CN101892559A - Hyaluronic acid and polyethylene glycol composite fiber membrane material and preparation method and application thereof - Google Patents
Hyaluronic acid and polyethylene glycol composite fiber membrane material and preparation method and application thereof Download PDFInfo
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- CN101892559A CN101892559A CN2009100843463A CN200910084346A CN101892559A CN 101892559 A CN101892559 A CN 101892559A CN 2009100843463 A CN2009100843463 A CN 2009100843463A CN 200910084346 A CN200910084346 A CN 200910084346A CN 101892559 A CN101892559 A CN 101892559A
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Abstract
The invention relates to a biodegradable and bioabsorbable hyaluronic acid and polyethylene glycol superfine composite fiber membrane material and a preparation method and application thereof. The composite fiber membrane material is prepared from 5 to 90 mass percent of hyaluronic acid and 10 to 95 mass percent of low-molecular-weight polyethylene glycol by taking water as a solvent, wherein fibers in the composite superfine fiber membrane have a spider silk structure and the fiber diameter is 100nm to 10mu m. The low-molecular-weight polyethylene glycol is adopted, so that the hyaluronic acid accounts for 5 mass percent of mixed solution of hyaluronic acid and polyethylene glycol, and the yield of the composite superfine fibers can be improved. The material has the advantages of high biocompatibility, biodegradability and bioabsorbability, light weight, softness, high air permeability and the like, and can be used as a hemostatic material, a wound dressing and a tissue engineering scaffold material.
Description
Technical field
But the invention belongs to the boiomacromolecule nonwoven cloth material field of biodegradable and bio-absorbable, but the hyaluronic acid of particularly biodegradable and bio-absorbable and superfine composite fiber membrane material and the method for making and the purposes of polyethylene glycol.
Background technology
Hyaluronic acid (HA) is a kind of polyanion type mucopolysaccharide, is the main component of extracellular matrix.Owing to have excellent biological compatibility and biodegradability, hyaluronic acid has been widely used in the biologic pharmacological science field.HA can be widely used in bio-medical material, pharmacy and cosmetic field, be because it has special physico-chemical property: the repetition disaccharide unit that contains in (1) hyaluronan molecule all is consistent at all species with in organizing, immunological rejection (the Cell Biochemistry and Function that therefore can not cause hyaluronan molecule self, 1994,12:281); (2) the hyaluronic acid work is a kind of polymerization anion electrolyte, on the hyaluronan molecule with a large amount of negative electrical charges, can regulate hyaluronan molecule negative ion concentrations on every side, suppress multiple biological enzyme activity (In viscoelastic materials:basic science and clinical application, 1986, Pergamon press, New York; Journal of Rheumatology 1993,20:3) (3) HA has good water retention and lubrication, can regulate the synthetic of collagen, suppressing the surface of a wound shrinks, reduce scar and form, good application (In Fourth International Workshop on Hyaluronan in Drug Delivery, 1996 are arranged in clinical, RSM Press, London; Embo Journal, 1994,13:286).
Electrostatic spinning is a kind of simple and effective processing technology for preparing polymer superfine fibre, and the electrostatic spinning goods are particularly suitable in Application as Medical Material owing to having characteristics such as super large specific area and super large porosity.By bioabsorbable polymer material is carried out electrostatic spinning, can make on 26S Proteasome Structure and Function similar to the n cell epimatrix, and has better biocompatibility, and the new bio medical material with certain intensity and stability, one of ideal material that this material is material implanted and human organ reproduces.
Hyaluronic electrostatic spinning is the earliest by people such as Chu (Biomacromolecules, 2004,5:1428; Polymer, 2005,46:4853) means that adopt electricity to blow electrospinning realize, the applicant utilizes the mixed solvent of DMF and water to realize the preparation of HA nonwoven fabric, sees CN200510011454.X.
Do not see yet at present about the pure water solution system and do not having report or the patent that electricity blows preparation hyaluronic acid superfine fibre film under the condition.The present invention has prepared the composite superfine fibre membrane material of hyaluronic acid and polyethylene glycol by the character of selecting for use the water soluble polymer polyethylene glycol to regulate the HA aqueous solution, this kind material has the light weight softness, and advantages such as high porosity can be used for hemostatic material, the wound clad material, tissue engineering bracket material.
