CN106750573A - A kind of shitosan alginate porous gel and its methods for making and using same - Google Patents

A kind of shitosan alginate porous gel and its methods for making and using same Download PDF

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CN106750573A
CN106750573A CN201611046222.2A CN201611046222A CN106750573A CN 106750573 A CN106750573 A CN 106750573A CN 201611046222 A CN201611046222 A CN 201611046222A CN 106750573 A CN106750573 A CN 106750573A
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alginate
shitosan
porous gel
quality
alginic acid
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CN106750573B (en
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姜勇
李艳丽
陆瞿亮
李慧
朱曼利
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Southeast university chengxian college
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Southeast university chengxian college
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    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
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Abstract

The invention discloses a kind of shitosan alginate porous gel and its methods for making and using same, the hydrogel has Multi-network, with good mechanical performance, swelling behavior and degradation property.The shitosan alginate porous gel, according to mass fraction, including following components：Shitosan：1~3 part, alginate：1~3 part, monovalent metal salting liquid：94~98 parts, the genipin of shitosan, the ion crosslinking agent of alginate, foaming agent, and surfactant；The mass concentration of monovalent metal salting liquid is 0.01~0.5%；The quality of the genipin of shitosan is the 0.5~5% of chitosan mass；The ion crosslinking agent of alginate is divalent metal salt, and divalent metal salt quality is the 2~30% of alginate quality；The quality of foaming agent is the 0.1~15% of porous gel gross mass；The quality of surfactant is the 0.1~15% of porous gel gross mass.

Description

A kind of chitin-alginic acid salt porous gel and its methods for making and using same
Technical field
The invention belongs to polymeric material field, it particularly relates to a kind of chitin-alginic acid salt porous gel and its Methods for making and using same.
Background technology
Hydrogel is swelling in water and keeps substantial amounts of moisture and undissolved polymer.Macromolecule hydrogel be by Macromolecular scaffold, water, the three-dimensional system of crosslinking agent composition, with complex space network structure, have a wide range of applications.In medical science Field：Carrier as insoluble drug release, hydrogel has both storage medicine, control release speed, drives three kinds of functions of release, can The intensity and hardness of preparation are adjusted, can play a part of to promote decomposition, figuration again, moreover it is possible to cover the bitter taste and smell of pharmaceuticals, Can be used for the methods of administration such as oral, nasal cavity, oral cavity, rectum, eye, injection.As wound dressing, hydrogel material is directly used in Contacted with tissue, the infection of micro-organisms in vitro can be prevented, suppress the loss of body fluid, transmission oxygen can accelerate epithelium thin to wound Intracellular growth, accelerates new capillary proliferation, and bacterium is invaded for isolation, suppresses bacterial reproduction, promotes the healing of wound.Hydrogel is because having Biocompatibility, biological degradability, high-moisture and cell membrane adhesiveness and be applied to organizational project.
In recent years, with the progress of medical technology, for the organ or tissue that is brought by wound, accident or cancer The recovery technique of damage is greatly improved, however, the transplanting of organ or tissue is still by controlling that patient accepts extensively Treatment method.Because autotransplantation can bring secondary injury and pain to patient, heteroplastic transplantation has many such as rejection, organ origins Limited the problems such as, slight illness is reduced with the method for organizational project (Tissue engineering) and is rejected bringing to treatment Very big hope.The method of organizational project is mainly with the structure of degradable three-dimensional (3-D) artificial material to induce patient certainly The growth of body cell, reaches the purpose of organ or tissue's regeneration.When new organ and tissue complete regeneration after, artificial material also with Time degraded to finish.
Although for the material that different organ or tissues needs different shape feature, these 3-D induced materials are but There are some common requirements：(1) 3-D materials will have similitude with the tissue for being substituted；(2) these materials need to have perforate Structure and hole size it is suitable；(3) material will have suitable mechanical performance to make it possible to the tissue for maintaining to be pre-designed Structure and can bear to be applied to the tote of original structure；(4) when material needs it is degradable and to have it is suitable Degradation rate；(5) material needs that inflammation symptom or can be with dephlogistication symptom will not be caused.To sum up, with degradability, good The porous aquagel of good biocompatibility and good mechanical performance is exactly a kind of very excellent organizational project 3-D induction materials Material.
The content of the invention
Technical problem：The technical problems to be solved by the invention are：There is provided a kind of chitin-alginic acid salt porous gel and Its methods for making and using same, the hydrogel has the structure of multimeshed network, with good mechanical performance, swelling behavior and degraded Performance so that it has application well in tissue engineering bracket.
