CN104988606B - Crosslinked pectin fiber and preparation method thereof - Google Patents
Crosslinked pectin fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a crosslinked pectin fiber and a preparation method thereof, and belongs to the field of macromolecular fiber. The method comprises the steps: firstly, mixing a pectin aqueous solution and a polyoxyethylene aqueous solution, then adding a surfactant and a cosolvent, to obtain a mixed solution, and spinning the mixed solution, to obtain an electrospinned nanofiber; and then crosslinking the obtained electrospinned nanofiber, to obtain a crosslinked nanofiber; and finally, washing the obtained crosslinked nanofiber, and thus obtaining the crosslinked pectin fiber. The invention also provides the crosslinked pectin fiber obtained by the preparation method. The pectin nanofiber contains no other chemical components and enables a stable nanofiber structure to be kept under a condition of water phase, so that the crosslinked pectin fiber has better biocompatibility and water resistance, has relatively high mechanical strength, and can meet a lot of biomedical requirements.
Description
Technical field
The invention belongs to macromolecular fibre field, more particularly to a kind of cross-linked pectin fiber and preparation method thereof.
Background technology
Pectin (pectin) is polyanionic natural heteropolysaccharide of the class from plant, based on its good gelling
Matter, in food industry gelling agent and thickener are widely used as.Because pectin has good biocompatibility, water imbibition, antibacterial
Property, pectin is also gradually applied in health and medical product.Additionally, pectin itself has various inherent biologically actives, bag
Include anti-inflammatory, antitumor, regulation complement system, support bone cell growth etc., the extensive concern of people has been attracted in recent years, be produced
Into Nano/micron particle, hydrogel, porous three-dimensional support etc., for treatment of cancer, colonic drug delivery, bone tissue engineer, sugar
The biomedical sectors (Munarin, F.et al.Int.J.Biol.Macromol.2012,51,681-689) such as urine disease treatment.
Pectin nanofiber in structure and is similar in composition natural extracellular matrix (Liu, W.et
Al.Adv.HealthcareMater.2012,1,10-25), the abundant biologically active in conjunction with pectin uniqueness, in biological doctor
Field has a extensive future.
In preparing the technology of high polymer nanometer fiber at present, electrostatic spinning is generally acknowledged side simple, direct, with low cost
Method.However, due to the polyelectrolyte property of pectin, pure aqueous pectin solution can not form stable jet under electric field action, no
Can directly electrospinning obtain pectin nanofiber (Stijnman, A.C.et al.Food hydrocolloids 2011,25,
1393–1398).By synthesis polyphosphazene polymer ethylene oxide (PEO) that easy spinning is added in aqueous pectin solution, by PEO
Auxiliary pectin spinning together, obtains mixing nanofiber (Rockwell, the P.L.et of pectin and PEO
al.Carbohyd.Polym.2014,107,110–118).However, there are two big defects in these pectin nanofibers：
(1) it is up to 50% synthesis macromolecule PEO containing mass fraction in nanofiber.These synthesis macromolecules are a lot
Bio-medical scene is not needed, once and be placed in physiological water phase condition will dissolution, cause material to lose nanometer
Fibre structure, mechanical performance reduce, it is also possible to cause toxicity in vivo (Duan, B.et al.Eur.Polym.J.2006,42,
2013–2022)。
(2) water is met instant.The pectin nanofiber that pectin has excellent water solubility, non-crosslinked fixation once faces water
Phase environment, swelling immediately or dissolving, causes material to lose nanofibrous structures, cannot apply under a number of conditions.
The content of the invention
The invention aims to solve the problems, such as that existing pectin nanofiber is instant due to uncrosslinked chance water, and carry
For a kind of cross-linked pectin fiber and preparation method thereof.