Summary of the invention
The object of the present invention is to provide a kind of have excellent biological compatibility, biological degradability and bioresorbable, has the light weight softness simultaneously, characteristics such as good permeability can be used as hemostatic material, wound clad material, but the hyaluronic acid of the biodegradable and bio-absorbable that tissue engineering bracket material uses and the composite superfine fibre membrane material of polyethylene glycol.
It is simple that a further object of the present invention provides a kind of preparation method, the composite superfine fibre membrane preparation methods of eco-friendly hyaluronic acid of preparation process and polyethylene glycol.
An also purpose of the present invention provides the purposes of the composite superfine fibre membrane material of hyaluronic acid and polyethylene glycol.
The composite superfine fibre membrane material of hyaluronic acid of the present invention and polyethylene glycol is to be made of the composite fibre of smooth composite fibre or pearl silk structure (bead-on-string fiber), and described complex fiber material is that 5%～90% hyaluronic acid and quality percentage composition are that 10%～95% polyethylene glycol is formed by the quality percentage composition.
The weight average molecular weight of described polyethylene glycol (Mw) is to less than 50,000 more than or equal to 0.1 ten thousand; The weight average molecular weight (Mw) of preferred polyethylene glycol is 0.1 ten thousand～20,000.
Described hyaluronic weight average molecular weight (Mw) is 200,000～2,000,000.
The diameter of the composite fibre in the described composite cellulosic membrane is 100nm～10 μ m.
The diameter of the pearl in the fiber of described pearl silk structure is not more than 10 μ m, and the diameter that connects the fiber of pearl is not less than 100nm.
The composite superfine fibre membrane preparation methods of hyaluronic acid of the present invention and polyethylene glycol is: hyaluronic acid is water-soluble, be mixed with hyaluronic acid aqueous solution, add polyethylene glycol then and obtain mixed liquor, wherein, the mass ratio of hyaluronic acid in the mixed liquor and polyethylene glycol is 5～90: 10～95; Mixed liquor is stirred under room temperature (as 25 ℃), obtain the mixed liquor of transparent and homogeneous; The mixed liquor injection electrostatic spinning apparatus of above-mentioned transparent and homogeneous is carried out electrostatic spinning, obtain the composite superfine fibre membrane material of hyaluronic acid and polyethylene glycol.
The mass percentage concentration of described hyaluronic acid aqueous solution is 0.5%～5%.
The condition of described electrostatic spinning can adopt prior art, is that 15～30kV, liquid inventory are that 10～100 μ L/min, receiving range are 5cm～25cm as voltage.
The described composite superfine fibre membrane material that obtains hyaluronic acid and polyethylene glycol can further carry out vacuumize under room temperature (as 25 ℃).
The weight average molecular weight of described polyethylene glycol (Mw) is to less than 50,000 more than or equal to 0.1 ten thousand; The weight average molecular weight (Mw) of preferred polyethylene glycol is 0.1 ten thousand～20,000.
Described hyaluronic weight average molecular weight (Mw) is=20 ten thousand～2,000,000.
Hyaluronic acid that relates among the present invention and polyethylene glycol composite superfine fibre membrane have excellent biological compatibility, biological degradability and bioresorbable, have the light weight softness simultaneously, advantage such as ventilative good, this material can be used for hemostatic material, the wound clad material, tissue engineering bracket material uses.
Because the present invention has adopted low-molecular-weight polyethylene glycol, can make the hyaluronic mass percentage concentration in hyaluronic acid and the polyethylene glycol mixed liquor reach 5%, therefore can improve the productive rate of gained composite ultrafine fiber, and the fiber that can obtain in the composite superfine fibre membrane can be pearl silk structure (bead-on-string fiber).
Method provided by the invention is simply effective, adopts water as solvent, has avoided with an organic solvent causing environmental pollution.
Description of drawings
Fig. 1. the SEM of hyaluronic acid and polyethylene glycol composite superfine fibre membrane figure in the embodiment of the invention 1, the hyaluronic quality percentage composition in this composite superfine fibre membrane is 90%, the quality percentage composition of polyethylene glycol is 10%.
Fig. 2. the SEM of hyaluronic acid and polyethylene glycol composite superfine fibre membrane figure in the embodiment of the invention 2, the hyaluronic quality percentage composition in this composite superfine fibre membrane is 50%, the quality percentage composition of polyethylene glycol is 50%.
