医用硅橡胶表面仿生制备磷灰石涂层的研究
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摘要
医用硅橡胶是一种高分子橡胶态弹性体,符合医用高分子材料的要求,在器官或组织代用品、医疗器械关键部件、整容和修复术、体外用品等领域的应用越来越广泛。但由于硅橡胶分子极性低,表现出极强的疏水性,导致植入后与机体的亲合力差。羟基磷灰石是人体硬组织骨和牙齿的主要矿物成分,具有良好的生物相容性。但羟基磷灰石陶瓷脆性大,不易加工成复杂的元件。在医用硅橡胶表面制备羟基磷灰石涂层得到的复合材料就可以结合二者的优点,是理想的生物医用材料。
仿生溶液法制备磷灰石涂层是近年来发展起来的制备磷灰石涂层的新方法。仿生合成具有独特的工艺优点,它适于在多种材质、各种形状的基体上制备磷灰石类涂层。采用生物活性玻璃对医用硅橡胶表面进行诱导,在硅橡胶表面形成了一定量的钙盐和磷酸盐。形成的预沉淀层在1.5倍模拟体液或钙磷饱和溶液中迅速诱导磷灰石晶核形成,晶核通过消耗模拟体液或钙磷饱和溶液中的离子而长大,硅橡胶表面表面就能自发生成有序、均匀的磷灰石涂层。
通过XRD、SEM和红外分析发现,预处理过的医用硅橡胶在1.5倍模拟体液和钙磷饱和溶液中浸渍3d后,样品表面就有少量磷灰石形成,在1.5倍模拟体液中浸渍10d后生成羽毛状磷灰石晶粒,在钙磷饱和溶液中浸渍10d后表面生成片状磷灰石晶粒。
为了考察蛋白质等生物大分子对羟基磷灰石形成的影响,在钙磷饱和溶液中添加了牛血清白蛋白,考察了蛋白调控下表面磷灰石涂层的生长情况。通过XRD、SEM和红外表征了磷灰石涂层的特性。结果表明:牛血清白蛋白掺杂后与磷灰石在硅橡胶表面发生共沉积,蛋白质参与了晶体的形成,在牛血清白蛋白单层膜的作用下,羟基磷灰石的形貌和晶体生长的取向性发生了变化。
对未处理硅橡胶片,钙磷饱和溶液、1.5倍模拟体液、钙磷/牛血清白蛋白复合溶液中分别浸渍10天的样品进行生物相容性实验,结果表明材料均没有细胞毒性和溶血作用。
Medical silicon rubber is a kind of polymer rubbery elastomer.Meeting the demands of medical polymer material,it is more and more widely used as substitutes of organs,key parts of medical device,vitro products and for plastic surgery and Restoration.However,due to the low polarity of silicon rubber molecule,it shows a strong hydrophobicity and a poor bond with body after being implanted. Hydroxyapatite,the main mineral matter of hard tissue and tooth of human body,has good biocompatibility.But it is difficult to machining hydroxyapatite ceramic into complex components because of its high embrittlement.However,when hydroxyapatite coating is prepared on the surface of silicon rubber,a composite, which is quite a good medical precutaneous material,is formed.
Preparing apatite coating by the biomimetic synthesizing is a newly-developed means to form apatite coating in recent years.Biomimetic synthesis can be applied to various materials of different shapes to prepare apatite coating.When induced by bioactive-glass at the surface of medical silicon rubber,some calcium and silicon salts are formed.When dipped into 1.5s simulated body fluid or CP solution,apatite nuclei is formed quickly induced by the CP preformed precipitation.By consuming the ions of simulated body fluid or CP solution,the nuclei grows,thus a highly-ordered and well-proportioned apatite coating is formed onto the surface of silicon rubber.
According to XRD,SEM and infrared spectra analysis,trace amounts of apatite is formed on the surface after the pretreated medical silicon rubber is dipped in the 1.5s simulated body fluid or CP solution for 3 days.Feathery apatite crystals are formed after the silicon rubber is dipped in the 1.5s simulated body fluid for 10 days, and plate-like apatite crystals are formed in CP solution.
