CN103993422B - A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof - Google Patents
A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof Download PDFInfo
- Publication number
- CN103993422B CN103993422B CN201410165983.4A CN201410165983A CN103993422B CN 103993422 B CN103993422 B CN 103993422B CN 201410165983 A CN201410165983 A CN 201410165983A CN 103993422 B CN103993422 B CN 103993422B
- Authority
- CN
- China
- Prior art keywords
- silk fibroin
- regenerated silk
- chitosan
- blended fiber
- chitosan derivatives
- 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.)
- Active
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 126
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 113
- 239000000835 fiber Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 76
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000001523 electrospinning Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 18
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 18
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 17
- 229940054190 hydroxypropyl chitosan Drugs 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- -1 carboxyethyl Chemical group 0.000 claims description 6
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 241000255791 Bombyx Species 0.000 claims 2
- 241001274660 Modulus Species 0.000 claims 2
- 241001597008 Nomeidae Species 0.000 claims 1
- 238000000502 dialysis Methods 0.000 claims 1
- 238000010041 electrostatic spinning Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 241000255789 Bombyx mori Species 0.000 abstract description 17
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000002407 tissue scaffold Substances 0.000 abstract 1
- 239000011550 stock solution Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- IELOKBJPULMYRW-NJQVLOCASA-N D-alpha-Tocopheryl Acid Succinate Chemical compound OC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C IELOKBJPULMYRW-NJQVLOCASA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- AZKVWQKMDGGDSV-BCMRRPTOSA-N Genipin Chemical compound COC(=O)C1=CO[C@@H](O)[C@@H]2C(CO)=CC[C@H]12 AZKVWQKMDGGDSV-BCMRRPTOSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229940099418 d- alpha-tocopherol succinate Drugs 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- AZKVWQKMDGGDSV-UHFFFAOYSA-N genipin Natural products COC(=O)C1=COC(O)C2C(CO)=CCC12 AZKVWQKMDGGDSV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000028709 inflammatory response Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Nonwoven Fabrics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
本发明涉及一种再生丝素蛋白/壳聚糖衍生物共混纤维毡及其制备方法,所述共混纤维毡中壳聚糖衍生物的质量百分含量为1~5%,其余为再生丝素蛋白;所述共混纤维毡断裂强度为1.75~2.8MPa,初始模量为70~280MPa。制备方法包括:以蚕茧为原料,制备再生丝素蛋白水溶液;将水溶性壳聚糖衍生物溶于水中,获得壳聚糖衍生物水溶液;将上述两种溶液按一定比例混合制备再生丝素蛋白/壳聚糖衍生物共混水溶液,再采用静电纺丝技术制备共混纤维毡。该方法制备的共混纤维毡不仅力学性能相比纯再生丝素蛋白纤维毡大幅度提高,还具有良好的生物相容性、吸湿保湿性、广谱抑菌性等性能,适用于纺织、生物医学特别组织支架等领域。The invention relates to a regenerated silk fibroin/chitosan derivative blended fiber mat and a preparation method thereof, wherein the mass percentage of chitosan derivatives in the blended fiber mat is 1 to 5%, and the rest is regenerated Silk fibroin: the breaking strength of the blended fiber mat is 1.75-2.8 MPa, and the initial modulus is 70-280 MPa. The preparation method comprises: using silkworm cocoons as raw materials to prepare an aqueous solution of regenerated silk fibroin; dissolving water-soluble chitosan derivatives in water to obtain an aqueous solution of chitosan derivatives; mixing the above two solutions in a certain proportion to prepare regenerated silk fibroin / chitosan derivatives blending aqueous solution, and then using electrospinning technology to prepare blended fiber mat. The blended fiber mat prepared by this method not only has greatly improved mechanical properties compared with pure regenerated silk fibroin fiber mat, but also has good biocompatibility, moisture absorption and moisture retention, and broad-spectrum antibacterial properties. It is suitable for textile, biological Medical special tissue scaffolds and other fields.
Description
技术领域technical field
本发明属于共混纤维毡制备技术领域,涉及一种再生丝素蛋白/壳聚糖衍生物共混纤维毡及其制备方法。The invention belongs to the technical field of blended fiber mat preparation, and relates to a regenerated silk fibroin/chitosan derivative blended fiber mat and a preparation method thereof.
背景技术Background technique
丝素蛋白是由蚕丝脱胶而来,作为一种对人体炎症反应小,透气透氧性好,生物相容性良好的天然材料,越来越受到人们关注。将丝素蛋白溶解获得的再生丝素蛋白可以被加工成凝胶、薄膜和纤维毡等多种形式的材料。可根据材料使用要求,通过加工后处理改变再丝素蛋白材料结晶度,控制其降解速率和力学性能。但纯丝素蛋白材料力学性能偏低,存在含水率低时,脆性变大,在低湿环境里力学强度又严重下降等缺陷,这严重限制其广泛应用。Silk fibroin is degummed from silk. As a natural material that has little inflammatory response to human body, good air permeability and good biocompatibility, it has attracted more and more attention. The regenerated silk fibroin obtained by dissolving silk fibroin can be processed into various forms of materials such as gel, film and fiber mat. According to the requirements of material use, the crystallinity of re-silk fibroin material can be changed through post-processing to control its degradation rate and mechanical properties. However, the mechanical properties of pure silk fibroin materials are relatively low, and there are defects such as increased brittleness when the moisture content is low, and a serious decrease in mechanical strength in low-humidity environments, which seriously limits its wide application.