The present invention provides a kind of preparation method of cross-linked pectin fiber, and the method includes：
Step one：Aqueous pectin solution and polyoxyethylene aqueous solution are mixed, surfactant and cosolvent is subsequently adding,
Mixed solution is obtained, mixed solution is carried out into spinning, obtain electro spinning nano fiber；
Step 2：The electro spinning nano fiber that step one is obtained is crosslinked, crosslinking nano fiber is obtained；
Step 3：The crosslinking nano fiber that step 2 is obtained is washed, and obtains cross-linked pectin fiber.
Preferably, the source of pectin is oranges and tangerines, lemon, apple, sunflower, beet or people in described aqueous pectin solution
Ginseng.
Preferably, in described aqueous pectin solution and polyoxyethylene aqueous solution pectin and polyethylene glycol oxide mass ratio
For 70：30～96：4.
Preferably, described surfactant is Triton X-100, Tween 80, polysorbas20 or Poloxamer 127.
Preferably, described cosolvent is dimethyl sulfoxide (DMSO), dimethylformamide, glycerine or propane diols.
Preferably, described spinning is that spinning is carried out under the high voltage electric field of 5～30kV.
Preferably, described crosslinking is chemically crosslinked again to be physical crosslinking or being first physical crosslinking.
Preferably, the method for described physical crosslinking, including：
(1) ethanol is added to be soaked in electro spinning nano fiber；
(2) ethanol is removed, adds ethanol to carry out precrosslink with the mixed solution of calcium chloride or zinc chloride；
(3) ethanol and calcium chloride or the mixed solution of zinc chloride are removed, adds calcium chloride or solder(ing)acid to be handed over
Connection, obtains being physical crosslinking nanofiber.
Preferably, it is described to be first physical crosslinking the method being chemically crosslinked again, including：
(1) ethanol is added to be soaked in electro spinning nano fiber；
(2) ethanol is removed, adds ethanol to carry out precrosslink with the mixed solution of calcium chloride or zinc chloride；
(3) ethanol and calcium chloride or the mixed solution of zinc chloride are removed, adds calcium chloride or solder(ing)acid to be handed over
Connection, obtains being physical crosslinking nanofiber.
(4) calcium chloride or solder(ing)acid are removed, add in physical crosslinking nanofiber glutaraldehyde water solution or
The adipic dihydrazide aqueous solution, is chemically crosslinked, and is first physical crosslinking and be chemically crosslinked again nanofiber.
The present invention also provides the cross-linked pectin fiber that above-mentioned preparation method is obtained.
Beneficial effects of the present invention
Present invention firstly provides a kind of preparation method of cross-linked pectin fiber, the method is first by aqueous pectin solution and polyoxygenated
The ethene aqueous solution mixes, and is subsequently adding surfactant and cosolvent, obtains mixed solution, and mixed solution is carried out into spinning, obtains
To electro spinning nano fiber；Then the electro spinning nano fiber for obtaining is crosslinked, is obtained crosslinking nano fiber；Finally will obtain
Crosslinking nano fiber is washed, and obtains cross-linked pectin fiber.The preparation method of the present invention is simple, be easily achieved, by electrospinning,
Crosslinking, three steps of washing, successfully eliminate the supplemental chemicals used in preparation process, while effectively securing Nanowire
The structure of dimension, the cross-linked pectin fiber for preparing has excellent mechanical performance and water resistance.
The present invention also provides the cross-linked pectin fiber that above-mentioned preparation method is obtained, and does not contain in the pectin nanofiber for being provided
Other chemical compositions, and stable nanofibrous structures can be kept under the conditions of water phase, therefore the cross-linked pectin fiber tool
There are more preferable biocompatibility and resistance to water, and possess higher mechanical strength, disclosure satisfy that the requirement of many bio-medicals, by
There is abundant biologically active in pectin, pectin nanofiber has at aspects such as trauma dressing, tissue engineering bracket, oncotherapies
Wide application prospect.
