CN104491910A - Preparation method of mesoporous molecular sieve for haemostasis - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 14
- 230000023597 hemostasis Effects 0.000 title abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims 6
- 238000001914 filtration Methods 0.000 claims 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229960004756 ethanol Drugs 0.000 claims 2
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 14
- 239000011575 calcium Substances 0.000 abstract description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 abstract description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 abstract description 7
- 108010039209 Blood Coagulation Factors Proteins 0.000 abstract description 6
- 102000015081 Blood Coagulation Factors Human genes 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003114 blood coagulation factor Substances 0.000 abstract description 6
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 4
- 108090000190 Thrombin Proteins 0.000 abstract description 2
- 210000001124 body fluid Anatomy 0.000 abstract description 2
- 239000010839 body fluid Substances 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 2
- 229960004072 thrombin Drugs 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000001506 calcium phosphate Substances 0.000 description 6
- 230000002439 hemostatic effect Effects 0.000 description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 6
- 229940078499 tricalcium phosphate Drugs 0.000 description 6
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 6
- 235000019731 tricalcium phosphate Nutrition 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 241000700159 Rattus Species 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 108010094028 Prothrombin Proteins 0.000 description 1
- 102100027378 Prothrombin Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940039716 prothrombin Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
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- Materials For Medical Uses (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Abstract
本发明公开了一种用于止血的介孔分子筛的制备方法,该方法的步骤为:将十二胺加到水和无水乙醇的混合液中进行搅拌,得到混合液;向混合液中1~2秒一滴的滴加速度滴加正硅酸乙酯,继续搅拌;抽滤,水洗;抽滤,用无水乙醇进行深度洗涤;抽滤,烘干,得到白色粉体;将白色粉体加入到硝酸钙和磷酸二氢铵混合液中,调节pH;抽滤,得到的白色物质,先后置于去离子和无水乙醇中洗涤,抽滤;将抽滤出的物质放置于烘箱中进行烘干;烘干后,进行煅烧,得到HMS-TCP,即用于止血的介孔分子筛。HMS具有介孔结构,可以过滤体液中的水分子,使得血小板和凝血因子浓缩,激活凝血因子,TCP中的钙能提高某些凝血酶的活性,从而起到止血的作用。The invention discloses a method for preparing a mesoporous molecular sieve for hemostasis. The steps of the method are: adding dodecylamine to a mixed solution of water and absolute ethanol and stirring to obtain the mixed solution; adding 1 Add tetraethyl orthosilicate drop by drop at a rate of ~2 seconds, and continue to stir; filter with suction and wash with water; filter with suction and wash deeply with absolute ethanol; filter with suction and dry to obtain a white powder; add the white powder to into the mixed solution of calcium nitrate and ammonium dihydrogen phosphate, adjust the pH; filter the obtained white substance, wash it in deionized and absolute ethanol successively, and filter it with suction; place the filtered substance in an oven for drying Drying; after drying, it is calcined to obtain HMS-TCP, which is a mesoporous molecular sieve for hemostasis. HMS has a mesoporous structure, which can filter water molecules in body fluids, concentrate platelets and coagulation factors, and activate coagulation factors. Calcium in TCP can increase the activity of certain thrombin, thereby playing the role of hemostasis.
Description
技术领域 technical field
本发明涉及皮肤止血修复药物材料的制备方法,具体涉及到一种用于止血的介孔分子筛的制备方法。 The invention relates to a preparation method of a medicinal material for skin hemostasis repair, in particular to a preparation method of a mesoporous molecular sieve for hemostasis.
背景技术 Background technique
当今用于止血的材料中,介孔二氧化硅因为其具有很高的孔隙率和比表面积、其孔道的高度有序性、孔壁无定型且孔壁上有大量的硅醇键、具有良好的吸附性能等特征,从而可以充分的吸收水分子,起到止血作用。 Among the materials used for hemostasis today, mesoporous silica has a good Adsorption performance and other characteristics, so that it can fully absorb water molecules and play a hemostatic effect.