The specific embodiment
Embodiment 1
With weight average molecular weight (Mw) is that 2,000,000 hyaluronic acid is water-soluble, be mixed with mass percentage concentration and be 2% hyaluronic acid aqueous solution, add weight average molecular weight then and be 10,000 polyethylene glycol and obtain mixed liquor, wherein, the hyaluronic acid in the mixed liquor and the mass ratio of polyethylene glycol are 90: 10; Mixed liquor is stirred under 25 ℃, obtain the mixed liquor of transparent and homogeneous; The mixed liquor injection electrostatic spinning apparatus of above-mentioned transparent and homogeneous is carried out electrostatic spinning, at voltage is that 20kV, liquid inventory are that 50 μ L/min, receiving range are to carry out electrostatic spinning under the condition of 15cm, obtain can be used in hemostatic material, the hyaluronic acid that wound clad material and/or tissue engineering bracket material use and the composite superfine fibre membrane material of polyethylene glycol.This hyaluronic acid and polyethylene glycol composite superfine fibre membrane are that the average diameter of composite fibre is 2 μ m, sees Fig. 1 by the composite fibre formation of pearl silk structure (bead-on-string fiber).
Embodiment 2
With weight average molecular weight (Mw) is that 200,000 hyaluronic acid is water-soluble, be mixed with mass percentage concentration and be 5% hyaluronic acid aqueous solution, add weight average molecular weight then and be 50,000 polyethylene glycol and obtain mixed liquor, wherein, the hyaluronic acid in the mixed liquor and the mass ratio of polyethylene glycol are 50: 50; Mixed liquor is stirred under 25 ℃, obtain the mixed liquor of transparent and homogeneous; The mixed liquor injection electrostatic spinning apparatus of above-mentioned transparent and homogeneous is carried out electrostatic spinning, at voltage is that 20kV, liquid inventory are that 50 μ L/min, receiving range are to carry out electrostatic spinning under the condition of 15cm, obtain can be used in hemostatic material, the hyaluronic acid that wound clad material and/or tissue engineering bracket material use and the composite superfine fibre membrane material of polyethylene glycol.The average diameter of the composite fibre in this hyaluronic acid and the polyethylene glycol composite superfine fibre membrane is 2 μ m, sees Fig. 2.
Embodiment 3
With weight average molecular weight (Mw) is that 1,500,000 hyaluronic acid is water-soluble, be mixed with mass percentage concentration and be 2% hyaluronic acid aqueous solution, add weight average molecular weight then and be 0.1 ten thousand polyethylene glycol and obtain mixed liquor, wherein, the hyaluronic acid in the mixed liquor and the mass ratio of polyethylene glycol are 5: 95; Mixed liquor is stirred under 25 ℃, obtain the mixed liquor of transparent and homogeneous; The mixed liquor injection electrostatic spinning apparatus of above-mentioned transparent and homogeneous is carried out electrostatic spinning, at voltage is that 20kV, liquid inventory are that 50 μ L/min, receiving range are to carry out electrostatic spinning under the condition of 15cm, obtain can be used in hemostatic material, the hyaluronic acid that wound clad material and/or tissue engineering bracket material use and the composite superfine fibre membrane material of polyethylene glycol.This hyaluronic acid and polyethylene glycol composite superfine fibre membrane are that the average diameter of composite fibre is 10 μ m by the composite fibre formation of pearl silk structure (bead-on-string fiber).
Embodiment 4
With weight average molecular weight (Mw) is that 1,000,000 hyaluronic acid is water-soluble, be mixed with mass percentage concentration and be 0.5% hyaluronic acid aqueous solution, add weight average molecular weight then and be 20,000 polyethylene glycol and obtain mixed liquor, wherein, the hyaluronic acid in the mixed liquor and the mass ratio of polyethylene glycol are 30: 70; Mixed liquor is stirred under 25 ℃, obtain the mixed liquor of transparent and homogeneous; The mixed liquor injection electrostatic spinning apparatus of above-mentioned transparent and homogeneous is carried out electrostatic spinning, at voltage is that 20kV, liquid inventory are that 50 μ L/min, receiving range are to carry out electrostatic spinning under the condition of 15cm, obtain can be used in hemostatic material, the hyaluronic acid that wound clad material and/or tissue engineering bracket material use and the composite superfine fibre membrane material of polyethylene glycol.This hyaluronic acid and polyethylene glycol composite superfine fibre membrane are that the average diameter of composite fibre is 100nm by the composite fibre formation of pearl silk structure (bead-on-string fiber).
