CN106835367B - A kind of cross-linked polysaccharides fiber and preparation method thereof - Google Patents
A kind of cross-linked polysaccharides fiber and preparation method thereof Download PDFInfo
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- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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Abstract
The present invention provides a kind of cross-linked polysaccharides fiber and preparation method thereof, belongs to macromolecular fibre field.This method first uses sodium periodate oxidation polysaccharide, obtains dialdehyde polysaccharide, and dialdehyde polysaccharide and polyethylene glycol oxide, surfactant and cosolvent co-formulation mixed aqueous solution are then carried out electrostatic spinning, obtain electrospinning fibre；Electrospinning fibre is placed in adipic dihydrazide solution again and is crosslinked, cross-linked polysaccharides fiber is obtained.This preparation method is suitable for a variety of polysaccharide, has wide applicability.The present invention also provides the cross-linked polysaccharides fibers that above-mentioned preparation method obtains.Cross-linked polysaccharides fiber of the present invention has good water resistance, adjustable mechanics and degradation property and good biocompatibility, can satisfy the requirement of many biomedical applications.
Description
Technical field
The invention belongs to macromolecular fibre fields, more particularly to a kind of cross-linked polysaccharides fiber and preparation method thereof.
Background technique
Natural polysaccharide has good biocompatibility, biological degradability and bioactivity abundant, nanofiber material
Material has a extensive future in composition with natural extracellular matrix similar in structure in field of biomedicine.
Since most polysaccharide have good water solubility, non-crosslinked polysaccharide fiber once faces aqueous environment can be immediately
Swelling or dissolution, cause material to lose fibre structure, can not apply under a number of conditions.Therefore, cross-linked polysaccharides fiber has more
For broad application prospect (Zhang Y.et al.Journal ofMaterials Science:Materials
inMedicine 2005,16,933-946).The method of cross-linked polysaccharides fiber can be divided into two major classes at present:
(1) ionomer.It is crosslinked using uronic acid unit of the polyvalent cation to polysaccharide.This method is only applicable to
Anionic polysaccharides, such as alginate, pectin etc. (Andersen T.et al.CarbohydratePolymers 2014,
99,249–256；Munarin F.et al.InternationalJournal of BiologicalMacromolecules
2012,51,681–689)。
(2) it is chemically crosslinked.Utilize the functional groups such as hydroxyl, carboxyl, amino on multi-group crosslink agent and polysaccharide molecule chain
Crosslinking is realized in reaction.The wider crosslinking agent of applicability is the glutaraldehyde, epichlorohydrin, polyisocyanates reacted with hydroxy functional group,
But they all toxicity with higher (Cui S.et al.Carbohydrate Polymers, 2016,157,766-774；Pottery
It is forever refined, national Safety science technology academic exchange conference thesis summary set, 2002, Beijing, 239-242；Bartley,B.L.et
al.In:Proceedings ofthe 101stAnnual Meeting of the American Association for
Cancer Research；2010Apr 17–21；Washington,DC.Philadelphia(PA):AACR；CancerRes
2010,70(8Suppl),Abstract nr 1695).Adipic dihydrazide and Geniposide toxicity are lower, but are only applicable to be crosslinked
Ionic polysaccharide (Molinos, M.et al.Biomacromolecules 2012,13,517-527 containing carboxyl or amino；
Sung,H.W.et al.Journal ofBiomaterials Science-PolymerEdition 1999,10,63–78)。
It can thus be seen that the ionic polysaccharide containing carboxyl or amino is resistance to convenient for being obtained by ion or chemical crosslinking
The fiber of water, therefore the cross-linked polysaccharides fiber reported at present mainly includes a small number of ionic polysaccharides such as chitosan, alginate.And
Many polysaccharide are free of carboxyl and amino, can not carry out ion, adipic dihydrazide or genipin cross-linked, hydroxyl can be used penta
Dialdehyde, epichlorohydrin, polyisocyanates are crosslinked, but these crosslinking agents may cause bio-toxicity.Therefore, still lack and be applicable in
Property the wide and safely and effectively method of cross-linked polysaccharides fiber.
