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研究生: 李政宏
Li, Cheng-Hung
論文名稱: 合成奈米材料及其在生醫與能源上之應用
Synthesis of Nanomaterials for Biomedical and Energy Applications
指導教授: 陳家俊
Chen, Chia-Chun
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2015
畢業學年度: 104
語文別: 中文
論文頁數: 92
中文關鍵詞: 金奈米粒子鋰離子電池斷層掃描顯影劑鈉離子電池
英文關鍵詞: gold nanoparticle, lithium ion battery, CT contrast agent, sodiumion battery
DOI URL: https://doi.org/10.6345/NTNU202205077
論文種類: 學術論文
相關次數: 點閱:74下載:16
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  • 近年來螢光導引手術使用分子影像探針的技術已經大幅的進步,可以精準地來切除腫的位置.此篇我們合成出螢光奈米粒子(金和參雜銪的釓氧化物)結合標靶適體AS-1411.此種奈米粒子可以有好的水溶性、生物相容性、可見螢光、和應在斷層掃瞄時有不錯的X光吸收能力(金)並有好的磁化率可應用在核磁共振裡(參雜銪的釓氧化物).螢光奈米粒子可以拿來應用在斷層掃描中以老鼠進行實驗當作顯影試劑,進一步得知腫瘤的位置.更進一步的是我們可以利用奈米粒發出的螢光讓肉眼輕易地直接看到來進行切除.經由切除下來的腫瘤,我們進行IVIS的測試發現,其螢光強度遠大於對照組.所以可以清楚的說明從螢光圖上螢光奈米粒子可以被用來當作標靶癌症腫瘤的螢光標籤.我們的目標就是讓功能化的奈米粒子成功地成為有潛力應用在臨床上螢光導引的手術中.而結果顯示,螢光奈米粒子不僅可以當作醫藥的顯影試劑,未來也可以當作自體螢光探針來應用在手術中.

    奈米粒子不僅可以應用在生醫應用中,也可以拿來用在能量儲存,像是锂電磁.近年來科學家試著用矽來取代電極中的碳材來改善電磁效能.最好的情形下可以改善將近10倍儲存電容量.但矽在幾次充放電過後會產生結構上的崩壞,使電池死亡.而新型以矽為電極材料的锂離子電池就是克服在充放電後所導致的電容量損失所發展出來的.此篇研究裡,我們拿矽與參雜SPA(5-sulfoisophthalic acid)的聚苯胺做結合來當锂離子電池的電極.此一複合材料在經過一千圈的充放電後還有99.6%的庫倫效率並高達925 mAh g-1.代表經由參雜SPA可以有效改善電極強度.
    這個發現開啟了一個讓矽成為電極的可能.除了矽我們還使用了以碳為基材的氧化鉛複合物來嘗試作為電池,首先PVP經由水熱法碳化成含碳基材,再來氧化鉛參雜銅元素來增加導電度.此一材料和其他報導過含鉛材料相比有不錯的電容量(420 mAh g-1),在5.5 A g−1電流下可以充達9500圈還有大於90%的電容量.

    Recent development of molecular imaging probes for fluorescence-guided surgery has shown great progresses for precisely determining tumor margin to execute the tissue resection. Here we synthesize the fluorescent nanoparticles (gold and europium-doped gadolinium oxide) conjugated with nucleolin-targeted AS1411 aptamer. The nanoparticle conjugates exhibit high water-solubility, good biocompatibility, visible fluorescence, strong X-ray attenuation for computed tomography(CT) contrast enhancement and high magnetic susceptibility (europium-doped gadolinium oxide (Gd2O3:Eu) nanoparticles) . The fluorescent nanoparticle conjugates are applied as a molecular contrast agent to reveal the tumor location in CL1-5 tumor-bearing mice by CT imaging. Furthermore, the fluorescence emitting from the conjugates in the CL1-5 tumor can be easily visualized by the naked eyes. After the resection, the IVIS measurements show that the fluorescence signal of the nanoparticle conjugates in the tumor is greatly enhanced in comparison to that in the controlled experiment. The fluorescent imaging clearly reveals that the nanoparticles can be applied as fluorescent tags for cancer-targeting molecular imaging. Our work has shown potential application of functionalized nanoparticles as a multi-function imaging agent in clinical fluorescence-guided surgery. Overall, our results demonstrate that the fluorescence nanoparticles could not only be served as new medical contrast agents but also as intraoperative fluorescent imaging probes for guided surgery in the near future.
    Nanomaterials not only use on bio-application but also energy storage source, such as lithium battery. For more than a decade, scientists have tried to improve lithium-based batteries by replacing the graphite in one terminal with silicon, which can store 10 times more charge. But after just a few charge / discharge cycles, the
    I
    silicon structure would crack and crumble, rendering the battery useless. The new silicon based anodic materials in lithium ion battery (Si-based LIB) are worldwide developed to overcome the capacity decay during the lithiation/delithiation process. In this study, Si nanoparticles coated with 5-sulfoisophthalic acid (SPA) doped polyaniline (core/shell SiNPs@PANi/SPA) composite were prepared and applied as the anodic materials for LIB applications. The detailed structure of core/shell SiNPs@PANi/SPA composite was characterized by high-resolution scanning electron microscopy before and after the charging/discharging. The electrochemical measurements showed that the SiNPs@PANi/SPA anode exhibited high capacity of 925 mAh g-1 and high Columbic efficiency (99.6%) after long-term cyclic life (1000 cycles). Overall results indicated that the SPA dopant doped polyaniline served as a conductive matrix to improve electrical contact and to provide adhesive force in Si-based LIB. Our approach opens a route for the design of efficient silicon nanocomposites for LIB applications. Not only one way we want to approach high performance on anode of battery. We tried different materials like carbon-based metal oxide. Nanostructure composites of lead oxide/copper–carbon (PbO/Cu–C) were synthesized through in situ solvothermal synthesis and heat treatment of PbO/Cu with polyvinylpyrrolidone (PVP) and used as lithium-ion battery anodes. A PbO active particle was embedded in the Cu and PVP–C matrix, accommodating volume changes and maintaining the electronic conductivity of PbO. The composite exhibits superior electrochemical performance, with a capacity of 420 mAh g-1 at a current density of 165 mA g−1, compared with previously reported Pb and PbO composite anodes. The developed anode exhibits >90% capacity retention after 9500 cycles, beginning from the second cycle, at a current density of 5.5 A g−1.

    總目錄 Abstract……………………………………………………………………………..I 總目錄………………………………………………………………………………III Part I Fluorescence-Guided Probes of Aptamer-Targeted Gold Nanoparticles with Computed Tomography Imaging Accesses for in Vivo Tumor Resection 1.1 Abstract…………………………………………………………………………1 1.2 Introduction…………………………………………………………………….1 1.3 Experiment Section…………………………………………………………….4 1.3.1 Preparation of Fluorescent Gold Nanoparticles……………………...4 1.3.2 Conjugation of Fluorescent Gold Nanoparticles with Meglumine Diatrizoate……………………………………………………………….5 1.3.3 Synthesis of DA-AuNPs Conjugated with Aptamer………………….6 1.3.4 Characterization Techniques…………………………………………..6 1.3.5 Cell Viability Assays of AS1411-DA-AuNPs by MCF-7 Cells……….7 1.3.6 Confocal Imaging of AS1411-DA-AuNPs Targeted to CL1-5 Cells …………………………………………………………………………………7 1.3.7 CT Imaging of AS1411-DA-AuNPs in Mice…………………………..8 1.4 Result and Discussion………………………………………………………….8 1.4.1 Characterization of AS1411-DA-AuNPs……………………………...8 1.4.2 Optical Properties of AS1411-DA-AuNPs…………………………….10 1.4.3 Cell Viability Assays of AS1411-DA-AuNPs…………………………..11 1.4.4 Cell Targeting and Imaging……………………………………………12 1.4.5 In Vitro CT Imaging of AS1411-DA-AuNPs…………………………13 1.4.6 In Vivo CT Imaging to Detect CL1-5 Tumor Location……………..14 1.4.7 AS1411-DA-AuNPs for Intraoperative Fluorescence-Guided Resection in Mouse Model………………………………………………………...15 1.4.8 Targeting Enhancement Analysis of AS1411-DA-AuNPs…………..16 1.5 Conclusion……………………………………………………………………..18 1.6 References……………………………………………………………………...19 Part II AS1411 Aptamer-Conjugated Gd2O3:Eu Nanoparticles for Target-Specific CT/MR/Fluorescence Molecular Imaging 2.1 Abstract………………………………………………………………………..25 2.2 Introduction…………………………………………………………………...26 2.3 Experiment Section…………………………………………………………...29 2.3.1 Synthesis of A-GdO:Eu Nanoparticles……………………………….29 2.3.2 Characterization of A-GdO:Eu Nanoparticles……………………....31 2.3.3 Quantitative Polymerase Chain Reaction Protocol for A-GdO:Eu Nanoparticles……………………………………………………………31 2.3.4 Cell Viability Assays of MCF-7 Cells after Incubation with A-GdO:Eu Nanoparticles……………………………………………………………32 2.3.5 Confocal Imaging of A-GdO:Eu Nanoparticles Targeted to CL1-5 Cells ……………………………………………………………………………32 2.4 Result and Discussion………………………………………………………….33 2.4.1 Structural Characterization of A-GdO:Eu Nanoparticles…………..33 2.4.2 Optical Properties of A-GdO:Eu Nanoparticles…………………...35 2.4.3 Magnetic Properties of A-GdO:Eu Nanoparticles………………...36 2.4.4 CT Imaging and HU Measurements………………………………..37 2.4.5 Cell Viability Assays of A-GdO:Eu Nanoparticles…………………38 2.4.6 Cell Targeting and Imaging…………………………………………39 2.4.7 CT Imaging of A-GdO:Eu Nanoparticles in Mice…………………40 2.4.8 Fluorescence Imaging of A-GdO:Eu Nanoparticles into Tumor -Bearing Mice…………………………………………………………41 2.5 Conclusion……………………………………………………………………...42 2.6 References………………………………………………………………………43 Part III Highly stable cycling of lead oxide/copper nanocomposite as an anode material in lithium ion battery 3.1 Abstract…………………………………………………………………………52 3.2 Introduction…………………………………………………………………….52 3.3 Experiment Section…………………………………………………………….56 3.4 Result and Discussion………………………………………………………….58 3.5 Conclusion……………………………………………………………………...68 3.6 References………………………………………………………………………70 Part IV Chemical Doped Polyaniline Coating on Silicon Nanoparticles as High performance Lithium Ion Battery Anode 4.1 Abstract…………………………………………………………………………75 4.2 Introduction…………………………………………………………………….75 4.3 Experiment Section…………………………………………………………….78 4.3.1 Synthesis of SiNPs@PANi/SPA composite........................................78 4.3.2 Synthesis of SiNPs@PANi/Cl composite...........................................78 4.3.3 Electrode fabrication…………………………………………………79 4.3.4 Cell packing and electrochemical test………………………………79 4.3.5 Characterizations…………………………………………………….80 4.4 Result and Discussion…………………………………………………………..80 4.5 Conclusion………………………………………………………………………89 4.6 References……………………………………………………………………….90

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    PARTII
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