钙能减小体外凝血酶原时间和促进一些凝血因子的活性,能够起到加速止血的效果。将磷酸三钙(TCP)引入到介孔二氧化硅中,当介孔二氧化硅将水分过筛后,浓缩血小板和凝血因子,使得钙可以与皮肤受伤部位接触,促进相应的酶和凝血因子的活性,促进介孔分子筛的止血效果。HMS是一种具有高的比表面积和孔隙率的介孔材料。而单纯利用介孔二氧化硅的吸水性或者利用Ca的止血性能对于止血效果并不理想。 Calcium can reduce the prothrombin time in vitro and promote the activity of some coagulation factors, which can accelerate hemostasis. Introduce tricalcium phosphate (TCP) into mesoporous silica, when the mesoporous silica sieves the water, it concentrates the platelets and coagulation factors, so that the calcium can contact the injured part of the skin and promote the corresponding enzymes and coagulation factors activity, promoting the hemostatic effect of mesoporous molecular sieves. HMS is a mesoporous material with high specific surface area and porosity. However, simply using the water absorption of mesoporous silica or the hemostatic performance of Ca is not ideal for the hemostatic effect.
发明内容 Contents of the invention
本发明克服上述缺陷,提供一种用于止血的介孔分子筛的制备方法,通过制备HMS-TCP,使得其既能拥有HMS的介孔结构,发挥分子筛的作用,同时使得HMS能够引入钙,钙的引入能提高一些凝血酶的活性,加速止血。 The present invention overcomes the above-mentioned defects and provides a method for preparing mesoporous molecular sieves for hemostasis. By preparing HMS-TCP, it can not only have the mesoporous structure of HMS, but also play the role of molecular sieves. At the same time, HMS can introduce calcium, calcium The introduction of can increase the activity of some thrombin and accelerate hemostasis.
本发明的技术方案如下。 The technical scheme of the present invention is as follows.
一种用于止血的介孔分子筛的制备方法,包括下列步骤: A preparation method for a mesoporous molecular sieve for hemostasis, comprising the following steps:
(1)将十二胺(DDA)加到水和无水乙醇的混合液中进行搅拌,得到混合液; (1) Add dodecylamine (DDA) to the mixture of water and absolute ethanol and stir to obtain the mixture;
(2)向(1)混合液中1~2秒一滴的滴加速度滴加正硅酸乙酯(TEOS),继续搅拌; (2) Add tetraethyl orthosilicate (TEOS) dropwise to the mixture (1) at a rate of 1-2 seconds per drop, and continue stirring;
(3)抽滤,将得到的白色物质置于去离子水中进行水洗; (3) Suction filtration, washing the obtained white substance in deionized water;
(4)抽滤,将得到的白色物质置于无水乙醇进行深度洗涤; (4) Suction filtration, place the obtained white substance in absolute ethanol for deep washing;
(5)抽滤,对得到的白色物质进行烘干,得到白色粉体; (5) Suction filtration, drying the obtained white substance to obtain a white powder;
(6)将白色粉体加入到硝酸钙和磷酸二氢铵混合液中,用氨水调节pH; (6) Add the white powder to the mixture of calcium nitrate and ammonium dihydrogen phosphate, and adjust the pH with ammonia water;
(7)抽滤,得到的白色物质,先后置于去离子和无水乙醇中洗涤,抽滤; (7) Suction filtration, the obtained white substance was washed in deionized and absolute ethanol successively, and suction filtration;
(8)将抽滤出的物质放置于烘箱中进行烘干; (8) Place the filtered substance in an oven for drying;
(9)烘干后,进行煅烧,得到HMS-TCP,即用于止血的介孔分子筛。 (9) After drying, it is calcined to obtain HMS-TCP, which is a mesoporous molecular sieve for hemostasis.
上述方法中,步骤(1)中,所述DDA的加入量为1.8~2.2g,无水乙醇和水均为23.5~24.5ml。 In the above method, in step (1), the amount of DDA added is 1.8-2.2g, and both absolute ethanol and water are 23.5-24.5ml.
上述方法中,步骤(2)中,所述正硅酸乙酯为8.92~8.50ml,搅拌时间为18~24小时。 In the above method, in step (2), the ethyl orthosilicate is 8.92-8.50ml, and the stirring time is 18-24 hours.
上述方法中,步骤(3)中,所述去离子水的加入量为200~300ml,所述水洗时间为30~50分钟。 In the above method, in step (3), the amount of deionized water added is 200-300ml, and the washing time is 30-50 minutes.
上述方法中,步骤(4)中,所述无水乙醇的加入量为200~300ml,所述乙醇洗时间为3~5小时。 In the above method, in step (4), the amount of absolute ethanol added is 200-300ml, and the washing time with ethanol is 3-5 hours.
上述方法中,步骤(5)中,所述烘干温度为75~85℃,时间为4~5小时。 In the above method, in step (5), the drying temperature is 75-85° C., and the drying time is 4-5 hours.
上述方法中,步骤(6)中,所述硝酸钙和磷酸二氢铵混合液中硝酸钙和磷酸二氢铵均为45~55ml,硝酸钙和磷酸二氢铵的浓度分别为0.4~0.6mol/L和0.6~0.9mol/L,钙磷比为1.5,pH值为9~10.5。 In the above method, in step (6), the calcium nitrate and ammonium dihydrogen phosphate in the mixed solution of calcium nitrate and ammonium dihydrogen phosphate are both 45-55ml, and the concentrations of calcium nitrate and ammonium dihydrogen phosphate are respectively 0.4-0.6mol /L and 0.6~0.9mol/L, the ratio of calcium to phosphorus is 1.5, and the pH value is 9~10.5.
上述方法中,在步骤(7)中,去离子水和无水乙醇的量为300~350ml,水洗时间为1~1.5小时,乙醇洗时间为4~6小时。 In the above method, in step (7), the amount of deionized water and absolute ethanol is 300-350 ml, the washing time with water is 1-1.5 hours, and the washing time with ethanol is 4-6 hours.
上述方法中,在步骤(8)中,所述烘干的温度为75~85℃,时间为24~32小时。 In the above method, in step (8), the drying temperature is 75-85° C., and the drying time is 24-32 hours.
上述方法中,在步骤(9)中,所述煅烧的温度为800~850℃,时间为24~32小时。 In the above method, in step (9), the temperature of the calcination is 800-850° C., and the time is 24-32 hours.
与现有技术相比,本发明的优势在于: Compared with the prior art, the present invention has the advantages of:
(1)HMS的高表面积和高孔隙率为吸收的水分提供了空间; (1) The high surface area and high porosity of HMS provide space for absorbed moisture;
(2)HMS表面的硅醇键能够充分的与水分结合,吸收体液中的水分; (2) The silanol bonds on the surface of HMS can fully combine with water and absorb water in body fluids;
(3)HMS-TCP中的Ca能够激活相应的止血酶和凝血因子,加速止血; (3) Ca in HMS-TCP can activate corresponding hemostatic enzymes and coagulation factors to accelerate hemostasis;
(4)TCP降解为碱性,中和HMS降解时产生的酸性物质。 (4) TCP is degraded into alkaline, which neutralizes the acidic substances generated when HMS is degraded.
附图说明 Description of drawings
图1为实施例1和实施例2所得产品的XRD衍射图; Fig. 1 is the XRD diffractogram of embodiment 1 and embodiment 2 gained products;
图2为实施例4中三组组大鼠的止血时间的对比图。 FIG. 2 is a comparison chart of the hemostasis time of the three groups of rats in Example 4. FIG.
具体实施方式 Detailed ways
下面结合具体实施例对本发明作进一步地具体详细描述,但本发明的实施方式不限于此,对于未特别注明的工艺参数,可参照常规技术进行。 The present invention will be further described in detail below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto, and for process parameters not specifically indicated, conventional techniques can be referred to.
实施例1Example 1
(1)2gDDA加入到装有24ml水和24ml无水乙醇的混合液的烧杯中,将烧杯置于磁力搅拌器上对混合液体进行搅拌。 (1) Add 2g of DDA to a beaker containing a mixture of 24ml of water and 24ml of absolute ethanol, and place the beaker on a magnetic stirrer to stir the mixed liquid.
(2)以2秒一滴的滴加速度将8.92mlTEOS滴加上上述混合液中。 (2) Add 8.92ml TEOS dropwise to the above mixture at a drop rate of 2 seconds.
(3)将混合液体搅拌18小时。 (3) The mixed liquid was stirred for 18 hours.
(4)停止搅拌,陈化30分钟,进行抽滤。 (4) Stop stirring, age for 30 minutes, and perform suction filtration.
(5)将抽滤出的物质加到200ml水中,搅拌30分钟,进行抽滤。 (5) Add the substance filtered out by suction to 200ml of water, stir for 30 minutes, and perform suction filtration.
(6)将抽滤出的物质加到200ml无水乙醇中,搅拌3小时,进行抽滤。 (6) Add the substance filtered out by suction to 200ml of absolute ethanol, stir for 3 hours, and perform suction filtration.
(7)将抽滤出的物质放置于80℃的烘箱中进行烘干,烘干时间为4小时。 (7) Place the filtered substance in an oven at 80° C. for 4 hours for drying.
(8)烘干后,进行煅烧,煅烧温度为640℃,煅烧时间为4小时,得到HMS。 (8) After drying, calcining is carried out at a temperature of 640° C. and a calcining time of 4 hours to obtain HMS.
实施例2Example 2
(1)2gDDA加入到装有22.4ml水和24ml无水乙醇的混合液的烧杯中,将烧杯置于磁力搅拌器上对混合液体进行搅拌。 (1) Add 2g of DDA to a beaker containing a mixture of 22.4ml of water and 24ml of absolute ethanol, and place the beaker on a magnetic stirrer to stir the mixed liquid.
(2)以2秒一滴的滴加速度将8.92mlTEOS滴加上上述混合液中。 (2) Add 8.92ml TEOS dropwise to the above mixture at a drop rate of 2 seconds.
(3)将混合液体搅拌18小时。 (3) The mixed liquid was stirred for 18 hours.
(4)停止搅拌,陈化30分钟,进行抽滤。 (4) Stop stirring, age for 30 minutes, and perform suction filtration.
(5)将抽滤出的物质加到200ml水中,搅拌30分钟,进行抽滤。 (5) Add the substance filtered out by suction to 200ml of water, stir for 30 minutes, and perform suction filtration.
(6)将抽滤出的物质加到200ml无水乙醇中,搅拌3小时,进行抽滤。 (6) Add the substance filtered out by suction to 200ml of absolute ethanol, stir for 3 hours, and perform suction filtration.
(7)将抽滤出的物质放置于80℃的烘箱中进行烘干,烘干时间为4小时。 (7) Place the filtered substance in an oven at 80° C. for 4 hours for drying.
(8)将上述得到的白色粉体加入到50ml硝酸钙和50ml磷酸二氢铵混合液中,硝酸钙和磷酸二氢铵的浓度分别为0.4mol/L和0.6mol/L,用氨水调节PH值为10。 (8) Add the white powder obtained above to 50ml of calcium nitrate and 50ml of ammonium dihydrogen phosphate mixture, the concentrations of calcium nitrate and ammonium dihydrogen phosphate are 0.4mol/L and 0.6mol/L respectively, adjust the pH with ammonia water The value is 10.
(9)搅拌2h,室温陈化12h,抽滤。 (9) Stir for 2 hours, age at room temperature for 12 hours, and filter with suction.
(10)将抽滤出的物质加到300ml水中,搅拌1小时,进行抽滤。 (10) Add the substance filtered out by suction to 300ml of water, stir for 1 hour, and perform suction filtration.
(11)将抽滤出的物质加到300ml无水乙醇中,搅拌4小时,进行抽滤。 (11) Add the substance filtered out by suction to 300ml of absolute ethanol, stir for 4 hours, and perform suction filtration.
(12)将抽滤出的物质放置于80℃的烘箱中进行烘干,烘干时间为24小时。 (12) Place the filtered substance in an oven at 80°C for 24 hours.
(13)烘干后,进行煅烧,煅烧温度为800℃,煅烧时间为24小时,得到HMS-TCP。 (13) After drying, it is calcined at 800° C. for 24 hours to obtain HMS-TCP.
实施例3Example 3
XRD衍射图对比实验 XRD diffraction pattern comparison experiment
从图1中可以看到HMS在XRD衍射图谱中存在唯一的吸收峰,位于2°~3°之间且峰形较宽,此衍射峰说明介孔材料(110)面具有六角形结构。图1所示,纯HMS的衍射强度强于HMS-TCP,说明TCP成功的引入到HMS中。 It can be seen from Figure 1 that HMS has a unique absorption peak in the XRD diffraction pattern, which is located between 2° and 3° and has a broad peak shape. This diffraction peak indicates that the (110) surface of the mesoporous material has a hexagonal structure. As shown in Figure 1, the diffraction intensity of pure HMS is stronger than that of HMS-TCP, indicating that TCP was successfully introduced into HMS.
实施例4Example 4
皮肤止血对比实验 Skin hemostasis comparison experiment
取30只200g左右的SD大鼠分成2组,均将其右耳缘静脉割破,第一组将介孔二氧化硅HMS涂抹于大鼠耳缘伤口处,第二组将HMS/TCP涂抹于大鼠耳缘伤口处,第三组不做任何处理。伤口愈合所用时间如图2所示。可以看出,HMS/TCP有较好的止血效果。 Take 30 SD rats with a weight of about 200g and divide them into 2 groups, cut their right ear veins, the first group will apply mesoporous silica HMS to the ear wounds of the rats, and the second group will apply HMS/TCP The third group did not receive any treatment on the ear wounds of the rats. The time taken for wound healing is shown in Figure 2. It can be seen that HMS/TCP has better hemostatic effect.
Claims (10)
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CN106606799A (en) * | 2016-08-18 | 2017-05-03 | 中国人民解放军第二军医大学 | Porous starch composite material, and preparation method and applications thereof |
US12016901B2 (en) | 2019-12-13 | 2024-06-25 | Massachusetts Institute Of Technology | Tissue catalyzed growth of polymer as epithelial linings for therapy |
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CN101347452A (en) * | 2008-09-03 | 2009-01-21 | 华东理工大学 | Mesoporous calcium-silica xerogel for treating skin ulcers and its preparation method and application |
CN101389297A (en) * | 2005-12-30 | 2009-03-18 | 环球油品有限责任公司 | Adsorbent-containing hemostatic devices |
US20120308509A1 (en) * | 2008-03-11 | 2012-12-06 | Materials Modification, Inc. | Method and Composition for In Situ Formation of an Artificial Blockage to Control Blood Loss |
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US20120308509A1 (en) * | 2008-03-11 | 2012-12-06 | Materials Modification, Inc. | Method and Composition for In Situ Formation of an Artificial Blockage to Control Blood Loss |
CN101347452A (en) * | 2008-09-03 | 2009-01-21 | 华东理工大学 | Mesoporous calcium-silica xerogel for treating skin ulcers and its preparation method and application |
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CN106606799A (en) * | 2016-08-18 | 2017-05-03 | 中国人民解放军第二军医大学 | Porous starch composite material, and preparation method and applications thereof |
US12016901B2 (en) | 2019-12-13 | 2024-06-25 | Massachusetts Institute Of Technology | Tissue catalyzed growth of polymer as epithelial linings for therapy |
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