壳聚糖是由甲壳素经脱乙酰化处理得到的产物,一般来说,甲壳素N-乙酰基脱去55%以上的就可称之为壳聚糖。甲壳素广泛存在于节肢动物虾、蟹等外壳,昆虫甲壳,以及真菌类细胞壁中,是地球上存量仅次于纤维素的生物多糖。处理得到的壳聚糖及壳聚糖衍生物由于具有无毒副作用、无免疫原性,优异的生物相容性,生物可降解性,广谱抑菌性等,已在纺织,生物医学等领域得到广泛应用。一些壳聚糖衍生物如羟丙基壳聚糖、羟乙基壳聚糖、羧甲基壳聚糖、羧乙基壳聚糖等不但保留了壳聚糖原有的优异性能,而且还具有良好的水溶性,显著提高的可加工性。壳聚糖以及部分壳聚糖衍生物已被纺制成纤维,用于可吸收医用缝合线,免除了病人拆线痛苦;用做医用敷料,适合治疗各种创伤;还可用来织布加工成各种功能性产品,如保健内衣,抗菌防臭床上用品,抑菌医用护士服等。然而纯壳聚糖及其衍生物纤维线密度偏大,强度偏低,纺织后加工物理机械性能差,价格昂贵,加工生产成本高。Chitosan is a product obtained by deacetylation of chitin. Generally speaking, chitin with more than 55% of its N-acetyl group removed can be called chitosan. Chitin is widely found in the shells of arthropods such as shrimps and crabs, the carapaces of insects, and the cell walls of fungi. It is the second most abundant biological polysaccharide on earth after cellulose. The processed chitosan and chitosan derivatives have been used in textile, biomedicine and other fields due to their non-toxic side effects, non-immunogenicity, excellent biocompatibility, biodegradability, and broad-spectrum antibacterial properties. be widely used. Some chitosan derivatives such as hydroxypropyl chitosan, hydroxyethyl chitosan, carboxymethyl chitosan, carboxyethyl chitosan, etc. not only retain the original excellent properties of chitosan, but also have Good water solubility, significantly improved processability. Chitosan and some chitosan derivatives have been spun into fibers for absorbable medical sutures, eliminating the pain of stitch removal for patients; used as medical dressings, suitable for treating various wounds; can also be used for weaving and processing into Various functional products, such as health underwear, antibacterial and deodorant bedding, antibacterial medical nurse clothing, etc. However, pure chitosan and its derivative fibers have high linear density, low strength, poor physical and mechanical properties in post-spinning processing, high price, and high processing and production costs.
Yuhui Ruan等于2011年发表的“Preparation of3D Fibroin/Chitosan BlendPorous Scaffold for Tissue Engineering Via a Simplified Method”中涉及3D丝素蛋白/壳聚糖共混多孔支架的制备,这种方法制备的加入壳聚糖的共混支架拉伸强度远比纯丝素蛋白支架低得多,共混多孔支架拉的伸强度低于0.055MPa;随丝素蛋白含量增加,共混支架拉伸强度先略有提高后下降,含量75wt%丝素蛋白的共混支架拉伸强度最高,仅达到0.045MPa。Kuihua Zhang等于2010年发表的“Genipin-crosslinked silk fibroin/hydroxybutyl chitosan nanofibrous scaffolds for tissue-engineeringapplication”中制备了京尼平交联的丝素蛋白/羟丁基壳聚糖纳米纤维支架,改变交联剂含量和交联时间,文献中所制备的支架最大拉伸强度为39.5MPa,最大断裂伸长率为11%,但是额外交联剂的使用会降低共混支架的生物相容性,增加制备步骤,提高生产成本。公开号为CN103436985A中国发明专利,公开了一种丝素蛋白/壳聚糖共混纳米纤维的制备方法,以再生丝素蛋白甲酸溶液与壳聚糖三氟乙酸溶液混合的纺丝原液,进行静电纺丝获得丝素蛋白/壳聚糖共混纳米纤维膜。但是此方法步骤繁多,使用有机溶剂不仅对环境不友好,而且降低了材料的生物相容性,且此专利未提到壳聚糖对共混纳米纤维膜力学性能的影响。公开号为CN102936794A的中国发明专利,公开了一种丝素蛋白/羧甲基壳聚糖/聚环氧乙烷/聚乙二醇维生素E琥拍酸酯/维生素C磷酸酯钠复合纳米纤维膜的制备方法,该方法采用水作为溶剂,无毒无污染,生物相容性良好,但该方法制备的纤维膜仅具有适当的力学性能,且此专利未提到壳聚糖衍生物对共混纳米纤维膜力学性能的影响。到目前为止,国内外还未见以再生丝素蛋白/壳聚糖衍生物水溶液,通过静电纺丝制备力学性能大幅度提高的再生丝素蛋白/壳聚糖衍生物共混纤维毡相关研究、文献报道或专利。"Preparation of3D Fibroin/Chitosan Blend Porous Scaffold for Tissue Engineering Via a Simplified Method" published by Yuhui Ruan in 2011 involves the preparation of 3D silk fibroin/chitosan blended porous scaffolds. The tensile strength of the blended scaffold is much lower than that of the pure silk fibroin scaffold, and the tensile strength of the blended porous scaffold is lower than 0.055 MPa; with the increase of the silk fibroin content, the tensile strength of the blended scaffold first increases slightly and then decreases, The blended scaffold with 75wt% silk fibroin had the highest tensile strength, only reaching 0.045MPa. In "Genipin-crosslinked silk fibroin/hydroxybutyl chitosan nanofibrous scaffolds for tissue-engineering application" published by Kuihua Zhang in 2010, genipin crosslinked silk fibroin/hydroxybutyl chitosan nanofiber scaffolds were prepared, and the crosslinking agent was changed. Content and crosslinking time, the maximum tensile strength of the scaffold prepared in the literature is 39.5MPa, and the maximum elongation at break is 11%, but the use of additional crosslinking agent will reduce the biocompatibility of the blended scaffold and increase the preparation steps , to increase production costs. The publication number is CN103436985A Chinese invention patent, which discloses a preparation method of silk fibroin/chitosan blended nanofibers. The spinning stock solution mixed with regenerated silk fibroin formic acid solution and chitosan trifluoroacetic acid solution is used for electrostatic The silk fibroin/chitosan blend nanofiber membrane was obtained by spinning. However, this method has many steps, and the use of organic solvents is not only environmentally unfriendly, but also reduces the biocompatibility of the material, and this patent does not mention the impact of chitosan on the mechanical properties of the blended nanofiber membrane. The Chinese invention patent with the publication number CN102936794A discloses a silk fibroin/carboxymethyl chitosan/polyethylene oxide/polyethylene glycol vitamin E succinate/vitamin C sodium phosphate composite nanofiber membrane The preparation method, which uses water as a solvent, is non-toxic, non-polluting, and has good biocompatibility, but the fiber membrane prepared by this method only has appropriate mechanical properties, and this patent does not mention the effect of chitosan derivatives on blending Influence of nanofibrous membrane mechanical properties. So far, there has been no research on the preparation of regenerated silk fibroin/chitosan derivative blended fiber mats with greatly improved mechanical properties by electrospinning an aqueous solution of regenerated silk fibroin/chitosan derivatives at home and abroad. Literature reports or patents.
