羟基磷灰石的合成

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,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,文 献 汇 报,1,主要内容,引言,仿生合成,晶体生长基本原理,羟基磷灰石,羟基磷灰石研究现状,2,引言,仿生合成,3,仿生合成,4,5,6,生物矿物合成-模板合成法,模板合成方法中,模板只是提供一个支架让不同材料在一定位置形成纳米材料,其结构与模板的形状互补,所以可以合成一些一般方法很难合成的纳米结构或其它复杂有序的超级结构。双亲嵌段共聚物包含一个与无机矿物质表面强烈作用的亲水段(绑缚嵌段)和另外一个作用很弱但可以提高水中溶解性的亲水段 (溶剂化嵌段).,7,晶体生长的基本原理,仿生合成制备鲍鱼壳结构示意图,8,9,羟基磷灰石(HAP)简介,羟基磷灰石是组成人体骨骼和牙齿的重要组成部分,HAP是一种生物活性材料,具有良好的生物相容性、生物活性和生物稳定性,广泛应用于生物医药,催化和污水处理等领域。纳米羟基磷灰石在其功能上有一定的特性,如可以对一些肿瘤具有抑制作用,可以作为药物缓释材料抗生素、抗炎类等药物缓释载体,并且还可以作为某些化学反应的催化剂。,10,纳米羟基磷灰石文献综述,纳米HAP的制备方法主要有共沉淀法、水热法、溶胶-凝胶法、仿生合成和溶剂热法等,。,11,Supported Silver-Nanoparticle-Catalyzed Highly Efficient AqueousOxidation of Phenylsilanes to Silanols,Takato Mitsudome, Shusuke Arita, Haruhiko Mori, Tomoo Mizugaki, Koichiro Jitsukawa, and,Kiyotomi Kaneda*,Angew. Chem. Int. Ed. 2008, 47, 7938 7940,12,Gold Supported on Hydroxyapatite as a Versatile Multifunctional Catalyst for the Direct Tandem Synthesis of Imines and Oximes,Hao Sun, Fang-Zheng Su, Ji Ni, Yong Cao,* He-Yong He, and Kang-Nian Fan,Angew. Chem. Int. Ed. 2009, 48, 4390 4393,13,主要内容,Silanols,building blocks for silicon-,based polymeric materials,nucleophilic coupling partners,in organic synthesis,toxic reagents,and,vast waste,synthesized,14,New idea,Ag-HAP,high catalitic activities,water as an oxidant,without,organic solvents,15,Ag-HAP合成,Ca,5,(PO4),3,(OH),Ca/P=1.68,2.0g,AgNO,3,6.7,10,-3,M,150ml,加入,室温下搅拌6小时,solid,硼氢化钠还原,Ag-HAP,16,17,Bioactive, luminescent and mesoporous europium-doped hydroxyapatiteas a drug carrier,Piaoping Yang,a,b, Zewei Quan,b, Chunxia Li,b, Xiaojiao Kang,b, Hongzhou Lian,b, Jun Lin,b,*,a,College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, PR China,b,State Key laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China,Biomaterials 29 (2008) 43414347,18,Multifunctional Hydroxyapatite Nanofibers and Microbelts as Drug Carriers,Zhiyao Hou, Piaoping Yang, Hongzhou Lian, Lili Wang, Cuimiao Zhang, Chunxia Li,Ruitao Chai, Ziyong Cheng, and Jun Lin,*a,Chem. Eur. J. 2009, 15, 6973 6982,19,主要内容,主要内容,novel drug storage/,release systems,conventional forms,of dosage,相比,优点,1.加强生物药效,2.高功效,3.安全性,4.可控性,5.延长释药时间,20,HAP,biocompatible,osteoconductive,nontoxic,noninflammatory,good properties,drug carriers,21,Therefore,the design and development of luminescence functionalized HAP with nano-sized and mesoporous characteristics should be able to reach this goal.,Herein,they propose the one-step synthesis of novel luminescence functionalized mesoporous HAP materials by droping Eu,3+,during the synthesis of mesoporous HAP,resulting in the formating of multifunctional materimal.,22,合成发光功能的中孔羟基磷灰石,3.168g (NH,4,),2,HPO,4,8.740gCTAB,100ml 去离子水,PH=12,+,4.218gCaCl,2,0.676gEu(NO,3,),2,60ml 去离子水,中孔羟基磷灰石,23,It is found that both pure HAP and Eu:HAP consist of relatively uniform rod-like particles with the width of 20-40nm and the length of 100-200nm.The results suggest that the droping of Eu,3+,has little influence on the morphology of pure HAP.,24,This material is hierarchically structured and exhibits a nanoscale rod-like,mesoporous,crystalline structure, which is suitable for drug(IBU) release as a drug carrier.Especially, it exhibits strong red luminscence even after loading of drug molecules,and the PL intersity increases with the cumulative released amount of IBU,which can be easily tracked and monitored in the drug release process by the change of PL emission intersity.,25,The in vivo performance of biomagnetic hydroxyapatite nanoparticles in cancerhyperthermia therapy,Chun-Han Hou,a,b,Sheng-Mou Hou,a,c, Yu-Sheng Hsueh,a, Jinn Lin,c,Hsi-Chin Wu,a, Feng-Huei Lin,a,*,a Institute of Biomedical Engineering, College of Medicine and College of Engineering, National Taiwan University, Taipei, Taiwan,b Department of Orthopaedic Surgery, Taiwan University Hospital, Yun-Lin Branch, Yun-Lin County, Taiwan,c Department of Orthopaedic Surgery, Taiwan University Hospital, Taipei, Taiwan,Biomaterials 30 (2009) 39563960,26,在鼠模型活体内研究新型的磁性纳米羟基磷灰石对癌症及恶性肿瘤的作用。将纳米羟基磷灰石和磁性纳米羟基磷灰石分别于磷酸盐缓冲液混合,注射到肿块附近,将鼠放进具有高频和交变磁场的感应加热器中。,27,磁性纳米羟基磷灰石的合成,HAP合成:,10Ca(OH),2,+6H,3,PO,4,Ca,10,(PO,4,),6,(OH),2,+,18H,2,O,磁性,HAP合成:,加入FeCl,2,.,4H,2,O,PH=8.5,搅拌2小时陈化10小时,洗涤,冷冻干燥。Fe/Ca摩尔比为1.,28,29,结论,新合成的磁性纳米HAP表现出良好的生物相容性和注射入皮下组织的几乎无毒性,并且具有令人满意的热效率。在两周内可以快速的治疗鼠的结肠癌,肿块不再复发。,30,Monodisperse F-Substituted Hydroxyapatite Single-Crystal Nanotubes withAmphiphilic Surface Properties,Junfeng Hui,Guolei Xiang,Xiangxing Xu,Jing Zhuang,and Xun Wang*,Department of Chemistry, Tsinghua University, Beijing 100084, Peoples Republic of China, and R&D Center,of Biomaterial and Fermentation Engineering, Shaanxi Key Laboratory of Degradable Biomedical Materials,Department of Chemical Engnineering, Northwest University, Xian 710069, Peoples Republic of China,Inorg. Chem. 2009, 48, 56145616,31,由水热法合成均匀的不同纵横比和表面性质的F,-,替代HAP纳米管。少量3%F,-,加入HAP可以得到单晶纳米管。在合成单晶纳米管过程中加入PEG和油酸可以得到双亲性HAP纳米管。,32,合成方法,4ml油酸和0.5g十八胺/,0.5 g PEG (20000, MW),溶入16ml乙醇,+,Ca(NO,3,),2,.,4H,2,O(0.5g/7.5ml去离子水),NaF(0.003-0.025 g / 5 ml去离子水),Na,3,PO,4,.12H,2,O(0.5g/7.5ml去离子水),搅拌十分钟,放入40ml高压釜中,90-150,o,C/200-220,o,C,十小时,单晶F取代HAP纳米管,33,34,Solvothermal Synthesis and Characterization of Hierarchically NanostructuredHydroxyapatite Hollow Spheres,Ming-Guo Ma*,a,and Jie-Fang Zhu,b,a,College of Materials Science and Technology, Beijing,ForestryUniversity,Beijing 100083, P. R. China,Fax: +86-10-62338149,E-mail:,b,Department of Materials Chemistry, The ngstrm,Laboratory,Uppsala University,Uppsala 75121, Sweden,Eur. J. Inorg. Chem. 0000, 00,35,主要内容:,This is the report on the fabrication of the hierarchically nanostructured HAPhollow spheres assembled from nanorods.,36,37,实验部分,CaCl,2,(0.110g),C,4,H,4,O,6,KNa,.,4H,2,O(0.282g),NaH,2,PO,4,(0.094g)加入混合溶剂(DMF11ml/去离子水4ml)搅拌30分钟,然后将混合液转入20ml高压釜中,200,o,C煅烧2小时。产物离心,洗涤,在60,o,C烘干。,38,Preparation and characterization of hollow hydroxyapatite microspheres by spraydrying method,Ruixue Sun,a, Yupeng Lu,b,*,Kezheng Chen,a,a College of Materials Science and Engineering, Qingdao,University of Science and Technology, Qingdao 266042, China,b School of Materials Science and Engineering, Shandong,University, Jinan 250061, China,Materials Science and Engineering C 29 (2009) 10881092,39,Ca(NO,3,),2,4H,2,O,+,(NH4),2,HPO,4,Ca/P=1.67,PH=10-11,HAP,加入碳酸氢铵喷雾干燥,hollow hydroxyapatite microspheres,40,41,Solgel synthesis and characterization of hydroxyapatite nanorods,Sanosh Kunjalukkal Padmanabhan,a,b, Avinash Balakrishnan,a,b, Min-Cheol Chu,b,Yong Jin Lee,a, Taik Nam Kim,a, Seong-Jai Cho,b,a,Department of Information and Electronic Materials Engineering, College of Engineering, Paichai University, Daejeon 302-735, Republic of Korea,b,Division of Metrology for Emerging Technology, Korea Research Institute of Standards and Science, 1 Doryong-Dong, Yuseong-Gu, Daejeon 305-340, Republic of Korea,Particuology 7 (2009) 466470,42,主要内容,CaNO,3,4H,2,O,和,KH,2,PO,4,为前驱体用溶胶,-,凝胶法合成六角形的纳米棒状羟基磷灰石。氨水调,PH=9,。,HA,凝胶在,60,o,C,烘干并在不同温度下煅烧,300,o,C-700,o,C,。得到直径为,70-90nm,,长为,400-500nm,的羟基磷灰石纳米棒。,43,实验部分,1M CaNO,3,4H,2,O,去离子水,0.67M KH,2,PO,4,去离子水,逐滴的加入,Ca/P=1.67,氨水调PH=9,搅拌1h,室温下陈化48h,60,o,C烘干,300-700,o,C煅烧,羟基磷灰石,44,45,AnEffectiveMorphologyControlofHydroxyapatiteCrystalsviaHydrothermalSynthesis,Ine sS.Neira, YuryV.Kolenko, OlegI.Lebedev, GustaafVanTendeloo, HimadriS.Gupta,FranciscoGuitia n,and MasahiroYoshimura,CrystalGrowth&Design,Vol.9,No.1,2009 467,46,47,谢谢,48,
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