CN103272264A - Sulfated polysaccharide calcium salt and chitosan organic acid calcium composite porous stent and preparation method thereof - Google Patents
Sulfated polysaccharide calcium salt and chitosan organic acid calcium composite porous stent and preparation method thereof Download PDFInfo
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- CN103272264A CN103272264A CN2013102028967A CN201310202896A CN103272264A CN 103272264 A CN103272264 A CN 103272264A CN 2013102028967 A CN2013102028967 A CN 2013102028967A CN 201310202896 A CN201310202896 A CN 201310202896A CN 103272264 A CN103272264 A CN 103272264A
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Abstract
The invention discloses a sulfated polysaccharide calcium salt and chitosan organic acid calcium composite porous stent and a preparation method thereof. The porous stent contains 45-80% of chitosan organic acid salt, 10-50% of sulfated polysaccharide and 5-10% of chitosan organic acid calcium. The porous stent has better mechanical strength and compression performance and appropriate degradation rate and is a biologically degradable composite material with great development potential.
Description
Technical field
The invention belongs to the biological medical polymer chemical field, also belong to natural polymer field and filed of functional, be specifically related to a kind of sulfur-bearing acidify polysaccharide calcium salt recombination chitosan calcium of organic acid porous support and manufacture method thereof, it is the functional material that a class has excellent mechanical performances, biological degradability and antibiotic and sterilizing ability.
Background technology
Modern society causes the damaged patient of bone more and more because of reasons such as wound, tumor or osteopathia, and the demand of bone grafting material has been stimulated the development of artificial bone graft's material greatly, becomes the important means of bone defect repair.
(chitosan is by a kind of natural polycation biological polyoses of 2-amino-2-deoxidation-β-D-glucose by the polymerization of β-1,4 glycosidic bond CS) to chitosan, can present non-special interaction with cell membrane negative electricity composition.Experiment confirm, CS have the good cell compatibility, and biological degradability can promote the deposition of osteoblastic growth and mineral.A lot of researchs are own through having shown that CS is at the application potential aspect the bone tissue engineer.In addition, the derivant of chitosan-Sulfation chitosan has mucopolysaccharide GAG(heparin and the chondroitin sulfate that is similar among the animal body inner cell epimatrix ECM) structure and anticoagulation function, so as GAG, its sulfate radical very likely is the receptor of some cytokine, growth for cell, adhere to, propagation plays an important role with differentiation.Also be used to the effect that the manufacture of intraocular blood vessel is just considered itself and vascular endothelial cell based on the material of Sulfation chitosan derivatives.
Calcium sulfate has passed through long-term clinical verification as a kind of bone grafting material as the damaged filling repairing and treating of bone.Clinical practice confirms that the calcium sulfate biocompatibility is good, is used for the filling bone defects district and can forms local slightly acidic biotic environment, is conducive to blood vessel and osteoblastic growing into, and can stop growing into of fibrous tissue again, is a kind of safe and effective bone graft substitute.Can be fully by biodegradation after calcium sulfate implants, histological observation finds that osteoblast accumulates in around the calcium sulfate of implantation, produces osteoid, but does not see FBGCR.And the calcium sulfate wide material sources, low price is compared with collagen, the calcium phosphate bone cement of isodose, and obvious price advantage is arranged, and has a good application prospect clinically.Calcium sulfate more is the effect of bringing into play carrier in bone tissue engineer as support.The carrier of implanting as the part has several advantages: (1) good tolerability; (2) space filling characteristic, infiltration rate is suitable with new bone formation speed; (3) bio-absorbable is complete; (4) bone conduction effect.Calcium sulfate is through the development in a century, demonstrates its good effect in the repairing and treating of, spinal fusion damaged at bone, bone does not connect and chronic osteomyelitis.Yet calcium sulfate also comes with some shortcomings, and vivo degradation speed is very fast, thereby causes its intensity decreases very fast (complete degradation time is 45-72 days in the calcium sulfate body, than many from the fast twice of body bone).