发明内容Contents of the invention
本发明的目的是提供一种再生丝素蛋白/壳聚糖衍生物共混纤维毡及其制备方法,本发明是将再生丝素蛋白与壳聚糖衍生物共混,以得到力学性能优于单组分性能的新型纤维毡。壳聚糖衍生物的加入大大提高了纤维毡的力学性能,这是由于壳聚糖衍生物分子链上含有大量羟基能够与丝素蛋白链上的氨基形成氢键,壳聚糖先破坏原有丝素蛋白分子内氢键,形成重排的壳聚糖与丝素蛋白分子间的氢键,氢键的作用力远比分子间的范德华力强,会提高力学性能。壳聚糖衍生物与乙醇提高共混纤维毡力学强度的作用机理不同,乙醇水溶液后处理,主要是水分子先增加丝素蛋白分子链的自由体积,乙醇再分子进入纤维间促进形成丝素蛋白分子链之间的氢键。The purpose of the present invention is to provide a kind of regenerated silk fibroin/chitosan derivative blend fiber felt and its preparation method, the present invention is to regenerate silk fibroin and chitosan derivative blend, to obtain the New fiber mat with one-component properties. The addition of chitosan derivatives greatly improves the mechanical properties of the fiber mat. This is because the chitosan derivative molecular chain contains a large number of hydroxyl groups that can form hydrogen bonds with the amino groups on the silk fibroin chain. Chitosan first destroys the original The hydrogen bond in the silk fibroin molecule forms the hydrogen bond between the rearranged chitosan and the silk fibroin molecule. The force of the hydrogen bond is much stronger than the Van der Waals force between the molecules, which will improve the mechanical properties. Chitosan derivatives and ethanol have different mechanisms for improving the mechanical strength of the blended fiber mat. After treatment with ethanol aqueous solution, the main reason is that water molecules first increase the free volume of silk fibroin molecular chains, and ethanol then enters the fibers to promote the formation of silk fibroin. Hydrogen bonds between molecular chains.
本发明的一种再生丝素蛋白/壳聚糖衍生物共混纤维毡,所述共混纤维毡中壳聚糖衍生物的质量百分含量为1~5%,其余为再生丝素蛋白;所述共混纤维毡断裂强度为1.75~2.8MPa,初始模量为70~280MPa,分别比相同条件下制得的纯再生丝素蛋白纤维毡提高了25~100%、15~350%。A regenerated silk fibroin/chitosan derivative blended fiber mat of the present invention, the mass percentage of chitosan derivatives in the blended fiber mat is 1-5%, and the rest is regenerated silk fibroin; The breaking strength of the blended fiber mat is 1.75-2.8 MPa, and the initial modulus is 70-280 MPa, which are respectively 25-100% and 15-350% higher than that of the pure regenerated silk fibroin fiber mat prepared under the same conditions.
作为优选的技术方案:As a preferred technical solution:
如上所述的一种再生丝素蛋白/壳聚糖衍生物共混纤维毡,所述共混纤维毡经乙醇水溶液浸泡处理后,其断裂强度为4~7.5MPa,初始模量为360~450MPa,断裂能为60~120J·Kg-1,分别比经相同条件后处理的纯再生丝素蛋白纤维毡提高了30~150%、100~150%、50~200%。A regenerated silk fibroin/chitosan derivative blended fiber mat as described above, after the blended fiber mat is soaked in an aqueous ethanol solution, its breaking strength is 4-7.5 MPa, and the initial modulus is 360-450 MPa , the breaking energy is 60-120J·Kg -1 , which are respectively 30-150%, 100-150%, and 50-200% higher than the pure regenerated silk fibroin fiber mat after the same post-treatment.
如上所述的一种再生丝素蛋白/壳聚糖衍生物共混纤维毡,所述的经乙醇处理是指将共混纤维毡定长浸泡于80~95vol%乙醇水溶液中10~30min。In the aforementioned regenerated silk fibroin/chitosan derivative blended fiber mat, the ethanol treatment refers to soaking the blended fiber mat in 80-95 vol% ethanol aqueous solution for 10-30 minutes at fixed length.
如上所述的一种再生丝素蛋白/壳聚糖衍生物共混纤维毡,所述的壳聚糖衍生物为羟丙基壳聚糖、羟乙基壳聚糖、羧甲基壳聚糖、羧乙基壳聚糖中的一种。A kind of regenerated silk fibroin/chitosan derivative blending fiber felt as above, described chitosan derivative is hydroxypropyl chitosan, hydroxyethyl chitosan, carboxymethyl chitosan , one of carboxyethyl chitosan.
如上所述的一种再生丝素蛋白/壳聚糖衍生物共混纤维毡,所述共混纤维毡的孔隙率为65~80%,构成纤维毡的共混纤维直径的范围为200nm~2.4μm。A regenerated silk fibroin/chitosan derivative blended fiber mat as described above, the porosity of the blended fiber mat is 65-80%, and the diameter of the blended fibers constituting the fiber mat ranges from 200nm to 2.4 nm. μm.