Summary of the invention
The object of the present invention is to provide a kind of cross-linked polysaccharides fibers and preparation method thereof, and this method applicability is wide, and obtains
Cross-linked polysaccharides fiber have excellent mechanical performance, water resistance and biocompatibility.
Present invention firstly provides a kind of preparation methods of cross-linked polysaccharides fiber, this method comprises:
Step 1: polysaccharide solution is mixed with sodium metaperiodate aqueous solution, stirring is protected from light, obtains dialdehyde polysaccharide；
Step 2: dialdehyde polysaccharide and polyethylene glycol oxide, surfactant, cosolvent co-formulation that step 1 obtains are mixed
Then Heshui solution carries out electrostatic spinning, obtains electrospinning fibre；
Step 3: the electrospinning fibre that step 2 is obtained, which is dipped into adipic dihydrazide solution, to react, and it is more to obtain crosslinking
Sugared fiber.
Preferably, the polysaccharide includes pectin, alginate, hyaluronic acid, gellan gum, xanthan gum, Amorphophallus rivieri glucomannan
Glycan, starch, glucan, xylan or cellulose.
Preferably, the mixing speed is 50~800rpm, and mixing time is 3~72 hours.
Preferably, the molar ratio of monosaccharide unit is (5~80) in the sodium metaperiodate and polysaccharide: 100.
Preferably, the mass ratio of the dialdehyde polysaccharide and polyethylene glycol oxide is 70:30~96:4.
Preferably, the surfactant be triton x-100, Tween 80, polysorbas20 or Poloxamer 127,
Mass percentage in mixed solution is 0.5%~3%.
Preferably, the electrostatic spinning is that spinning is carried out under the high voltage electric field of 5~30kV.
Preferably, the adipic dihydrazide solution is that adipic dihydrazide is dissolved in ethanol/water mixed solvent
What preparation obtained.
Preferably, the reaction temperature of the step three is room temperature, and the reaction time is 2~48 hours.
The present invention also provides the cross-linked polysaccharides fibers that above-mentioned preparation method obtains.
Beneficial effects of the present invention
Present invention firstly provides a kind of preparation methods of cross-linked polysaccharides fiber, and this method is first by polysaccharide sodium metaperiodate oxygen
Change, converts dialdehyde for the o-dihydroxy of part in polysaccharide molecule chain, obtain dialdehyde polysaccharide；Then by dialdehyde polysaccharide and polyoxygenated
Ethylene, surfactant, cosolvent co-formulation mixed aqueous solution carry out electrostatic spinning, obtain electrospinning fibre；Then by electrospinning
Fiber is soaked in the ethanol/water mixed solvent solution of adipic dihydrazide, makes the aldehyde radical and adipic dihydrazide of dialdehyde polysaccharide
Schiffbase reaction occurs for the amino at molecule both ends, realizes crosslinking, then carry out washing drying to it, obtains cross-linked polysaccharides fibre
Dimension.Preparation method of the invention is simple, is easily achieved.Since many polysaccharide all contain o-dihydroxy, preparation method of the invention
Applicability is very extensive.
The present invention also provides the cross-linked polysaccharides fiber that above-mentioned preparation method obtains, which is resistant to water phase
Environment.By the degree of regulation oxidation, the mechanics and degradation property of cross-linked polysaccharides fiber can be regulated and controled.Due to use low toxicity oneself
Dihydrazi crosslinking agent, obtained cross-linked polysaccharides fiber have good biocompatibility.Consider further that the biology of Polysaccharide-Rich
Activity, cross-linked polysaccharides fiber provided by the invention have wide biomedical applications prospect.
