Chitosan nano superfine fibrous membrane materials and preparation method thereofTechnical field
The present invention relates to a kind of preparation method of chitosan nano superfine fibrous membrane materials, belong to the tissue renovation material technology.
Background technology
Chitosan is the deacetylated product of chitin, has the chemical constitution that is similar to glycosaminoglycans in the extracellular matrix, and can be degraded by lysozyme, has been used for bio-medical products such as artificial skin, operation suture thread.
In the reparation of skin and cartilage, chitosan can provide the avtive spot that combines with cell and bioactive substance, and biocompatibility is good.Existing chitosan restoration mostly is the porous foam film of thickness more than 1mm, or be non-woven fabrics or the fabric that the ultimate fibre about 10 μ m constitutes with diameter, collagen and glycosaminoglycans differ greatly in its structure dimension and the extracellular matrix, and the latter is fiber or the fibril of 50nm～500nm.
Be different from traditional spinning, electrostatic spinning is by means of the spinning process under the extra electric field effect.Under the high voltage electric field effect, be subjected to electrostatic repulsion forces, Coulomb force and capillary combined effect itself, the polymer thread that ejects from the capillary tube top is along unsettled helical trajectory curvilinear motion, drafted thousands of times in a few tens of milliseconds, thereby form superfine fibre (Reneker DH, Yarin AL, Fong H, et al.Bending instability of electrically charged liquid jets ofpolymer solutions in electrospinning.J.Appl Phys 2000,87 (9): 4531).Superfine fibre directly is collected on the receiving screen, forms the nonwoven superfine fibre film.Utilize the method can prepare the superfine fibrous membrane materials of diameter for 50nm～500nm.
The research work of Zong etc. shows, utilize the poly-Alpha-hydroxy acid esters superfine fibre film of biological degradability of electrostatic spinning preparation, carrier (the Zong XH that can be used as the cell storage and discharge, Chu B, Fang DF, et al.Cell storage anddelivery system.US Patent 2,003 054035).Luu etc. integrate with lactide glycolide copolymer (PLGA) solution with DNA and carry out electrostatic spinning, the DNA that has formed nanofibrous structures reprints support (Luu YK, Kim K, HsiaoBS el al.Development of a nanostructured DNA delivery scaffold via electrospinning of PLGAand PLA-PEG block copolymer.J Control Release 2003,89 (2): 341).Li etc. have prepared the PLGA nonwoven web with electrostatic spinning, point out that from the aspects such as adhesion of porosity, mechanical property and pair cell it can satisfy the basic demand of tissue engineering bracket (Li WJ, Laurencin CT, Caterson EJ et al.Electrospun nanofirousstructure:a novel scaffold for tissue engineering.J Biomed Mater Res 2002,60 (4): 613).
Existing superfine fibre repair membrane material is not seen simple research report or patent of invention to the chitosan superfine fibre film.
Summary of the invention
The object of the present invention is to provide a kind of chitosan nano superfine fibrous membrane materials and preparation method thereof, this membrane material is as artificial skin or artificial cartilage material, have liquid absorption greatly, degradable, cellular affinity reach the advantage that promotes corrupted to organize rehabilitation well in vivo, its preparation method process is simple.
For achieving the above object, the present invention is realized by following technical proposals.A kind of chitosan nano superfine fibrous membrane materials, it is characterized in that, this membrane material is to be 10～90% chitosan by mass percent, with mass percent be the diameter of 90～10% polyvinyl alcohol (PVA) be 50nm～500nm superfine fibre or with mass percent be that the diameter of 90～10% polyethylene glycol oxide (PEO) is that to form thickness be the thin film of 10 μ m～50 μ m for the superfine fibre of 50nm～500nm.
The preparation method of above-mentioned nanometer superfine fibrous membrane materials is characterized in that comprising following process: will glue all molecular mass (M relativelyη) be that 50,000～1,000,000 chitosan is dissolved in 1%～5% the acetic acid aqueous solution, be 10/90～90/10 in solution, to add PVA or PEO by chitosan/second constituent mass ratio then, the spinning solution that is mixed with concentration 4～8% is injected in the electrostatic spinning apparatus, is that 5kV～30kV, liquid inventory are that 0.1mL/h～0.5mL/h, receiving range are electrostatic spinning film forming under the condition of 5cm～25cm at voltage.
The invention has the advantages that this membrane material is as artificial skin or artificial cartilage material, have liquid absorption greatly, degradable, cellular affinity reach the advantage that promotes corrupted to organize rehabilitation well in vivo, its preparation method process is simple.
The specific embodiment
Embodiment 1:
Get MηBe 200,000 chitosan 0.6g, get the degree of polymerization and be 1750 ± 50, alcoholysis degree is 98% PVA 0.6g, be dissolved in 10mL 2% acetic acid,diluted in room temperature under magnetic agitation respectively, both mix and form the transparent spinning solution of 20mL then.In having the 50mL syringe that internal diameter is the flat lancet head of 0.8mm, inject spinning solution, syringe is fixed on the micro-injection pump, the vertical metal receiving screen of placing ground connection at distance syringe needle 10cm place.Syringe needle is linked to each other with the high-voltage DC power supply of 10kV, set the 0.1mL/h flow and carry out electrostatic spinning,, contain a spot of fusiformis pearl in the superfine fibre on receiving screen, to collect the superfine fibre film of diameter behind the 72h less than 200nm.
Embodiment 2:
Get MηBe 650,000 chitosan 0.6g, get MηBe 2,300,000 PEO 0.6g, under magnetic agitation, be dissolved in 20mL 2% acetic acid,diluted, obtain transparent spinning solution in room temperature.The same use has the 50mL syringe of internal diameter as the flat lancet head of 0.8mm, at receiving range is that 20cm, voltage are that 15kV, liquid inventory are to carry out electrostatic spinning under the 0.1mL/h condition, to collect the superfine fibre film that diameter is 100nm～300nm behind the 72h on receiving screen.
Embodiment 3:
Get MηBe 100,000 chitosan 0.8g, get the degree of polymerization and be 1750 ± 50, alcoholysis degree is 98% PVA 1.2g, be dissolved in 25mL 2% acetic acid,diluted in room temperature under magnetic agitation respectively, both mix and form the transparent spinning solution of 50mL then.The same use has the 50mL syringe of internal diameter as the flat lancet head of 0.8mm, at receiving range is that 15cm, voltage are that 15kV, liquid inventory are to carry out electrostatic spinning under the 0.1mL/h condition, to collect the superfine fibre film of diameter less than 200nm behind the 72h on receiving screen.
Embodiment 4:
Get MηBe 650,000 chitosan 0.8g, get MηBe 1,500,000 PEO 0.4g, under magnetic agitation, be dissolved in 20mL 2% acetic acid,diluted, obtain transparent spinning solution in room temperature.The same use has the 50mL syringe of internal diameter as the flat lancet head of 0.8mm, at receiving range is that 20cm, voltage are that 15kV, liquid inventory are to carry out electrostatic spinning under the 0.1mL/h condition, to collect the superfine fibre film that diameter is 100nm～300nm behind the 72h on receiving screen.