Claims (9)
1. the composite fiber membrane material of hyaluronic acid and polyethylene glycol, it is characterized in that: described composite cellulosic membrane is that the composite fibre by smooth composite fibre or pearl silk structure constitutes, and described complex fiber material is that 5%～90% hyaluronic acid and quality percentage composition are that 10%～95% polyethylene glycol is formed by the quality percentage composition;
The weight average molecular weight of described polyethylene glycol is to less than 50,000 more than or equal to 0.1 ten thousand.
2. the composite fiber membrane material of hyaluronic acid according to claim 1 and polyethylene glycol is characterized in that: the weight average molecular weight of described polyethylene glycol is 0.1 ten thousand～20,000.
3. the composite fiber membrane material of hyaluronic acid according to claim 1 and polyethylene glycol is characterized in that: described hyaluronic weight average molecular weight is 200,000～2,000,000.
4. according to the composite fiber membrane material of claim 1 or 3 described hyaluronic acids and polyethylene glycol, it is characterized in that: the diameter of the composite fibre in the described composite cellulosic membrane is 100nm～10 μ m.
5. preparation method according to the composite fiber membrane material of any described hyaluronic acid of claim 1～4 and polyethylene glycol, it is characterized in that: hyaluronic acid is water-soluble, be mixed with hyaluronic acid aqueous solution, add polyethylene glycol then and obtain mixed liquor, wherein, the mass ratio of hyaluronic acid in the mixed liquor and polyethylene glycol is 5～90: 10～95; Mixed liquor is at room temperature stirred, obtain the mixed liquor of transparent and homogeneous; The mixed liquor injection electrostatic spinning apparatus of above-mentioned transparent and homogeneous is carried out electrostatic spinning, obtain the composite fiber membrane material of hyaluronic acid and polyethylene glycol;
The weight average molecular weight of described polyethylene glycol is to less than 50,000 more than or equal to 0.1 ten thousand.
6. method according to claim 5 is characterized in that: the weight average molecular weight of described polyethylene glycol is 0.1 ten thousand～20,000.
7. method according to claim 5 is characterized in that: the mass percentage concentration of described hyaluronic acid aqueous solution is 0.5%～5%.
8. according to claim 5 or 7 described methods, it is characterized in that: described hyaluronic weight average molecular weight is 200,000～2,000,000.
9. purposes according to the composite fiber membrane material of any described hyaluronic acid of claim 1～4 and polyethylene glycol, it is characterized in that: the composite fiber membrane material of described hyaluronic acid and polyethylene glycol can be used in hemostatic material, the wound clad material, tissue engineering bracket material uses.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936312A (en) * | 2017-11-29 | 2018-04-20 | 桂林华诺威生物科技有限公司 | The preparation method of cross-linking hyaluronic acid sodium biomembrane |
| CN111793854A (en) * | 2020-08-13 | 2020-10-20 | 山东华熙海御生物医药有限公司 | Hyaluronic acid fiber material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100514582B1 (en) * | 2001-09-05 | 2005-09-13 | 한스바이오메드 주식회사 | A Process for Preparing a Biomaterial for Tissue Repair |
| CN1515323A (en) * | 2003-01-09 | 2004-07-28 | 成都博联医疗信息产业有限责任公司 | Preparation method of flexible absorbable medical film material |
| CN1515232A (en) * | 2003-01-09 | 2004-07-28 | 成都博联医疗信息产业有限责任公司 | Preparation method of medical film for dentistry |
| CN101011331A (en) * | 2007-01-17 | 2007-08-08 | 成都死海盐疗健康馆服务有限公司 | Dead sea salt hydrotherapy face pack |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936312A (en) * | 2017-11-29 | 2018-04-20 | 桂林华诺威生物科技有限公司 | The preparation method of cross-linking hyaluronic acid sodium biomembrane |
| CN111793854A (en) * | 2020-08-13 | 2020-10-20 | 山东华熙海御生物医药有限公司 | Hyaluronic acid fiber material and preparation method thereof |
| CN111793854B (en) * | 2020-08-13 | 2023-03-10 | 山东华熙海御生物医药有限公司 | Hyaluronic acid fiber material and preparation method thereof |
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Granted publication date: 20111019 Termination date: 20200521 |