Detailed description of the invention
Fig. 1 is the stereoscan photograph for the cross-linked pectin fiber that the oxidizability that the embodiment of the present invention 1 obtains is 40%；
Fig. 2 is answering for the cross-linked pectin fiber that the oxidizability that Example 1 and Example 2 of the present invention obtains is 40% and 20%
Force-strain curve；
Fig. 3 is the cell survival rate for the cross-linked pectin fiber that the oxidizability that the embodiment of the present invention 1 obtains is 40%；
Fig. 4 is the drop for the cross-linked pectin fiber that the oxidizability that Example 1 and Example 2 of the present invention obtains is 40% and 20%
Solve performance；
Fig. 5 is the cross-linked corn starch fiber and oxidation that the oxidizability that the embodiment of the present invention 3 and embodiment 4 obtain is 20%
The electron scanning micrograph for the cross-linked kojacmannan fiber that degree is 20%.
Specific embodiment
The present invention provides a kind of preparation method of cross-linked polysaccharides fiber, this method comprises:
Present invention firstly provides a kind of preparation methods of cross-linked polysaccharides fiber, this method comprises:
Step 1: polysaccharide solution is mixed with sodium metaperiodate aqueous solution, stirring is protected from light, obtains dialdehyde polysaccharide；
Step 2: dialdehyde polysaccharide and polyethylene glycol oxide, surfactant, cosolvent co-formulation that step 1 obtains are mixed
Then Heshui solution carries out electrostatic spinning, obtains electrospinning fibre；
Step 3: the electrospinning fibre that step 2 is obtained, which is dipped into adipic dihydrazide solution, to react, and it is more to obtain crosslinking
Sugared fiber.
According to the present invention, polysaccharide solution and sodium metaperiodate aqueous solution are first prepared respectively, then the two is mixed, is being protected from light
It is reacted under stirring condition, mixture is transferred to bag filter a large amount of water dialysis and removes unreacted sodium metaperiodate, is freeze-dried,
Obtain dialdehyde polysaccharide；The present invention first aoxidizes polysaccharide with sodium metaperiodate, and the polysaccharide need to contain adjacent two in position
Hydroxyl group, preferably pectin, alginate, hyaluronic acid, gellan gum, xanthan gum, konjaku glucomannan, starch, glucan,
Xylan or cellulose, the molar ratio of the monosaccharide unit in the sodium metaperiodate and polysaccharide are preferably (5~80): 100, it is more excellent
It is selected as (20~40): 100, mixing speed is preferably 50~800rpm, and reaction temperature is preferably room temperature, and the reaction time is preferably 3
~72 hours.The concentration of polysaccharide solution is preferably 0.05~5%；The concentration of sodium metaperiodate aqueous solution is preferably 10%.
According to the present invention, by dialdehyde polysaccharide obtained above and polyethylene glycol oxide, surfactant, cosolvent co-formulation
Mixed aqueous solution, the mass percent concentration of macromolecule (dialdehyde polysaccharide and polyethylene glycol oxide) is preferred in the mixed aqueous solution
It is 2%~10%, the viscosity average molecular weigh of the polyethylene glycol oxide is preferably 500,000~10,000,000, the dialdehyde polysaccharide and poly-
The mass ratio of ethylene oxide is preferably 70:30~96:4, more preferably 80:20；The surfactant is preferably that Qula is logical
X-100, Tween 80, polysorbas20 or Poloxamer 127, the mass percent concentration of the surfactant are preferably 0.5%
~3%, more preferably 0.5%~2%；The cosolvent is preferably dimethyl sulfoxide, dimethylformamide, glycerine or third
Glycol, the mass percent concentration of addition are preferably 2%~10%, and more preferably 5%~10%.
According to the present invention, above-mentioned mixed aqueous solution is subjected to electrostatic spinning, the electrostatic spinning is preferably 5~30kV's
It is carried out under high voltage electric field, more preferable voltage is 7~15kV, is then collecting fiber at 5~20cm of spinning head, is more preferably spraying
Silk head is 10~15cm at a distance from collector, obtains electrospinning fibre.
According to the present invention, electrospinning fibre obtained above is dipped into adipic dihydrazide solution and is reacted, is then used
A large amount of water are washed, and re-dry obtains cross-linked polysaccharides fiber.The adipic dihydrazide solution is by adipic dihydrazide
It is dissolved in what preparation in ethanol/water mixed solvent obtained, the volume ratio of second alcohol and water is preferably in the ethanol/water mixed solvent
50:50~90:10, the reaction temperature are preferably room temperature, and the reaction time is preferably 2~48 hours.The adipic acid two
Adipic dihydrazide concentration is preferably 50mmol/L, the quality (mg) of electrospinning fibre: adipic dihydrazide solution in hydrazides solution
Volume (mL) be 1:1.
According to the present invention, above-mentioned cross filament is washed, obtains cross-linked polysaccharides fiber, the washing methods is preferred
It for washing methods commonly used in the art, is not particularly limited, preferably are as follows: impregnate crosslinking nano fiber in deionized water, often
Every 10 minutes old aqueous solution of removal, fresh water is added, replaces 12 times in total, freeze-drying or with ethyl alcohol and chloroform according to
Air drying after secondary elution obtains dry cross-linked polysaccharides fiber not soluble in water.
The present invention also provides the cross-linked polysaccharides fibers that above-mentioned preparation method obtains.
The present invention is further illustrated using specific embodiment below, but the present invention is not limited thereto.
Embodiment 1: the cross-linked pectin fiber that oxidizability is 40%
1) sodium periodate oxidation pectin: 5% aqueous pectin solution is prepared first, then by its sodium metaperiodate water with 10%
Solution mixing, makes the molar ratio 40:100 of galacturonic acid units in sodium metaperiodate and pectin, is supplemented appropriate amount of deionized water,
Concentration of pectin is adjusted to 2%, is protected from light and is stirred to react 16 hours under room temperature.It is 3500 that mixed solution, which is transferred to molecular cut off,
Bag filter in, it is every all over 4 hours with a large amount of deionized water dialysises 5 times.Then it is water-soluble oxidation pectin to be lyophilized with freeze drier
Liquid obtains the dialdehyde pectin that oxidizability is 40%；
2) electrostatic spinning: the oxidizability for preparing 15% respectively first is 40% dialdehyde aqueous pectin solution and 5% polyoxy
Change ethylene (molecular weight is 5,000,000) aqueous solution, is then that 80:20 will be aoxidized according to the mass ratio of dialdehyde pectin and polyethylene glycol oxide
Aqueous pectin solution and the mixing of polyoxyethylene aqueous solution, and triton x-100 and quality that mass percent concentration is 1% is added
The dimethyl sulfoxide that percent concentration is 5%, stands overnight after mixed liquor is stirred at room temperature 12 hours, obtains bubble-free
Above-mentioned mixed solution is placed in spinning under the high voltage electric field of 8kV by homogeneous mixture solotion, fine collecting at spinning head 15cm
Dimension, obtains electrospinning fibre；
3) adipic dihydrazide is crosslinked: the above-mentioned electrospinning fibre of 10mg is placed in the adipic acid two that 10mL concentration is 50mmol/L
In the mixed solvent solution of the ethanol/water (volume ratio 80:20) of hydrazides, 100rpm oscillation is reacted 8 hours at room temperature, is then gone
Except crosslinked fluid, with deionized water washing by soaking crosslinking nano fiber 12 times, with remove polyethylene glycol oxide, surfactant, altogether it is molten
Agent and extra crosslinking agent are successively dehydrated with ethyl alcohol and chloroform, air drying, obtain the crosslinking that oxidizability is 40%
Pectin fiber.
It weighs the oxidizability that 10mg embodiment 1 is prepared and is placed in 10mL simulated body fluid for 40% cross-linked pectin fiber
In, it is cultivated in 37 DEG C of constant incubators, takes out fiber sample after 14 days, be washed with water, then be freeze-dried, use scanning electron
The pattern of micro- sem observation fiber, as shown in Figure 1, a is cross-linked pectin fiber, b is that 14 are impregnated in simulated body fluid (SBF)
Its later cross-linked pectin fiber, the results show that cross-linked pectin fiber be still able to maintain after being cultivated in SBF 14 days it is good
Fiber morphology, it was demonstrated that it is with good water resistance.
The cross-linked pectin that the oxidizability that the embodiment 1 of the long 25mm wide 6mm thickness 0.015mm of clip is prepared is 40% is fine
Dimension, is soaked with SBF, fixes (gauge length 10mm) with the collet of mechanics machine, with the speed tensile of 1mm/min, monitor stress-is answered
Varied curve calculates as a result as shown in the curve a in Fig. 2, Young's modulus 9.6MPa.
The oxidizability that 20mg embodiment 1 is prepared is weighed as 40% cross-linked pectin fiber, is placed in 2mL DMEM cell
In culture solution, it is incubated overnight in 37 DEG C of constant incubators.Leachate is taken, various concentration is diluted to, is added to every hole plantation
In 3000 fibroblastic tissue culture plates of L929, continue culture 24 hours.MTT detection method detects cell survival rate, such as
Shown in Fig. 3, the results show that the cell survival rate measured in all Steep cencentrations shows fiber 90% or so or more
With good cell compatibility.
The fiber after 10mg crosslinking is weighed, is placed in 10mL SBF, 37 DEG C of constant temperature incubations, at interval of one week taking-up sample
Product are cleaned 6 times with deionized water, are successively dehydrated with ethyl alcohol and chloroform, air drying, weighing.Then 10mL is launched again
It is cultivated in SBF.As shown in Fig. 4 curve a, fiber is degraded completely within 4 weeks.
Embodiment 2: the cross-linked pectin fiber that oxidizability is 20%
1) sodium periodate oxidation pectin: first match 5% aqueous pectin solution, then by its with 10% sodium metaperiodate it is water-soluble
Liquid mixing, makes the molar ratio 20:100 of galacturonic acid units in sodium metaperiodate and pectin, is supplemented appropriate amount of deionized water, will
Concentration of pectin is adjusted to 2%, is protected from light and is stirred to react 16 hours under room temperature.It is 3500 that mixed solution, which is transferred to molecular cut off,
It is every all over 4 hours with a large amount of deionized water dialysises 5 times in bag filter.Then oxidation aqueous pectin solution is lyophilized with freeze drier,
Obtain the dialdehyde pectin that oxidizability is 20%；
2) electrostatic spinning: the oxidizability for preparing 13% respectively first is 20% dialdehyde aqueous pectin solution and 5% polyoxy
Change ethylene (molecular weight is 5,000,000) aqueous solution, is then that 80:20 will be aoxidized according to the mass ratio of dialdehyde pectin and polyethylene glycol oxide
Aqueous pectin solution and the mixing of polyoxyethylene aqueous solution, and triton x-100 and quality that mass percent concentration is 1% is added
The dimethyl sulfoxide that percent concentration is 5%, stands overnight after mixed liquor is stirred at room temperature 12 hours, obtains bubble-free
Above-mentioned mixed solution is placed in spinning under the high voltage electric field of 8kV by homogeneous mixture solotion, fine collecting at spinning head 15cm
Dimension, obtains electrospinning fibre；
3) adipic dihydrazide is crosslinked: the above-mentioned electrospinning fibre of 10mg is placed in the adipic acid two that 10mL concentration is 50mmol/L
In the mixed solvent solution of the ethanol/water (volume ratio 80:20) of hydrazides, 100rpm oscillation is reacted 8 hours at room temperature, is then gone
Except crosslinked fluid, with deionized water washing by soaking crosslinking nano fiber 12 times, with remove polyethylene glycol oxide, surfactant, altogether it is molten
Agent and extra crosslinking agent are successively dehydrated with ethyl alcohol and chloroform, air drying, obtain the crosslinking that oxidizability is 20%
Pectin fiber.
The cross-linked pectin fiber that the oxidizability that embodiment 2 is obtained is 20% carries out water resistance, intensity, degradation and cell toxicant
Property test.The results show that it keeps 14 days or more fibre structures not change in simulated body fluid, without apparent cell
Toxicity.Load-deformation curve is as shown in the b curve in Fig. 2, Young's modulus 3.0MPa.Degradation behavior as shown in Fig. 4 curve b,
It is complete in degradation in 3 weeks.
Embodiment 3: the cross-linked corn starch fiber that oxidizability is 20%
1) sodium periodate oxidation cornstarch: cornstarch is added in suitable quantity of water first, heating stirring 30 minutes, makes jade
Rice starch dissolution, obtains 5% cornstarch aqueous solution.Then by cornstarch aqueous solution and 10% sodium metaperiodate aqueous solution
Mixing makes the molar ratio 20:100 of glucose unit in sodium metaperiodate and starch, supplements appropriate amount of deionized water, makes cornstarch
Ultimate density be 2%, 1mol/L aqueous hydrochloric acid solution is then added, pH value of solution is transferred to 4, be protected from light be stirred to react 16 at normal temperature
Hour.Then mixed solution is transferred in the bag filter that molecular cut off is 3500, with a large amount of deionized water dialysises 5 times, often
It all over 4 hours, is then lyophilized with freeze drier, obtains the dialdehyde cornstarch that oxidizability is 20%；
2) 11% dialdehyde cornstarch aqueous solution and 5% polyethylene glycol oxide (molecule electrostatic spinning: are prepared respectively first
Amount is 500 ten thousand) aqueous solutions, then according to dialdehyde cornstarch and the mass ratio of polyethylene glycol oxide is that 80:20 mixes the two, and
The triton x-100 that mass percent concentration is 1% and the dimethyl sulfoxide that mass percent concentration is 5% is added, will mix
Liquid is stood overnight after being stirred at room temperature 12 hours, obtains the homogeneous mixture solotion of bubble-free, and above-mentioned mixed solution is placed in 8kV
High voltage electric field under spinning, at spinning head 15cm collect fiber, obtain electro spinning nano fiber；
3) adipic dihydrazide is crosslinked: the above-mentioned electrospinning fibre of 10mg is placed in the adipic acid two that 10mL concentration is 50mmol/L
In the mixed solvent solution of the ethanol/water (volume ratio 80:20) of hydrazides, 100rpm oscillation is reacted 8 hours at room temperature, is then gone
Except crosslinked fluid, with deionized water washing by soaking crosslinking nano fiber 12 times, with remove polyethylene glycol oxide, surfactant, altogether it is molten
Agent and extra crosslinking agent are successively dehydrated with ethyl alcohol and chloroform, air drying, obtain the crosslinking that oxidizability is 20%
Corn starch fibre.
The cross-linked corn starch fiber that embodiment 3 is obtained carries out pattern, intensity, cytotoxicity and Water Resistance Test.It is fine
Dimension pattern is as shown in Figure 5 a, it keeps 7 days or more fibre structures not change in SBF simulated body fluid, Young's modulus
Show it with good water resistance, certain mechanical strength and good cell without apparent cytotoxicity for 0.66MPa
Compatibility.
Embodiment 4: the cross-linked kojacmannan fiber that oxidizability is 20%
1) sodium periodate oxidation konjaku glucomannan: konjaku glucomannan being added in suitable quantity of water first, stirs 2 days, makes
Konjaku glucomannan is completely dissolved, and obtains 0.5% konjak portuguese gansu polyose sugar aqueous solution.Then by konjak portuguese gansu polyose sugar aqueous solution with
10% sodium metaperiodate aqueous solution mixing, makes the molar ratio 20 of glucose unit in sodium metaperiodate and konjaku glucomannan:
100,1mol/L aqueous hydrochloric acid solution is added by pH and is transferred to 4, is protected from light is stirred to react 16 hours at normal temperature.Then mixed solution is turned
It moves on in the bag filter that molecular cut off is 3500, it is every all over 4 hours with a large amount of deionized water dialysises 5 times, then with freeze-drying
Machine freeze-drying obtains the dialdehyde konjaku glucomannan that oxidizability is 20%；
2) 4% dialdehyde konjak portuguese gansu polyose sugar aqueous solution and 5% polyethylene glycol oxide electrostatic spinning: are prepared respectively first
Then (molecular weight be 5,000,000) aqueous solution is 80:20 by oxygen according to the mass ratio of oxidized konjac glucomannan and polyethylene glycol oxide
Change konjak portuguese gansu polyose sugar aqueous solution and the mixing of polyoxyethylene aqueous solution, and it is logical that the Qula that mass percent concentration is 1% is added
The dimethyl sulfoxide that X-100 and mass percent concentration are 10%, stands overnight after mixed liquor is stirred at room temperature 24 hours,
The homogeneous mixture solotion of bubble-free is obtained, above-mentioned mixed solution is placed in spinning under the high voltage electric field of 14kV, apart from spinning head
Fiber is collected at 15cm, obtains electro spinning nano fiber；
3) adipic dihydrazide be crosslinked: by the above-mentioned electro spinning nano fiber of 10mg be placed in 10mL concentration be 50mmol/L oneself two
In the mixed solvent solution of the ethanol/water (volume ratio 80:20) of acid dihydrazide, 100rpm vibrates, at room temperature reaction 8 hours, so
After remove crosslinked fluid, with deionized water washing by soaking crosslinking nano fiber 12 times, with remove polyethylene glycol oxide, surfactant,
Cosolvent and extra crosslinking agent, freeze-drying obtain the cross-linked kojacmannan fiber that oxidizability is 20%.
The cross-linked kojacmannan fiber that embodiment 4 is obtained carries out pattern, intensity, cytotoxicity and water resistance examination
It tests.Fiber morphology is as shown in Figure 5 b, it keeps 3 days or more fibre structures not change in SBF simulated body fluid, Young
Modulus is 6.42MPa, and no cytotoxicity shows it with preferable water resistance, higher mechanical strength and good biology
Compatibility.
Claims (9)
1. a kind of preparation method of cross-linked polysaccharides fiber, which is characterized in that this method comprises:
Step 1: polysaccharide solution is mixed with sodium metaperiodate aqueous solution, stirring is protected from light, obtains dialdehyde polysaccharide；The high iodine
The molar ratio of monosaccharide unit is (20~40) in sour sodium and polysaccharide: 100；
Step 2: the dialdehyde polysaccharide and polyethylene glycol oxide, surfactant, cosolvent co-formulation mixing water that step 1 is obtained
Then solution carries out electrostatic spinning, obtains electrospinning fibre；
Step 3: the electrospinning fibre that step 2 is obtained, which is dipped into adipic dihydrazide solution, to react, and obtains cross-linked polysaccharides fibre
Dimension.
2. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the polysaccharide includes
Pectin, alginate, hyaluronic acid, gellan gum, xanthan gum, konjaku glucomannan, starch, glucan, xylan or cellulose.
3. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the mixing speed
For 50~800rpm, mixing time is 3~72 hours.
4. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the dialdehyde polysaccharide
Mass ratio with polyethylene glycol oxide is 70:30~96:4.
5. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the surface-active
Agent is triton x-100, Tween 80, polysorbas20 or Poloxamer 127, and the mass percentage in mixed solution is 0.5%
~3%.
6. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the electrostatic spinning
It is that spinning is carried out under the high voltage electric field of 5~30kV.
7. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the adipic acid two
Hydrazides solution is to be dissolved in adipic dihydrazide to prepare in ethanol/water mixed solvent obtaining.
8. a kind of preparation method of cross-linked polysaccharides fiber according to claim 1, which is characterized in that the step three
Reaction temperature is room temperature, and the reaction time is 2~48 hours.
9. the cross-linked polysaccharides fiber that the claim 1~8 any one preparation method obtains.
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