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研究生: 湯騏勳
Tang, Qi-Xun
論文名稱: 藉由中孔洞氧化石墨烯奈米粒子結合微滴陣列應用於表面輔助雷射游離/脫附檢測濫用藥物
Using Mesoporous Graphene Oxide Nanoparticles in combination with a microarray for Surface-Assisted Laser Desorption/Ionization detection of drug abuse.
指導教授: 劉沂欣
Liu, Yi-Hsin
口試委員: 劉沂欣
Liu, Yi-Hsin
陳珮珊
Chen, Pai-Shan
廖尉斯
Liao, Wei-Ssu
口試日期: 2024/07/08
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2024
畢業學年度: 112
語文別: 中文
論文頁數: 99
中文關鍵詞: 中孔洞氧化石墨烯奈米粒子基質輔助雷射游離/脫附表面輔助雷射游離/脫附濫用藥物微滴陣列
英文關鍵詞: mesoporous graphene oxide nanoparticles, MALDI-TOF MS, SALDI-TOF MS, abuse drugs, microdroplet array
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202401555
論文種類: 學術論文
相關次數: 點閱:108下載:1
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  • 在一般的Matrix-Assisted Laser Desorption/Ionization (MALDI)技術中,使用有機酸基質時常面臨兩大挑戰:一是在乾燥結晶過程中的不均勻性,導致低再現性;二是在低分子量區間背景訊號的干擾。本研究提出了一種創新的解決方案,使用中孔氧化石墨烯奈米粒子(mesoporous graphene oxide nanoparticles, MGNs)作為新型奈米基質。MGNs展現了諸多優勢:首先,它們在低分子量區間(m/z 100-500)產生更低的背景訊號;其次,由於其獨特的孔洞結構(mesoporous 3–8 nm and microporous <1.5nm)和表面氧化石墨烯,MGNs具有高效的吸附能力(1.1-1.2 mL/g)和能量轉移效率,並且有強大的吸光能力(200-1100 nm)以及在近紅外放光(600-1100 nm),這些都有助於分析物質的有效解離。此外,為了進一步解決不均勻性和再現性的問題,將MGNs與微滴陣列晶片結合應用於Surface-Assisted Laser Desorption/Ionization (SALDI) 技術。以期利用優化過後的溶劑條件 (H2O+1% EG) 及儀器參數提升檢測不同濫用藥物(例如:芽子鹼甲酯)的均勻性及再現性,進而降低定量分析中的相對標準偏差。

    In conventional Matrix-Assisted Laser Desorption/Ionization (MALDI) techniques, using organic acid matrices often faces two major challenges: uneven crystallization during the drying process, leading to low reproducibility, and background interference in the low molecular weight region. This study proposes an innovative solution by using mesoporous graphene oxide nanoparticles (MGNs) as a novel nanomaterial matrix. MGNs exhibit several advantages: firstly, they produce lower background signals in the low molecular weight range (m/z 100-500); secondly, due to their unique mesoporous (3–8 nm) and microporous (<1.5 nm) structures and surface graphene oxide, MGNs possess high adsorption capacity (1.1-1.2 mL/g) and efficient energy transfer capabilities. Additionally, they have strong light absorption (200-1100 nm) and near-infrared emission (600-1100 nm), which contribute to the effective desorption of analytes. To further address issues of uniformity and reproducibility, MGNs were combined with microarray chips in Surface-Assisted Laser Desorption/Ionization (SALDI) technology. By optimizing solvent conditions (H2O + 1% EG) and instrument parameters, the study aims to enhance the uniformity and reproducibility in detecting various drugs of abuse (e.g., ecgonine methyl ester), thereby reducing the relative standard deviation in quantitative analysis.

    謝誌 I 摘要 II ABSTRACT III 目錄 IV 圖目錄 VII 表目錄 XI 第一章 緒論 1 1.1 藥物類型與檢測困難 1 1.1.1 濫用藥物概述 1 1.1.2 現行檢測發展挑戰性 2 1.2 雷射脫附游離概述 3 1.2.1 MALDI-MS簡介 3 1.2.2 SALDI-MS簡介 6 1.3 中孔洞氧化石墨烯 7 1.3.1 微滴陣列晶片 9 1.4 研究目的與動機 11 第二章 實驗方法 12 2.1 實驗化學藥品 12 2.2 沸石晶種合成(BETA ZEOLITE SEEDS, BZS) 14 2.3 中孔洞材料合成 14 2.3.1中孔洞沸石奈米粒子之合成 (MZNs) 14 2.3.2中孔洞氧化石墨烯奈米粒子之合成 (MGNs) 15 2.4 複合電漿材料之合成 16 2.4.1表面官能基化 16 2.4.2銀前驅物之吸附 17 2.4.3電漿法還原銀奈米粒子 17 2.5 微滴陣列晶片及樣品製備 18 2.5.1微滴陣列晶片製備 (由台大化學所-涂育翎 學姊製備) 18 2.5.2標準品樣品製備 18 2.6 MALDI-TOF-MS校正及測量條件 19 2.6.1 MALDI質譜校正 19 2.6.2 MALDI質譜參數設定 20 2.7 材料鑑定儀器 21 2.7.1 化學氣象沉積儀 (chemical vapor deposition, CVD) 21 2.7.2 反射式紫外-可見光光譜儀 (diffused reflectance ultraviolet–visible spectroscopy, DRS) 22 2.7.3 顯微拉曼光譜儀 (Microscope Raman spectrometer) 22 2.7.4 穿透式電子顯微鏡 (transmission electron microscopy, TEM) 23 2.7.5 基質輔助雷射脫附游離飛行時間式質譜儀 (Matrix-assisted laser desorption ionization-time of flight Mass Spectrometry, MALDI-TOF-MS) 23 2.7.6 X光粉末繞射儀 (powder X-ray diffraction, PXRD) 23 2.7.7 電子順磁共振光譜儀 (Electron Paramagnetic Resonance Spectrometer, EPR) 24 2.7.8 X光吸收光譜-X光吸收延伸區精細結構 (Extend X-ray Absorption Fine Structure, EXAFS) 24 2.7.9 常壓微電漿電化學反應器 (Atmospheric-Pressure Microplasma electrochemical reactor) 24 第三章 結果與討論 26 3.1 最佳基質之選擇 26 3.1.1 MALDI與SALDI基質比較 26 3.1.2 SALDI基質之優化 34 3.2最佳化基質結合微滴陣列晶片 45 3.2.1 微滴陣列之選擇 46 3.2.2 基質在微滴晶片上之優化 48 3.3 均勻性及再現性之優化 61 3.3.1 MGN在陣列上的備製方法 62 3.3.2點樣手法 63 3.4 SALDI基質之探討 70 3.4.1材料性質 71 3.4.2 孔洞深層水 79 3.4.3 氧氣對無機材料之影響 83 第四章 結論與未來展望 87 REFERENCE 88

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