Description of the drawings
Fig. 1 is the load-deformation curve of the low ester sunflower pectin fiber of crosslinking that the embodiment of the present invention 1 is obtained；
Fig. 2 is the cell survival rate of the low ester sunflower pectin fiber of crosslinking that the embodiment of the present invention 1 is obtained；
Fig. 3 is the low ester sunflower pectin fiber stereoscan photograph of crosslinking that the embodiment of the present invention 1 is obtained.
Specific embodiment
The present invention provides a kind of preparation method of cross-linked pectin fiber, and the method includes：
Step one：Aqueous pectin solution and polyoxyethylene aqueous solution are mixed, surfactant and cosolvent is subsequently adding,
Mixed solution is obtained, mixed solution is carried out into spinning, obtain electro spinning nano fiber；
Step 2：The electro spinning nano fiber that step one is obtained is crosslinked, crosslinking nano fiber is obtained；
Step 3：The crosslinking nano fiber that step 2 is obtained is washed, and obtains cross-linked pectin fiber.
According to the present invention, first respectively pectin and polyethylene glycol oxide is made into into aqueous pectin solution and polyoxyethylene aqueous solution,
The mass percent concentration of described aqueous pectin solution is preferably 2%～10%, it is proposed, according to the invention, the source of described pectin does not have
Have specifically limited, preferably oranges and tangerines, lemon, apple, sunflower, beet or ginseng, the weight average molecular weight of described pectin is preferred
For 100,000～1,500,000, esterification degree is 20%～80%, and degree of amidation is 0～40%, and described the viscous of polyethylene glycol oxide is divided equally
Son amount is preferably 500,000～10,000,000, and the mass percent concentration of polyoxyethylene aqueous solution is preferably 2%～10%, then will
Aqueous pectin solution and polyoxyethylene aqueous solution mix, pectin and poly- in described aqueous pectin solution and polyoxyethylene aqueous solution
The mass ratio of ethylene oxide is preferably 70：30～96：4, surfactant and cosolvent are subsequently adding, mixed solution is obtained, will
Mixed solution is preferably stirred at room temperature to be stood after 3～24h and removes bubble removing, then mixed solution is carried out into spinning, described spinning
Silk is preferably being carried out under the high voltage electric field of 5～30kV, and more preferably voltage is 5～20kV, then apart from 5～20cm of spinning head
Fiber is collected at place, and more preferably spinning head and the distance of collector are 10～15cm, obtain electro spinning nano fiber；
Described surfactant is preferably Triton X-100, Tween 80, polysorbas20 or Poloxamer 127, described surface
The mass percent concentration of activating agent is preferably 0.5%～3%, more preferably 0.5%～2%；Described cosolvent is preferably
Dimethyl sulfoxide (DMSO), dimethylformamide, glycerine or propane diols, the mass percent concentration of addition is preferably 2%～10%, more
Preferably 5%～10%.
According to the present invention, described crosslinking is chemically crosslinked again to be physical crosslinking or being first physical crosslinking.
Described physical crosslinking is bivalent cation physical crosslinking, and concrete grammar is preferably included：
(1) electro spinning nano fiber is placed in ethanol and is soaked, described soak time is preferably 5～30min；
(2) ethanol in (1) is removed, is subsequently adding ethanol molten with the mixing of calcium chloride water or solder(ing)acid
Liquid carries out precrosslink；Described ethanol is with ethanol in the mixed solution of calcium chloride water and the volume ratio of calcium chloride water
80：20～95：5；The mass percent concentration of calcium chloride water is 10%～50%；Described ethanol and solder(ing)acid
Mixed solution in the volume ratio of ethanol and solder(ing)acid be 80：20～95：5；The mass percent of solder(ing)acid
Concentration is 10%～50%；The time of described precrosslink is preferably 10～60min；
(3) precrosslink solution in (2) is removed, is subsequently adding calcium chloride water or solder(ing)acid is crosslinked,
Obtain being physical crosslinking nanofiber；The mass percent concentration of described calcium chloride water is 10%～50%；Zinc chloride water
The mass percent concentration of solution is 10%～50%；Described crosslinking time is preferably 1～6h.