本发明还提供了一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,包括如下步骤:The present invention also provides a method for preparing a regenerated silk fibroin/chitosan derivative blended fiber mat, comprising the following steps:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.0~9.3mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为25~35%再生丝素蛋白水溶液;(1) Using silkworm cocoons as raw materials, silkworm cocoons are degummed with 0.5% by mass percent sodium carbonate aqueous solution, and then dissolved in an aqueous lithium bromide solution with a molar concentration of 9.0 to 9.3mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the obtained The mass percentage is 25-35% regenerated silk fibroin aqueous solution;
(2)将壳聚糖衍生物溶解于去离子水中,制备质量百分比为1~5%的壳聚糖衍生物水溶液;(2) Dissolving chitosan derivatives in deionized water to prepare an aqueous solution of chitosan derivatives with a mass percentage of 1 to 5%;
(3)将所述再生丝素蛋白水溶液与所述壳聚糖衍生物水溶液按再生丝素蛋白/壳聚糖衍生物质量比为100:1~5混合,制备再生丝素蛋白/壳聚糖衍生物共混水溶液;(3) Mix the regenerated silk fibroin aqueous solution with the chitosan derivative aqueous solution at a mass ratio of 100:1 to 5 of the regenerated silk fibroin/chitosan derivative to prepare the regenerated silk fibroin/chitosan Derivative blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/壳聚糖衍生物共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/壳聚糖衍生物共混纤维毡。(4) The regenerated silk fibroin/chitosan derivative blended aqueous solution prepared in step (3) is used as the spinning stock solution for electrospinning to obtain the regenerated silk fibroin/chitosan derivative blended fiber mat.
如上所述的一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,所述步骤(4)中静电纺丝条件为:纺丝电压为15~30kV,纺丝液流速为0.1~1.0mL/h,接收距离为5~15cm,相对湿度为45~55%。A kind of preparation method of regenerated silk fibroin protein/chitosan derivative blended fiber mat as mentioned above, the electrospinning condition in the described step (4) is: the spinning voltage is 15~30kV, and the spinning solution flow rate is 0.1~1.0mL/h, the receiving distance is 5~15cm, and the relative humidity is 45~55%.
本发明提供一种原料可天然再生,产品可降解的再生蚕丝蛋白与壳聚糖衍生物共混纤维毡及其制备方法,该方法简单,操作方便,整个过程中没有使用有机溶剂,对环境无污染;所得的再生蚕丝蛋白/壳聚糖衍生物共混纤维毡与纯再生丝素蛋白纤维毡相比,其断裂能、断裂强度和初始模量都得到大幅度提高,还具有抗菌除臭、抗静电、透气性强、良好的吸湿保温性等优异性能。The invention provides a regenerated silk protein and chitosan derivative blended fiber mat with natural regeneration of raw materials and degradable products and a preparation method thereof. The method is simple, easy to operate, no organic solvent is used in the whole process, and it is environmentally friendly. pollution; the resulting regenerated silk protein/chitosan derivative blend fiber mat compared with pure regenerated silk fibroin fiber mat, its breaking energy, breaking strength and initial modulus are greatly improved, and it also has antibacterial, deodorizing, Excellent properties such as antistatic, strong air permeability, good moisture absorption and heat preservation.
有益效果:Beneficial effect:
本发明采用再生丝素蛋白与壳聚糖衍生物共混,一方面保持了再生丝素蛋白生物相容性,另一方面又改善了其力学性能,共混纤维毡断裂强度、初始模量、断裂能大幅度提高,此外还使得共混纤维毡具有抗菌作用,适合开发功能保健衣物,更适合应用于具有抗菌或抑菌需求的组织工程支架,避免组织发生感染;本发明使用了水溶性良好的壳聚糖衍生物,避免了有机溶剂,如甲酸、三氟乙酸、六氟异丙醇等的使用,减少对环境污染,大大降低成本,符合现代绿色工业生产理念。The present invention uses regenerated silk fibroin and chitosan derivatives to blend, on the one hand, maintains the biocompatibility of regenerated silk fibroin, and on the other hand improves its mechanical properties, blending fiber mat breaking strength, initial modulus, The fracture energy is greatly improved, and in addition, the blended fiber mat has antibacterial effect, which is suitable for the development of functional health care clothing, and is more suitable for tissue engineering scaffolds with antibacterial or antibacterial requirements to avoid tissue infection; the present invention uses a fiber with good water solubility Chitosan derivatives, avoiding the use of organic solvents, such as formic acid, trifluoroacetic acid, hexafluoroisopropanol, etc., reduce environmental pollution, greatly reduce costs, and conform to the concept of modern green industrial production.
具体实施方式detailed description
下面结合具体实施方式,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.0mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为25%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after the silkworm cocoons are degummed with 0.5% by mass percent sodium carbonate aqueous solution, they are dissolved in a lithium bromide aqueous solution with a molar concentration of 9.0mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 25% regenerated silk fibroin aqueous solution;
(2)将羟丙基壳聚糖解于去离子水中,制备质量百分比为1%的羟丙基壳聚糖水溶液;(2) dissolving hydroxypropyl chitosan in deionized water to prepare a 1% aqueous solution of hydroxypropyl chitosan;
(3)将所述再生丝素蛋白水溶液与所述羟丙基壳聚糖水溶液按再生丝素蛋白/羟丙基壳聚糖质量比为100:1混合,制备再生丝素蛋白/羟丙基壳聚糖共混水溶液;(3) The aqueous solution of regenerated silk fibroin and the aqueous solution of hydroxypropyl chitosan are mixed according to the mass ratio of regenerated silk fibroin/hydroxypropyl chitosan to 100:1 to prepare regenerated silk fibroin/hydroxypropyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羟丙基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羟丙基壳聚糖衍生物共混纤维毡。静电纺丝条件为:纺丝电压为15kV,纺丝液流速为0.1mL/h,接收距离为5cm,相对湿度为45%。(4) Using the regenerated silk fibroin/hydroxypropyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, electrospinning is carried out to obtain the regenerated silk fibroin/hydroxypropyl chitosan derivative co- Mixed fiber felt. The electrospinning conditions are as follows: the spinning voltage is 15kV, the flow rate of the spinning solution is 0.1mL/h, the receiving distance is 5cm, and the relative humidity is 45%.
