臺灣博碩士論文加值系統

近年來奈米科技蓬勃發展，金奈米材料優異生物相容性被受重視，根據結構及粒徑大小而有更多元的應用性。金奈米棒依據入射光頻率產生表面電漿共振效應(SPR)吸收，其SPR吸收波段介於可見光與近紅外光間，廣泛應用於生醫、光電及顯影技術。包覆金奈米棒表面介面活性劑-十六烷三甲基溴化銨(CTAB)，易脫附金奈米棒表面因而產生細胞毒性，因此發展各種金奈米棒表面方法，如聚電解質(polyelectrolyte)包覆、二氧化矽(silica)殼層，配位鍵結硫醇基(-SH)分子及親疏水性作用力的磷脂質(phospholipid)批覆，種種改質辦法皆克服了金奈米棒表面改質的問題，但反應時間過於冗長及其改質辦法影響金奈米棒原有光學特性。本論文提出新型、簡便且快速的表面改質辦法，以靜電作用力(electrostatic force)的原理，合成具有羧基表面的螢光金奈米團簇(AuNCs@DHLA)吸附於金奈米棒表面的CTAB，以紫外光-可見光吸收光光譜儀分析奈米粒子特徵吸收波峰變化量，穿隧式電子顯微鏡觀察奈米粒子結構，瓊脂糖凝膠電泳分析奈米粒子表面官能化特性及其泳動狀況；市售巰基化合物(TMAC)取代金奈米棒表面CTAB，提供良好的穩定性於金奈米棒且解決了介面活性劑脫附的現象；本論文也比較了六奈米金粒子與AuNCs@DHLA吸附金奈米棒之差異性，結果發現AuNCs@DHLA提供的單位電荷密度優於於六奈米金粒子，並且其羧基表面黏附金奈米棒效果優於其他的螢光金奈米團簇，如AuNCs@BSA、AuNCs@GSH。最後，使用本研究中最佳的AuNCs@DHLA吸附於以CTAB和TMAC修飾後的金奈米棒，並進行各種聚乙二醇化的探討，以提供良好的生物介面於各種應用。

In recent years nanotechnology is flourishing, gold based materials have excellent biocompatibility. By tuning the particle size and shape, a diverse range of applications are readily available. For a certain range of frequency of an incident light irradiated upon gold nanorod (AuNR), surface plasmon resonance (SPR) effect can be produced. The SPR effect was utilized to acquire the absorption bands between visible and near-infrared light (NIR) of the AuNR for biomedical, optical electronics, and imaging applications. Capping agents like cetyltrimethylammonium bromide (CTAB) enhances the stability of gold nanorod but the problem is its cytotoxicity, so CTAB was replaced by a surface modification method using polyelectrolyte coating, silica shell, and dative bonding of thiol group molecules or hydrophilic and hydrophobic phospholipid coating. Most modifications to overcome gold nanorod surface problems took long reaction time and it influenced the original optical properties of gold nanorod. This research proposed a novel, simple, electrostatic force based principle approach to modify the surface of the AuNR, the surface of gold nanoclusters (AuNCs@DHLA) contain carboxyl groups which are anionic and were used to attach on the AuNR’ cationic surface, AuNCs@DHLA is more efficient than other gold nanoclusters. To verify the nanoparticle specific absorption wavelength, structure, functionalization and mobility status; UV-Vis absorption spectra, transmission electron microscopy and agarose gel electrophoresis was done respectively. The commercialized mercapto compounds (N, N, N-trimethyl (11-mercaptoundecyl) ammonium chloride, TMAC) replaced the AuNR’ CTAB on the surface, then the attachment efficiency and bio-functionalization of TMAC to gold nanoclusters was analyzed. The attachment efficiency between 6 nm nanoparticles and AuNCs@DHLA was compared. As a result, AuNCs@DHLA provides superior unit charge density than 6 nm gold nanoparticles, carboxylic groups attached more efficiently on AuNR compared to other gold nanoclusters (AuNCs@BSA, AuNCs@GSH). Finally, AuNCs@DHLA was attached on the gold nanorod surface containing CTAB or TMAC, and a variety of PEGylation was done. As a result, better biological interface can be provided in a variety of applications.

摘要 I
Abstract II
誌謝 IV
目錄 VI
圖目錄 IX
表目錄 XII
第一章 前言 1
1-1研究背景 1
1-1-1金奈米粒子之進展 1
1-1-2金奈米棒之表面特性 2
1-1-3金奈米棒複合材料 3
1-2研究目的 5
第二章 文獻回顧 6
2-1金屬奈米粒子 6
2-1-1奈米金屬材料－金奈米棒 8
2-2金奈米棒表面修飾與衍生化 10
2-2-1金奈米棒表面改質聚電解質(polyelectrolyte) 13
2-2-2金奈米棒表面改質巰基化合物(alkanethiol) 15
2-2-3金奈米棒表面改質磷脂體(phospholipid) 17
2-2-4金奈米棒表面改質二氧化矽(silica)殼層 19
2-3陽離子介面活性劑(CTAB) 20
2-4螢光奈米材料 22
2-4-1螢光金屬奈米團簇合成 23
2-4-2藍色螢光金奈米團簇 24
2-4-3綠色螢光金奈米團簇 25
2-4-4紅色螢光金奈米團簇 27
2-5螢光金奈米團簇生物接枝 29
第三章 研究材料與方法 30
3-1研究架構 30
3-2製備金奈米棒複合材料與方法 31
3-2-1合成金奈米棒(AuNR@CTAB) 31
3-2-2水相金奈米粒子(AuNP@CTAB) 32
3-2-3合成六奈米金粒子(6 nm AuNP)&;水相改質 34
3-2-4合成兩性高分子 34
3-2-5螢光金奈米團簇合成 35
3-2-6紅色螢光金奈米團簇(AuNCs@DHLA)表面修飾雙官能化聚乙二醇(NH2-PEG6k-NH2, NH2-PEG5k-Biotin, NH2-PEG5k-OCH3) 37
3-2-7巰基化合物表面改質 38
3-2-8金奈米粒子與螢光金奈米團簇之複合物 39
3-2-9聚乙二醇化金奈米棒複合材料 40
3-3分析金奈米粒子複合物材料與方法 41
3-3-1瓊脂糖凝膠電泳分析(Agarose gel electrophoresis) 41
3-3-2紫外光-可見光吸收光光譜儀分析(UV-Vis absorption spectra) 41
3-3-3穿透式電子顯微鏡(Transmission electron microscopy) 41
第四章　結果與討論 42
4-1金奈米棒 42
4-2金奈米棒表面吸附螢光金奈米團簇(AuNCs@DHLA)或聚乙二醇(HS-PEG3k-COOH)之比較 43
4-3金奈米棒與螢光金奈米團簇交互作用之複合物 45
4-4不同粒徑及特性金奈米粒子吸附金奈米棒表面之比較 49
4-5金奈米棒表面四級銨結構探討 52
4-6螢光金奈米團簇與金奈米棒之濃度比 55
4-7金奈米棒複合粒子(AuNR@CTAB@NC, AuNR@TMAC@NC)聚乙二醇化(NH2-PEGn-CH3O, n=2k, 5k, 10k, 20k) 58
4-8水相金奈米粒子(AuNP@CTAB)吸附螢光金奈米團簇之探討 63
4-9紅色螢光金奈米團簇(AuNCs@DHLA)表面修飾雙官能化聚乙二醇(NH2-PEG6k-NH2, NH2-PEG5k-Biotin, NH2-PEG5k-OCH3)吸附於金奈米棒表面 65
第五章　結論 69
參考文獻 71
附錄一、實驗藥品 80
附錄二、實驗儀器 82

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