Technical scheme：In order to solve the above technical problems, the technical solution adopted by the present invention is：
In a first aspect, the embodiment of the present invention provides a kind of chitin-alginic acid salt porous gel, the porous gel is according to matter Amount number, including following components：
Shitosan：1~3 part,
Alginate：1~3 part,
Monovalent metal salting liquid：94~98 parts,
The genipin of shitosan, the ion crosslinking agent of alginate, foaming agent, and surfactant；
The mass concentration of monovalent metal salting liquid is 0.01~0.5%；
The quality of the genipin of the shitosan is the 0.5~5% of the chitosan mass；
The ion crosslinking agent of the alginate is divalent metal salt, and the divalent metal salt quality is the alginate The 2~30% of quality；
The quality of the foaming agent is the 0.1~15% of porous gel gross mass；
The quality of the surfactant is the 0.1~15% of porous gel gross mass.
With reference in a first aspect, used as the first possible embodiment, the genipin of described shitosan is Geniposide.
With reference in a first aspect, used as second possible embodiment, described divalent metal salt is calcium salt, strontium salt or barium Salt, and slaine has soluble or microsolubility.
With reference in a first aspect, used as the third possible embodiment, described foaming agent is carbonate or bicarbonic Salt.
With reference in a first aspect, used as the 4th kind of possible embodiment, described surfactant is cationic work Property agent, anionic surfactant or nonionic surfactant.
With reference in a first aspect, used as the 5th kind of possible embodiment, described monovalent metal salting liquid is sodium chloride solution Or Klorvess Liquid.
With reference in a first aspect, as the 6th kind of possible embodiment, triplicated network is formed in described porous gel, respectively For the covalent cross-linking network that the genipin of shitosan and shitosan is formed, the ion crosslinking agent of alginate and alginate Between the ionomer network that is formed, the and-NH on shitosan2Interaction shape and the-COOH on sodium alginate between Into triple networkings.
Second aspect, the embodiment of the present invention provides a kind of preparation method of chitin-alginic acid salt porous gel, the preparation Method is comprised the following steps：
Step 10) shitosan that mass fraction is 1~3 part is added 47~49 parts univalent metal salt acetic acid solution In, stir, shitosan is completely dissolved, form chitosan solution；
By in the monovalent metal salting liquid of 47~49 parts of the alginate addition that mass fraction is 1~3 part, stir, Alginate is completely dissolved, alginic acid saline solution is formed molten；
Step 20) stirring alginate solution, to the genipin that shitosan is added in alginate solution, surface is lived Property agent, be subsequently adding foaming agent, chitosan solution, be eventually adding the ion crosslinking agent of sodium alginate, stir 1~15min, it is on the rocks Bag cooling 1~60min of ultrasound, is then encapsulated with sealed membrane, forms uniform foaming system；
Step 30) by step 20) foaming system that is formed, in 15~60 DEG C of water-bath 4~48h of culture, obtains shitosan-sea Mosanom porous gel.
With reference to second aspect, used as the first possible embodiment, the mass concentration of the monovalent metal salting liquid is 0.01~0.5%；
The quality of the genipin of the shitosan is the 0.5~5% of the chitosan mass；
The ion crosslinking agent of the alginate is divalent metal salt, and the divalent metal salt quality is the alginate The 2~30% of quality；
The quality of the foaming agent is the 0.1~15% of porous gel gross mass；
The quality of the surfactant is the 0.1~15% of porous gel gross mass.
The third aspect, the embodiment of the present invention provides a kind of described chitin-alginic acid salt porous gel and is cured as biology With the application of material.
Beneficial effect：Compared with prior art, the porous gel of the shitosan sodium alginate prepared by the present invention, has Good mechanical performance.Compared with the hydrogel or single aquagel of single alginate, the present invention is made Improved a lot in mechanical performance for the porous gel for going out.Shitosan sodium alginate porous gel prepared by the present invention, tool There is the intensity for being better than aquagel, Sodium Alginate Hydrogel Films, while there is loose structure again, additionally with good molten Swollen and degradation property.Therefore, porous gel of the invention can be in terms of tissue engineering bracket by with good application.
Brief description of the drawings
Fig. 1 is that the structural diagrams of the triple interpenetrating networks formed in prepared porous gel in the present invention are intended to；
Fig. 2 is the loose structure microscope figure of the gel prepared by embodiment of the present invention 1-6；
Fig. 3 is the lines figure that gel prepared by embodiment of the present invention 1-6 carries out measuring mechanical property；
Fig. 4 is the swelling behavior figure of the embodiment of the present invention 1 and the porous gel prepared by comparative example under different pH；
Fig. 5 is the degradation property figure of the embodiment of the present invention 1 and the porous gel prepared by comparative example under pH7.4.
Specific embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art is further Understand the present invention, but following examples and the invention is not limited in any way.
The chitin-alginic acid salt porous gel of the embodiment of the present invention, according to mass fraction, including following components：
Shitosan：1~3 part,
Alginate：1~3 part,
Monovalent metal salting liquid：94~98 parts,
The genipin of shitosan, the ion crosslinking agent of alginate, foaming agent, and surfactant；
The mass concentration of monovalent metal salting liquid is 0.01~0.5%；
The quality of the genipin of the shitosan is the 0.5~5% of the chitosan mass；
The ion crosslinking agent of the alginate is divalent metal salt, and the divalent metal salt quality is the alginate The 2~30% of quality；
The quality of the foaming agent is the 0.1~15% of porous gel gross mass；
The quality of the surfactant is the 0.1~15% of porous gel gross mass.
In above-described embodiment, preferably, the genipin of described shitosan is Geniposide (genipin).It is described Divalent metal salt be calcium salt, strontium salt or barium salt, and slaine has soluble or microsolubility.Soluble calcium salt, strontium Salt, barium salt, by G sections in ionomer sodium alginate structure or MG sections of formation cross-linked network；The calcium salt of microsolubility, strontium salt, Barium salt, because the solubilized part ion for solving is crosslinked with sodium alginate so that promote dissolving of the slightly soluble salt in water and Ionization, finally makes the divalent ion in slightly soluble salt all discharge, and participates in the cross-linking process of sodium alginate.Described foaming Agent is carbonate or acid carbonate.Described surfactant is cationic surface active agent, the work of anionic surface Property agent or nonionic surfactant.Described monovalent metal salting liquid is sodium chloride solution or Klorvess Liquid.
Triplicated network is formed in above-mentioned chitin-alginic acid salt porous gel, respectively shitosan and shitosan is natural The covalent cross-linking network that crosslinking agent is formed, the ionomer net formed between alginate and the ion crosslinking agent of alginate - NH on network, and shitosan2Triple networkings that interaction and the-COOH on sodium alginate between is formed.
The preparation method of above-mentioned chitin-alginic acid salt porous gel, the preparation method is comprised the following steps：
Step 10) shitosan that mass fraction is 1~3 part is added 47~49 parts univalent metal salt acetic acid solution In, stir, shitosan is completely dissolved, form chitosan solution；The alginate that mass fraction is 1~3 part is added In 47~49 parts of monovalent metal salting liquid, stir, be completely dissolved alginate, form alginic acid saline solution molten.
Step 20) stirring alginate solution, to the genipin that shitosan is added in alginate solution, surface is lived Property agent, be subsequently adding foaming agent, chitosan solution, be eventually adding the ion crosslinking agent of sodium alginate, stir 1~15min, it is on the rocks Bag cooling 1~60min of ultrasound, is then encapsulated with sealed membrane, forms uniform foaming system.
Step 30) by step 20) foaming system that is formed, in 15~60 DEG C of water-bath 4~48h of culture, obtains shitosan-sea Mosanom porous gel.
Above-mentioned chitin-alginic acid salt porous gel can be used as bio-medical material.
As shown in figure 1, with Ca2+As ion crosslinking agent, NaCl as slaine as a example by, according to above-mentioned preparation method prepare Porous gel be internally formed triplicated network structure, including the covalent cross-linking network that shitosan and Geniposide are formed, alginic acid - the NH on ionomer network and shitosan formed between sodium and ion crosslinking agent2And-the COOH on sodium alginate between Interaction formed triplicated network.
In preparation process, the genipin of shitosan can be chemically crosslinked with shitosan, form first and hand over again Networking road, bivalent metal ion can be cross-linked to form the second heavy cross-linked network with the G in alginate structure sections and MG sections.Simultaneously After shitosan and alginate are mixed, due to the two because electrostatic interaction forms polyelectrolyte in boundary, and can not The two is set to form uniform cross-linked network.In the system, the addition of univalent metal salt reduces shitosan and alginate Interact so that be mixed uniformly, while still being deposited between alginate and shitosan by stirring alginate and shitosan In the interaction of ion, the triple cross-linked network is formed.Because the formation of triplicated network so that porous gel can have While excellent loose structure, swelling behavior and degradation property, can also have good mechanical performance.
Below by experiment, specifically to verify that inventive gel has good loose structure, swelling behavior, degradation property And mechanical performance.
Experiment provides six embodiments and three comparative examples.Six embodiments are prepared according to preparation method of the invention Gel (CA porous).The consumption of each material, unit in each embodiment：Mg, as shown in table 1；The specific species that each material is used As shown in table 2.Three comparative examples are respectively comparative example 1：Chitosan gel rubber (chitosan)；Comparative example 2：Sodium alginate gel (alginate)；Comparative example 3：Shitosan sodium alginate plural gel (CA).
Table 1
Table 2
Porous gel to above-mentioned 6 embodiments carries out microscope photographing, as shown in Figure 2.In fig. 2, figure A correspondences are implemented The microscope figure of example 1, the microscope figure of figure B correspondence embodiments 2, the microscope figure of figure C correspondence embodiments 3, figure D correspondence embodiments 4 microscope figure, the microscope figure of figure E correspondence embodiments 5, the microscope figure of figure F correspondence embodiments 6.As can be seen from Figure 2： With the increase of foaming agent and amount of surfactant, bubble and hole in chitin-sodium alginate porous aquagel constantly increase. In embodiment 6, at most, hole size is also most uniform for the hole in aquogel system.
To above-described embodiment and comparative example, the test of mechanical performance, swelling behavior and degradation property is carried out respectively.
Wherein, measuring mechanical property rotational rheometer, the fixture of 30mm, at 25 DEG C, under the frequency of 1Hz, in 0.1rad s-1-110rad s-1Lower hydrogel, the sodium alginate-Ca for testing prepared chitosan-genipin respectively2+Water-setting The mechanical performance of the porous gel of glue, chitosan- sodium alginate composite hydrogels and different foaming agent consumptions.Use storage modulu (G ') and loss modulus (G ") are represented.Result is as shown in Figure 3.Can be obvious from storage modulu (the G ') curve in Fig. 3 Find out, the mechanical performance of embodiment 1 is optimal.
Swelling behavior test is carried out as follows：The prepared hydrogel blade of swelling equilibrium is cut into sample Block, every kind of hydrogel cuts out 12 parts, and freeze-drying after weighing, is respectively put into HCl solution, the acetic acid-acetic acid of pH5.6 of pH1.2 In the borate buffer solution of the cushioning liquid of sodium, the PBS of pH7.4 and pH9.3,3 are put in every kind of solution and is put down Row sample.After swelling 24h, the moisture on surface is sucked with filter paper, the weight in wet base weighed after obtaining swelling behavior is re-weighed every 2h, Untill quality is not further added by, the dry weight of hydrogel is obtained.Hydrogel is calculated by formula (1) swelling under condition of different pH Performance.
Wherein：Swellingratio represents the swelling behavior of hydrogel；wdRepresent the dry weight of hydrogel；wsRepresent hydrogel Weight in wet base after swelling；
The average swelling behavior for calculating 3 Duplicate Samples in every kind of solution by formula (1) is used as the hydrogel in the solution In swelling behavior.
Fig. 4 shows that chitosan gel rubber (chitosan), sodium alginate gel (algiante), shitosan sodium alginate are answered Close gel (CA) and porous gel (CA porous) swellability at various ph values prepared by the embodiment of the present invention 1 Energy.From fig. 4, it can be seen that porous gel provided in an embodiment of the present invention under different pH environment, with good swellability Energy.
Degradation property test is carried out as follows：The sample blocks that the hydrogel of swelling equilibrium is cut out, every kind of water-setting Glue takes 3 parts, be respectively put into each hole fill 5mL 1.5ug/mL lysozyme soln 12 porocyte culture plates in, daily The lysozyme soln for more renewing, it is ensured that the activity of enzyme.Hydrogel sample is taken out in timing, after the moisture with filter paper adsorption surface, is claimed Amount weight, degradation in vitro is represented with gel weight-loss ratio (Weightloss%), as shown in formula (2).
Wherein：w0Represent the original quality of hydrogel, wtRepresent degradation time be t after, the quality of hydrogel.
Fig. 5 provides chitosan gel rubber (chitosan), sodium alginate gel (algiante), shitosan sodium alginate and answers Close gel (CA) and the embodiment of the present invention 1 prepared by porous gel (CA porous) pH7.4 PBS cushioning liquid In degradation property schematic diagram.From fig. 5, it can be seen that porous gel prepared by the embodiment of the present invention can keep certain in early stage Stability, and show degradation property higher in the later stage.
Those skilled in the art it should be appreciated that the present invention is not limited by above-mentioned specific embodiment, above-mentioned specific implementation Description in example and specification is intended merely to further illustrate principle of the invention and its effect, do not depart from spirit of the invention and On the premise of scope, various changes and modifications of the present invention are possible, and these changes and improvements both fall within claimed invention In the range of.The scope of protection of present invention is by claims and its equivalent thereof.

Claims (10)

1. a kind of chitin-alginic acid salt porous gel, it is characterised in that the porous gel is according to mass fraction including following Component：
Shitosan：1~3 part,
Alginate：1~3 part,
Monovalent metal salting liquid：94~98 parts,
The genipin of shitosan, the ion crosslinking agent of alginate, foaming agent, and surfactant；
The mass concentration of monovalent metal salting liquid is 0.01~0.5%；
The quality of the genipin of the shitosan is the 0.5~5% of the chitosan mass；
The ion crosslinking agent of the alginate is divalent metal salt, and the divalent metal salt quality is the alginate quality 2~30%；
The quality of the foaming agent is the 0.1~15% of porous gel gross mass；
The quality of the surfactant is the 0.1~15% of porous gel gross mass.
2. according to the chitin-alginic acid salt porous gel described in claim 1, it is characterised in that the day of described shitosan Right crosslinking agent is Geniposide.
3. according to the chitin-alginic acid salt porous gel described in claim 1, it is characterised in that described divalent metal salt It is calcium salt, strontium salt or barium salt, and slaine has soluble or microsolubility.
4. according to the chitin-alginic acid salt porous gel described in claim 1, it is characterised in that described foaming agent is carbon Hydrochlorate or acid carbonate.
5. according to the chitin-alginic acid salt porous gel described in claim 1, it is characterised in that described surface-active Agent is cationic surface active agent, anionic surfactant or nonionic surfactant.
6. according to the chitin-alginic acid salt porous gel described in claim 1, it is characterised in that described monovalent metal Salting liquid is sodium chloride solution or Klorvess Liquid.
7. according to the chitin-alginic acid salt porous gel described in claim 1, it is characterised in that described porous gel The covalent cross-linking network that the genipin of middle formation triplicated network, respectively shitosan and shitosan is formed, alginate and The ionomer network formed between the ion crosslinking agent of alginate, the and-NH on shitosan2With on sodium alginate- Triple networkings that interaction between COOH is formed.
8. the preparation method of the chitin-alginic acid salt porous gel described in a kind of claim 1, its feature is in the preparation Method is comprised the following steps：
Step 10) shitosan that mass fraction is 1~3 part adds 47~49 parts of the acetic acid solution of univalent metal salt, stir Mix uniform, be completely dissolved shitosan, form chitosan solution；
By in the monovalent metal salting liquid of 47~49 parts of the alginate addition that mass fraction is 1~3 part, stir, make sea Alginates are completely dissolved, and form alginic acid saline solution molten；
Step 20) stirring alginate solution, to the genipin that shitosan is added in alginate solution, surface-active Agent, is subsequently adding foaming agent, chitosan solution, is eventually adding the ion crosslinking agent of sodium alginate, stirs 1~15min, bag on the rocks Cooling 1~60min of ultrasound, is then encapsulated with sealed membrane, forms uniform foaming system；
Step 30) by step 20) foaming system that is formed, in 15~60 DEG C of water-bath 4~48h of culture, obtains chitin-alginic acid Sodium porous gel.
9. according to the preparation method of the chitin-alginic acid salt porous gel described in claim 8, it is characterised in that described one The mass concentration of valency metal salt solution is 0.01~0.5%；
The quality of the genipin of the shitosan is the 0.5~5% of the chitosan mass；
The ion crosslinking agent of the alginate is divalent metal salt, and the quality of the divalent metal salt is the alginate matter The 2~30% of amount；
The quality of the foaming agent is the 0.1~15% of porous gel gross mass；
The quality of the surfactant is the 0.1~15% of porous gel gross mass.
10. the chitin-alginic acid salt porous gel described in a kind of claim 1 as bio-medical material application.
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