CN102605466A - Preparation method of natural polyelectrolyte-based core-shell structured nano-fiber - Google Patents
Preparation method of natural polyelectrolyte-based core-shell structured nano-fiber Download PDFInfo
- Publication number
- CN102605466A CN102605466A CN2012100526179A CN201210052617A CN102605466A CN 102605466 A CN102605466 A CN 102605466A CN 2012100526179 A CN2012100526179 A CN 2012100526179A CN 201210052617 A CN201210052617 A CN 201210052617A CN 102605466 A CN102605466 A CN 102605466A
- Authority
- CN
- China
- Prior art keywords
- solution
- polyelectrolyte
- hours
- shell structure
- obtains
- 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.)
- Pending
Links
Images
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a preparation method of natural polyelectrolyte-based core-shell structured nano-fiber. According to the invention, natural products of hyaluronic acid, sodium polymannuronate, heparin, gamma-polyglutamic acid, chitosan, and epsilon-polylysine, and synthesized polymers of polyoxyethylene, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and polycaprolactone are adopted as raw materials; a soluble composite solution of the materials are prepared; and the natural polyelectrolyte-based core-shell structured nano-fiber is prepared with a high-pressure electrospinning technology. According to the invention, polyelectrolyte and synthesized polymers are separated through the induction of electric fields, such that the core-shell structured nano-fiber is successfully prepared. The nano-fiber prepared by the invention has special potential application in respects such as bioactive compound or medicine packaging, chemical modification, cell stents, medicine releasing, and gene transferring.
Description
Technical field
The invention belongs to the preparation field of boiomacromolecule composite nano-fiber material, relate to polyelectrolyte base nuclear shell structure nano fiber preparation method.
Background technology
Electrostatic spinning is a kind of processing method that makes charged polymer solution or melt in electrostatic field, spray the preparation polymer superfine fibre; When extra electric field reaches certain critical value; Fiber will and go out from the spinning nozzle injection; Solvent volatilizees gradually and leaves charged fiber simultaneously, and dry fiber drops on the collecting board, forms ultra-fine nano fiber non-woven fabric.Advantages such as the nano fiber non-woven fabric of preparation has that specific area is big, porosity is high, the fine degree of fiber and homogeneity height, draw ratio are big make it have higher in fields such as bio-medical material such as bioengineered tissue, wound repair, skin burn and post-operation adhesion preventings and using value widely.The nuclear shell structure nano fiber also has distinctive potential application at the aspects such as encapsulation, chemical modification, cytoskeleton, drug and gene reprinting of bioactive compound or medicine except that having the application in above field.Therefore, the preparation of nuclear shell structure nano fiber and application have attracted the concern of a lot of seminars.
There are a large amount of natural polymers in occurring in nature; Like hyaluronic acid, shitosan, sodium alginate etc.; Have advantages such as good biodegradable and biocompatibility, can prepare into nano fibrous membrane through electrical spinning method and be applied to fields such as bioengineered tissue, bio-medical material.Hyaluronic acid (Hyaluronic acid; HA) have another name called sodium hyaluronate; Be to be present in a kind of acid mucopolysaccharide in the extracellular matrix in the biological tissue; By β-D-N-acetylglucosamine and β-D-glucose sulfonic acid be construction unit with β-1, a kind of chain macromolecule that the 4-glycosidic linkage is linked to be is a kind of polyelectrolyte that has negative electrical charge.Owing to characteristics such as its excellent biological compatibility and biodegradable are widely used in fields such as organizational project.(Sodium Algenate is the natural polymer that is present in the brown algae SA) to sodium alginate, is the natural polyanionic polysaccharide that from brown alga or bacterium, extracts, and is made up of guluronic acid and two kinds of construction units of its stereoisomer mannuronic acid.Sodium alginate possesses excellent biological compatibility, no subacute/reaction of chronic toxicity or carcinogenic, can be used as edible food additives, also can be used as timbering material and be used for medical usage.