Synthesis, Characterization, and Application of Nanostructured Silica Materials

此論文主要以二氧化矽材料作為主軸，依結構與應用上的不同，此論文內容分成四個主題；第一個部份為骨架含稀土元素(釔, 釓, 鋱)的中孔洞奈米顆粒的合成、鑑定與應用，由於近年來核磁共振造影已成為臨床醫療診斷上的重要工具之一，其中核磁造影對比劑方面的研究更是此領域相當重要的一部分，而此研究特點便是將釓金屬離子嵌在中孔洞材料的骨架上，來增強其對水的鬆弛率，進一步增強影像的對比；此結果使中孔洞材料不但具有其本身的特點，如高表面積、孔洞一致性等，亦提供做為核磁造影對比劑應用上的可能性，並利用此材料做為核磁共振影像追蹤劑，並應用到藥物的釋放上。第二部份是合成殼層結構的奈米顆粒，此部份我們成它b鹼性下合成出含有稀土元素的殼層結構氧化矽材料，其殼的部份由稀土元素的氫氧化物組成如氫氧化鋱、氫氧化釔，此外並可控制包覆在殼外層氧化矽的厚度，此殼層結構的膠體粒子具有相當好的顆粒大小分布均勻性，此外由於稀土元素其特殊的放光性質與一般傳統染料具有相當寬的放光波帶，另外可藉由不同的稀土元素作為殼，即可調變不同的放光波段，由於此殼層結構氧化矽球大小的一致性，便可作為形成光子晶體的建構單元，往後的發展著重在進一步探討發光元素在光晶中的特殊光學性質。第三部份為製備具有六方堆積孔洞規則性結構與大小均勻的奈米顆粒，並同時在此氧化矽奈米顆粒的骨架嵌入染料分子作為螢光影像追蹤劑，將此中孔洞奈米顆粒與老鼠的纖維組織母細胞同時培養，並利用共軛焦顯微鏡可進一步發現此中孔洞奈米顆粒可進入老鼠的纖維組織母細胞內，並主要分布積聚在細胞膜內，表示此奈米級中孔洞材料可被細胞吞噬進入細胞，此結果顯示中孔洞材料在藥物分子儲存與釋放上具有相當的發展潛力。第四部份，主要是著重在一般較為傳統孔洞材料的合成，此部份我們成孕H簡單的共界面活性劑方法合成孔洞介於一奈米與兩奈米間並具有相當規則的六方堆積孔洞材料，一般稱為super-microporous silica，此小孔洞的材料在表面氣體吸附行為的研究與分子形狀選擇性的催化反應上具有相當的應用潛力。My research goal is exploring new properties for silica based materials. In this thesis, the topics are divided into four sections: (i) lanthanide incorporated nanosized mesoporous silica and the potential as MRI contrast agent, (ii) synthesis and characterization of lanthanide hydroxide@silica colloidal sphere, (iii) well-ordered mesoporous nanoparticle and the potential in biological application, and (iv) simple synthesis of well-ordered super-microporous aluminosilicate. In the first part, we have successfully synthesized Ln(III) incorporated mesoporous silica nanoparticels (Ln-MS) by acid-to-base and high dilution method. In addition to the inherent properties of mesoporous silica, the Gd-MS porous silica exhibits an additional ability on the enhancement of water proton relaxation. We believe these materials may be useful in biological tracking and imaging applications. In the second part, we have synthesized monodisperse lanthanide hydroxide@silica core sphere in base condition. The monodisperse core-shell spheres are promising to serve as building blocks to fabricate photonic crystals for further optical investigations. In the third part, we have demonstrated for the first time that the mesoporous silica nanoparticles can translocate into cell and have no short term toxicity on the cell; hence, open up an exciting field of mesoporous silica in biomedical applications. In the fourth part, we have provided a simple method for the synthesis of highly ordered super-microporous aluminosilicates by using co-surfactant system. We expect the materials to be useful in catalysis and gas adsorption studies. All in all, we have demonstrated the great potential of mesoporous and spherical silica nanoparticles in the exciting biomedical field.Section One Introduction to Nanostructured Silica Materials.................................................1 1.1 Mesoporous Materials..................................1 1.1.1 Brief Description of Mesoporous Materials...........1 1.1.2 Mesoporous Silica in Biological Application.........3 1.2 Core-shell Structured Materials.......................5 1.3 References............................................8 Section Two Lanthanide Incorporated Mesoporous Nanoparticles and the Potential as MRI Contrast Agent....10 2.1 Background and Introduction..........................10 2.2.1 Background.........................................10 2.2.2 Introduction.......................................15 2.2 Experimental Section.................................17 2.2.1 Materials..........................................17 2.2.2 Synthesis Procedure................................18 2.2.3 Characterization...................................18 2.3 Results and Discussion...............................20 2.4 Conclusion...........................................38 2.5 References...........................................39 Section Three Synthesis and Characterization of Lanthanide Hydroxide@Silica Core-Shell Colloidal Sphere.............41 3.1 Introduction.........................................41 3.2 Experimental Section.................................43 3.2.1 Materials..........................................43 3.2.2 Synthesis Procedure................................44 3.2.3 Characterization...................................44 3.3 Results and Discussion...............................45 3.4 Conclusions..........................................65 3.5 References...........................................66 Section Four Well-Ordered Mesoporous Nanoparticles and the Potential in Biological Application......................69 4.1 Introduction.........................................69 4.2 Experimental Section.................................72 4.2.1 Materials..........................................72 4.2.2 Synthesis of Mesoporous Nanoparticles..............72 4.2.3 Cell Uptake Assay..................................74 4.2.4 Characterization...................................74 4.3 Results and Discussion...............................75 4.3.1 Synthesis and Characterization of Mesoporous Silica Nanoparticles............................................75 4.3.2 Cell Uptake of Mesoporous Silica Nanoparticles.....85 4.4 Conclusion...........................................90 4.5 References...........................................91 Section Five Simple Synthesis of Well-Oredered Super-Microporous Aluminosilicate..............................93 5.1 Introduction.........................................93 5.2 Experimental Section.................................95 5.2.1 Materials..........................................95 5.2.2 Synthesis Procedure................................95 5.2.3 Characterization...................................96 5.3 Results and Discussion...............................97 5.4 Conclusion..........................................106 5.5 References..........................................107 Figure Index: Fig.1.1...................................................1Fig.1.2...................................................2 Fig.1.3...................................................3 Fig.1.4...................................................4 Fig.1.5...................................................5 Fig.1.6...................................................6 Fig.1.7...................................................7 Fig.2.1..................................................11 Fig.2.2..................................................11 Fig.2.3..................................................12 Fig.2.4..................................................13 Fig.2.5..................................................15 Fig.2.6..................................................24 Fig.2.7..................................................24 Fig.2.8..................................................26 Fig.2.9..................................................27 Fig.2.10.................................................30 Fig.2.11.................................................31 Fig.2.12.................................................32 Fig.2.13.................................................32 Fig.2.14.................................................35 Fig.2.15.................................................36 Fig.2.16.................................................37 Fig.3.1..................................................47 Fig.3.2..................................................49 Fig.3.3(A)...............................................50 Fig.3.3(B)...............................................50 Fig.3.3(C)...............................................51 Fig.3.3(D)...............................................51 Fig.3.3(E)...............................................51 Fig.3.3(F)...............................................52 Fig.3.4..................................................53 Fig.3.5..................................................56 Fig.3.6(A)...............................................56 Fig.3.6(B)...............................................57 Fig.3.6(C)...............................................57 Fig.3.6(D)...............................................58 Fig.3.7..................................................59 Fig.3.8..................................................60 Fig.3.9..................................................61 Fig.3.10.................................................62 Fig.3.11.................................................62 Fig.3.12.................................................64 Fig.4.1..................................................78 Fig.4.2..................................................79 Fig.4.3..................................................81 Fig.4.4..................................................82 Fig.4.5..................................................82 Fig.4.6..................................................83 Fig.4.7..................................................83 Fig.4.8..................................................83Fig.4.9..................................................87 Fig.4.10.................................................88 Fig.4.11.................................................89 Fig.5.1..................................................98 Fig.5.2..................................................99 Fig.5.3.................................................102 Fig.5.4.................................................103 Fig.5.5.................................................105 Fig.5.6.................................................105 Table Index: Table 2.1 Structural and textural data of X%Gd-MS........25 Table 2.2 Relaxivities of Gd-MS at 9.4T..................33 Table 2.3 Relaxivities of Gd-MS at 0.47T.................33 Table 2.4 Relaxivities of Eu-Gd-MS at 9.4T...............34 Table 3.1 Measured PL lifetimes of core-shell spheres....61 Table 4.1 Structural and textural data of mesoporous silica nanopparticles....................................84 Table 5.1 Structural and textural data of calcined C10MS porous silica...........................................101 Scheme Index: Scheme 2.1..............................................21 Scheme 2.2..............................................29 Scheme 4.1..............................................77 Scheme 4.2..............................................8