劉如熹臺灣大學：化學研究所黃景弘Huang, Jing-HongJing-HongHuang2007-11-262018-07-102007-11-262018-07-102007http://ntur.lib.ntu.edu.tw//handle/246246/51824近年來各種領域之科學家更加重視粒子之多功能化，例如於粒子表面建構不同之金屬或非金屬化合物之殼，以增加不同之性質，甚至進而促使兩物質作用，改變兩者之物性或化性形成特殊之核-殼(core-shell)結構。奈米粒子之表面修飾之應用，於生物醫學領域之使用相對重要，為提升奈米粒子對於生物之相容性與對生物之無毒性，使本質為無機材料之奈米粒子能於人體內之生存期可更久並不遭排斥，故奈米粒子表面修飾使多功能化與生物體之相容性更為當務之急。 本研究乃利用化學之高溫分解法還原部份之三價鐵離子，於高溫環境下經由溫和之還原作用，促使起始物進行核化與成長之反應而形成奈米粒子，過程中調控其生長溶液離子濃度與反應時間，利用穿透式電子顯微鏡觀察其成長過程之機制，並藉由控制成長溶液之濃度與成長溫度，進而合成出不同尺寸與狹窄粒徑分布之四氧化三鐵奈米粒子，最後將合成於有機相中之奈米粒子經由交換配位基之相轉移(phase transfer)方法將奈米粒子轉至水相中，一方面應用於生物化學方面之測試，便經過生物之細胞毒性測試(cytotoxic test)，探討其奈米粒子之尺寸效應(size effect)是否對生物體有所毒害，另一方面使四氧化三鐵表面包覆金之金屬殼，使得粒子具有磁性並有光學之雙重性質，所合成之產物均經由穿透式電子顯微鏡觀察其型態及粒徑、超導量子干涉磁量儀獲得粒子之磁特性與粒徑分佈之關係、利用同步輻射之光源測得粉體繞射之圖譜並分析其粒徑及結構與利用熱重分析、紅 外線光譜了解其不同粒子之粒徑組成等。In this regard, there has been much interest among the scientists towards the synthesis of multifunctional composite materials using two or more materials e.g. core-shell particles. The core shell nanoparticles have been of great potential in bionanotechnology due to improvement in its biocompatibility and decreased toxicity on account of surface modification of core shell nanomaterials. The prolonged circulation time of inorganic nanomaterials in our body is important task in front of the scientists, which also needs surface modification. In the present thesis, the syntheses of Fe3O4 (magnetite) nanoparticles were carried out by controlling the reaction time and concentration of ferric cation using high temperature decomposition method. The morphology of nanoparticles was analyzed by transmission electron microscopy (TEM). The magnetic properties were measured by superconducting quantum interference device (SQUID) and X-ray magnetic circular dichrism (XMCD). The crystal structure of nanoparticles was explored by X-ray diffraction (XRD). The composition of nanoparticles were analyzed by thermal gravimetric analysis (TGA) and Infrared spectrum (IR). We have successfully prepared magnetite nanoparticles of different sizes which were then transferred from oil phase to aqueous phase for carrying out cytotoxicity studies on cancer cells. The part of the research also involves synthesis of core-shell Fe3O4@Au nanoparticles to exploit magnetic properties of core and optical properties of shell in diagnostic and hyperthermia of cancer.目錄 目錄......................................................I 表目錄....................................................V 圖目錄...................................................VI 第一章 緒論...............................................1 1.1奈米材料之特性.........................................1 1.1.1奈米材料之基本定義...................................1 1.1.2奈米效應.............................................2 1.2氧化鐵之介紹...........................................5 1.2.1氧化鐵...............................................5 1.2.2四氧化三鐵之結構.....................................6 1.2.3超交換作用力.........................................7 1.2.4四氧化三鐵之自旋排列.................................8 1.3奈米科技於生醫上之應用.................................9 1.3.1磁性分離.............................................9 1.3.2藥物導引............................................10 1.3.3核磁共振造影........................................10 1.3.4磁流體溫熱療........................................11 1.3.5生化感測............................................12 1.4鐵氧體之合成法........................................13 1.4.1機悈研磨法..........................................13 1.4.2化學共沉法..........................................13 1.4.3微乳(微胞)與溶膠凝膠法..............................15 1.4.4水熱法..............................................16 1.4.5高溫分解法..........................................16 1.4.6超聲化學法..........................................18 第二章 實驗步驟與儀器分析原理............................19 2.1 化學藥品.............................................19 2.2奈米粒子之製備........................................21 2.2.1鐵氧體奈米粒子之晶種製備............................21 2.2.2晶種於高溫溶液下之成長..............................23 2.2.3油相中之奈米粒子轉移至水相中........................25 2.2.4分散於水中之奈米粒子毒性測試........................27 2.2.5金-鐵氧體之殼-核結構................................28 2.3儀器分析原理..........................................30 2.3.1穿透式電子顯微鏡....................................30 (Transmission electron microscope；TEM) 2.3.2 X光吸收光譜........................................33 (X-ray absorption spectroscopy；XAS) 2.3.3 X光粉末繞射儀......................................35 (X-ray powder diffractometer；XRD) 2.3.4超導量子干涉磁量儀..................................39 (Superconducting quantum interference device magnetometer； SQUID magnetometer) 2.3.5熱分析原理..........................................40 (Thermal gravimetric analysis；TGA) 2.3.6紅外線光譜..........................................42 (Infrared spectrum；IR) 2.3.7 X光磁圓偏振二向性..................................46 (X-ray magnetic circular dichrism；XMCD) 2.3.8紫外光/可見光吸收光譜儀.............................48 (Ultraviolet/visible absorption spectrometer；UV/vis) 第三章 結果與討論........................................52 3.1奈米粒子成長之過程....................................52 3.1.1穿透式電子顯微鏡分析-晶種於二苯基醚中成長過程.......53 3.1.2奧斯華成熟過程......................................58 3.1.3奈米粒子成長之過程-統計學之分析.....................61 3.1.4穿透式電子顯微鏡分析-晶種於二苯甲基醚中成長.........66 3.1.5比較於二苯基醚與二苯甲基醚中之成長..................69 3.2奈米粒子晶體結構之分析................................71 3.2.1不同粒徑之晶體結構分析..............................71 3.2.2熱重分析-對不同粒徑奈米粒子之剖面分析...............73 3.2.3熱處理後之奈米粒子之結晶相..........................75 3.2.4熱處理後之奈米粒子表面官能基之分析..................77 3.2.5 X光吸收光譜-不同粒徑之氧化數分析...................79 3.3奈米粒子尺寸對磁性之效應..............................83 3.3.1藉X光磁圓偏振二向性討論磁性.........................83 3.3.2測量不同粒徑之奈米粒子其磁性性質....................87 3.3.3磁性奈米物質之單一磁區..............................93 3.4合成金Fe3O4@Au之分析..................................98 3.4.1穿透式電子顯微鏡之影像分析..........................98 3.4.2 Fe3O4@Au晶體結構分析..............................100 3.4.3藉紫外可見光光譜對Fe3O4@Au結構之分析...............101 3.4.4藉TEM-EDS對Fe3O4@Au之定性分析......................105 3.4.5合成殼核結構之金包四氧化三鐵之結論.................107 3.5生化之分析與應用.....................................108 3.5.1奈米粒子由油相轉移至水相之分析.....................108 3.5.2毒性測試...........................................111 第四章 結論.............................................115 參考文獻................................................1186009566 bytesapplication/pdfen-US四氧化三鐵奈米粒子magnetitenanoparticles[SDGs]SDG3thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51824/1/ntu-96-R94223064-1.pdf