近年來電腦模擬計算對於實務上開發研究的輔助已日益漸增，然而在化學分析方面，到目前為止並沒有能與實際情形相匹配的模擬研究，本研究主要是以實驗室獨自開發程式為主，商用模擬軟體為輔，進行混合溶液的分離模擬運算。混合溶液中以甲醇及乙腈分子當作溶劑，待分離的溶質主要為炸藥分子：硝化甘油(nitroglycerin, NG)、黑索金 (1,3,5-trinitroperhydro-1,3,5-triazine, RDX)、奧托金(octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, HMX) 及三硝基甲苯(2-methyl-1,3,5-trinitrobenzene, TNT)，溶劑分子與炸藥分子混合形成一移動相，而固定相分別建構兩種不同性質的體系，一種具有正相層析性質的異黃樟油素分子(Poly-1,2-methylenedioxy-4-propenyl benzene, PISAF)，另一種具有類似逆相層析性質的有機矽氧烷分子 [O-(CH3)2-Si-C8]，將移動相與多個重覆結構的固定相接合，並以物理方式進行分離模擬，炸藥分子的模擬分離結果與實驗趨勢相近，而在不同的固定相進行分離也得到不同的分離結果，也記錄了被分離的分子在分離過程的構形變化，有利於我們理解層析物理分離機制，也充分顯示出我們所開發的程式可以成功進行分離模擬。此項技術日後也可以用來做藥物分子的分離、軍事防護衣毒氣隔離等研究，使得開發人員在材料評估、研究成本、實驗設計上能有所幫助。

Molecular dynamics (MD) simulations have been employed to assist the investigation on chemical engineering research for theoretical analysis in recent years. However, the MD simulations were less successfully to research project regarding to analytical chemistry. The computational simulations on liquid chromatography of explosive ingredients were comprehensively investigated by self-development program design and a commercial simulations software as an assistance. An innovative computational program was applied to separating the explosive ingredients physically, of which liquid chromatographic mechanism was thoroughly investigated by MD simulations in this study. The explosive ingredients including nitroglycerin (NG), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2-methyl-1,3,5-trinitrobenzene (TNT) were assigned as solutes and methanol (CH3OH) and acetonitrile (CH3CN) as solvents in the solution system. The polymeric-molecular species consisting of [O-(CH3)2-Si-C8] as a reversed phase and poly-1,2-methylenedioxy-4-propenyl benzene (PISAF) compounds as a normal phase were tested as stationary phase, respectively.
The research results showed that the different species of explosive ingredients were separated successfully in the solutions by each of the constructed stationary phase of [O-(CH3)2-Si-C8] and PISAF after a total simulation time of 300.0 ps approximately, which were consistent with the experimental analysis of HPLC spectrum. In addition, the effects of the constructed stationary phase on the separation dynamics was investigated to clarify the mechanism on the liquid chromatography. The results indicated that the efficient separation can be attributed to the configuration variation of explosive ingredients, and the variation of the configuration and the net charges of [O-(CH3)2-Si-C8] and PISAF, respectively. The MD simulation designed by self-development program was confirmed to compute the liquid chromatography process effectively in this study. The computational techniques can be widely applied to the theoretical analysis of separation of pharmaceutical ingredients and military protective clothing against poison gases, which are beneficial to the selection of function materials, the cost reduction and the experimental design.

論文審定書 i
論文公開授權書 ii
誌謝 iii
中文摘要 iv
Abstract v
圖次 x
表次 xii
第壹章 緒論 1
1-1 分子動力模擬 1
1-2 炸藥化合物 2
1-3 高效能液相層析 7
1-4 研究動機與方法 9
第貳章 原理及方法 10
2-1 分子動力模擬 (Molecular Dynamics Simulation) 10
2-1-1 簡介 10
2-1-2 分子動力學基本假設 10
2-1-3 基本流程架構 11
2-2 分子力場 14
2-3 牛頓運動方程式的數值方法 16
2-4 週期性邊界條件 19
第參章 系統建構方法及參數設定 20
3-1 系統建構 20
3-2 模擬軟體 25
3-3 模擬參數設定 27
3-3-1 結構最佳化參數設定 27
3-3-2 分子動力模擬參數設定 28
第肆章 結果與討論 29
4-1 分子動力模擬初始分離結果 29
4-1-1 硝化甘油 (NG) / 黑索金 (RDX) 混合系統分離移動情形 29
4-1-2 奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統分離移動情形 30
4-2 移動相混合炸藥分子分離結果 31
4-2-1 硝化甘油 (NG) / 黑索金 (RDX) 混合系統分離比較 31
4-2-2奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統分離比較 32
4-3 不同固定相系統分離動態分佈 33
4-3-1 硝化甘油 (NG) / 黑索金 (RDX) 混合系統分佈 33
4-3-2奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統分佈 34
4-4 溶液相炸藥分子在不同固定相材料扭轉角度分佈 35
4-4-1 硝化甘油 (NG) / 黑索金 (RDX) 混合系統扭轉角分佈 35
4-4-2 奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統扭轉角分佈 37
4-5未考量固定相電荷影響之移動相混合炸藥分子分離結果 39
4-5-1 硝化甘油 (NG) / 黑索金 (RDX) 混合系統分離比較 39
4-5-2 奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統分離比較 40
4-6 未考量固定相電荷影響混合系統分離移動結果 41
4-6-1 硝化甘油 (NG) / 黑索金 (RDX) 混合系統分離移動情形 41
4-6-2 奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統分離移動情形 43
4-7炸藥分子在異黃樟油素材料考量電荷影響與否之扭轉角度分佈 44
4-7-1硝化甘油 (NG) / 黑索金 (RDX) 混合系統扭轉角分佈 44
4-7-2 奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統扭轉角分佈 45
4-8炸藥分子在辛基矽氧烷材料考量電荷影響與否之扭轉角度分佈 46
4-8-1硝化甘油 (NG) / 黑索金 (RDX) 混合系統扭轉角分佈 46
4-8-2奧托金 (HMX) / 三硝基甲苯 (TNT) 混合系統扭轉角分佈 48
第伍章 結論 49
參考文獻 51

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