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研究生： 仁可娜
Rizkiana, Meta Fitri
論文名稱： 含膽固醇基二量化膠體元對鏡像性螺旋結構體的誘導研究
Enantiomeric Helical Constructions Induced by Dimeric Gelators Derived from Cholesterol
指導教授： 劉瑞祥
Liu, Jui Hsiang
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2014
畢業學年度： 102
語文別： 英文
論文頁數： 72
中文關鍵詞： 吡啶 、雙聚物膽固醇 、奈米管結構 、左-右螺旋結構
外文關鍵詞： pyridine, dimeric cholesterol, para, meta, nanotube structures, left-right handed helical
相關次數： 點閱：128  下載：0 
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    • 本研究合成兩種含膽固醇基團的二聚吡啶衍生物，藉由導入不同位向之苯環和醯胺基鍵結連接吡啶及膽固醇基團，形成對位 (PyPC) 及間位 (PyMC) 之同分異構物，並探討兩種異構物在不同溶劑下形成膠體的特性，根據實驗結果顯示，PyMC比PyPC具有更優異之凝膠化性質。實驗以SEM、TEM、1H-NMR、XRD以及CD進行鑑定兩種化合物形成之乾凝膠型態與堆疊方式，由TEM觀察凝膠表面型態及微結構之結果顯示，分子結構及溶劑性質均對凝膠網狀結構型態有顯著影響。分子設計導入膽固醇基團之有機凝膠體分子可自組裝形成高秩序性的螺旋纖維結構，由結果顯示PyPC於正十二烷醇中形成之纖維鬈曲成奈米管狀結構；值得一提的是，由TEM觀察結果發現此掌性系統中同時具有左旋及右旋結構，SEM觀察亦鑑定出具有螺旋結構的奈米管柱之形成，並從CD分析亦可證明螺旋結構確實存在，根據SEM、TEM的圖像結果可推知左旋與右旋並不相等。

    Two dimeric pyridine derivatives containing cholesteryl group were synthesized. The connecting group between cholesterol and pyridine contains benzene rings and amide groups. The structures of the compounds are changed by varying the relative positions of amide groups on the benzene rings (at para and meta). Gelation properties of the synthesized two compounds (PyPC and PyMC) were studied. From gelation results, PyMC has higher gelation ability than PyPC. The results suggest that connecting position affect polarity of molecules, thus it leads to the difference of molecular interaction resulting in different gelation behavior of the two compounds. The morphologies and packing arrangements of xerogels were studied using SEM, TEM, 1H-NMR, XRD, and CD spectra. SEM measurements observe the formation of nanotube structures with helical structures. TEM measurements reveal that the molecular structures, nature of solvents show significant effect on the morphologies of the gel networks. It was observed that PyPC in dodecanol forms nanotube structures in which the nanotubes were constructed by twisted fibers. Interestingly, TEM observations show that both left and right handed helical constructions were formed although the system is chiral system. However, CD analysis indicates the existence of helical constructions. The results suggest that both left and right handed helical constructions shown in TEM images should be unequal amount.

    ABSTRACT I 摘要 II ACKNOWLEDGEMENTS III TABLE OF CONTENTS IV LIST OF TABLES VII LIST OF FIGURES VIII LIST OF SCHEMES XII CHAPTER ONE INTRODUCTION 1 1.1 Research background 1 1.2 Research motivation 3 CHAPTER TWO LITERATURE REVIEW 5 2.1 Supramolecular self assembly 5 2.1.1 Hydrogen bonding 6 2.1.2 - stacking 6 2.1.3 Coordination interaction 7 2.2 Classification of gels 8 2.2.1 LMOG (Low Molecular Weight Organogelator) 9 2.2.2 LMHG (Low Molecular Weight Hydrogelator) 13 2.3 Cholesterol based organogelator 15 2.3.1 ALS organogelators 17 2.3.2 A(LS)2 organogelator) 19 2.3.2.1 Dimeric cholesterol-based A(LS)2 with different relative position on the benzene 19 2.3.2.2 Dimeric cholesterol-based A(LS)2 with different aromatic part 21 2.4 Multi-responsive organogel 26 2.5 Phase-selective gelation and dye adsorption study for water purification 27 2.6 Supramolecular chirality and applications 29 CHAPTER THREE RESEARCH DESIGN AND METHODOLOGY 33 3.1 Materials 33 3.2 Instruments 34 3.3 Synthesis of cholesteryl derivatives 35 3.4 Typical gelation test procedure 38 3.5 SEM and TEM measurement 38 3.6 1H-NMR T-dependence measurement 39 3.7 FTIR measurement 39 3.8 X-ray Diffraction (XRD) measurement 39 3.9 Circular Dichroism (CD) measurement 39 CHAPTER FOUR RESEARCH RESULTS AND DISCUSSION 40 4.1 Synthesis of two cholesteryl derivatives 40 4.1.1 Determination of para and meta structure from 1H-NMR spectra 44 4.2 Gelation behavior of the compounds 44 4.2.1 Molecular dynamics modeling 46 4.3 Morphology study of xerogel and molecular packing 49 4.3.1 1H-NMR Temperature Dependence 58 4.3.2 X-ray Diffraction (XRD) 59 4.3.3 Circular Dichroism (CD) 61 4.3.4 Molecular packing arrangement 61 CHAPTER FIVE CONCLUSION 67 REFERENCES 68

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