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文献汇报,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,引言,仿生合成,仿生合成,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).,晶体生长的基本原理,仿生合成制备鲍鱼壳结构示意图,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。,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。,SupportedSilver-Nanoparticle-CatalyzedHighlyEfficientAqueousOxidationofPhenylsilanestoSilanols,TakatoMitsudome,ShusukeArita,HaruhikoMori,TomooMizugaki,KoichiroJitsukawa,andKiyotomiKaneda*Angew.Chem.Int.Ed.2008,47,79387940,GoldSupportedonHydroxyapatiteasaVersatileMultifunctionalCatalystfortheDirectTandemSynthesisofIminesandOximes,HaoSun,Fang-ZhengSu,JiNi,YongCao,*He-YongHe,andKang-NianFanAngew.Chem.Int.Ed.2009,48,43904393,主要内容,Silanols,buildingblocksforsilicon-basedpolymericmaterials,nucleophiliccouplingpartnersinorganicsynthesis,toxicreagentsandvastwaste,synthesized,Newidea,Ag-HAP,highcataliticactivities,waterasanoxidant,without,organicsolvents,Ag-HAP合成,Ca5(PO4)3(OH)Ca/P=1.682.0g,AgNO36.710-3M150ml,加入,室温下搅拌6小时,solid,硼氢化钠还原,Ag-HAP,Bioactive,luminescentandmesoporouseuropium-dopedhydroxyapatiteasadrugcarrier,PiaopingYanga,b,ZeweiQuanb,ChunxiaLib,XiaojiaoKangb,HongzhouLianb,JunLinb,*aCollegeofMaterialScienceandChemicalEngineering,HarbinEngineeringUniversity,Harbin150001,PRChinabStateKeylaboratoryofRareEarthResourceUtilization,ChangchunInstituteofAppliedChemistry,ChineseAcademyofSciences,Changchun130022,PRChinaBiomaterials29(2008)43414347,MultifunctionalHydroxyapatiteNanofibersandMicrobeltsasDrugCarriers,ZhiyaoHou,PiaopingYang,HongzhouLian,LiliWang,CuimiaoZhang,ChunxiaLi,RuitaoChai,ZiyongCheng,andJunLin*aChem.Eur.J.2009,15,69736982,主要内容,主要内容,noveldrugstorage/releasesystems,conventionalformsofdosage,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,HAP,biocompatible,osteoconductive,nontoxic,noninflammatory,goodproperties,drugcarriers,Therefore,thedesignanddevelopmentofluminescencefunctionalizedHAPwithnano-sizedandmesoporouscharacteristicsshouldbeabletoreachthisgoal.Herein,theyproposetheone-stepsynthesisofnovelluminescencefunctionalizedmesoporousHAPmaterialsbydropingEu3+duringthesynthesisofmesoporousHAP,resultingintheformatingofmultifunctionalmaterimal.,合成发光功能的中孔羟基磷灰石,3.168g(NH4)2HPO48.740gCTAB100ml去离子水PH=12,+,4.218gCaCl20.676gEu(NO3)260ml去离子水,中孔羟基磷灰石,ItisfoundthatbothpureHAPandEu:HAPconsistofrelativelyuniformrod-likeparticleswiththewidthof20-40nmandthelengthof100-200nm.TheresultssuggestthatthedropingofEu3+haslittleinfluenceonthemorphologyofpureHAP.,Thismaterialishierarchicallystructuredandexhibitsananoscalerod-like,mesoporous,crystallinestructure,whichissuitablefordrug(IBU)releaseasadrugcarrier.Especially,itexhibitsstrongredluminscenceevenafterloadingofdrugmolecules,andthePLintersityincreaseswiththecumulativereleasedamountofIBU,whichcanbeeasilytrackedandmonitoredinthedrugreleaseprocessbythechangeofPLemissionintersity.,Theinvivoperformanceofbiomagnetichydroxyapatitenanoparticlesincancerhyperthermiatherapy,Chun-HanHoua,b,Sheng-MouHoua,c,Yu-ShengHsueha,JinnLinc,Hsi-ChinWua,Feng-HueiLina,*aInstituteofBiomedicalEngineering,CollegeofMedicineandCollegeofEngineering,NationalTaiwanUniversity,Taipei,TaiwanbDepartmentofOrthopaedicSurgery,TaiwanUniversityHospital,Yun-LinBranch,Yun-LinCounty,TaiwancDepartmentofOrthopaedicSurgery,TaiwanUniversityHospital,Taipei,TaiwanBiomaterials30(2009)39563960,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。,磁性纳米羟基磷灰石的合成,HAP合成:10Ca(OH)2+6H3PO4Ca10(PO4)6(OH)2+18H2O磁性HAP合成:加入FeCl2.4H2O,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.,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。,MonodisperseF-SubstitutedHydroxyapatiteSingle-CrystalNanotubeswithAmphiphilicSurfaceProperties,JunfengHui,GuoleiXiang,XiangxingXu,JingZhuang,andXunWang*,DepartmentofChemistry,TsinghuaUniversity,Beijing100084,PeoplesRepublicofChina,andR&DCenterofBiomaterialandFermentationEngineering,ShaanxiKeyLaboratoryofDegradableBiomedicalMaterials,DepartmentofChemicalEngnineering,NorthwestUniversity,Xian710069,PeoplesRepublicofChinaInorg.Chem.2009,48,56145616,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。,合成方法,4ml油酸和0.5g十八胺/0.5gPEG(20000,MW)溶入16ml乙醇,+,Ca(NO3)2.4H2O(0.5g/7.5ml去离子水)NaF(0.003-0.025g/5ml去离子水)Na3PO4.12H2O(0.5g/7.5ml去离子水),搅拌十分钟,放入40ml高压釜中,90-150oC/200-220oC,十小时,单晶F取代HAP纳米管,SolvothermalSynthesisandCharacterizationofHierarchicallyNanostructuredHydroxyapatiteHollowSpheres,Ming-GuoMa*aandJie-FangZhub,aCollegeofMaterialsScienceandTechnology,BeijingForestryUniversity,Beijing100083,P.R.ChinaFax:+86-10-62338149E-mail:mg_mabDepartmentofMaterialsChemistry,ThengstrmLaboratory,UppsalaUniversity,Uppsala75121,Sweden,Eur.J.Inorg.Chem.0000,00,主要内容:,ThisisthereportonthefabricationofthehierarchicallynanostructuredHAPhollowspheresassembledfromnanorods.,实验部分,CaCl2(0.110g),C4H4O6KNa.4H2O(0.282g),NaH2PO4(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,200oC煅烧2小时。产物离心,洗涤,在60oC烘干。,Preparationandcharacterizationofhollowhydroxyapatitemicrospheresbyspraydryingmethod,RuixueSuna,YupengLub,*,KezhengChena,aCollegeofMaterialsScienceandEngineering,QingdaoUniversityofScienceandTechnology,Qingdao266042,ChinabSchoolofMaterialsScienceandEngineering,ShandongUniversity,Jinan250061,China,MaterialsScienceandEngineeringC29(2009)10881092,Ca(NO3)24H2O,+,(NH4)2HPO4,Ca/P=1.67,PH=10-11,HAP,加入碳酸氢铵喷雾干燥,hollowhydroxyapatitemicrospheres,Solgelsynthesisandcharacterizationofhydroxyapatitenanorods,SanoshKunjalukkalPadmanabhana,b,AvinashBalakrishnana,b,Min-CheolChub,YongJinLeea,TaikNamKima,Seong-JaiChob,aDepartmentofInformationandElectronicMaterialsEngineering,CollegeofEngineering,PaichaiUniversity,Daejeon302-735,RepublicofKoreabDivisionofMetrologyforEmergingTechnology,KoreaResearchInstituteofStandardsandScience,1Doryong-Dong,Yuseong-Gu,Daejeon305-340,RepublicofKoreaParticuology7(2009)466470,主要内容,CaNO34H2O和KH2PO4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60oC烘干并在不同温度下煅烧300oC-700oC。得到直径为70-90nm,长为400-500nm的羟基磷灰石纳米棒。,实验部分,1MCaNO34H2O去离子水,0.67MKH2PO4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,60oC烘干,300-700oC煅烧,羟基磷灰石,AnEffectiveMorphologyControlofHydroxyapatiteCrystalsviaHydrothermalSynthesis,InesS.Neira,YuryV.Kolenko,OlegI.Lebedev,GustaafVanTendeloo,HimadriS.Gupta,FranciscoGuitian,andMasahiroYoshimura,CrystalGrowth&Design,Vol.9,No.1,2009467,谢谢,
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