In order to study the effects of bio-macromolecules(like protein molecular) to the formation of hydroxyapatite,bovine serum albumin(BSA) is added into CP solution to study the growth and formation of apatite coating.XRD,SEM and infrared spectra analysis are used to analyze the characteristics of apatite coating. According to the result,BSA and apatite co-deposit onto the surface of silicon rubber. Under the effect of BSA monolayer,the morphology and orientation of crystal change. The result of biocompatibility experiment shows that all the materials,including untre ated silicon rubber and samples that have been dipped in the CP solution,1.5s simulat ed body fluid or CP/BSA complex solution for 10 days,have no cytotoxicity or hemol ysis.
The result of biocompatibility experiment shows that none of the materials, including untreated silicon rubber and samples that have been dipped in the CP solution,1.5s simulated body fluid or CP/BSA complex solution for 10 days,have no cytotoxicity or hemolysis.
仿生溶液法制备磷灰石涂层是近年来发展起来的制备磷灰石涂层的新方法。仿生合成具有独特的工艺优点,它适于在多种材质、各种形状的基体上制备磷灰石类涂层。采用生物活性玻璃对医用硅橡胶表面进行诱导,在硅橡胶表面形成了一定量的钙盐和磷酸盐。形成的预沉淀层在1.5倍模拟体液或钙磷饱和溶液中迅速诱导磷灰石晶核形成,晶核通过消耗模拟体液或钙磷饱和溶液中的离子而长大,硅橡胶表面表面就能自发生成有序、均匀的磷灰石涂层。
通过XRD、SEM和红外分析发现,预处理过的医用硅橡胶在1.5倍模拟体液和钙磷饱和溶液中浸渍3d后,样品表面就有少量磷灰石形成,在1.5倍模拟体液中浸渍10d后生成羽毛状磷灰石晶粒,在钙磷饱和溶液中浸渍10d后表面生成片状磷灰石晶粒。
为了考察蛋白质等生物大分子对羟基磷灰石形成的影响,在钙磷饱和溶液中添加了牛血清白蛋白,考察了蛋白调控下表面磷灰石涂层的生长情况。通过XRD、SEM和红外表征了磷灰石涂层的特性。结果表明:牛血清白蛋白掺杂后与磷灰石在硅橡胶表面发生共沉积,蛋白质参与了晶体的形成,在牛血清白蛋白单层膜的作用下,羟基磷灰石的形貌和晶体生长的取向性发生了变化。
对未处理硅橡胶片,钙磷饱和溶液、1.5倍模拟体液、钙磷/牛血清白蛋白复合溶液中分别浸渍10天的样品进行生物相容性实验,结果表明材料均没有细胞毒性和溶血作用。
Medical silicon rubber is a kind of polymer rubbery elastomer.Meeting the demands of medical polymer material,it is more and more widely used as substitutes of organs,key parts of medical device,vitro products and for plastic surgery and Restoration.However,due to the low polarity of silicon rubber molecule,it shows a strong hydrophobicity and a poor bond with body after being implanted. Hydroxyapatite,the main mineral matter of hard tissue and tooth of human body,has good biocompatibility.But it is difficult to machining hydroxyapatite ceramic into complex components because of its high embrittlement.However,when hydroxyapatite coating is prepared on the surface of silicon rubber,a composite, which is quite a good medical precutaneous material,is formed.
Preparing apatite coating by the biomimetic synthesizing is a newly-developed means to form apatite coating in recent years.Biomimetic synthesis can be applied to various materials of different shapes to prepare apatite coating.When induced by bioactive-glass at the surface of medical silicon rubber,some calcium and silicon salts are formed.When dipped into 1.5s simulated body fluid or CP solution,apatite nuclei is formed quickly induced by the CP preformed precipitation.By consuming the ions of simulated body fluid or CP solution,the nuclei grows,thus a highly-ordered and well-proportioned apatite coating is formed onto the surface of silicon rubber.
According to XRD,SEM and infrared spectra analysis,trace amounts of apatite is formed on the surface after the pretreated medical silicon rubber is dipped in the 1.5s simulated body fluid or CP solution for 3 days.Feathery apatite crystals are formed after the silicon rubber is dipped in the 1.5s simulated body fluid for 10 days, and plate-like apatite crystals are formed in CP solution.
In order to study the effects of bio-macromolecules(like protein molecular) to the formation of hydroxyapatite,bovine serum albumin(BSA) is added into CP solution to study the growth and formation of apatite coating.XRD,SEM and infrared spectra analysis are used to analyze the characteristics of apatite coating. According to the result,BSA and apatite co-deposit onto the surface of silicon rubber. Under the effect of BSA monolayer,the morphology and orientation of crystal change. The result of biocompatibility experiment shows that all the materials,including untre ated silicon rubber and samples that have been dipped in the CP solution,1.5s simulat ed body fluid or CP/BSA complex solution for 10 days,have no cytotoxicity or hemol ysis.
The result of biocompatibility experiment shows that none of the materials, including untreated silicon rubber and samples that have been dipped in the CP solution,1.5s simulated body fluid or CP/BSA complex solution for 10 days,have no cytotoxicity or hemolysis.
引文
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[2]张承焱.医用硅橡胶应用广泛.2002,12(3):13-15
[3]刘爱堂,高桂芝.医用硅橡胶的最新进展.有机硅氟资讯,2003,4(5):60-61.
[4]杨清华等.硅橡胶人工颅骨研制及临床应用[J].有机硅材料,2001,(2):19-20
[5]夏毅然等.现代医用硅橡胶制品的性能及应用[J].有机硅材料,2002,(3):22-24
[6]谢遂志,刘登祥.周鸣峦主编.橡胶工业手册第1分册[M].北京:化学工业出版社,1989:585
[7]张承众.硅橡胶在生物医学领域的应用.有机硅材料,2002,16(6):14-17
[8]Erlich MA,Parhiscar A.Nasal dorsal augmentation with silicone implants[J].Facial Plast Surg,2003,19(4):325
[9]Lu H,Nguyen B.Powers JM.Mechanical properties of 3 hydrophilic addition silicone and polyether elastomeric impression materials[J].J Prosthet Dent,2004,92(2):151
[10]Lu H,Nguyen B.Powers JM.Mechanical properties of 3 hydrophilic addition silicone and polyether elastomeric im-pression materials[J].J Prosthet Dent,2004,92(2):151
[11]Maldonado CC,Morgan PB,Efron N.et al.Characterization of the surface of conventional hydrogel and silicone hydrogel contact lenses by time-of-flight secondary ion mass spectrometry[J].Optom Vis Sci,2004,81(6):455
[12]Aziz T,Waters M,Jagger R.Surface modification of an experimental silicone rubber maxillofacial material to im-prove wettability[J].J Dent,2003,31(3):213
[13]Furuzono T,Sonoda K,Tanaka J.A hydroxyapatite coating covalently linked onto a silicone implant material[J].J Biomed Mater Res,2001,56(1):9
[14]Ito A,Nakamura S,Aoki H.et al.Hydrothermal growth of carbonate-containing hydroxyapatite single crystals[J].J Crystal Growth,1996,163:311-317
[15]肖秀峰,刘榕芳,郑炀曾等.水热电沉积法制备羟基磷灰石/氧化钛复合涂层的研究.硅酸盐学报,2004.32(6):728-733.
[16]陈晓明,许传波,李世普等.冰醋酸介质中电泳共沉积制备生物玻璃/羟基磷灰石涂层.硅酸盐学报,2003.31(8):815-817
[17]Salyer K.E,Hall C.D.Porous hydroxyapatite as an only bone graftsubstitute for maxillofocid surgery[J].Plast Reconstr.Surg.,1989,84:236-244
[18]李祖兵,黄洪章.骨代用材料及其在牙种植中的应用[J]口腔医学纵横杂志,1995,11:121-123
[19]吴新荣.国产羟基磷灰石眼座眶内植入的临床探讨[J].眼外伤职业眼病杂志,2002,24(6):697-698
[20]Ayako Oyanea,Masaki Uchidab.Simple surface modification of poly(ε-caprolactone)for apatite deposition from simulated body fluid.Biomaterials,2005,26:2407-2413
[21]Zhang X.,Gubbels GH.M.,Terpstra R.A.,Metselaar R..Toughnening of calcium hydroxyapatite with silver particles[J].J.Mater.Sci.,1997,32:235-243
[22]Li H.,Marquis P M..Sintering behavior of hydroxyapatite reinforced with 20wt%Al_2O_3[J].J.Mater.Sci.,1993,28:1941-1945
[23]M.Kawashita,M.Nakao,M.Minoda.Apatite-forming ability of carboxyl group-containing polymer gels in a simulated body fluid.Biomaterials 2003,24:2477-2484
[24]Piconi C,Maccauro G.Zirconia as a ceramic biomaterials[J].Biomaterials,1999,20:1-25
[25]Mashers N J,Czernuszka J T.Growth of hydroxyapatite on type collagen[J].J.Mater.Sci.Lett.,1991,10:992-993
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