(Chitosan is the product of chitin after deacetylation is handled CS) to shitosan, is the natural alkaline polysaccharide that occurring in nature exists, and it is a kind of polycation natural polymer.Advantages such as that shitosan not only has is nontoxic, excellent biological compatibility, biodegradability; Also have many excellent physiological properties such as cancer resistance, antibiotic property, hemostatic, enhances human body immunocompetence, be widely used in aspects such as organizational project, drug carrier material and wound dressing.Heparin (Heparin) is a kind of by gucosamine, and the glutinous polysaccharide sulfuric acid ester that L-idose aldehyde glycosides, N-acetylglucosamine and D-glucuronic acid are alternately formed has highly acid, and the altitudinal belt negative electrical charge.Simultaneously, heparin all has blood coagulation resisting function in vivo and in vitro as a kind of anti-coagulants.Be mainly used in thrombotic disease, myocardial infarction, operation on vessels of heart, cardia catheterization, extracorporal circulatory system, haemodialysis etc. clinically.Along with pharmacology and clinical medical progress, the application of heparin constantly enlarges.Gamma-polyglutamic acid-(Poly-γ-glutamic acid; γ-PGA) is the water-soluble polyamino acid that the occurring in nature microbial fermentation produces; Be a kind of special anion nature polymer, its structure is the high molecular polymer that glutamic acid units is passed through alpha-amido and γ-carboxyl formation peptide bond.γ-PGA is a Main Ingredients and Appearance of forming natto viscoloid, has the effect that promotes that mineral matter absorbs.γ-PGA specific molecule structure makes it have extremely strong moisture-retaining capacity, adds γ-PGA in cosmetics or skin care products, can increase the moisture-retaining capacity of skin effectively, promotes skin health.(there are a large amount of primary amino radicals in ε-PL) have high molecular characteristic to epsilon-polylysine in the strand, amino protonated in solution, having a large amount of positive charges becomes cationic polymer.As a kind of natural microbial metabolism product, its cost is low, and environmental friendliness can be decomposed into lysine in vivo and absorbed by catapepsis, has no toxic and side effect.
The nanofiber of nucleocapsid structure can well combine the performance of two or more materials.At present, the existing big quantity research of nanofiber that is equipped with nucleocapsid structure with electric spinning method.The nanofiber process that the electricity spinning prepares nucleocapsid structure mainly contains coaxial spin processes [Palanikkumaran Muthiah, Shu-Hau Hsu.Coaxially electrospun PVDF-Teflon AF and Teflon af-PVDF core-Sheath Nanofiber Matswith Superhydrophobic Properties.Langmuir, 2010; 26,12483-12487.], single shower nozzle phase separation method [Jian-Feng Zhang; Dong-Zhi Yang, Fei Xu, Zi-Ping Zhang; Rui-Xue Yin, Jun Nie.Electrospun Core-Shell Structure Nanofibers from Homogeneous Solution of Poly (ethylene oxide)/Chitosan.Macromolecules, 2009; 42,5278-5284.] and post treatment method [Haoqing Hou, Zeng Jun; Arndt Reuning, Andreas Schaper, Joachim H.Wendorff; Andreas Greiner.Poly (p-xylylene) nanotubes by coating and removal of ultrathin polymer template fibers. [J] Macromolecules; 2002,35,2429-2431.].But, also do not utilize the phase-splitting of electric field controls electricity spinning solution component to prepare the report of polyelectrolyte base nuclear shell structure nano.
Summary of the invention
1, the object of the invention is to provide a kind of single needle head electricity to spin the method for polyelectrolyte base nuclear shell structure nano fiber;
2, the invention provides the controlled polyelectrolyte base nuclear shell structure nano fiber of a kind of stratum nucleare and shell material;
3, the method for the prepared polyelectrolyte base nuclear shell structure nano tunica fibrosa of the present invention is simple;
4, there is potential using value in the prepared polyelectrolyte base nuclear shell structure nano tunica fibrosa of the present invention at aspects such as drug and slowly-releasing, tissue engineering bracket materials.
The method for preparing polyelectrolyte base nuclear shell structure nano fiber provided by the present invention may further comprise the steps:
(1) preparation of polyelectrolyte solution: polyelectrolyte is dissolved in the water, is mixed with the solution that percentage by weight is 1～10wt%, then solution is fully stirred, so that dissolving fully, promptly obtain polyelectrolyte solution.
Described polyelectrolyte is: hyaluronic acid (HA) M
W=5000～2 000 000g/mol, sodium alginate (SA) viscosity average molecular weigh are 2 * 10
6, heparin (Heparin) M
W=1200～40 000g/mol, the gamma-polyglutamic acid-(M of γ-PGA)
W=100 000～10 000 000g/mol, shitosan (CS) M
W=3000～200 000g/mol, the epsilon-polylysine (M of ε-PL)
W=5000～100 000g/mol.
(2) preparation of electrostatic spinning solution: synthetic polymer is dissolved in the water, is mixed with the solution that percentage by weight is 2～10wt%, then solution is fully stirred, so that dissolving fully, promptly obtain synthetic polymer solution.With polyelectrolyte solution and synthetic polymer solution is 1～9: 9～1 mixed by volume, obtains electrostatic spinning solution.
Described synthetic polymer is: polyoxy ethane (PEO), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA) or polycaprolactone (PCL).