Summary of the invention
In view of aforementioned prior art, the present invention prepares the calcium sulfate of high molecular functionalization as artificial bone supporting material by the sulfated polysaccharides calcification, simultaneously provide the intensity of support with chitosan as the basic framework material, obtain the suitable artificial bone scaffold porous support materials that possesses bone conduction effect of degraded and absorbed cycle.
Sulfur-bearing acidify polysaccharide calcium salt recombination chitosan calcium of organic acid porous support of the present invention has mechanical strength and compression performance preferably, and suitable degradation rate, is a kind of biodegradable composite with the potentiality that develop on a large scale very much.
Sulfur-bearing acidify polysaccharide calcium salt recombination chitosan calcium of organic acid porous support of the present invention has advantages such as good biocompatibility, degradation property be controlled, can be widely used in fields such as biomedicine, organizational project.
Technical solution of the present invention is as follows: sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support comprises: the chitosan acylate of 45-80%, 10-50% sulfated polysaccharides, 5-10% chitosan calcium of organic acid; Above percentage ratio is mass percent.
Preferably, the chitosan calcium of organic acid is chitosan calcium lactate, chitosan calcium malate, chitosan calcium ascorbate or chitosan calcium acetate.
Preferably, chitosan is dissolved in organic acid or the mineral acid, is mixed with described chitosan acylate; The molecular weight of chitosan is 60 ten thousand-140 ten thousand, deacetylation 80%-90%.
Preferably, sulfated polysaccharides is sulphation carboxymethyl chitosan, sulphation chitosan, sulphation ganoderan, sulphation pachyman, sulphation lentinan, sulphation grifolan or chondroitin sulfate.Sulphation carboxymethyl chitosan preferably.The Sulfation degree is not less than 80%.
The present invention is raw material with the sulfated polysaccharides, prepares the porous support of above-mentioned sulfated polysaccharides calcium salt recombination chitosan by the blend lyophilization, and concrete steps are as described below:
The manufacture method of sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support, as follows:
(1) polysaccharide is dissolved in concentrated sulphuric acid or chlorosulfonic acid makes sulfated polysaccharides, and sulfated polysaccharides is mixed with aqueous solution;
(2) chitosan is dissolved in organic acid or the mineral acid, is mixed with the chitosan acid solution; The sulfated polysaccharides aqueous solution of chitosan acid solution and step (1) is mixed;
(3) the mixed liquid with step (2) places-5 ℃--196 ℃ freezing lyophilizing down, obtains porous support;
(4) porous support that step (3) is obtained is immersed in CaCl
2The ethanol/water mixed solution in take out after leaving standstill a few hours; Clean through sodium bicarbonate aqueous solution, washed with de-ionized water is carried out freezing lyophilizing (preferred, lyophilizing behind-196 ℃ of liquid nitrogen freezings), namely again.
Preferably, gained sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support comprises: the chitosan acylate of 45-80%, 10-50% sulfated polysaccharides, 5-10% chitosan calcium of organic acid.
Preferably, step (1), the concentration of concentrated sulphuric acid or chlorosulfonic acid are 98.3%(quality percent by volume W/V).
Preferably, step (1), the sulphation time is 30 minutes.
Preferably, step (1), polysaccharide is selected from chitosan, ganoderan, grifolan, carboxymethyl chitosan, lentinan or pachyman.
Preferably, step (1) is mixed with 0.1-10% aqueous solution (quality percent by volume W/V) with sulfated polysaccharides.
Preferably, step (2), the concentration that obtains the chitosan acid solution is 4-15%(quality percent by volume W/V).
Preferably, step (2) mixes chitosan acid solution and sulfated polysaccharides aqueous solution with (volume ratio) according to the 80:20 ratio.
Preferably, step (2), the molecular weight of chitosan raw material is 60 ten thousand-140 ten thousand, deacetylation 80%-90%.
Preferably, step (3), cryogenic temperature are-20 ℃.
Preferably, step (1) adopts cryosel to bathe, mechanical agitation rotating speed 200-600rpm, and the sulphation time is 10-50 minute, precipitates by dehydrated alcohol with the alkali neutralization under low temperature, dialysis can obtain the sulfated polysaccharides that sulfonation degree is 50%-100% behind the lyophilizing purification.
Preferably, step (2), the solvent of dissolving chitosan is organic acid or inorganic acid aqueous solution, as lactic acid, ascorbic acid, malic acid, acetic acid, hydrochloric acid etc., preferably lactic acid.
Preferably, step (4), the porous support that step (3) is obtained is immersed in CaCl
2Ethanol/water (the quality percent by volume W/V) mixed solution of 60%-95% in leave standstill after 24-72 hour and take out; Support is through 1%-5%(quality percent by volume W/V) sodium bicarbonate aqueous solution cleaned 1 hour, and washed with de-ionized water is carried out freezing lyophilizing after 1 hour again.
Above-mentioned steps (1), (2) can carry out or exchange synchronously.
The inventive method adopts original position ion exchange sedimentation with the calcium sulfate high molecular functionalization, on the basis of chitosan as bone tissue engineering stent material, is the function ingredients material with the calcium salt of controlling sulfate polyose, makes the timbering material of sulfur-bearing acidify polysaccharide calcium salt.The porous support materials that makes by the present invention can be used for bone renovating material etc., can urge damaged tissues and heal rapidly.
Description of drawings
Fig. 1 forms the process sketch map of calcium salt composition structure for the sulphation chitosan.
Fig. 2 is the macroscopic view cardinal principle shape appearance figure of chitosan malate/sulphation ganoderan porous support.
Fig. 3 is the degradation rate under the lysozyme effect of 20mg/L of the support of the crosslinked sulphation lentinan of calcium ion/chitosan Ascorbate.
Fig. 4 is the sem photograph of the support of the crosslinked sulphation carboxymethyl chitosan of calcium ion/chitosan calcium lactate.
The specific embodiment
Below the preferred embodiment of the present invention is elaborated.
Embodiment 1
(1) 30 gram chitosans (degree of deacetylation〉85%) are slowly added in the 20mL chlorosulfonic acid, cryosel is bathed cooling, 500rpm high-speed stirred.After 45 minutes, reactant liquor is slowly poured into the 2mol/LNaHCO of 90mL cold preservation
3In, the control temperature is no more than 35 ℃.Regulate pH value to neutral, aqueous solution is adopted the dehydrated alcohol precipitation, filter.Precipitate is dissolved in the 50mL deionized water, dialysis, lyophilizing obtains the sulphation chitosan of 80% substitution value.
(2) 4 gram chitosan (molecular weight 900,000, deacetylation 85%) high-speed stirred are dissolved in the acetic acid aqueous solution of 100mL1%, add 2 gram sulphation chitosans, stirring is evenly mixed, pours in the mould.
(3) it is freezing to put into-20 ℃ of refrigerators.Freezing mould is put into the freezer dryer vacuum drying, obtain porous polysaccharide support.
(4) support is immersed in ethanol/water (ethanol: 60mL, the water: 40mL) in the mixed liquor of 10% calcium chloride of 100mL.Left standstill 48 hours.NaHCO through 1%
3Washing support 5min, behind the tri-distilled water washing 10min, continue to put into place-20 ℃ freezing, through freezer dryer again lyophilizing can obtain the support of the crosslinked sulphation lentinan of calcium ions/chitosan ascorbic acid hydrochlorate.
Form the process sketch map of calcium salt composition structure referring to Fig. 1 sulphation chitosan.
(1) 40 kairine sesame polysaccharide (polyoses content〉40%) is slowly added in the 25mL concentrated sulphuric acid ice-water bath cooling, 600rpm high-speed stirred.After 25 minutes, reactant liquor is slowly poured into the 1mol/LNa of 100mL cold preservation
2CO
3In, the control temperature is no more than 30 ℃.Regulate pH value to neutral, aqueous solution is adopted the dehydrated alcohol precipitation, filter.Precipitate is dissolved in the 30mL deionized water, dialysis, lyophilizing obtains the sulphation ganoderan of 100% substitution value.
(2) 1.8 gram chitosan (molecular weight 800,000, deacetylation 92%) high-speed stirred are dissolved in the aqueous solution of malic acid of 80mL2%, add 1.2 gram sulphation ganoderans, stir evenly mixed.
(3) pour in the mould, it is freezing to put into-10 ℃ of refrigerators.Freezing mould is put into the freezer dryer vacuum drying, obtain porous polysaccharide support.
(4) support is immersed in ethanol/water (ethanol: 85mL, the water: 15mL) in the mixed liquor of 4% calcium chloride of 80mL.Left standstill 36 hours.NaHCO through 0.5%
3Washing support 3min behind the tri-distilled water washing 4min, continues to put into and places liquid nitrogen freezing, through freezer dryer again lyophilizing can obtain the support of sulfur-bearing acidify carboxymethyl chitosan calcium salt/chitosan calcium lactate salt.
Macroscopic view cardinal principle pattern referring to Fig. 2 chitosan malate/sulphation ganoderan porous support.
(1) 20 gram lentinan (polyoses content〉35%) are slowly added in the 15mL concentrated sulphuric acid, cryosel is bathed cooling, 700rpm high-speed stirred.After 40 minutes, reactant liquor is slowly poured into the 0.8mol/LNaHCO of 70mL cold preservation
3In, the control temperature is no more than 25 ℃.Regulate pH value to neutral, aqueous solution is adopted the dehydrated alcohol precipitation, filter.Precipitate is dissolved in the 50mL deionized water, dialysis, lyophilizing obtains the sulphation lentinan of 100% substitution value.
(2) 2.5 gram chitosan (molecular weight 1,200,000, deacetylation 95%) high-speed stirred are dissolved in the aqueous ascorbic acid of 100mL1%, add 1 gram sulphation lentinan, stir evenly mixed.
(3) pour in the mould, it is freezing to put into-5 ℃ of refrigerators.Freezing mould is put into the freezer dryer vacuum drying, obtain porous polysaccharide support.
(4) support is immersed in ethanol/water (ethanol: 70mL, the water: 30mL) in the mixed liquor of 8% calcium chloride of 100mL.Left standstill 24 hours.NaHCO through 0.8%
3Washing support 1min, behind the tri-distilled water washing 5min, continue to put into place-20 ℃ freezing, through freezer dryer again lyophilizing can obtain the support of the crosslinked sulphation lentinan of calcium ions/chitosan Ascorbate.
The degradation rate under the lysozyme effect of 20mg/L referring to the support of the crosslinked sulphation lentinan of Fig. 3 calcium ion/chitosan Ascorbate.
Embodiment 4
(1) 25 gram carboxymethyl chitosans (carboxy methylation degree〉80%) is slowly added in the 20mL concentrated sulphuric acid ice-water bath cooling, 800rpm high-speed stirred.After 35 minutes, reactant liquor is slowly poured into the 1mol/LNaHCO of 100mL cold preservation
3In, the control temperature is no more than 30 ℃.Regulate pH value to neutral, aqueous solution is adopted the dehydrated alcohol precipitation, filter.Precipitate is dissolved in the 40mL deionized water, dialysis, lyophilizing obtains the sulphation carboxymethyl chitosan of 100% substitution value.
(2) 2 gram chitosan (molecular weight 600,000, deacetylation 85%) high-speed stirred are dissolved in the lactic acid aqueous solution of 100mL1%, add 1 gram sulphation carboxymethyl chitosan, stir evenly mixed.
(3) pour in the mould, it is freezing to put into-20 ℃ of refrigerators.Freezing mould is put into the freezer dryer vacuum drying, obtain porous polysaccharide support.
(4) support is immersed in ethanol/water (ethanol: 80mL, the water: 20mL) in the mixed liquor of 5% calcium chloride of 100mL.Left standstill 24 hours.NaHCO through 1%
3Washing support 2min behind the tri-distilled water washing 5min, continues to put into and places liquid nitrogen freezing, through freezer dryer again lyophilizing can obtain the support of sulfur-bearing acidify carboxymethyl chitosan calcium salt/chitosan calcium lactate salt.
Sem photograph referring to the support of the crosslinked sulphation carboxymethyl chitosan of Fig. 4 calcium ion/chitosan calcium lactate.
Blended gel lyophilizing support of the present invention by chitosan solution and sulfated polysaccharides solution mix homogeneously after lyophilizing, the crosslinked back of calcium ion secondary freeze drying makes, this lyophilizing support has the good mechanical performance, micropore diameter is controlled and excellent biological compatibility and advantages such as high ventilation performance and biodegradable performance, and production process is simple, convenient, can be used as engineering material of bone tissue etc., have good potential applicability in clinical practice.
Claims (10)
1. sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support is characterized in that comprising: the chitosan acylate of 45-80%, 10-50% sulfated polysaccharides, 5-10% chitosan calcium of organic acid.
2. according to the described sulfated polysaccharides calcium salt of claim 1 recombination chitosan calcium of organic acid porous support, it is characterized in that: the chitosan calcium of organic acid is chitosan calcium lactate, chitosan calcium malate, chitosan calcium ascorbate or chitosan calcium acetate.
3. according to the described sulfated polysaccharides calcium salt of claim 1 recombination chitosan calcium of organic acid porous support, it is characterized in that: chitosan is dissolved in organic acid or the mineral acid, is mixed with described chitosan acylate; The molecular weight of chitosan is 60 ten thousand-140 ten thousand, deacetylation 80%-90%.
4. according to each described sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support of claim 1-3, it is characterized in that: sulfated polysaccharides is sulphation carboxymethyl chitosan, sulphation chitosan, sulphation ganoderan, sulphation pachyman, sulphation lentinan, sulphation grifolan or chondroitin sulfate.
5. the manufacture method of sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support is characterized in that as follows:
(1) polysaccharide is dissolved in concentrated sulphuric acid or chlorosulfonic acid makes sulfated polysaccharides, and sulfated polysaccharides is mixed with aqueous solution;
(2) chitosan is dissolved in organic acid or the mineral acid, is mixed with the chitosan acid solution; The sulfated polysaccharides aqueous solution of chitosan acid solution and step (1) is mixed;
(3) the mixed liquid with step (2) places-5 ℃--196 ℃ freezing lyophilizing down, obtains porous support;
(4) porous support that step (3) is obtained is immersed in CaCl
2The ethanol/water mixed solution in take out after leaving standstill a few hours; Clean through sodium bicarbonate aqueous solution, washed with de-ionized water is carried out freezing lyophilizing, namely again.
6. as the manufacture method of sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support as described in the claim 5, it is characterized in that: step (1), the concentration of concentrated sulphuric acid or chlorosulfonic acid are 98.3%.
7. as the manufacture method of sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support as described in the claim 5, it is characterized in that: step (1), the sulphation time is 30 minutes.
8. as the manufacture method of claim 5-7 sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support as described in each, it is characterized in that: step (1), polysaccharide is selected from chitosan, ganoderan, grifolan, carboxymethyl chitosan, lentinan or pachyman;
And/or step (1) is mixed with the 0.1-10% aqueous solution with sulfated polysaccharides.
9. as the manufacture method of sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support as described in the claim 5, it is characterized in that: step (2), the concentration that obtains the chitosan acid solution is 4-15%;
And/or, step (2), chitosan acid solution and sulfated polysaccharides aqueous solution is mixed according to the 80:20 ratio;
And/or, step (2), the molecular weight of chitosan raw material is 60 ten thousand-140 ten thousand, deacetylation 80%-90%.
10. as the manufacture method of sulfated polysaccharides calcium salt recombination chitosan calcium of organic acid porous support as described in the claim 5, it is characterized in that: step (3), cryogenic temperature are-20 ℃.
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| CN112245647A (en) * | 2020-10-26 | 2021-01-22 | 杭州电子科技大学 | Preparation method of sponge wound dressing |
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Application publication date: 20130904 |