting, electrostatic spinning Close film.

Chicken, duck, the goose feather etc. that step (1) feather is discarded from the market of farm produce are repeatedly clear through alcohol, dish washing liquid etc. It washes, petroleum ether degreasing processing.

Step (2) the dissolution keratin is 2~5% trihydroxy methyl amino-compound aqueous solutions.

Step (2) the trihydroxy methyl amino-compound includes trishydroxymethylaminomethane, trihydroxy methyl aminoethane, three Methylol propane etc..

(hydrochloric acid) dopamine is added in keratin solution the step (2) step (3), in 30 ~ 60 DEG C of thermostatted waters Bath stirs 10 ~ 20h, prepares dopamine-keratin composite solution.

Dopamine hydrochloride is added in keratin solution the step (3), stirs 20h, preparation in 40 DEG C of thermostat water baths Dopamine-keratin composite solution.

The step (4) can also select the high molecular polymerizations such as polyethylene oxide, pla-pcl other than polyvinyl alcohol Object.

Step (4) the poly-vinyl alcohol solution mass fraction is 10~14%.

The solid masses content of step (5) composite solution is 8~12%.

Step (5) film build method has casting, electrostatic spinning film forming etc..

The step (5) such as casting film, casts at room temperature, the mold equipped with composite solution is placed in 30 ~ In 60 DEG C of baking ovens, keratin-composite membrane of polyvinyl alcohol 5 ~ 10h of freeze-day with constant temperature modified to get dopamine.As electrostatic spinning at The composite spinning liquid of preparation is carried out electrostatic spinning, and receives nano wire with aluminium foil etc. by film, and keratin is obtained after continuous spinning Composite nano-fiber membrane.Wherein electrostatic spinning process parameter are as follows: voltage 18~35k V receives 8~12cm of distance, spinning speed Rate be 0.5~1.0ml/h, spinneret orifice internal diameter be 0.3~0.6mm, 25~40 DEG C of spinning temperature, spinning humidity 45~65%.

Detailed description of the invention

Fig. 1 keratin composite membrane prepared by the present invention.

The size that Fig. 2 is cut into 75mm × 10mm carries out the film of Mechanics Performance Testing.

Specific embodiment

The present invention will be further described with reference to the examples below, but it should be recognized that embodiment is not to this hair Bright claimed range is construed as limiting.

Example 1^。

Chicken feather is added in the peracetic acid soln that concentration is 10~35%, is stirred evenly, in 60 DEG C of water-baths Sufficiently reaction 80min, is centrifugated and filters off impurity, obtain feather keratin solution；By feather keratin solution in deionization It after dialysing in water, filters, is freeze-dried, crush, obtain feather keratin powder.

Keratin is added in 2.5% Tris solvent, dissolution 30min is sufficiently stirred in 40 DEG C of thermostat water baths, obtains Keratin solution.0.02g Dopamine hydrochloride is added in keratin solution, dissolution is sufficiently stirred in 40 DEG C of thermostat water baths, It polymerize 20h, obtains dopamine-keratin composite solution.Polyvinyl alcohol is soluble in water, and 80 DEG C of water-baths stir 4h, prepare matter Amount score is 12% poly-vinyl alcohol solution.9ml poly-vinyl alcohol solution is added in dopamine-keratin solution, in 40 DEG C of thermostatted waters It is sufficiently stirred in bath 60 minutes, obtains solid masses than the keratin-polyvinyl alcohol composite solution modified for 9% dopamine.

The modified keratin of above-mentioned gained dopamine-polyvinyl alcohol composite spinning liquor is carried out electrostatic spinning preparation to receive Rice tunica fibrosa, electrostatic spinning process parameter are as follows: voltage 18kV receives distance 12cm, and spinning rate is 0.5ml/h, in spinneret orifice Diameter is 0.33mm, 30 DEG C of spinning temperature, spinning humidity 50%.

Example 2^。

Chicken feather is added in the mercaptoethanol solution that concentration is 1mol/L, is stirred evenly, adjusts pH with sodium hydroxide About 10.0,12h is sufficiently then reacted in 40 DEG C of water-baths, is centrifugated and filters off impurity, obtains feather keratin solution； It after feather keratin solution is dialysed in deionized water, filters, is freeze-dried, crush, obtain feather keratin powder.

Keratin is added in 2.5% Tris solvent, dissolution 30min is sufficiently stirred in 40 DEG C of thermostat water baths, obtains Keratin solution.0.05g Dopamine hydrochloride is added in keratin solution, dissolution is sufficiently stirred in 40 DEG C of thermostat water baths, It polymerize 20h, obtains dopamine-keratin composite solution.Polyvinyl alcohol is soluble in water, and 80 DEG C of water-baths stir 4h, prepare matter Amount score is 12% poly-vinyl alcohol solution.9ml poly-vinyl alcohol solution is added in dopamine-keratin solution, in 40 DEG C of thermostatted waters It is sufficiently stirred in bath 60 minutes, obtains solid masses than the keratin-polyvinyl alcohol composite solution modified for 9% dopamine.

The modified keratin of above-mentioned gained dopamine-polyvinyl alcohol composite spinning liquor is subjected to casting film.It will dress There is the mold of composite solution to be placed in 50 DEG C of baking ovens, freeze-day with constant temperature 7h is multiple to get the modified keratin-polyvinyl alcohol of dopamine Close film.

Example 3^。

Chicken feather is added in the peracetic acid soln that concentration is 10~35%, is stirred evenly, in 60 DEG C of water-baths Sufficiently reaction 80min, is centrifugated and filters off impurity, obtain feather keratin solution；By feather keratin solution in deionization It after dialysing in water, filters, is freeze-dried, crush, obtain feather keratin powder.

Keratin is added in 2.5% Tris solvent, dissolution 30min is sufficiently stirred in 40 DEG C of thermostat water baths, obtains Keratin solution.0.02,0.05,0.07g Dopamine hydrochloride are separately added into different keratin solutions, in 40 DEG C of thermostatted waters Dissolution is sufficiently stirred in bath, polymerize 20h, obtains DOPAMINE CONTENT IN RABBIT different keratin composite solution A, B, C.By polyvinyl alcohol Soluble in water, 80 DEG C of water-baths stir 4h, and preparing mass fraction is 12% poly-vinyl alcohol solution.9ml poly-vinyl alcohol solution is distinguished It is added in keratin composite solution A, B, C, is sufficiently stirred in 40 DEG C of thermostat water baths 60 minutes, obtaining solid masses ratio is 9% Modified keratin-polyvinyl alcohol composite solution A, B, the C of dopamine.

The modified keratin of above-mentioned gained dopamine-polyvinyl alcohol composite spinning liquor is subjected to casting film.It will dress There is the mold of composite solution to be placed in 50 DEG C of baking ovens, freeze-day with constant temperature 7h is multiple to get the modified keratin-polyvinyl alcohol of dopamine Close film A, B, C.

Film: being cut into the size of 75mm × 10mm by Mechanics Performance Testing, and fixture spacing is 40mm, rate of extension 10mm/ Min, each sample are surveyed 3 times and are averaged.

1 each sample mechanical performance testing result of table

Sample	Elasticity modulus (MPa)	Tensile strength (MPa)	Elongation at break (%)
				A	107.34	14.64	524.83
B	117.37	12.50	544.73
				C	84.61	11.00	579.80

As can be seen that the mechanical performance for the keratin composite membrane that dopamine is modified is more excellent in table 1, the sample in example 1-3 With the increase of DOPAMINE CONTENT IN RABBIT, elasticity modulus is reduced, and tensile strength reduces, and elongation at break increases.The increasing of DOPAMINE CONTENT IN RABBIT Add the toughness that can improve keratin composite membrane.