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研究生： 文彥傑
Wen, Yanjie
論文名稱： 「智能云+納米材料+分子設計」 探討 環境與食品之民生議題
Approaching Environment and Food Safety Issues by Intelligent Cloud, Nano Materials and Molecular Design
指導教授： 凌永健
Ling, Yong-Chien
口試委員: 黃賢達
Huang, Shang-Da
余靖
Yu, Chin
麥富德
Mai, Fu-Der
杜敬民
Duh, Jing-Min
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2017
畢業學年度： 106
語文別： 中文
論文頁數： 195
中文關鍵詞： PM2.5 、二噁英 、石墨烯 、分子設計 、納米材料 、智能云
外文關鍵詞： PM2.5, dioxin, graphene, Molecular Design, Nano Materials, Intelligent Cloud
相關次數： 點閱：2  下載：0 
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    • 本文主要圍繞日常生活中常遇到的有害物質的檢測、分析與危害減輕方案而展開探討。具體的工作有：
    （1）利用“智慧空氣品質監測雲”系統個人終端這種方便靈活的檢測手段，定量證實了a) 使用公共綠色交通工具出行的健康與環保優勢，b) 室內外空氣污染回避方案及室內空氣淨化設備的效果，c) 全社會公眾參與的空氣品質監測平臺將發揮“大智移雲”特性，為政府之環保政策提供定量的第一手資料；
    （2）針對分子層面的環境有害物質（以二噁英為例），本文結合垃圾焚化廠周邊二噁英分佈情況，探討了二噁英的危害，並從其分子結構、分子光譜等物理化學特性入手，分析了降解或無害化處理的策略理論；
    （3）針對食品中可能攝入的有害物質（以棒曲黴素為例），製備了基於磁性納米氧化石墨烯的固相萃取材料，設計了基於紫外-可見檢測器的高效液相色譜檢測法，發現磁性材料對棒曲黴素萃取與脫附性能較好，有很好的食品安全檢測與應用潛力；
    （4）針對上述性能優良的磁性氧化石墨烯納米材料，本文通過密度泛函方法，設計了分子片段模型，分析了材料磁性性能的控制因素，並基於這些因素提出了磁性氧化石墨烯納米材料的定向設計策略。
    （5）綜述了石墨烯基材料作為人工酶催化劑之催化中心、作用位點、載體功能與的結構特點，為以後之石墨烯基材料設計提供了設計策略參考。石墨烯基材料作為人工酶催化劑其綠色高效的生物化學反應最終目標，是解決當今世界能源與環境危機的一個很實用且有前途的思路，也是當代先進化學工程技術的發展方向。

    In this work, conbined experimental and therotical research has been carried out, mainly focusing on the detection, analysis and mitigation plan of hazardous substances frequently encountered in daily life:
    (1) With the convenient personal device iDetector of ‘intelligent air quality monitoring cloud system’ we have testified a) the advantage of public transport in air pollution prevention, b) the suggested indoor and outdoor protection method from air pollution and the effect of indoor air purification equipment, c) the air quality intelligent cloud platform the whole community involved in would provide quantitative first-hand PMs’ information and support the government’s environmental policy.
    (2) For the notorious dioxin molecules in ambient air, both experimental and theoretical work has been carried out. Based on the distribution of dioxin around the incinerator, the dioxin molecules are discussed theoretically; based on the characteristics of molecular structure and molecular spectrum, the strategy of degradation or harmless treatment was evaluated.
    (3) For the harmful molecules contained in food (patulin), solid phase extraction material based on magnetic nano graphene oxide (MGO) was prepared. Then, patulin’s high performance liquid chromatograph analysis method based on UV-Vis detector was designed. It is found that MGO have good performance in sorption and desorption of patulin. It would have great potential on the harmful substance detection in food industry.
    (4) To establish the basic understandary of the design stratigy of MGO molecules, theoretical investigation in the MGO structure has been carried out. The molecular fragment model was designed by density functional theory (DFT) method, and the controlling factors of magnetic properties of the material were analyzed. Based on these factors, the directional design strategy of MGO nanomaterials is proposed.
    (5) Based on the viewpoints of stereo chemistry and molecular kinetic and dynamics in heterogeneous system, we evaluate and compare the suitability of different NMs as artificial enzyme constituent. We propose that reevaluates design strategies of graphene-based peroxidase (G-POD) mimetics materials and emphasizes on their selectivity (role as catalytic center, binding site, or carrier) is of uttermost.

    摘　　要 1 Abstract 2 誌 謝 辭 3 目　　次 7 圖 目 次 13 表 目 次 17 式 目 次 19 第一章 前言 20 第二章 “智能空氣品質監測雲”系統對大氣PM2.5等污染物的檢測研究 24 2.1 引言 25 2.2 檢測工具：“智能空氣品質監測雲”系統 30 2.2.1 系統組成 30 2.2.2 iDetector和iCellphone 32 2.2.2.1 PM激光粉塵傳感器 32 2.2.2.2 主電路板 34 2.2.2.3 溫度濕度與VOC傳感器 35 2.2.2.4 組裝成型的iDetector 37 2.2.2.5 iCellphone 37 2.2.3 iCloud和iExplorer 39 2.3 檢測方法 41 2.3.1 溫濕度校正 41 2.3.2 與當地環保部門監測站測值的比較 42 2.4 檢測目的 44 2.5 結果與討論 45 2.5.1 通勤交通工具上的PM狀況 45 2.5.1.1 地鐵：明显高出室外的PM濃度 45 2.5.1.2 普通小客車：車载空调有較好的降低PM的作用 47 2.5.1.3 大巴車：車载空调具有降低PM的作用 50 2.5.1.4 遠距離出行工具：高鐵列車上非常低的PM值 51 2.5.1.5 遠距離出行工具：飛機上的PM2.5濃度近乎零 52 2.5.1.6 小結 53 2.5.2 室內的PM2.5等污染 54 2.5.2.1 污染現狀 54 2.5.2.2 部分空氣净化器具有較好的降低PM的作用 56 2.5.2.3 家用空調在降低室内PM濃度方面的劣势 57 2.5.3 人流聚集區具有較高PM值 59 2.5.4 室外的“空氣净化器”——綠色植物 60 2.5.5 PM的普通全天吸入量 62 2.5.6 普及“智能空氣品質監測雲”系統的必要性 64 2.6 本章總結 65 第三章 大氣二噁英類污染物的危害及理論光譜分析法治理初探 66 3.1 引言 67 3.2 目標焚化廠與採樣點 70 3.3 分子光譜計算方法 72 3.4 結果與討論 73 3.4.1 焚化爐周界空氣二噁英污染的危害 74 3.4.2 二噁英類分子的分子結構與分子軌道 75 3.4.3 二噁英類分子的電子分佈和自然鍵軌道分析 77 3.4.4 二噁英類分子的激發態理化性質和理論光譜 81 3.5 本章總結 86 第四章 磁性氧化石墨烯納米材料之於蘋果汁中棒曲黴素污染物的檢測研究 88 4.1 引言 89 4.2 儀器與藥品 91 4.3 磁性氧化石墨烯納米材料的製備與應用 93 4.3.1 磁性氧化石墨烯納米材料的製備 93 4.3.2 磁性氧化石墨烯納米材料應用於蘋果汁樣品的前處理 95 4.3.3 蘋果汁中棒曲黴素的檢測 97 4.4 磁性氧化石墨烯納米材料的鑑定與吸脫附條件優化 99 4.4.1 磁性氧化石墨烯納米材料的性質研究 99 4.4.2 磁性氧化石墨烯納米材料應用於棒曲黴素吸脫附的條件優化 102 4.4.2.1 吸附劑用量之於吸附效率 102 4.4.2.2 吸附時間之於吸附效率 102 4.4.2.3 樣品pH值之於吸附效率 103 4.4.2.4 離子強度之於吸附效率 104 4.4.2.5 淋洗液種類之於脫附效率 104 4.4.2.6 淋洗液體積之於脫附效率 105 4.4.2.7 小結 105 4.4.3 磁性氧化石墨烯納米材料的可重複利用性 105 4.5 棒曲黴素的高效液相色譜檢測 106 4.5.1 建立HPLC-UV檢測棒曲黴素的方法 106 4.5.2 所提取棒曲黴素的HPLC-UV分析 107 4.5.3 本章建立的方法與相關已有方法的比較 109 4.6 本章總結 111 第五章 磁性氧化石墨烯納米材料的分子磁性設計 112 5.1 引言 113 5.2 理論模型設計 115 5.2.1 2a→6a的設計策略 116 5.2.2 2b→6b的設計策略 117 5.2.3 2c→6c的設計策略 117 5.2.4 2d→6d的設計策略 117 5.2.5 4e→6e的設計策略 118 5.2.6 6f的設計策略 118 5.2.7 小結 119 5.3 計算方法 120 5.4 結果與討論 123 5.4.1 雙自由基分子與凱庫勒結構破壞對分子磁性的影響 129 5.4.2 共軛體系與電子離域狀態對雙自由基及分子磁性的影響 132 5.4.3 吸電子基團對雙自由基和分子磁性的影響 135 5.4.4 分子中部橋連結構對雙自由基及分子磁性的影響 137 5.4.5 多個雙自由基共軛體系的分子磁性 139 5.4.6 雙自由基結構個數對分子磁性的影響 142 5.5 本章總結 145 第六章 石墨烯基過氧化物酶仿生材料的設計策略 146 6.1 引言 147 6.2 過氧化物酶的氧化還原化學 149 6.3 作為催化中心的石墨烯基納米材料 152 6.3.1 石墨烯、氧化石墨烯及還原氧化石墨烯 152 6.3.2 石墨烯基-金屬絡合物或石墨烯基-金屬蛋白 153 6.3.3 石墨烯基-金属颗粒雜化體 153 6.3.4 石墨烯基碳量子點 154 6.4 作為結合位點的石墨烯基納米材料 155 6.4.1. 石墨烯、氧化石墨烯及還原氧化石墨烯 155 6.4.2. 石墨烯基-金屬絡合物或石墨烯基-金屬蛋白 156 6.4.3. 石墨烯基-金屬顆粒雜化體 156 6.5 作為載體的石墨烯基納米材料 158 6.5.1. 氧化石墨烯及還原氧化石墨烯等納米材料 158 6.5.2. 石墨烯基-金屬絡合物或石墨烯基-金屬蛋白 159 6.5.3. 無機納米材料 159 6.6 石墨烯基納米材料作為各催化部位的優劣綜論 161 6.6.1 作為催化中心和作用位點的優劣比較 162 6.6.2 作為載體的優劣比較 164 6.7 本章總結 165 第七章 綜論與展望 166 參考文獻 171 附錄1 PM2.5濃度相關官方測值 188 附錄2 車載空調降低PM作用的效果圖 189 附錄3 二噁英大氣污染物採樣點衛星座標 191 附錄4 二噁英分子光譜計算方法 192 附錄5 博士班期間發表文章列表 195

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