CN102580685A - Porous polysaccharide cell adsorption material as well as preparation method and application thereof - Google Patents
Porous polysaccharide cell adsorption material as well as preparation method and application thereof Download PDFInfo
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- CN102580685A CN102580685A CN2011104211120A CN201110421112A CN102580685A CN 102580685 A CN102580685 A CN 102580685A CN 2011104211120 A CN2011104211120 A CN 2011104211120A CN 201110421112 A CN201110421112 A CN 201110421112A CN 102580685 A CN102580685 A CN 102580685A
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Abstract
The invention discloses a porous organic inorganic hybrid polysaccharide cell adsorption material as well as a preparation method and application thereof. The adsorption material provided by the invention is prepared through the method comprising the following steps: silicon dioxide collosol, chitosan solution and cross-linking agent water solution are mixed uniformly to obtain hydrogel, and the hydrogel is treated through seasoning and freeze drying in sequence to obtain the porous organic inorganic hybrid polysaccharide cell adsorption material, wherein cross-linking agent in the cross-linking agent water solution is aldehyde benzoic acid terminated polyethyleneglycol. According to the invention, the organic inorganic hybrid chitosan porous material taking a silicon dioxide network as the skeleton is formed in situ through a novel hydrogel preparation technology; and the material has favorable red blood cell adsorption capacity and is a potential admirable hemostatic material.
Description
Technical field
The present invention relates to a kind of polysaccharide cell sorbing material and preparation method thereof and application of porous.
Background technology
Present hemostatic material on the market mainly is divided into fibrin class, polysaccharide and micro-pore zeolite class.Mostly the hemostasis principle of hemostatic material is near the concentration of haemocyte, blood platelet, clotting factor increase wound under the physics of material or the chemical action, forms blood coagulation, thereby reaches the purpose of hemostasis.Yet make a general survey of the hemostatic material of present listing; Existence such as complex manufacturing process, expensive, the strict problems such as (dry low humidities) of preservation condition of production cost; And the hemostatic material that has also can be followed other side effects when reaching the hemostasis purpose; Such as micro-pore zeolite class styptic, in the process of blood coagulation, can be accompanied by the illeffects such as heat release burn that cause because of suction-operated.
Summary of the invention
In order to overcome shortcomings such as existing hemostatic material complex manufacturing process, production cost costliness and toxic and side effect are many, the invention provides a kind of novel porous organic inorganic hybridization polysaccharide cell sorbing material and preparation method thereof.
Porous organic inorganic hybridization polysaccharide cell sorbing material provided by the present invention is that the method according to following step prepares: silicon dioxide gel, chitosan solution and cross-linking agent aqueous solution are mixed; Obtain hydrogel; And then said hydrogel carried out ageing, freeze drying successively until constant weight, obtain said porous organic inorganic hybridization polysaccharide cell sorbing material; Wherein, the crosslinking agent in the said cross-linking agent aqueous solution is the polyethylene glycol of terephthalaldehydic acid end-blocking.
Wherein, the mass ratio of silica, shitosan and crosslinking agent can be (30-80) in the said hydrogel: (10-70): (20-70), the preferred mass ratio is 60: 15: 25.
Among the present invention, said silicon dioxide gel prepares according to following method: positive esters of silicon acis is hydrolyzed under the acid condition of 2-6 (is good with 3.5-4.5) in the pH value, stirs until the lamination disappearance, obtain homogeneous phase aqueous solution and be silicon dioxide gel.The mass content of silica can be 5-21% in the said silicon dioxide gel.
Said chitosan solution is shitosan to be dissolved in the acetum that concentration is 0.005-0.1g/ml (is good with 0.02g/ml) obtain.The mass concentration of shitosan is 0.5%-5% in the said chitosan solution.
The molecular weight of the used shitosan of the present invention can be 1000Da-500000Da, and deacetylation can be 75%-100%.
The polyethylene glycol of said crosslinking agent terephthalaldehydic acid end-blocking (polyethylene glycol terephthalaldehydic acid diester) is that polyethylene glycol and terephthalaldehydic acid obtain through esterification; Concrete synthetic method is referring to document Biomacromolecules; 2011,12 (8), pp 2894-2901.The molecular weight of used polyethylene glycol is 200-10000Da.
The mass concentration of crosslinking agent is 5%-65% in the said cross-linking agent aqueous solution, is good with 20%-30%.
The condition of said ageing is that room temperature is placed more than 2 days or 40-60 ℃ of (is good with 50 ℃) constant temperature was placed 24 hours
Said method also comprises the step that the porous organic inorganic hybridization polysaccharide cell sorbing material for preparing is ground.Material particle size after the pulverizing is advisable at the 20-300 order.
The invention provides a kind of novel porous organic inorganic hybridization cell sorbing material, it mainly consists of shitosan, silica and contains aldehyde radical polyethylene glycol crosslinking agent.During preparation cross-linking agent aqueous solution and silicon dioxide gel (hydrating solution of positive esters of silicon acis) are mixed, then this mixed solution is mixed with chitosan solution, it is mixed through stirring operations such as perhaps vortex vibration.The amido that enriches on the shitosan and the aldehyde radical at polyethylene glycol crosslinking agent two ends form imine linkage (schiff bases), and the intersegmental cross-linking system that interts each other of chain can form hydrogel very soon in 1 minute.The silicon dioxide gel hydrogel is through polycondensation, and original position forms the network of silica skeleton, obtains the chitosan multi-porous material of organic inorganic hybridization.This material possesses good red blood cell adsorption capacity, is a kind of potential splendid hemostatic material.Gained hemostatic material five minutes adsorption rates in the in-vitro blood cells adsorption experiment are more than 80%.
The present invention prepare sorbing material needed raw material wide material sources, cheap, the preparation method is simple.The sorbing material environmental protection that is provided not only can be satisfied the requirement of hemostasis, can also overcome the multiple deficiency of at present selling hemostatic material, is easy to realize large-scale commercial production.
Cell sorbing material provided by the present invention has following outstanding feature:
1, the required raw material sources of preparation cell sorbing material of the present invention enrich, and are cheap.
2, the preparation technology of cell sorbing material of the present invention is simple, and technological parameter is more easy to control.
3, the environmental protection of cell sorbing material of the present invention, and hemostatic capability is stronger, and anthemorrhagic speed is very fast, and few side effects is easy to realize large-scale commercial production.
The specific embodiment
The present invention will be described through specific embodiment below, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is conventional method.
Material therefor all can obtain through commercial sources except that the polyethylene glycol crosslinking agent of terephthalaldehydic acid end-blocking among the following embodiment.The preparation method of crosslinking agent terminal synthesizes for the polyethylene glycol of hydroxyl and terephthalaldehydic acid pass through esterification, specifically referring to document Biomacromolecules, and 2011,12 (8), pp 2894-2901.
The preparation of the polysaccharide cell sorbing material of embodiment, porous organic inorganic hybridization
1. the 3g shitosan is dissolved in the acetum of 97g 0.02g/ml, obtains mass concentration and be 3% chitosan solution;
2. ethyl orthosilicate hydrolysis under acid (the pH value is 3.5) condition is stirred until the lamination disappearance, and (be silicon dioxide gel, wherein, the mass content of silica is 21% to obtain the 3ml homogeneous phase aqueous solution;
3. the aqueous solution (mass concentration 20%) of the polyethylene glycol of 1ml terephthalaldehydic acid end-blocking and silicon dioxide gel in the step 2 are mixed, then this mixed solution is mixed with chitosan solution, it is mixed through stirring.
4. the colloidal sol that is dispersed in the hydrogel is carried out ageing (50 ℃ of constant temperature of ageing condition were placed 24 hours), the silicon dioxide gel original position is carried out polycondensation and is formed the network of silica support in ageing process.
With the network of silica support vacuum freeze-drying that obtains until constant weight, being ground into powder obtains particle diameter has loose structure for the 60-100 purpose hybrid inorganic-organic hemostatic material again.
The in-vitro blood cells adsorption experiment:
Get 30 milligrams of hemostatic material powder, be added to (pH is 7.2, and mass concentration is 0.9%) among 1 milliliter of PBS; The fresh mouse whole blood (being stored in the anticoagulant tube) that adds 50 microlitres then; Jiggle, wait solid sedimentation slightly, get supernatant liquid at regular intervals and carry out cell count.In 5 minutes, it is initial 20% that the cell number of supernatant liquor reduces to, and the haemocyte more than 80% and blood platelet in the blood etc. adsorbed in the present invention in 5 minutes.
Claims (10)
1. method for preparing porous organic inorganic hybridization polysaccharide cell sorbing material; Comprise the steps: silicon dioxide gel, chitosan solution and cross-linking agent aqueous solution are mixed; Obtain hydrogel; And then said hydrogel carried out ageing, freeze drying successively, obtain said porous organic inorganic hybridization polysaccharide cell sorbing material; Wherein, the crosslinking agent in the said cross-linking agent aqueous solution is the polyethylene glycol of terephthalaldehydic acid end-blocking.
2. method according to claim 1 is characterized in that: the mass ratio of silica, shitosan and crosslinking agent is (30-80) in the said hydrogel: (10-70): (20-70), concrete mass ratio is 60: 15: 25.
3. method according to claim 1 and 2 is characterized in that: the mass content of silica is 5-21% in the said silicon dioxide gel;
Said silicon dioxide gel prepares according to following method: positive esters of silicon acis is hydrolysis under the acid condition of 2-6 in the pH value, stirs until the lamination disappearance, obtain homogeneous phase aqueous solution and be silicon dioxide gel; Wherein, said acid condition is specially the acid condition of pH value for 3.5-4.5.
4. according to each described method among the claim 1-3, it is characterized in that: the mass concentration of shitosan is 0.5%-5% in the said chitosan solution; Said chitosan solution is shitosan to be dissolved in the acetum that concentration is 0.005-0.1g/ml obtain.
5. according to each described method among the claim 1-4, it is characterized in that: the molecular weight of said shitosan is 1000Da-500000Da, and deacetylation is 75%-100%.
6. according to each described method among the claim 1-5, it is characterized in that: the mass concentration of crosslinking agent is 5%-65% in the said cross-linking agent aqueous solution, is specially 20-30%.
7. according to each described method among the claim 1-6, it is characterized in that: the polyethylene glycol of said terephthalaldehydic acid end-blocking is to be obtained through esterification by polyethylene glycol and terephthalaldehydic acid; Wherein, the molecular weight of said polyethylene glycol is 200-10000Da.
8. according to each described method among the claim 1-7, it is characterized in that: the condition of said ageing is that room temperature is placed more than 2 days or 40-60 ℃ of constant temperature is placed more than 24 hours.
9. the porous organic inorganic hybridization polysaccharide cell sorbing material that each said method prepares among the claim 1-8.
10. the application of the described porous organic inorganic hybridization of claim 9 polysaccharide cell sorbing material in the preparation hemostatic material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102772820A (en) * | 2012-08-21 | 2012-11-14 | 中国人民解放军军事医学科学院卫生装备研究所 | Alkyl modified chitosan/mesoporous silicon dioxide composite quick hemostatic powder and preparation method thereof |
| CN104194066A (en) * | 2014-09-15 | 2014-12-10 | 中国科学院上海硅酸盐研究所 | Silicon oxide-chitosan composite aerogel and preparation method thereof |
| CN104758939A (en) * | 2015-02-26 | 2015-07-08 | 宁波大学 | Preparation and application of pH glucose dual sensitive hydrogel |
| CN106395820A (en) * | 2016-09-23 | 2017-02-15 | 郑州峰泰纳米材料有限公司 | Chitosan-supported foam activated carbon material and preparation method thereof |
| CN108578776A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method of magnesium-based bottom surface bio-vitric/hydrogel composite coating |
| CN110343268A (en) * | 2019-01-21 | 2019-10-18 | 福建农林大学 | A kind of tool adhesiveness of pH response, antibacterial, pressure resistance quick selfreparing collagen based aquagel preparation method |
| US10898878B2 (en) | 2016-08-23 | 2021-01-26 | Showa Denko Materials Co., Ltd. | Adsorbent material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080145455A1 (en) * | 2006-12-13 | 2008-06-19 | Bedard Robert L | Combination of Inorganic Hemostatic Agents with Other Hemostatic Agents |
| CN102205231A (en) * | 2011-04-12 | 2011-10-05 | 浙江温州轻工研究院 | Adsorption microspheres of chitosan coated silica gel and preparation method thereof |
-
2011
- 2011-12-15 CN CN 201110421112 patent/CN102580685B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080145455A1 (en) * | 2006-12-13 | 2008-06-19 | Bedard Robert L | Combination of Inorganic Hemostatic Agents with Other Hemostatic Agents |
| CN102205231A (en) * | 2011-04-12 | 2011-10-05 | 浙江温州轻工研究院 | Adsorption microspheres of chitosan coated silica gel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YALING ZHANG ET AL.: "Synthesis of Multiresponsive and Dynamic Chitosan-Based Hydrogels", 《BIOMACROMOLECULES》, 23 June 2011 (2011-06-23) * |
| 杨越冬等: "应用于生物医学领域的化学改性壳聚糖", 《高分子通报》, 28 February 2006 (2006-02-28) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102772820A (en) * | 2012-08-21 | 2012-11-14 | 中国人民解放军军事医学科学院卫生装备研究所 | Alkyl modified chitosan/mesoporous silicon dioxide composite quick hemostatic powder and preparation method thereof |
| CN102772820B (en) * | 2012-08-21 | 2014-06-18 | 中国人民解放军军事医学科学院卫生装备研究所 | Alkyl modified chitosan/mesoporous silicon dioxide composite quick hemostatic powder and preparation method thereof |
| CN104194066A (en) * | 2014-09-15 | 2014-12-10 | 中国科学院上海硅酸盐研究所 | Silicon oxide-chitosan composite aerogel and preparation method thereof |
| CN104758939A (en) * | 2015-02-26 | 2015-07-08 | 宁波大学 | Preparation and application of pH glucose dual sensitive hydrogel |
| US10898878B2 (en) | 2016-08-23 | 2021-01-26 | Showa Denko Materials Co., Ltd. | Adsorbent material |
| CN106395820A (en) * | 2016-09-23 | 2017-02-15 | 郑州峰泰纳米材料有限公司 | Chitosan-supported foam activated carbon material and preparation method thereof |
| CN106395820B (en) * | 2016-09-23 | 2018-11-23 | 郑州峰泰纳米材料有限公司 | A kind of foam active Carbon Materials of loading chitosan and preparation method thereof |
| CN108578776A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method of magnesium-based bottom surface bio-vitric/hydrogel composite coating |
| CN110343268A (en) * | 2019-01-21 | 2019-10-18 | 福建农林大学 | A kind of tool adhesiveness of pH response, antibacterial, pressure resistance quick selfreparing collagen based aquagel preparation method |
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