所制备的共混纤维毡断裂强度为2.1MPa,初始模量为100MPa;所述共混纤维毡定长浸泡于80vol%乙醇水溶液中10min后,其断裂强度为5.5MPa,初始模量为360MPa,断裂能为90J·Kg-1;所述共混纤维毡的孔隙率为78%,构成纤维毡的共混纤维直径的范围为400nm~1.8μm。The prepared blended fiber mat has a breaking strength of 2.1 MPa and an initial modulus of 100 MPa; after the blended fiber mat is soaked in 80vol% ethanol aqueous solution for 10 minutes, its breaking strength is 5.5 MPa and its initial modulus is 360 MPa, The fracture energy is 90J·Kg -1 ; the porosity of the blended fiber mat is 78%, and the diameter of the blended fibers constituting the fiber mat ranges from 400nm to 1.8μm.
实施例2Example 2
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.1mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为30%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after silkworm cocoons are degummed with a 0.5% aqueous sodium carbonate solution by mass percentage, they are dissolved in an aqueous lithium bromide solution with a molar concentration of 9.1mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 30% aqueous solution of regenerated silk fibroin;
(2)将羟乙基壳聚糖溶解于去离子水中,制备质量百分比为2%的羟乙基壳聚糖水溶液;(2) Dissolving hydroxyethyl chitosan in deionized water to prepare a 2% aqueous solution of hydroxyethyl chitosan by mass;
(3)将所述再生丝素蛋白水溶液与所述羟乙基壳聚糖水溶液按再生丝素蛋白/羟乙基壳聚糖质量比为100:1混合,制备再生丝素蛋白/羟乙基壳聚糖共混水溶液;(3) The aqueous solution of regenerated silk fibroin and the aqueous solution of hydroxyethyl chitosan are mixed according to the mass ratio of regenerated silk fibroin/hydroxyethyl chitosan to 100:1 to prepare regenerated silk fibroin/hydroxyethyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羟乙基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羟乙基壳聚糖衍生物共混纤维毡。静电纺丝条件为:纺丝电压为20kV,纺丝液流速为0.3mL/h,接收距离为10cm,相对湿度为50%。(4) Using the regenerated silk fibroin/hydroxyethyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, electrospinning is carried out to obtain the regenerated silk fibroin/hydroxyethyl chitosan derivative co- Mixed fiber felt. The electrospinning conditions are as follows: the spinning voltage is 20kV, the flow rate of the spinning solution is 0.3mL/h, the receiving distance is 10cm, and the relative humidity is 50%.
所制备的共混纤维毡断裂强度为1.75MPa,初始模量为160MPa。所述共混纤维毡定长浸泡于80vol%乙醇水溶液中20min后,其断裂强度为4MPa,初始模量为380MPa,断裂能为95J·Kg-1;所述共混纤维毡的孔隙率为80%,构成纤维毡的共混纤维直径的范围为200nm~2μm。The fracture strength of the prepared blended fiber mat is 1.75MPa, and the initial modulus is 160MPa. After the blended fiber felt was soaked in 80vol% ethanol aqueous solution for 20min at fixed length, its breaking strength was 4MPa, the initial modulus was 380MPa, and the breaking energy was 95J·Kg -1 ; the porosity of the blended fiber felt was 80 %, the diameter of the blended fibers constituting the fiber mat ranges from 200 nm to 2 μm.
实施例3Example 3
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.2mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为33%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after silkworm cocoons are degummed with 0.5% aqueous sodium carbonate solution by mass percentage, they are dissolved in a lithium bromide aqueous solution with a molar concentration of 9.2mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 33% regenerated silk fibroin aqueous solution;
(2)将羧甲基壳聚糖溶解于去离子水中,制备质量百分比为3%的羧甲基壳聚糖水溶液;(2) carboxymethyl chitosan is dissolved in deionized water to prepare a 3% carboxymethyl chitosan aqueous solution;
(3)将所述再生丝素蛋白水溶液与所述羧甲基壳聚糖水溶液按再生丝素蛋白/羧甲基壳聚糖质量比为100:2混合,制备再生丝素蛋白/羧甲基壳聚糖共混水溶液;(3) The aqueous solution of regenerated silk fibroin and the aqueous solution of carboxymethyl chitosan are mixed according to the mass ratio of regenerated silk fibroin/carboxymethyl chitosan to 100:2 to prepare regenerated silk fibroin/carboxymethyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羧甲基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羧甲基壳聚糖共混纤维毡。静电纺丝条件为:纺丝电压为20kV,纺丝液流速为0.5mL/h,接收距离为15cm,相对湿度为50%。(4) With the regenerated silk fibroin/carboxymethyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, electrospinning is carried out to obtain the regenerated silk fibroin/carboxymethyl chitosan blended fiber felt. The electrospinning conditions are as follows: the spinning voltage is 20kV, the flow rate of the spinning solution is 0.5mL/h, the receiving distance is 15cm, and the relative humidity is 50%.
所制备的共混纤维毡断裂强度为2.3MPa,初始模量为70MPa。所述共混纤维毡定长浸泡于85vol%乙醇水溶液中30min后,其断裂强度为6.4MPa,初始模量为400MPa,断裂能为105J·Kg-1;所述共混纤维毡的孔隙率为75%,构成纤维毡的共混纤维直径的范围为400nm~2.2μm。The fracture strength of the prepared blended fiber mat is 2.3MPa, and the initial modulus is 70MPa. After the blended fiber felt was soaked in 85vol% ethanol aqueous solution for 30 minutes, its breaking strength was 6.4MPa, the initial modulus was 400MPa, and the breaking energy was 105J·Kg -1 ; the porosity of the blended fiber felt was 75%, the diameter of the blended fibers constituting the fiber mat ranges from 400nm to 2.2μm.
实施例4Example 4
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.3mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为35%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after silkworm cocoons are degummed with 0.5% by mass percent sodium carbonate aqueous solution, they are dissolved in a lithium bromide aqueous solution with a molar concentration of 9.3mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 35% aqueous solution of regenerated silk fibroin;
(2)将羧乙基壳聚糖溶解于去离子水中,制备质量百分比为5%的羧乙基壳聚糖水溶液;(2) Carboxyethyl chitosan is dissolved in deionized water to prepare a 5% carboxyethyl chitosan aqueous solution;
(3)将所述再生丝素蛋白水溶液与所述羧乙基壳聚糖水溶液按再生丝素蛋白/羧乙基壳聚糖质量比为100:3混合,制备再生丝素蛋白/羧乙基壳聚糖共混水溶液;(3) Mix the regenerated silk fibroin aqueous solution with the carboxyethyl chitosan aqueous solution according to the regenerated silk fibroin/carboxyethyl chitosan mass ratio of 100:3 to prepare regenerated silk fibroin/carboxyethyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羧乙基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羧乙基壳聚糖共混纤维毡。静电纺丝条件为:纺丝电压为25kV,纺丝液流速为1mL/h,接收距离为10cm,相对湿度为50%。(4) With the regenerated silk fibroin/carboxyethyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, electrospinning is carried out to obtain the regenerated silk fibroin/carboxyethyl chitosan blended fiber felt. The electrospinning conditions are as follows: the spinning voltage is 25kV, the flow rate of the spinning solution is 1mL/h, the receiving distance is 10cm, and the relative humidity is 50%.
所制备的共混纤维毡断裂强度为2.5MPa,初始模量为280MPa。所述共混纤维毡定长浸泡于90vol%乙醇水溶液中20min后,其断裂强度为5.9MPa,初始模量为450MPa,断裂能为110J·Kg-1;所述共混纤维毡的孔隙率为76%,构成纤维毡的共混纤维直径的范围为400nm~2.4μm。The fracture strength of the prepared blended fiber mat is 2.5MPa, and the initial modulus is 280MPa. After the blended fiber mat was soaked in 90vol% ethanol aqueous solution for 20min at fixed length, its breaking strength was 5.9MPa, the initial modulus was 450MPa, and the breaking energy was 110J·Kg -1 ; the porosity of the blended fiber felt was 76%, the diameter of the blended fibers constituting the fiber mat ranges from 400nm to 2.4μm.
实施例5Example 5
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.0mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为30%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after the silkworm cocoons are degummed with 0.5% by mass percent sodium carbonate aqueous solution, they are dissolved in a lithium bromide aqueous solution with a molar concentration of 9.0mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 30% aqueous solution of regenerated silk fibroin;
(2)将羟丙基壳聚糖溶解于去离子水中,制备质量百分比为3%的羟丙基壳聚糖水溶液;(2) dissolving hydroxypropyl chitosan in deionized water to prepare an aqueous solution of 3% hydroxypropyl chitosan by mass percent;
(3)将所述再生丝素蛋白水溶液与所述羟丙基壳聚糖水溶液按再生丝素蛋白/羟丙基壳聚糖质量比为100:2混合,制备再生丝素蛋白/羟丙基壳聚糖共混水溶液;(3) Mix the regenerated silk fibroin aqueous solution with the hydroxypropyl chitosan aqueous solution at a mass ratio of regenerated silk fibroin/hydroxypropyl chitosan of 100:2 to prepare regenerated silk fibroin/hydroxypropyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羟丙基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羟丙基壳聚糖共混纤维毡。静电纺丝条件为:纺丝电压为25kV,纺丝液流速为1mL/h,接收距离为10cm,相对湿度为55%。(4) Using the regenerated silk fibroin/hydroxypropyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, carry out electrospinning to obtain the regenerated silk fibroin/hydroxypropyl chitosan blended fiber felt. The electrospinning conditions are as follows: the spinning voltage is 25kV, the flow rate of the spinning solution is 1mL/h, the receiving distance is 10cm, and the relative humidity is 55%.
所制备的共混纤维毡断裂强度为1.9MPa,初始模量为260MPa。所述共混纤维毡定长浸泡于90vol%乙醇水溶液中30min后,其断裂强度为7.5MPa,初始模量为420MPa,断裂能为120J·Kg-1;所述共混纤维毡的孔隙率为73%,构成纤维毡的共混纤维直径的范围为400nm~1.8μm。The fracture strength of the prepared blended fiber mat is 1.9MPa, and the initial modulus is 260MPa. After the blended fiber felt was soaked in 90vol% ethanol aqueous solution for 30 minutes, its breaking strength was 7.5MPa, the initial modulus was 420MPa, and the breaking energy was 120J·Kg -1 ; the porosity of the blended fiber felt was 73%, the diameter of the blended fibers constituting the fiber mat ranges from 400nm to 1.8μm.
实施例6Example 6
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.0mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为30%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after the silkworm cocoons are degummed with 0.5% by mass percent sodium carbonate aqueous solution, they are dissolved in a lithium bromide aqueous solution with a molar concentration of 9.0mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 30% aqueous solution of regenerated silk fibroin;
(2)将羟乙基壳聚糖溶解于去离子水中,制备质量百分比为4%的羟乙基壳聚糖水溶液;(2) hydroxyethyl chitosan is dissolved in deionized water to prepare a 4% aqueous solution of hydroxyethyl chitosan;
(3)将所述再生丝素蛋白水溶液与所述羟乙基壳聚糖水溶液按再生丝素蛋白/羟乙基壳聚糖质量比为100:3混合,制备再生丝素蛋白/羟乙基壳聚糖共混水溶液;(3) The aqueous solution of regenerated silk fibroin and the aqueous solution of hydroxyethyl chitosan are mixed according to the mass ratio of regenerated silk fibroin/hydroxyethyl chitosan to 100:3 to prepare regenerated silk fibroin/hydroxyethyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羟乙基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羟乙基壳聚糖共混纤维毡。静电纺丝条件为:纺丝电压为25kV,纺丝液流速为1mL/h,接收距离为10cm,相对湿度为50%。(4) Using the regenerated silk fibroin/hydroxyethyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, electrospinning is carried out to obtain the regenerated silk fibroin/hydroxyethyl chitosan blended fiber felt. The electrospinning conditions are as follows: the spinning voltage is 25kV, the flow rate of the spinning solution is 1mL/h, the receiving distance is 10cm, and the relative humidity is 50%.
所制备的共混纤维毡断裂强度为2.8MPa,初始模量为150MPa。所述共混纤维毡定长浸泡于90vol%乙醇水溶液中30min后,其断裂强度为7.3MPa,初始模量为370MPa,断裂能为60J·Kg-1;所述共混纤维毡的孔隙率为76%,构成纤维毡的共混纤维直径的范围为400nm~1.6μm。The fracture strength of the prepared blended fiber mat is 2.8MPa, and the initial modulus is 150MPa. After the blended fiber felt was soaked in 90vol% ethanol aqueous solution for 30min at fixed length, its breaking strength was 7.3MPa, the initial modulus was 370MPa, and the breaking energy was 60J·Kg -1 ; the porosity of the blended fiber felt was 76%, the diameter of the blended fibers constituting the fiber mat ranges from 400nm to 1.6μm.
实施例7Example 7
一种再生丝素蛋白/壳聚糖衍生物共混纤维毡的制备方法,其步骤为:A preparation method for a regenerated silk fibroin/chitosan derivative blended fiber mat, the steps of which are:
(1)以蚕茧为原料,蚕茧用质量百分比0.5%的碳酸钠水溶液脱胶后,溶解于摩尔浓度为9.0mol/L的溴化锂水溶液中;将此溶液离心、过滤、透析和浓缩后,得到质量百分比为30%再生丝素蛋白水溶液;(1) Taking silkworm cocoons as raw materials, after the silkworm cocoons are degummed with 0.5% by mass percent sodium carbonate aqueous solution, they are dissolved in a lithium bromide aqueous solution with a molar concentration of 9.0mol/L; after the solution is centrifuged, filtered, dialyzed and concentrated, the mass percent is obtained 30% aqueous solution of regenerated silk fibroin;
(2)将羧甲基壳聚糖溶解于去离子水中,制备质量百分比为5%的羧甲基壳聚糖水溶液;(2) carboxymethyl chitosan is dissolved in deionized water to prepare a 5% carboxymethyl chitosan aqueous solution;
(3)将所述再生丝素蛋白水溶液与所述羧甲基壳聚糖水溶液按再生丝素蛋白/羧甲基壳聚糖质量比为100:5混合,制备再生丝素蛋白/羧甲基壳聚糖共混水溶液;(3) Mix the regenerated silk fibroin aqueous solution with the carboxymethyl chitosan aqueous solution according to the regenerated silk fibroin/carboxymethyl chitosan mass ratio of 100:5 to prepare the regenerated silk fibroin/carboxymethyl chitosan Chitosan blended aqueous solution;
(4)以步骤(3)制备的再生丝素蛋白/羧甲基壳聚糖共混水溶液为纺丝原液,进行静电纺丝,即得到再生丝素蛋白/羧甲基壳聚糖共混纤维毡。静电纺丝条件为:纺丝电压为30kV,纺丝液流速为1mL/h,接收距离为15cm,相对湿度为50%。(4) With the regenerated silk fibroin/carboxymethyl chitosan blended aqueous solution prepared in step (3) as the spinning stock solution, electrospinning is carried out to obtain the regenerated silk fibroin/carboxymethyl chitosan blended fiber felt. The electrospinning conditions are as follows: the spinning voltage is 30kV, the flow rate of the spinning solution is 1mL/h, the receiving distance is 15cm, and the relative humidity is 50%.
所制备的共混纤维毡断裂强度为1.8MPa,初始模量为210MPa。所述共混纤维毡定长浸泡于95vol%乙醇水溶液中30min后,其断裂强度为4.7MPa,初始模量为420MPa,断裂能为98J·Kg-1;所述共混纤维毡的孔隙率为65%,构成纤维毡的共混纤维直径的范围为200nm~1.4μm。The fracture strength of the prepared blended fiber mat is 1.8MPa, and the initial modulus is 210MPa. After the blended fiber felt was soaked in 95vol% ethanol aqueous solution for 30min at a fixed length, its breaking strength was 4.7MPa, its initial modulus was 420MPa, and its breaking energy was 98J·Kg -1 ; the porosity of the blended fiber felt was 65%, and the diameter of the blended fibers constituting the fiber mat ranges from 200nm to 1.4μm.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410165983.4A CN103993422B (en) | 2014-04-23 | 2014-04-23 | A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410165983.4A CN103993422B (en) | 2014-04-23 | 2014-04-23 | A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103993422A CN103993422A (en) | 2014-08-20 |
CN103993422B true CN103993422B (en) | 2017-03-15 |
Family
ID=51307740
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410165983.4A Active CN103993422B (en) | 2014-04-23 | 2014-04-23 | A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103993422B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160206780A1 (en) * | 2014-08-15 | 2016-07-21 | Suzhou Cancercell Biotechnology Co. Ltd | Matrix Scaffold for Three-Dimensional Cell Cultivation, Methods of Construction Thereof and Uses Thereof |
CN106693030A (en) * | 2015-08-31 | 2017-05-24 | 青岛新智源健康科技有限公司 | Chitosan nanofibers as well as large-scale electrospinning preparation method and application thereof |
CN107118361B (en) * | 2017-04-21 | 2020-04-28 | 浙江大学 | Silk fibroin/carboxymethyl chitosan composite gel and preparation method thereof |
CN107012525A (en) * | 2017-06-01 | 2017-08-04 | 合肥创沃科技有限公司 | A kind of preparation method of the composite regenerated cellulose tissue repair materials of chitosan |
CN109989119A (en) * | 2018-01-03 | 2019-07-09 | 浙江大学 | A kind of preparation method, product and application of porous fiber with oriented pore structure |
CN109646706A (en) * | 2018-12-28 | 2019-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing anti-scar overlay film using method of electrostatic spinning and products thereof and application |
CN109758602B (en) * | 2019-01-31 | 2019-10-29 | 深圳市源兴医药股份有限公司 | High suction type, strong antibacterial dressing and preparation method thereof |
CN111188194B (en) * | 2020-02-24 | 2022-03-22 | 淮阴工学院 | Preparation method of silk fibroin/gelatin fiber reinforced chitosan composite hemostatic material |
CN112275260A (en) * | 2020-07-13 | 2021-01-29 | 广西科技大学 | Chitosan/fibroin-based dual-structure porous adsorption filter material with polyethylene glycol as pore-foaming agent and preparation method thereof |
CN116585521A (en) * | 2023-04-28 | 2023-08-15 | 现代纺织技术创新中心(鉴湖实验室) | Preparation method of chitosan-loaded silk fibroin-based antibacterial hemostatic material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101445971A (en) * | 2008-12-19 | 2009-06-03 | 东华大学 | Method for preparing bionic extracellular matrix silk fibroin/chitosan composite nanometer fibre |
CN102936794A (en) * | 2012-11-20 | 2013-02-20 | 东华大学 | Method for preparing composite nanofiber membrane based on natural material silk fibroin and chitosan |
CN103861145A (en) * | 2014-03-10 | 2014-06-18 | 武汉大学 | Immediately crosslinking technology for preparing macroporous three-dimensional nanofiber bracket |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101201412B1 (en) * | 2011-04-19 | 2012-11-14 | 한양대학교 에리카산학협력단 | Preparation method for highly porous core-shell nanoweb |
-
2014
- 2014-04-23 CN CN201410165983.4A patent/CN103993422B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101445971A (en) * | 2008-12-19 | 2009-06-03 | 东华大学 | Method for preparing bionic extracellular matrix silk fibroin/chitosan composite nanometer fibre |
CN102936794A (en) * | 2012-11-20 | 2013-02-20 | 东华大学 | Method for preparing composite nanofiber membrane based on natural material silk fibroin and chitosan |
CN103861145A (en) * | 2014-03-10 | 2014-06-18 | 武汉大学 | Immediately crosslinking technology for preparing macroporous three-dimensional nanofiber bracket |
Non-Patent Citations (3)
Title |
---|
丝素蛋白/壳聚糖共混纳米纤维的制备;王永攀等;《浙江理工大学学报》;20090731;第26卷(第4期);第481-485页 * |
壳聚糖静电纺纳米纤维的制备和特点;孙康等;《应用化学》;20110228;第28卷(第2期);第123-130页 * |
静电纺丝素蛋白纤维毡在乙醇水溶液中的拉伸后处理;范苏娜等;《功能材料》;20121231;第43卷(第18期);第2509-2512页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103993422A (en) | 2014-08-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103993422B (en) | A kind of regenerated silk fibroin/chitosan derivatives blended fiber felt and preparation method thereof | |
Han et al. | A review: current status and emerging developments on natural polymer‐based electrospun fibers | |
Zhao et al. | Preparation of nanofibers with renewable polymers and their application in wound dressing | |
CN106521706B (en) | A kind of preparation method of cellulose nanometer fibril/alginate composite fiber | |
CN103469351B (en) | The preparation method of load ascorbic fibroin albumen/hyaluronic acid composite nano fiber | |
CN103993424B (en) | Preparing method of polyurethane-keratin composite nano fiber film | |
CN103341209B (en) | Silk fibroin nanofiber membrane and preparation method thereof | |
CN100457990C (en) | Producing method and use for common and functional calcium alginate fiber | |
CN102199810B (en) | Method for preparing chitosan fibers | |
CN103418021B (en) | In-situ-crossly-linked electrospun fibrous membrane dressing made from collangen I and preparation method of in-situ crosslinking electrospun fibrous membrane dressing | |
CN104726963A (en) | Chitosan fiber and preparation method thereof | |
CN104018247B (en) | The preparation method of a kind of urethane-Keratin sulfate composite nano fiber tubular material | |
CN102146594A (en) | Oxidized cellulose nanofibers and preparation method thereof | |
WO2014044011A1 (en) | Alginate woven fabrics and method for preparing the same | |
CN103320886A (en) | Bionic regenerated silk fibroin filament fiber and preparation method thereof | |
CN106758217A (en) | A kind of crosslinking preparation method of gelatin/chitosan composite nano-fiber membrane | |
CN107130333A (en) | A kind of alginic acid and chitosan shuffling fiber and preparation method thereof | |
CN104711702A (en) | Collagen aggregate compound medical fiber with antibacterial/bacteriostatic function | |
CN104005179A (en) | Method for preparing polycaprolactone-keratin composite nanometer fiber pipe | |
CN111519280A (en) | Preparation method of chitosan fiber material | |
CN110760943B (en) | Preparation and application of fresh flower fiber filament for spinning | |
CN105839294A (en) | Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method | |
CN107287884A (en) | A kind of preparation method for attaching ventilative artificial skin receptor | |
CN106498554A (en) | A kind of boracic chitosan/polyvinyl alcohol composite fibre and preparation method thereof, non-weaving cloth | |
CN103668617B (en) | Natural polymer yarn and its manufacturing method, mesh fabric and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |