CN101401962B - Gelatin spherical porous particle material and its preparation method and device - Google Patents
Gelatin spherical porous particle material and its preparation method and device Download PDFInfo
- Publication number
- CN101401962B CN101401962B CN2008102350752A CN200810235075A CN101401962B CN 101401962 B CN101401962 B CN 101401962B CN 2008102350752 A CN2008102350752 A CN 2008102350752A CN 200810235075 A CN200810235075 A CN 200810235075A CN 101401962 B CN101401962 B CN 101401962B
- Authority
- CN
- China
- Prior art keywords
- gelatin
- spherical
- spherical porous
- particle
- storage tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 108010010803 Gelatin Proteins 0.000 title claims abstract description 63
- 229920000159 gelatin Polymers 0.000 title claims abstract description 63
- 239000008273 gelatin Substances 0.000 title claims abstract description 63
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 63
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 63
- 239000002245 particle Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000012798 spherical particle Substances 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract 4
- 239000008187 granular material Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical group O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 4
- 229940083037 simethicone Drugs 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 230000017423 tissue regeneration Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000011049 filling Methods 0.000 description 13
- 239000004005 microsphere Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 210000003722 extracellular fluid Anatomy 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 201000008283 Atrophic Rhinitis Diseases 0.000 description 1
- 208000017234 Bone cyst Diseases 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 206010039088 Rhinitis atrophic Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 210000001909 alveolar process Anatomy 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 230000012292 cell migration Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000002316 cosmetic surgery Methods 0.000 description 1
- 210000004262 dental pulp cavity Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 210000001595 mastoid Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 208000028169 periodontal disease Diseases 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Landscapes
- Medicinal Preparation (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
一、技术领域 1. Technical field
本发明属于一种应用于生物医学领域的球状颗粒材料的制备技术，具体涉及一种天然聚合物明胶球形多孔颗粒材料的制备方法。The invention belongs to a preparation technology of a spherical granular material applied in the field of biomedicine, and in particular relates to a preparation method of a natural polymer gelatin spherical porous granular material.
二、背景技术 2. Background technology
现有技术：current technology:
明胶是一种将胶原三螺旋结构转化为无规则链而获得的蛋白质，是一种热水可溶的多肽混合物，因而具有生物可降解性及良好的生物相容性。由于具有良好的成膜性，明胶在口服药品的胶囊中得到广泛应用；同时，明胶还具有活化巨噬细胞和止血作用，可用于制造伤口包扎、止血材料和人造皮肤，以及硬组织修复用填充材料。除用来制备块体多孔支架外，明胶也可用于制备颗粒形填充材料。。Gelatin is a protein obtained by converting the collagen triple helix structure into random chains. It is a hot water soluble polypeptide mixture, so it is biodegradable and has good biocompatibility. Due to its good film-forming properties, gelatin is widely used in capsules of oral medicines; at the same time, gelatin also has the effect of activating macrophages and hemostasis, and can be used to make wound dressings, hemostatic materials and artificial skin, as well as filling for hard tissue repair Material. In addition to being used to prepare bulk porous scaffolds, gelatin can also be used to prepare granular filling materials. .
微球材料具有很多不规则颗粒所没有的优异性能，如高的流动性、高的堆积密度、不易团聚、填充后不易引起应力集中等。目前，在牙根管和拔牙窝的充填、牙周病所致牙槽骨吸收的修复、牙槽嵴增高、颌骨骨囊腔填塞、萎缩性鼻炎充填、乳突腔充填、整形(如鞍鼻美容)及以人体骨骼其它部位的骨缺损充填中，微球颗粒填充材料得到广泛应用。聚合物基微球颗粒有多种制备方法，常用的有乳化-化学交联法、乳化-溶剂蒸发法及喷雾干燥法。应用这些方法制备的微球直径分布范围较大，填充密度大，应用于组织填充时，颗粒间的孔隙过少，不利于新生组织的长入。Microsphere materials have excellent properties that many irregular particles do not have, such as high fluidity, high bulk density, not easy to agglomerate, and not easy to cause stress concentration after filling. At present, it is used in the filling of root canals and extraction sockets, the restoration of alveolar bone absorption caused by periodontal disease, the increase of alveolar ridges, the filling of mandibular bone cysts, the filling of atrophic rhinitis, the filling of mastoid cavity, and plastic surgery (such as saddle bone filling). Nose beauty) and bone defect filling in other parts of the human skeleton, microsphere particle filling materials are widely used. There are many preparation methods for polymer-based microsphere particles, and the commonly used methods are emulsification-chemical cross-linking method, emulsification-solvent evaporation method and spray drying method. The microspheres prepared by these methods have a large diameter distribution range and a high packing density. When applied to tissue filling, the pores between the particles are too small, which is not conducive to the growth of new tissues.
三、发明内容 3. Contents of the invention
本发明针对上述技术缺陷，提供了一种制备具有均一分布颗粒直径的明胶球形多孔颗粒材料的制备方法。Aiming at the above-mentioned technical defects, the present invention provides a method for preparing gelatin spherical porous granular materials with uniformly distributed particle diameters.
本发明的技术方案为一种明胶球形多孔颗粒材料，所述的明胶球形多孔颗粒材料的球形颗粒，粒径为φ0.8～4mm，颗粒本体内部为孔径小于150μm的微孔，微孔之间互通，明胶球形多孔颗粒材料的孔隙率为80～95％。The technical solution of the present invention is a gelatin spherical porous particle material, the spherical particles of the gelatin spherical porous particle material have a particle diameter of φ0.8-4 mm, and inside the particle body are micropores with a pore diameter less than 150 μm. Interconnection, the porosity of the gelatin spherical porous particle material is 80-95%.
一种制备所述的明胶球形多孔颗粒材料的制备方法，制备步骤为：A preparation method for preparing the gelatin spherical porous granular material, the preparation steps are:
第一步，以蒸馏水配制质量浓度为5～20％的明胶溶液，搅拌使明胶完全溶解；The first step is to prepare a gelatin solution with a mass concentration of 5-20% with distilled water, and stir to completely dissolve the gelatin;
第二步，将第一步制备好的明胶溶液从加料口加入储料罐，通过压力表和压力控制阀控制储料罐中的压力为0.08～0.5MPa，以保证明胶溶液从管径为φ0.5～3mm的导液管以10～60滴/min的速度均匀流出。从导液管流出的明胶溶液在管口处长大到约φ0.8～4mm的近球形颗粒后滴落，在下落过程中，由于表面张力的作用形成球状，而后滴入保温容器内的温度为-(10～20)℃的冷凝液中冷凝，形成球形度好、粒径均一的明胶球形多孔颗粒材料。In the second step, the gelatin solution prepared in the first step is added to the storage tank from the feeding port, and the pressure in the storage tank is controlled by a pressure gauge and a pressure control valve to be 0.08 to 0.5 MPa to ensure that the gelatin solution starts from a pipe diameter of φ0 .5 ~ 3mm catheter outflow evenly at the speed of 10 ~ 60 drops / min. The gelatin solution flowing out from the catheter drips after growing to a nearly spherical particle of about φ0.8-4mm at the mouth of the tube. During the falling process, it forms a spherical shape due to the effect of surface tension, and then drips into the heat preservation container. It is condensed in the condensate at -(10-20)°C to form a gelatin spherical porous particle material with good sphericity and uniform particle size.
根据表面张力公式：According to the surface tension formula:
mg＝2πrσmg=2πrσ
式中：m为液滴质量；r为毛细管外半径；σ为表面张力；g为重力加速度。当明胶溶液的密度和粘度一定时，在无外界干扰的条件下，该法可以制备出球形度好、粒径均一的球形颗粒。In the formula: m is the mass of the droplet; r is the outer radius of the capillary; σ is the surface tension; g is the acceleration of gravity. When the density and viscosity of the gelatin solution are constant, under the condition of no external interference, this method can prepare spherical particles with good sphericity and uniform particle size.
第三步，将第二步冷凝后的球形颗粒分离、冷冻干燥；将冷冻干燥后的球形颗粒放入质量浓度为0.25～2.5％的交联剂交联处理，然后用无水乙醇清洗，得到明胶球形多孔颗粒材料。所述的冷凝液为二甲基硅油或植物油。所述的交联剂为甲醛、戊二醛、乙二醛中的任意一种。In the third step, the spherical particles condensed in the second step are separated and freeze-dried; the freeze-dried spherical particles are put into a cross-linking agent with a mass concentration of 0.25% to 2.5% for cross-linking treatment, and then washed with absolute ethanol to obtain Gelatin spherical porous granular material. The condensate is simethicone or vegetable oil. Described cross-linking agent is any one in formaldehyde, glutaraldehyde, glyoxal.
制备所述的明胶球形多孔颗粒材料的装置，由储料罐和保温容器组成，在储料罐顶部设有加料口，在储料罐上还设有压力表，压力表与压力控制阀连接，在储料罐的底部设有导液管，在导液管上设有流量控制阀，在导液管下方设有保温容器。The device for preparing the gelatin spherical porous granular material is composed of a storage tank and a heat preservation container, a feeding port is arranged on the top of the storage tank, a pressure gauge is also arranged on the storage tank, and the pressure gauge is connected with a pressure control valve. A guide pipe is arranged at the bottom of the storage tank, a flow control valve is arranged on the guide pipe, and a thermal insulation container is arranged under the guide pipe.
有益效果：本发明制备的明胶球形多孔颗粒材料：：Beneficial effects: the gelatin spherical porous granular material prepared by the present invention:
(1)在颗粒本体内部含有大量的互通微孔，形成三维网状立体结构，这种颗粒具有较高的比表面积，有利于细胞的粘附的组织液的流动；(1) There are a large number of intercommunicating micropores inside the particle body, forming a three-dimensional network structure. This particle has a high specific surface area, which is conducive to the flow of interstitial fluid for cell adhesion;
(2)明胶颗粒具有均一的粒径分布，不需要筛分处理即可得到具有相同粒径的颗粒材料；因为根据表面张力公式：(2) Gelatin particles have a uniform particle size distribution, and granular materials with the same particle size can be obtained without sieving; because according to the surface tension formula:
mg＝2πrσmg=2πrσ
式中：m为液滴质量；r为毛细管外半径；σ为表面张力；g为重力加速度。当胶原溶液的密度和粘度一定时，在无外界干扰的条件下，该法可以制备出球形度好、粒径均一的球形颗粒。In the formula: m is the mass of the droplet; r is the outer radius of the capillary; σ is the surface tension; g is the acceleration of gravity. When the density and viscosity of the collagen solution are constant, under the condition of no external interference, this method can prepare spherical particles with good sphericity and uniform particle size.
(3)因为根据本方法制备的明胶球形颗粒材料的粒径均一性好，而相同粒径的球形颗粒材料，充填后颗粒间空隙率最大，所以本发明的明胶球形颗粒材料充填后有利于组织液的流动和细胞的迁移生长。(3) Because the particle size uniformity of the gelatin spherical particle material prepared according to the present method is good, and the spherical particle material of the same particle size has the largest void ratio after filling, so the gelatin spherical particle material of the present invention is beneficial to interstitial fluid after filling. flow and cell migration.
四、说明书附图：4. Attached drawings:
图1球形颗粒成形装置示意图。Fig. 1 Schematic diagram of spherical particle forming device.
装置主要由加料口1、压力表2、压力控制阀3、储料罐4、流量控制阀5、导液管6、冷凝液7和保温容器8组成。The device is mainly composed of feeding port 1,
图2为明胶球形多孔颗粒的照片。Figure 2 is a photograph of gelatin spherical porous particles.
图3为明胶球形多孔颗粒的内部孔隙照片。Fig. 3 is a photo of internal pores of gelatin spherical porous particles.
五、具体实施方式： 5. Specific implementation methods:
实施例1：Example 1:
(1)用恒温水浴加热蒸馏水至60℃，将明胶加入蒸馏水中搅拌使其充分溶解，配制为质量浓度为5％的明胶溶液；(1) Heating distilled water to 60°C in a constant temperature water bath, adding gelatin to distilled water and stirring to make it fully dissolve, and preparing a gelatin solution with a mass concentration of 5%;
(2)如图1所示，将配制好的明胶溶液从加料口1加入储料罐4，通过压力表2和压力控制阀3控制储料罐4中的压力为0.08MPa，以保证明胶溶液从φ0.5mm导液管6均匀流出，通过流量控制阀5控制流速为10滴/min。从导液管6流出的明胶溶液在管口处长大到φ0.8mm的近球形颗粒后滴落，在下落过程中，由于表面张力的作用形成球状，而后滴入保温容器8内的冷凝液7中冷凝，冷凝液的温度为-10℃，形成球形颗粒。冷凝液为二甲基硅油。(2) As shown in Figure 1, the prepared gelatin solution is added to the storage tank 4 from the feed port 1, and the pressure in the storage tank 4 is controlled by the
(3)冷凝后的微球分离，并在-5℃的温度冷冻干燥处理8h；冷冻干燥后的球形颗粒先放入质量浓度为0.25％的戊二醛溶液交联处理3h，再用无水乙醇清洗，得到明胶球形多孔颗粒材料，如图2所示，颗粒的球形度好，粒径均一，粒径为0.8mm、如图3所示，颗粒的孔隙率高，孔隙率为80％，孔互通，形成三维网状立体结构。(3) The condensed microspheres were separated, and freeze-dried at -5°C for 8 hours; the freeze-dried spherical particles were first put into a glutaraldehyde solution with a mass concentration of 0.25% for 3 hours, and then dried with anhydrous Clean with ethanol, obtain gelatin spherical porous particle material, as shown in Figure 2, the sphericity of particle is good, and particle diameter is uniform, and particle diameter is 0.8mm, as shown in Figure 3, the porosity of particle is high, and porosity is 80%, The pores communicate with each other to form a three-dimensional network structure.
实施例2：Example 2:
(1)用恒温水浴加热蒸馏水至60℃，将明胶加入蒸馏水中搅拌使其充分溶解，配制为质量浓度为20％的明胶溶液；(1) Heating distilled water to 60°C in a constant temperature water bath, adding gelatin to distilled water and stirring to make it fully dissolve, and preparing a gelatin solution with a mass concentration of 20%;
(2)将配制好的明胶溶液从加料口1加入储料罐4，通过控制储料罐4中的压力为0.5MPa，以保证明胶溶液从φ3mm导液管6均匀流出。从导液管6流出的明胶溶液在管口处长大到φ4mm的近球形颗粒后滴落，在下落过程中，由于表面张力的作用形成球状，而后滴入保温容器8内的冷凝液7中冷凝，冷凝液的温度为-20℃，形成球形颗粒。冷凝液为植物油。(2) The prepared gelatin solution is added to the storage tank 4 from the feeding port 1, and the pressure in the storage tank 4 is controlled to be 0.5 MPa to ensure that the gelatin solution flows out evenly from the
(3)冷凝后的微球分离，并在-10℃的温度冷冻干燥处理24h；冷冻干燥后的球形颗粒先放入质量浓度为2.5％的甲醛溶液交联处理24h，再用无水乙醇清洗，得到明胶球形多孔颗粒材料。(3) Separation of condensed microspheres, and freeze-drying treatment at -10°C for 24 hours; the freeze-dried spherical particles were first placed in a formaldehyde solution with a mass concentration of 2.5% for cross-linking treatment for 24 hours, and then washed with absolute ethanol , to obtain gelatin spherical porous particle material.
实施例3：Example 3:
(1)用恒温水浴加热蒸馏水至60℃，将明胶加入蒸馏水中搅拌使其充分溶解，配制为质量浓度为12％的明胶溶液；(1) Heating distilled water to 60°C in a constant temperature water bath, adding gelatin to distilled water and stirring to make it fully dissolve, and preparing a gelatin solution with a mass concentration of 12%;
(2)将配制好的明胶溶液从加料口1加入储料罐4，通过控制储料罐4中的压力为0.28MPa，以保证明胶溶液从φ1.25mm导液管6均匀流出。从导液管6流出的明胶溶液在管口处长大到φ2.3mm的近球形颗粒后滴落，在下落过程中，由于表面张力的作用形成球状，而后滴入保温容器8内的冷凝液7中冷凝，冷凝液的温度为-15℃，形成球形颗粒。冷凝液为二甲基硅油。(2) The prepared gelatin solution is added to the storage tank 4 from the feeding port 1, and the pressure in the storage tank 4 is controlled to be 0.28MPa to ensure that the gelatin solution flows out from the
(3)冷凝后的微球分离，并在-7℃的温度冷冻干燥处理18h；冷冻干燥后的球形颗粒先放入质量浓度为1.25％的乙二醛溶液交联处理12h，再用无水乙醇清洗，得到明胶球形多孔颗粒材料。(3) The condensed microspheres were separated, and freeze-dried at a temperature of -7°C for 18 hours; the freeze-dried spherical particles were first put into a glyoxal solution with a mass concentration of 1.25% for cross-linking treatment for 12 hours, and then dried with anhydrous Wash with ethanol to obtain gelatin spherical porous particle material.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102350752A CN101401962B (en) | 2008-11-07 | 2008-11-07 | Gelatin spherical porous particle material and its preparation method and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102350752A CN101401962B (en) | 2008-11-07 | 2008-11-07 | Gelatin spherical porous particle material and its preparation method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101401962A CN101401962A (en) | 2009-04-08 |
| CN101401962B true CN101401962B (en) | 2013-02-27 |
Family
ID=40536210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102350752A Expired - Fee Related CN101401962B (en) | 2008-11-07 | 2008-11-07 | Gelatin spherical porous particle material and its preparation method and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101401962B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111632560A (en) * | 2020-05-08 | 2020-09-08 | 云南巴菰生物科技有限公司 | Preparation method of crystal ball particles capable of continuously releasing fragrance |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5810988A (en) * | 1994-09-19 | 1998-09-22 | Board Of Regents, University Of Texas System | Apparatus and method for generation of microspheres of metals and other materials |
| CN1272383A (en) * | 2000-05-19 | 2000-11-08 | 清华大学 | Preparation method of nanometer phase calcium-phosphorus salt/collagen/polylactic acid bone composite material |
| CN1546181A (en) * | 2003-12-12 | 2004-11-17 | 清华大学 | A degradable material for guiding hard tissue regeneration and repair and its preparation method |
| CN1607033A (en) * | 2003-10-15 | 2005-04-20 | 中国科学院过程工程研究所 | Chitose microsphere and microcapsule with uniform size and its preparation method |
| CN1931378A (en) * | 2006-09-29 | 2007-03-21 | 清华大学 | Micro rack for bone tissue engineering and its prepn process and application |
-
2008
- 2008-11-07 CN CN2008102350752A patent/CN101401962B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5810988A (en) * | 1994-09-19 | 1998-09-22 | Board Of Regents, University Of Texas System | Apparatus and method for generation of microspheres of metals and other materials |
| CN1272383A (en) * | 2000-05-19 | 2000-11-08 | 清华大学 | Preparation method of nanometer phase calcium-phosphorus salt/collagen/polylactic acid bone composite material |
| CN1607033A (en) * | 2003-10-15 | 2005-04-20 | 中国科学院过程工程研究所 | Chitose microsphere and microcapsule with uniform size and its preparation method |
| CN1546181A (en) * | 2003-12-12 | 2004-11-17 | 清华大学 | A degradable material for guiding hard tissue regeneration and repair and its preparation method |
| CN1931378A (en) * | 2006-09-29 | 2007-03-21 | 清华大学 | Micro rack for bone tissue engineering and its prepn process and application |
Non-Patent Citations (1)
| Title |
|---|
| 卢勰炜等.新型壳聚糖-海藻酸钠胃漂浮小丸的制备.《中国现代应用医学杂志》.2004,第21卷(第6期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101401962A (en) | 2009-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101401956B (en) | Chitosan spherical honeycombed grain material, producing method and apparatus thereof | |
| JP2018043013A5 (en) | ||
| JP6702979B2 (en) | Method for producing artificial blood vessel and method for producing porous tissue regeneration substrate | |
| CN101401960B (en) | Glutin-hydroxyapatite composite spheroidal particle, producing method and apparatus thereof | |
| CN104174342A (en) | Beta-tricalcium phosphate/alginic acid composite microsphere and preparation method and application of beta-tricalcium phosphate/alginic acid composite microsphere | |
| CN107376017A (en) | The sodium alginate type i collagen Ceramic Composite support of 3D printing, preparation method and application | |
| CN106362223B (en) | Porous fibroin albumen micropin drug delivery device and preparation method thereof | |
| CN113244178B (en) | Gellan gum composite drug-loaded microspheres with remote controllable drug release and preparation method and application thereof | |
| CN101401958A (en) | Chitosan-hydroxyapatite composite spheroidal particle, producing method and apparatus thereof | |
| CN104368046B (en) | A fiber-reinforced drug-loaded hydrogel artificial corneal skirt support and its preparation method | |
| CN105435305A (en) | Porous titanium composite material and preparation method thereof | |
| CN101401971B (en) | Collagen spherical honeycombed grain material, producing method and apparatus thereof | |
| CN101401962B (en) | Gelatin spherical porous particle material and its preparation method and device | |
| CN101401954B (en) | Degradable synthetic polymer spherical honeycombed grain material, producing method and apparatus thereof | |
| CN110141680A (en) | Method for manufacturing magnesium phosphate biological ceramic functionally-graded bone regeneration bracket | |
| CN101439202A (en) | Gelatine-chitosan sphere porous particle material as well as preparation method thereof and device | |
| CN101401970A (en) | Collagen-hydroxyapatite composite spheroidal particle, producing method and apparatus thereof | |
| CN101401961B (en) | Glutin-chitosan-hydroxyapatite spherical honeycombed grain material, producing method and apparatus thereof | |
| CN101401969B (en) | Producing method of collagen-chitosan-hydroxyapatite spherical honeycombed grain material | |
| CN101401963B (en) | Glutin-beta-tricalcium phosphate composite spheroidal particle, producing method and apparatus thereof | |
| CN101401959B (en) | Producing method of glutin-chitosan-beta-tricalcium phosphate spherical honeycombed grain material | |
| CN101401967B (en) | Producing method of collagen-beta-tricalcium phosphate composite spheroidal particle | |
| CN101401953A (en) | Phosphate biological ceramic microsphere, preparation method and apparatus thereof | |
| CN101401957B (en) | Chitosan-β-tricalcium phosphate composite spherical porous particle material and its preparation method and device | |
| CN102698321A (en) | Preparation method of bone repairing body with drug loading function |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SOWTHEAST UNIV. Effective date: 20131016 Owner name: HAIAN BROTHERS SYNTHETIC FIBER CO., LTD. Free format text: FORMER OWNER: SOWTHEAST UNIV. Effective date: 20131016 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 210096 NANJING, JIANGSU PROVINCE TO: 226600 NANTONG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20131016 Address after: 226600, Jiangsu province Nantong city Haian county head Town Industrial Park Patentee after: Haian County Brothers Synthetic Fiber Co.,Ltd. Patentee after: Southeast University Address before: 210096 Jiangsu city Nanjing Province four pailou No. 2 Patentee before: Southeast University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130227 Termination date: 20201107 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |