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研究生: 楊啟盤
Yang, Chi-Pan
論文名稱: 金奈米團簇利用多爪嵌段共聚物的製備與其螢光性質的研究
Preparation of Gold Nanoclusters Encapsulated with Multi-Arm Block-Copolymers and Study of Their Fluorescence Properties
指導教授: 陳家俊
Chen, Chia-Chun
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2019
畢業學年度: 107
語文別: 中文
論文頁數: 79
中文關鍵詞: 金奈米團簇螢光多爪數聚乙二醇化學還原法再加熱
英文關鍵詞: Gold Nanocluster, Photoluminescence, Multi-arm polyethylene glycol, Chemical reduction, Reheating
DOI URL: http://doi.org/10.6345/NTNU201900363
論文種類: 學術論文
相關次數: 點閱:127下載:10
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  • 金奈米團簇(Gold Nanoclusters, Au NCs)具有可發光的性質、低毒性且有極小的尺寸,容易在表面進行修飾,使其可應用於離子檢測、生物標記及生物顯影等。利用不同的高分子聚合物合成金奈米團簇,可調控其螢光放光波長和量子效率,並可更進一步修飾表面的配位基團。金奈米團簇的發光的性質主要是由於配體到金属的電荷轉移 (LMCT, ligand-to-metal charge transfer),利用波長範圍在300 nm - 400 nm光源的激發條件下,可發出不同顏色的光,因此具有在影像及感測方面應用的潛力。本研究首先將多爪數的聚乙二醇聚合合成PEG-p(Glu),並在各爪數的支鏈修飾上硫醇,將修飾後高分子做為配位基團利用化學還原的方式合成金奈米團簇。實驗發現用NaBH4合成¬出來的金奈米團簇隨著PEG-p(Glu)爪數的改變,會出現兩種放光波長,分別約在460 nm及650 nm,更進一步地利用水浴法加熱合成的金奈米團簇,其放光波長會再次產生變化。金奈米團簇的大小可能受到不同配位基團的化學結構和合成條件的影響,導致螢光出現變化。結果顯示出利用不同爪數的嵌段共聚物合成的金奈米團簇具有控制金奈米團簇放光波長的潛力。

    Gold Nanoclusters (Au NCs) have luminescent properties, low toxicity, extremely small size, and easy engineered surface modification, which make the gold nanoclusters can be applied in ion detection, biomarking and biological development. Using different functionalized polymers, gold nanoclusters can be synthesized to control the fluorescence emission wavelength, quantum efficiency, and further surface modification. The photoluminescence properties of the Au NCs are originated from ligand-to-metal charge transfer (LMCT), leading to the different emission wavelength under the excitation ranging from 300 nm - 400 nm. The unique luminescent properties of Au NCs possess the potential in the fields of imaging and sensing. In this study, the multi-arm PEG-p(Glu) with different number of arms were synthesized by a ring-opening polymerization method, and further modified with cystamine on the side chain. The thiolated polymers were used as the ligand to synthesize the Au NCs. With the usage of NaBH4 as the reducing agent, the photoluminescence spectra of Au NCs showed two emission wavelengths at 460 nm and 650 nm. Further, the emission wavelength changed again, when the Au NCs were annealed with water bath method. The size of the Au NCs may be affected by the synthesis conditions and the usage of different ligands, resulting in the change of photoluminescence wavelength. The results show that the Au NCs synthesized using multi-arm PEG-p(Glu) have the potential to control the cluster size and emission wavelength.

    謝誌 I 摘要 II Abstract III 目錄 IV 圖表附錄 VI 第一章 緒論 1 1-1奈米材料的簡介 1 1-2金奈米材料 6 1-3金屬奈米材料的製備 10 1-4金奈米團簇 13 1-4-1合成金奈米團簇 15 1-4-2金奈米團簇的放光機制 17 第二章 文獻回顧與研究動機 18 2-1 以聚乙二醇模板作為配位基團合成的金奈米團簇 18 2-2 調整金奈米團簇的放光 20 2-2-1不同配位基團的金奈米團簇 20 2-2-2表面配位基團影響金奈米團簇放光波長 23 2-2-3影響金奈米團簇放光強度 27 2-3 用二次的步驟合成金奈米團簇 29 2-4研究動機 30 第三章 實驗藥品及儀器 31 3-1實驗藥品 31 3-2 儀器設備及其基本原理 32 3-2-1紫外光-可見光吸收光譜儀( UV-Vis Spectrophotomer ) 32 3-2-2光致發光光譜儀(Photoluminescence Spectrometer, PL) 33 3-2-3穿透式電子顯微鏡(Transmission Electron Microscope,TEM) 34 3-2-4動態光散射儀( Dynamic Light Scattering,DLS ) 35 3-2-5 X-射線光電子光譜儀(X-ray photoelectron spectroscopy, XPS) 36 3-2-6核磁共振光譜(Nuclear Magnetic Resonance spectroscopy,NMR) 37 3-2-7超濾離心管(Vivaspin) 38 3-3 實驗步驟與方法 39 3-3-1合成多爪poly(BLG) (γ-benzyl-L-glutamate) 39 3-3-2多爪嵌段共聚物的水解 40 3-3-3將Cystamie修飾在多爪嵌段共聚物的支鏈上 40 3-3-4用Dithiothreitol將Cystamie的雙硫鍵還原 41 3-3-5合成金奈米團簇 42 第四章 結果與討論 43 4-1多爪嵌段共聚物的合成與鑑定 43 4-1-1 Multi-arm-PEG-p(Glu)的合成 43 4-1-2 多爪嵌段共聚物的分析 45 4-2金奈米團簇的鑑定 48 4-2-1金奈米團簇的光學鑑定 48 4-2-2金奈米團簇形狀及大小的鑑定 53 4-2-3 XPS分析 59 4-3 ESI-MS質譜鑑定 65 第五章結論 67 附錄 68 參考資料 76

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