(3) electrostatic spinning prepares polyelectrolyte base nuclear shell structure nano fiber: the electrostatic spinning solution of preparation in the step (2) is added in the solution feedway (Fig. 1), and adjustment voltage is-30～30kV; Spinning head is 8～20cm to the distance of collecting board; The flow of spinning head spinning solution is 0.5～2.0mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains polyelectrolyte base nuclear shell structure nano fiber.
(4) MTT cytotoxicity test: the PBS of the polyelectrolyte base nuclear shell structure nano tunica fibrosa that obtains in the step (3) is embathed liquid handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, and calculates its P value.
(5) cell inoculation experiment: the polyelectrolyte base nuclear shell structure nano tunica fibrosa that obtains in the step (3) is carried out the cell inoculation experiment, and resulting polyelectrolyte base nuclear shell structure nano tunica fibrosa is assessed.
The present invention spins polyelectrolyte through electricity and the synthetic polymer formulations prepared from solutions has gone out polyelectrolyte base nuclear shell structure nano fiber.The method of prepared polyelectrolyte base nuclear shell structure nano tunica fibrosa is simple, and there is potential using value in prepared polyelectrolyte base nuclear shell structure nano tunica fibrosa at aspects such as drug and slowly-releasing, tissue engineering bracket materials.
Description of drawings
Fig. 1 is the installation drawing in kind that uses in the implementation process of the present invention.
Fig. 2 is the SEM pattern of hyaluronic acid/polyoxy ethane spinning product of on aluminium foil, collecting by the technical scheme that the embodiment of the invention 1 is provided.
Fig. 3 is the TEM pattern of the chitosan/polyvinyl alcohol spinning product on aluminium foil, collected by the technical scheme that the embodiment of the invention 2 is provided.
Fig. 4 is the nano fibrous membrane MTT test result with the chitosan/polyvinyl alcohol preparation that obtains by the technical scheme that embodiment 2 is provided.
The specific embodiment
Embodiment 1:
(1) with molecular weight for the 5000g/mol hyaluronic acid is dissolved in the water, be mixed with the solution that percentage by weight is 10wt%, then solution is fully stirred so that fully the dissolving, promptly obtain hyaluronic acid solution.
(2) polyoxy ethane is dissolved in the water, is mixed with the solution that percentage by weight is 4wt%, then solution is fully stirred, so that dissolving fully, polyoxy ethane solution promptly obtained.With hyaluronic acid solution and polyoxy ethane solution is 1: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 30kV; Spinning head is 20cm to the distance of collecting board; The flow of spinning head spinning solution is 1mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains hyaluronic acid/polyoxy ethane nuclear shell structure nano fiber, and wherein hyaluronic acid is a stratum nucleare, and polyoxy ethane is shell.
(4) PBS of the hyaluronic acid that obtains in the step (3)/polyoxy ethane nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) hyaluronic acid that obtains in the step (3)/polyoxy ethane nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.Embodiment 2: (1) for the 3000g/mol shitosan is dissolved in the water, is mixed with the solution that percentage by weight is 5wt% with molecular weight, then solution is fully stirred, so that dissolving fully, promptly obtain chitosan solution.
(2) polyvinyl alcohol is dissolved in the water, is mixed with the solution that percentage by weight is 10wt%, then solution is fully stirred, so that dissolving fully, poly-vinyl alcohol solution promptly obtained.With chitosan solution and poly-vinyl alcohol solution is 5: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 25kV; Spinning head is 18cm to the distance of collecting board; The flow of spinning head spinning solution is 0.5mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains chitosan/polyvinyl alcohol nuclear shell structure nano fiber, and wherein polyvinyl alcohol is a stratum nucleare, and shitosan is a shell.
(4) PBS of the chitosan/polyvinyl alcohol nuclear shell structure nano tunica fibrosa that obtains in the step (3) is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) the chitosan/polyvinyl alcohol nuclear shell structure nano tunica fibrosa that obtains in the step (3) is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 3: (1) is that 2 000 000g/mol hyaluronic acids are dissolved in the water with molecular weight, is mixed with the solution that percentage by weight is 1wt%, then solution is fully stirred, so that dissolving fully, promptly obtain hyaluronic acid solution.
(2) polyvinylpyrrolidone is dissolved in the water, is mixed with the solution that percentage by weight is 10wt%, then solution is fully stirred, so that dissolving fully, polyvinylpyrrolidonesolution solution promptly obtained.With hyaluronic acid solution and polyvinylpyrrolidonesolution solution is 9: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is-30kV; Spinning head is 8cm to the distance of collecting board; The flow of spinning head spinning solution is 0.5mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains hyaluronic acid/polyvinylpyrrolidone nuclear shell structure nano fiber, and wherein polyvinylpyrrolidone is a stratum nucleare, and hyaluronic acid is a shell.
(4) PBS of the hyaluronic acid that obtains in the step (3)/polyvinylpyrrolidone nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) hyaluronic acid that obtains in the step (3)/polyvinylpyrrolidone nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 4: (1) is 2 * 10 with viscosity average molecular weigh
6Sodium alginate be dissolved in the water, be mixed with the solution that percentage by weight is 1wt%, then solution is fully stirred so that fully the dissolving, promptly obtain sodium alginate soln.
(2) polyethylene glycol is dissolved in the water, is mixed with the solution that percentage by weight is 1wt%, then solution is fully stirred, so that dissolving fully, polyglycol solution promptly obtained.With sodium alginate soln and polyglycol solution is 1: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 18kV; Spinning head is 15cm to the distance of collecting board; The flow of spinning head spinning solution is 2mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains sodium alginate/polyethylene glycol nuclear shell structure nano fiber, and wherein sodium alginate is a stratum nucleare, and polyethylene glycol is a shell.
(4) PBS of the sodium alginate/polyethylene glycol nuclear shell structure nano tunica fibrosa that obtains in the step (3) is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) the sodium alginate/polyethylene glycol nuclear shell structure nano tunica fibrosa that obtains in the step (3) is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 5: (1) is that 200 000g/mol shitosans are dissolved in the glacial acetic acid aqueous solution of 5wt% with molecular weight, is mixed with the solution that percentage by weight is 2wt%, then solution is fully stirred, so that dissolving fully, promptly obtain chitosan solution.
(2) polycaprolactone is dissolved in the water, is mixed with the solution that percentage by weight is 8wt%, then solution is fully stirred, so that dissolving fully, polycaprolactone solution promptly obtained.With chitosan solution and polycaprolactone solution is 4: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 15kV; Spinning head is 12cm to the distance of collecting board; The flow of spinning head spinning solution is 1mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains shitosan/polycaprolactone nuclear shell structure nano fiber, and wherein polycaprolactone is a stratum nucleare, and shitosan is a shell.
(4) PBS of the shitosan that obtains in the step (3)/polycaprolactone nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) shitosan that obtains in the step (3)/polycaprolactone nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 6: (1) for the 1200g/mol heparin is dissolved in the water, is mixed with the solution that percentage by weight is 10wt% with molecular weight, then solution is fully stirred, so that dissolving fully, promptly obtain heparin solution.
(2) polyoxyethylene is dissolved in the water, is mixed with the solution that percentage by weight is 1wt%, then solution is fully stirred, so that dissolving fully, polyoxyethylene solution promptly obtained.With heparin solution and polyoxyethylene solution is 1: 9 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 15kV; Spinning head is 12cm to the distance of collecting board; The flow of spinning head spinning solution is 1.5mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains heparin/polyoxyethylene nuclear shell structure nano fiber, and wherein heparin is a stratum nucleare, and polyoxyethylene is a shell.
(4) PBS of the heparin that obtains in the step (3)/polyoxyethylene nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) heparin that obtains in the step (3)/polyoxyethylene nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 7: (1) is that 40 000g/mol heparin are dissolved in the water with molecular weight, is mixed with the solution that percentage by weight is 5wt%, then solution is fully stirred, so that dissolving fully, promptly obtain heparin solution.
(2) polyvinylpyrrolidone is dissolved in the water, is mixed with the solution that percentage by weight is 8wt%, then solution is fully stirred, so that dissolving fully, polyvinylpyrrolidonesolution solution promptly obtained.With heparin solution and polyvinylpyrrolidonesolution solution is 5: 2 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is-20kV; Spinning head is 15cm to the distance of collecting board; The flow of spinning head spinning solution is 2mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains heparin/polyvinylpyrrolidone nuclear shell structure nano fiber, wherein is the polyvinylpyrrolidone stratum nucleare, and heparin is a shell.
(4) PBS of the heparin that obtains in the step (3)/polyvinylpyrrolidone nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) heparin that obtains in the step (3)/polyvinylpyrrolidone nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 8: (1) is that 100 000g/mol gamma-polyglutamic acid-s are dissolved in the water with molecular weight, is mixed with the solution that percentage by weight is 8wt%, then solution is fully stirred, so that dissolving fully, promptly obtain gamma-polyglutamic acid-solution.
(2) polyvinyl alcohol is dissolved in the water, is mixed with the solution that percentage by weight is 8wt%, then solution is fully stirred, so that dissolving fully, poly-vinyl alcohol solution promptly obtained.With gamma-polyglutamic acid-solution and poly-vinyl alcohol solution is 3: 8 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 24kV; Spinning head is 16cm to the distance of collecting board; The flow of spinning head spinning solution is 1.8mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains gamma-polyglutamic acid-/polyvinyl alcohol nuclear shell structure nano fiber, wherein is the gamma-polyglutamic acid-stratum nucleare, and polyvinyl alcohol is a shell.
(4) PBS of the gamma-polyglutamic acid-that obtains in the step (3)/polyvinyl alcohol nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) gamma-polyglutamic acid-that obtains in the step (3)/polyvinyl alcohol nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 9: (1) is that 10 000 000g/mol gamma-polyglutamic acid-s are dissolved in the water with molecular weight, is mixed with the solution that percentage by weight is 1wt%, then solution is fully stirred, so that dissolving fully, promptly obtain gamma-polyglutamic acid-solution.
(2) polyoxyethylene is dissolved in the water, is mixed with the solution that percentage by weight is 8wt%, then solution is fully stirred, so that dissolving fully, polyoxyethylene solution promptly obtained.With gamma-polyglutamic acid-solution and polyoxyethylene solution is 8: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is-24kV; Spinning head is 18cm to the distance of collecting board; The flow of spinning head spinning solution is 0.5mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains gamma-polyglutamic acid-/polyoxyethylene nuclear shell structure nano fiber, and wherein polyoxyethylene is a stratum nucleare, and gamma-polyglutamic acid-is a shell.
(4) PBS of the gamma-polyglutamic acid-that obtains in the step (3)/polyoxyethylene nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) gamma-polyglutamic acid-that obtains in the step (3)/polyoxyethylene nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Embodiment 10: (1) for the 5000g/mol epsilon-polylysine is dissolved in the water, is mixed with the solution that percentage by weight is 9wt% with molecular weight, then solution is fully stirred, so that dissolving fully, promptly obtain epsilon-polylysine solution.
(2) polyethylene glycol is dissolved in the water, is mixed with the solution that percentage by weight is 8wt%, then solution is fully stirred, so that dissolving fully, polyglycol solution promptly obtained.With epsilon-polylysine solution and polyglycol solution is 1: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is 30kV; Spinning head is 18cm to the distance of collecting board; The flow of spinning head spinning solution is 2mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains epsilon-polylysine/polyethylene glycol nuclear shell structure nano fiber, and wherein polyethylene glycol is a stratum nucleare, and epsilon-polylysine is a shell.
(4) PBS of the epsilon-polylysine that obtains in the step (3)/polyethylene glycol nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) epsilon-polylysine that obtains in the step (3)/polyethylene glycol nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.Embodiment 11: (1) for the 100000g/mol epsilon-polylysine is dissolved in the water, is mixed with the solution that percentage by weight is 5wt% with molecular weight, then solution is fully stirred, so that dissolving fully, promptly obtain epsilon-polylysine solution.
(2) polyvinyl alcohol is dissolved in the water, is mixed with the solution that percentage by weight is 7wt%, then solution is fully stirred, so that dissolving fully, poly-vinyl alcohol solution promptly obtained.With epsilon-polylysine solution and poly-vinyl alcohol solution is 2: 1 mixed by volume, obtains electrostatic spinning solution.
(3) electrostatic spinning solution with preparation in the step (2) adds in the solution feedway, and adjustment voltage is-30kV; Spinning head is 16cm to the distance of collecting board; The flow of spinning head spinning solution is 1.4mL/h.Starting drive carries out electrostatic spinning, on collecting board, obtains epsilon-polylysine/polyvinyl alcohol nuclear shell structure nano fiber, and wherein epsilon-polylysine is a stratum nucleare, and polyvinyl alcohol is a shell.
(4) PBS of the epsilon-polylysine that obtains in the step (3)/polyvinyl alcohol nuclear shell structure nano tunica fibrosa is embathed liquid and handle the L929 cell respectively after 24 hours, 48 hours, 72 hours, abandon supernatant, with PBS washing 2 times.ELIASA is measured light absorption value, and the mensuration wavelength is 490nm, compares with blank, and its 24 hours, 48 hours, 72 hours P value does not have significant difference all greater than 0.05, shows that there is not toxicity in resulting nano fibrous membrane.
(5) epsilon-polylysine that obtains in the step (3)/polyvinyl alcohol nuclear shell structure nano tunica fibrosa is carried out the cell inoculation experiment, have excellent cell and attach and multiplication characteristic.
Claims (3)
1. a natural polyelectrolyte base nuclear shell structure nano fiber production method is characterized in that, may further comprise the steps:
(1) preparation of polyelectrolyte solution: polyelectrolyte is dissolved in the water, is mixed with the solution that percentage by weight is 1～10wt%, then solution is fully stirred, so that dissolving fully, promptly obtain polyelectrolyte solution;
(2) preparation of electrostatic spinning solution: synthetic polymer is dissolved in the water, is mixed with the solution that percentage by weight is 2～10wt%, then solution is fully stirred, so that dissolving fully, promptly obtain synthetic polymer solution; With polyelectrolyte solution and synthetic polymer solution is 1～9: 9～1 mixed by volume, obtains electrostatic spinning solution;
(3) electrostatic spinning prepares polyelectrolyte base nuclear shell structure nano fiber: the electrostatic spinning solution of preparation in the step (2) is added in the special solution feedway, and adjustment voltage is-30～30kV; Spinning head is 8～20cm to the distance of collecting board; The flow of spinning head spinning solution is 0.5～2.0mL/h; Starting drive carries out electrostatic spinning, on collecting board, obtains polyelectrolyte base nuclear shell structure nano fiber.
2. according to the said method of claim 1, it is characterized in that polyelectrolyte is in the step (1): hyaluronic acid M
W=5000～2 000 000g/mol, sodium alginate viscosity average molecular weigh are 2 * 10
6, heparin M
W=1200～40 000g/mol, gamma-polyglutamic acid-M
W=100 000～10 000 000g/mol, shitosan M
W=3000～200 000g/mol, epsilon-polylysine M
W=5000～100 000g/mol.
3. according to the said method of claim 1, it is characterized in that synthetic polymer is polyoxy ethane, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol or polycaprolactone in the step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100526179A CN102605466A (en) | 2012-03-02 | 2012-03-02 | Preparation method of natural polyelectrolyte-based core-shell structured nano-fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100526179A CN102605466A (en) | 2012-03-02 | 2012-03-02 | Preparation method of natural polyelectrolyte-based core-shell structured nano-fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102605466A true CN102605466A (en) | 2012-07-25 |
Family
ID=46523214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100526179A Pending CN102605466A (en) | 2012-03-02 | 2012-03-02 | Preparation method of natural polyelectrolyte-based core-shell structured nano-fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102605466A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102961788A (en) * | 2012-12-04 | 2013-03-13 | 东华大学 | Heparin-loaded covered stent for treating arterial aneurysm and preparation method thereof |
| CN103505758A (en) * | 2013-09-17 | 2014-01-15 | 南通南京大学材料工程技术研究院 | Chitosan-nanofiber hemostatic material and preparation method thereof |
| CN103757742A (en) * | 2014-01-03 | 2014-04-30 | 北京化工大学常州先进材料研究院 | Preparation method of core-shell structured nanofibers with surfaces containing fluorine |
| CN103789874A (en) * | 2014-01-23 | 2014-05-14 | 北京化工大学常州先进材料研究院 | Method for preparing polyelectrolyte nano fibers in core-shell structures by parallel electric field inductive phase separation method |
| CN104480571A (en) * | 2014-11-24 | 2015-04-01 | 张家港保税区冠祥贸易有限公司 | Preparation method of polyelectrolyte core-shell structure nanofiber with adjustable shell thickness |
| CN104805598A (en) * | 2015-04-28 | 2015-07-29 | 武汉纺织大学 | Method for preparing vinyl polysiloxane nanofiber membrane through electrostatic spinning |
| WO2017116355A1 (en) | 2015-12-29 | 2017-07-06 | Atilim Universitesi | Tissue scaffold with enhanced biocompatibility and mechanical properties and a method for producing it |
| CN109208112A (en) * | 2018-07-19 | 2019-01-15 | 恒天纤维集团有限公司 | Fiber and preparation method thereof containing polyelectrolyte |
| CN109537163A (en) * | 2018-11-20 | 2019-03-29 | 大连工业大学 | A kind of chitosan/sodium alginate/polyvinyl alcohol polyelectrolyte nanofibers composite membrane and preparation method thereof |
| CN110387588A (en) * | 2019-08-15 | 2019-10-29 | 吉林大学 | A method of preparing the micro nanometer fiber film of core-shell structure using Janus syringe needle electrostatic spinning arranged side by side |
| CN110644232A (en) * | 2019-09-20 | 2020-01-03 | 南通大学 | Preparation method of natural antibacterial water-retention mask |
| CN110840862A (en) * | 2019-11-28 | 2020-02-28 | 广西科学院 | Near-infrared-excited core-shell-structure composite antibacterial nanofiber membrane and preparation method thereof |
| CN111441103A (en) * | 2020-05-27 | 2020-07-24 | 南京彼洲生物科技有限公司 | Medical nano-fiber composite material and preparation method and application thereof |
| 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 |
| CN112870439A (en) * | 2021-02-17 | 2021-06-01 | 太原理工大学 | Nano fiber bone tissue engineering scaffold with core-shell-series crystal structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724725A (en) * | 2005-07-01 | 2006-01-25 | 中国科学院长春应用化学研究所 | The emulsion electro spinning preparation method of superfine fiber medicine formulation |
| CN1807707A (en) * | 2006-01-13 | 2006-07-26 | 清华大学 | Core-shell composite micron/nano fiber and preparation method thereof |
| CN101187093A (en) * | 2007-11-28 | 2008-05-28 | 吉林大学 | Coaxial spinning method for preparing hollow molecular sieve fiber possessing grade structure |
| CN101805940A (en) * | 2010-03-23 | 2010-08-18 | 浙江大学 | Polymer electrospun fibers, preparation method thereof and application thereof |
-
2012
- 2012-03-02 CN CN2012100526179A patent/CN102605466A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724725A (en) * | 2005-07-01 | 2006-01-25 | 中国科学院长春应用化学研究所 | The emulsion electro spinning preparation method of superfine fiber medicine formulation |
| CN1807707A (en) * | 2006-01-13 | 2006-07-26 | 清华大学 | Core-shell composite micron/nano fiber and preparation method thereof |
| CN101187093A (en) * | 2007-11-28 | 2008-05-28 | 吉林大学 | Coaxial spinning method for preparing hollow molecular sieve fiber possessing grade structure |
| CN101805940A (en) * | 2010-03-23 | 2010-08-18 | 浙江大学 | Polymer electrospun fibers, preparation method thereof and application thereof |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102961788B (en) * | 2012-12-04 | 2015-08-12 | 东华大学 | A kind of heparin load aneurysm treatment overlay film frame and preparation method thereof |
| CN102961788A (en) * | 2012-12-04 | 2013-03-13 | 东华大学 | Heparin-loaded covered stent for treating arterial aneurysm and preparation method thereof |
| CN103505758A (en) * | 2013-09-17 | 2014-01-15 | 南通南京大学材料工程技术研究院 | Chitosan-nanofiber hemostatic material and preparation method thereof |
| CN103757742A (en) * | 2014-01-03 | 2014-04-30 | 北京化工大学常州先进材料研究院 | Preparation method of core-shell structured nanofibers with surfaces containing fluorine |
| CN103757742B (en) * | 2014-01-03 | 2015-10-28 | 北京化工大学常州先进材料研究院 | A kind of preparation method of nuclear shell structure nano fiber of fluorine-contained surface |
| CN103789874A (en) * | 2014-01-23 | 2014-05-14 | 北京化工大学常州先进材料研究院 | Method for preparing polyelectrolyte nano fibers in core-shell structures by parallel electric field inductive phase separation method |
| CN103789874B (en) * | 2014-01-23 | 2016-02-10 | 北京化工大学常州先进材料研究院 | Parallel electric field induction phase separation method prepares nucleocapsid structure natural polyelectrolyte nanofiber |
| CN104480571A (en) * | 2014-11-24 | 2015-04-01 | 张家港保税区冠祥贸易有限公司 | Preparation method of polyelectrolyte core-shell structure nanofiber with adjustable shell thickness |
| CN104805598A (en) * | 2015-04-28 | 2015-07-29 | 武汉纺织大学 | Method for preparing vinyl polysiloxane nanofiber membrane through electrostatic spinning |
| WO2017116355A1 (en) | 2015-12-29 | 2017-07-06 | Atilim Universitesi | Tissue scaffold with enhanced biocompatibility and mechanical properties and a method for producing it |
| CN109208112A (en) * | 2018-07-19 | 2019-01-15 | 恒天纤维集团有限公司 | Fiber and preparation method thereof containing polyelectrolyte |
| CN109208112B (en) * | 2018-07-19 | 2021-03-02 | 恒天纤维集团有限公司 | Polyelectrolyte-containing fiber and method for producing same |
| CN109537163A (en) * | 2018-11-20 | 2019-03-29 | 大连工业大学 | A kind of chitosan/sodium alginate/polyvinyl alcohol polyelectrolyte nanofibers composite membrane and preparation method thereof |
| CN109537163B (en) * | 2018-11-20 | 2021-08-31 | 大连工业大学 | Chitosan/sodium alginate/polyvinyl alcohol polyelectrolyte nanofiber composite membrane and preparation method thereof |
| CN110387588A (en) * | 2019-08-15 | 2019-10-29 | 吉林大学 | A method of preparing the micro nanometer fiber film of core-shell structure using Janus syringe needle electrostatic spinning arranged side by side |