Preferably, it is described to be first physical crosslinking the method being chemically crosslinked again, including：
(1) electro spinning nano fiber is placed in ethanol and is soaked, described soak time is preferably 5～30min；
(2) ethanol in (1) is removed, is subsequently adding ethanol molten with the mixing of calcium chloride water or solder(ing)acid
Liquid carries out precrosslink；Described ethanol is with ethanol in the mixed solution of calcium chloride water and the volume ratio of calcium chloride water
80：20～95：5；The mass percent concentration of calcium chloride water is 10%～50%；Described ethanol and solder(ing)acid
Mixed solution in the volume ratio of ethanol and solder(ing)acid be 80：20～95：5；The mass percent of solder(ing)acid
Concentration is 10%～50%；The time of described precrosslink is preferably 10～60min；
(3) precrosslink solution in (2) is removed, is subsequently adding calcium chloride water or solder(ing)acid is crosslinked,
Obtain being physical crosslinking nanofiber；The mass percent concentration of described calcium chloride water is 10%～50%；Zinc chloride water
The mass percent concentration of solution is 10%～50%；Described crosslinking time is preferably 1～6h.
(4) calcium chloride or solder(ing)acid are removed, to physical crosslinking nanofiber add glutaraldehyde water solution or oneself
The dihydrazi aqueous solution, is chemically crosslinked, and is first physical crosslinking and be chemically crosslinked again nanofiber；Described physical crosslinking
Before nanofiber is chemically crosslinked again, preferred elder generation's deionized water is rinsed 5～10 times, to remove unnecessary ion.
It is described to add glutaraldehyde water solution to carry out being chemically crosslinked method for optimizing and be to physical crosslinking nanofiber：By physics
Crosslinking nano fiber is placed in and is contained with the sealing container of the mixed solution of 25% glutaraldehyde water solution and concentrated hydrochloric acid, mixed solution
Middle glutaraldehyde water solution is preferably 3 with the volume ratio of concentrated hydrochloric acid：1～10：1, make physical crosslinking nanofiber be exposed to glutaraldehyde
In hydrochloric acid vapour, 12～48h is crosslinked；Or, physical crosslinking nanofiber is directly thrown to containing 0.5～2M glutaraldehydes and 2
In the solution of～20mM hydrochloric acid, 12～48h is crosslinked.
Described adds the adipic dihydrazide aqueous solution to be chemically crosslinked to physical crosslinking nanofiber, preferably includes：
1. the 2- morpholino ethanesulfonic acid buffers containing 2～50mM hydroxybenzotriazoles are added in physical crosslinking nanofiber
(in 0.01～0.1M, pH 5.5～7), react 1～3h；
2. and then in the 1. buffering mixed solution 2～50mM carbodiimides is added, continues to react 1～3h；
3. again in 2. mixed solution add 5～50mM adipic dihydrazides, 12～48h of cross-linking reaction.
According to the present invention, above-mentioned crosslinking nano fiber is washed, obtained cross-linked pectin fiber, described washing methods
Preferably：Crosslinking nano fiber is soaked in deionized water, every 6～12h the old aqueous solution is removed, add fresh water,
Change 5～10 times altogether, vacuum drying after freeze-drying or graded ethanol wash-out removes solvent, obtains the water-fast of drying
Cross-linked pectin fiber.
The present invention also provides the cross-linked pectin fiber that above-mentioned preparation method is obtained, and described cross-linked pectin fibre diameter is
100nm～1 μm.
Below the present invention is further illustrated using specific embodiment, but the present invention is not limited to this.
Embodiment 1：Ca2+The low ester sunflower pectin fiber of ion physical crosslinking
1) electrostatic spinning：First (molecular weight is 210,000 to the low ester sunflower aqueous pectin solution of preparation 5% respectively, esterification degree
44%) polyethylene glycol oxide (molecular weight the is 5,000,000) aqueous solution with 5%, then according to the mass ratio of pectin and polyethylene glycol oxide
For 95:5 mix low ester sunflower aqueous pectin solution and polyoxyethylene aqueous solution, and add mass percent concentration to be 1%
Triton X-100 and dimethyl sulfoxide (DMSO) that mass percent concentration is 5%, mixed liquor is stirred at room temperature after 3h and was stood
At night, bubble-free homogeneous mixture solotion is obtained, above-mentioned mixed solution is placed in into spinning under the high voltage electric field of 10kV, apart from spinneret
Fiber is collected at head 15cm, electro spinning nano fiber is obtained；
2)Ca2+Ion physical is crosslinked：The above-mentioned electro spinning nano fibers of 20mg are placed in into 20mL ethanol immersion 5min；Remove immersion
Liquid, adds the ethanol of 20mL and the mixed solution (volume ratio 95/5) of 40% calcium chloride water, precrosslink 10min；Remove pre-
Crosslinker solution, adds 40% calcium chloride water of 20mL, is crosslinked 2h, obtains being physical crosslinking nanofiber；
3) wash：Remove crosslinked fluid, deionized water washing by soaking crosslinking nano fiber 6 times, with remove polyethylene glycol oxide,
Surfactant, cosolvent and unnecessary ion, freeze-drying, obtain the low ester sunflower pectin fiber of crosslinking of drying.
The low ester sunflower pectin fiber of crosslinking that the embodiment 1 of the wide 6mm thickness 0.015mm of the long 25mm of clip is prepared, with
The chuck of mechanics machine fixes (gauge length 10mm), with the speed tensile of 1mm/min, monitor stress-strain curve such as Fig. 1 institutes
Show, as a result show, the Young's modulus for being crosslinked low ester sunflower pectin fiber is 270.8MPa.
The low ester sunflower pectin fiber of crosslinking that 5mg embodiments 1 are prepared is weighed, 1mL DMEM cell culture fluids are placed in
In, cultivate 48h in 37 DEG C of constant incubators.Leachate is taken, variable concentrations are diluted to, every hole is added to and is planted 5000 L929
In fibroblastic Tissue Culture Plate, continue to cultivate 48h.MTT detection methods detect cell survival rate, as shown in Fig. 2 result is aobvious
Show, in 2.5mg/mL fiber Steep cencentrations, cell survival rate is higher than still 90%.
Weigh the low ester sunflower pectin fiber of crosslinking that 5mg embodiments 1 prepare to be placed in 50mL water, in 37 DEG C of constant temperature
Cultivate in incubator, fiber sample is taken out after 30 days, observe the pattern of fiber after freeze-drying using SEM, such as
Shown in Fig. 3, in Fig. 3, a is the low ester sunflower pectin fiber of crosslinking, and b is the low ester sunflower of crosslinking after soaking 30 days in water
Pectin fiber, as a result shows, is crosslinked after low ester sunflower pectin fiber is cultivated 30 days in water and remains to keep good fibre
Dimension pattern, it was demonstrated that Ca2+Ion physical crosslinking effectively secures the structure of pectin fiber, it is ensured that pectin fiber is in water phase condition
Structural stability.
Embodiment 2：Jing Zn after elder generation2+The low amidation apple pectin fiber that ion physical is crosslinked and glutaraldehyde is chemically crosslinked
1) electrostatic spinning：First (molecular weight is 300,000 to the low amidation apple pectin aqueous solution of preparation 4% respectively, ester
Change degree 27%, degree of amidation 23%) and 4% polyethylene glycol oxide (molecular weight the be 2,000,000) aqueous solution, according to pectin and polyoxy
The mass ratio for changing ethene is 90:10 mix the low amidation apple pectin aqueous solution and polyoxyethylene aqueous solution, and add
The dimethylformamide that mass percent concentration is 0.5% Poloxamer 127 and mass percent concentration is 10%, will mix
Liquid is stirred at room temperature 5h, stands overnight, and obtains bubble-free homogeneous mixture solotion, and above-mentioned mixed solution is placed in into the height of 12kV
Spinning under piezoelectric field, is collecting fiber at spinning head 12cm, obtains electro spinning nano fiber；
2)Zn2+Ion physical is crosslinked：The above-mentioned electro spinning nano fibers of 20mg are placed in into 20mL ethanol immersion 10min；Remove leaching
Bubble liquid, adds the mixed solution (volume ratio 90/10) of the aqueous solution of the ethanol and 20% zinc chloride of 20mL, precrosslink 20min；
Precrosslink solution is removed, 20% solder(ing)acid of 20mL is added, 3h is crosslinked；Crosslinked fluid is removed, deionized water is rinsed fine
Dimension 3 times, to remove unnecessary ion, obtains Zn2+The nanofiber of ion physical crosslinking；
3) glutaraldehyde chemical crosslinking：By Zn2+Ion physical crosslinking after nanofiber be placed in the glutaraldehyde containing 750mM and
In the mixed aqueous solution of 5mM hydrochloric acid, 24h is crosslinked, obtains first Zn2+Again glutaraldehyde is chemically crosslinked nanofiber for ion physical crosslinking；
4) wash：Remove crosslinked fluid, deionized water washing by soaking fiber 8 times, to remove polyethylene glycol oxide, surface-active
Agent, cosolvent and unnecessary crosslinking agent, freeze-drying, obtain the low amidation apple pectin fiber of crosslinking of drying.
The low amidation apple pectin fiber of crosslinking that embodiment 2 is obtained carries out pattern, intensity, cytotoxicity and water-fast
Property test, as a result show, it is 305.8MPa to be crosslinked low amidation apple pectin fiber Young's modulus, no cytotoxicity, in water
More than 30 days fibre structures of middle holding do not change, it was demonstrated that its have higher mechanical strength and good cell compatibility and
Resistance to water.
Embodiment 3：Jing Ca after elder generation2+The high ester citrus pectin fiber that ion physical is crosslinked and adipic dihydrazide is chemically crosslinked
1) electrostatic spinning：First (molecular weight is 860,000 to the high ester citrus pectin aqueous solution of preparation 5% respectively, esterification degree
70%) polyethylene glycol oxide (molecular weight the is 1,000,000) aqueous solution with 5%.Mass ratio according to pectin and polyethylene glycol oxide is 80:
20 mix the high ester citrus pectin aqueous solution and polyoxyethylene aqueous solution, and add the tween that mass percent concentration is 1%
80 and glycerine that mass percent concentration is 3%, mixed liquor is stirred at room temperature after 4h and is stood overnight, obtain bubble-free
Homogeneous mixture solotion, by above-mentioned mixed solution spinning under the high voltage electric field of 20kV is placed in, and is collecting fine at spinning head 15cm
Dimension, obtains electro spinning nano fiber；
2)Ca2+Ion physical is crosslinked：The above-mentioned electro spinning nano fibers of 20mg are placed in into 20mL ethanol immersion 10min；Remove leaching
Bubble liquid, adds the mixed solution (volume ratio 95/5) of the aqueous solution of the ethanol and 40% calcium chloride of 20mL, precrosslink 20min；Go
Except precrosslink solution, 40% calcium chloride water of 20mL is added, be crosslinked 3h；Crosslinked fluid is removed, deionized water rinses fiber 3
Time, to remove unnecessary ion, obtain Ca2+The nanofiber of ion physical crosslinking；
3) adipic dihydrazide chemical crosslinking：By Ca2+The nanofiber of ion physical crosslinking is placed in containing 5mM hydroxy benzos
In 2- morpholino ethanesulfonic acid buffers (0.1M, pH 6.5) of triazole, after reaction 2h, the carbonization two of 5mM is added in crosslinked fluid
Imines, continues to react 1h, adds 10mM adipic dihydrazides, and cross-linking reaction 24h obtains first Ca2+Ion physical is crosslinked again oneself
Dihydrazide chemistry crosslinking nano fiber；
4) wash：Remove crosslinked fluid, deionized water washing by soaking fiber 8 times, to remove polyethylene glycol oxide, surface-active
Agent, cosolvent and unnecessary crosslinking agent, the vacuum drying Jing after 20%～100% ethanol gradient elution removes ethanol, obtains
Dry crosslinking high ester citrus pectin fiber.
Crosslinking high ester citrus pectin fiber row pattern, intensity, cytotoxicity and the examination of water phase stability that embodiment 3 is obtained
Test, as a result show, crosslinking high ester citrus pectin fiber Young's modulus is 585.6MPa, no cytotoxicity is kept for 30 days in water
Above fibre structure does not change, it was demonstrated that it has higher mechanical strength and good cell compatibility and resistance to water.
Claims (6)
1. a kind of preparation method of cross-linked pectin fiber, it is characterised in that the method includes：
Step one：Aqueous pectin solution and polyoxyethylene aqueous solution are mixed, surfactant and cosolvent is subsequently adding, is obtained
Mixed solution, by mixed solution spinning is carried out, and obtains electro spinning nano fiber；Described aqueous pectin solution and polyethylene glycol oxide is water-soluble
The mass ratio of pectin and polyethylene glycol oxide is 70 in liquid：30～96：4；
Step 2：The electro spinning nano fiber that step one is obtained is crosslinked, crosslinking nano fiber is obtained；
Step 3：The crosslinking nano fiber that step 2 is obtained is washed, and obtains cross-linked pectin fiber；
Described step two crosslinking is chemically crosslinked again to be physical crosslinking or being first physical crosslinking,
The method of described physical crosslinking, including：
1) ethanol is added to be soaked in electro spinning nano fiber；
2) ethanol is removed, adds ethanol to carry out precrosslink with the mixed solution of calcium chloride or zinc chloride；
3) ethanol and calcium chloride or the mixed solution of zinc chloride are removed, adds calcium chloride or solder(ing)acid to be crosslinked, obtained
To physical crosslinking nanofiber；
Described is first physical crosslinking the method being chemically crosslinked again, including：
1) ethanol is added to be soaked in electro spinning nano fiber；
2) ethanol is removed, adds ethanol to carry out precrosslink with the mixed solution of calcium chloride or zinc chloride；
3) ethanol and calcium chloride or the mixed solution of zinc chloride are removed, adds calcium chloride or solder(ing)acid to be crosslinked, obtained
To physical crosslinking nanofiber；
4) calcium chloride or solder(ing)acid are removed, in physical crosslinking nanofiber glutaraldehyde water solution or adipic acid is added
The two hydrazides aqueous solution, are chemically crosslinked, and are first physical crosslinking and be chemically crosslinked again nanofiber.
2. the preparation method of a kind of cross-linked pectin fiber according to claim 1, it is characterised in that described pectin is water-soluble
The source of pectin is oranges and tangerines, lemon, apple, sunflower, beet or ginseng in liquid.
3. a kind of preparation method of cross-linked pectin fiber according to claim 1, it is characterised in that described surface-active
Agent is Triton X-100, Tween 80, polysorbas20 or Poloxamer 127.
4. the preparation method of a kind of cross-linked pectin fiber according to claim 1, it is characterised in that described cosolvent is
Dimethyl sulfoxide (DMSO), dimethylformamide, glycerine or propane diols.
5. the preparation method of a kind of cross-linked pectin fiber according to claim 1, it is characterised in that described spinning be
Spinning is carried out under the high voltage electric field of 5～30kV.
6. the cross-linked pectin fiber that the preparation method described in Claims 1 to 5 any one is obtained.
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