| CN110387588B (en) * | 2019-08-15 | 2021-07-16 | 吉林大学 | Method for preparing micro-nano fiber membrane with core-shell structure by using electrostatic spinning of Janus parallel needle heads |
| CN110644232A (en) * | 2019-09-20 | 2020-01-03 | 南通大学 | Preparation method of natural antibacterial water-retention mask |
| CN110840862A (en) * | 2019-11-28 | 2020-02-28 | 广西科学院 | Near-infrared-excited core-shell-structure composite antibacterial nanofiber membrane and preparation method thereof |
| CN110840862B (en) * | 2019-11-28 | 2023-05-09 | 广西科学院 | Near-infrared excited core-shell structure composite antibacterial nanofiber membrane and preparation method thereof |
| CN111441103A (en) * | 2020-05-27 | 2020-07-24 | 南京彼洲生物科技有限公司 | Medical nano-fiber composite material and preparation method and application thereof |
| CN111441103B (en) * | 2020-05-27 | 2022-07-01 | 海南健达电子科技有限公司 | Medical nano-fiber composite material and preparation method and application thereof |
| 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 |
| CN112870439A (en) * | 2021-02-17 | 2021-06-01 | 太原理工大学 | Nano fiber bone tissue engineering scaffold with core-shell-series crystal structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102605466A (en) | Preparation method of natural polyelectrolyte-based core-shell structured nano-fiber | |
| Angel et al. | Recent advances in electrospinning of nanofibers from bio-based carbohydrate polymers and their applications | |
| Islam et al. | Fabrication and characterization of poly (vinyl alcohol)/alginate blend nanofibers by electrospinning method | |
| Toskas et al. | Nanofibers based on polysaccharides from the green seaweed Ulva rigida | |
| Torres‐Giner et al. | Development of active antimicrobial fiber‐based chitosan polysaccharide nanostructures using electrospinning | |
| Charernsriwilaiwat et al. | Preparation and characterization of chitosan-hydroxybenzotriazole/polyvinyl alcohol blend nanofibers by the electrospinning technique | |
| CN101230150B (en) | Method for preparing pure sodium alginate nano fiber membrane material | |
| CN101502671B (en) | Method for preparing silk fibroin/ P(LLA-CL) compound nano fiber structure repair stand | |
| CN103789874B (en) | Parallel electric field induction phase separation method prepares nucleocapsid structure natural polyelectrolyte nanofiber | |
| CN103276472B (en) | Collagen/polyvinyl alcohol composite microspheres as well as preparation method and application thereof | |
| JP2015522720A (en) | Polysaccharide fiber preparation method, wound dressing material containing polysaccharide fiber, wound dressing production method, and polysaccharide fiber preparation device | |
| EP2764146B1 (en) | Polysaccharide fibres for wound dressings | |
| CN102277654B (en) | Preparation method of hyaluronic acid and chitosan composite polyelectrolyte nanofibers | |
| CN109537163A (en) | A kind of chitosan/sodium alginate/polyvinyl alcohol polyelectrolyte nanofibers composite membrane and preparation method thereof | |
| WO2018056937A2 (en) | Nanofibrous adhesion barrier | |
| Cheng et al. | Pure chitosan and chitsoan/chitosan lactate blended nanofibres made by single step electrospinning | |
| CN104452106A (en) | Preparing method for nanofiber membrane of composite silica-based drug-carrying nano particles | |
| Koshy et al. | Recent progress and treatment strategy of pectin polysaccharide based tissue engineering scaffolds in cancer therapy, wound healing and cartilage regeneration | |
| Wardhani et al. | Preparation of chitosan-polyethylene oxide-Colocasia esculenta flour nanofibers using electrospinning method | |
| CN105327357A (en) | Catechol modified hyaluronic acid drug carrier system and preparation method thereof | |
| CN102908626B (en) | Method for preparing chitosan/ transparent acid derivative nanofiber composite film through freezing drying technology | |
| Mahendhran et al. | Biopolymer-based nanomaterials for biomedical applications: Biomedical applications of electrospun nanofibers | |
| Valizadeh et al. | Recent advances in electrospinning of some selected biopolymers | |
| Santillán-Mercado et al. | Electrospun cellulose and nanocellulose composites as a biomaterial | |
| CN103541041B (en) | A kind of preparation method of natural polymer short fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120725 |