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摘要
摘要
近年来,发展新材料和纳米器件的一种重要手段就是通过功能化小分子的自组装形成超分子结构。作为一种新型的自组装材料,有机小分子凝胶通过分子间氢键作用、范德华力、 QUOTE 相互作用等可以形成有序的三维网络结构,从而使适当的有机溶剂凝胶化。本论文设计合成了一种基于偶氮苯基团的有机小分子凝胶因子,并在此基础上详细研究了该凝胶的形貌结构、成胶机理和分子堆积结构。
成功制备出光敏凝胶(BNB-t8),即一种含有偶氮苯基团的新型小分子有机凝胶(LMOG)。该有机凝胶因子表现出良好的凝胶作用,可以在多种有机溶剂中形成临界浓度低达0.5毫克/毫升的稳定的有机凝胶。以DMSO/H2O混合物为溶剂的干凝胶呈现出左手和右手螺旋结构,而以三氯甲烷为溶剂的干凝胶则为直径大约是20 -30纳米的致密纠缠纤维状集合体。此有机结构表明在波长为365纳米的紫外线照射下,光诱导顺反异构化使凝胶向沉淀进行过渡,即由反式的BNB-t8转化成了顺式的BNB- t8。这种BNB- t8凝胶的顺反异构化进一步导致了在超分子水平上从纤维到小囊泡的形态变化。
关键词 偶氮苯;光致变色;有机凝胶;形态转变
Abstract
Abstract
The self-assembling of small functional molecules into supramolecular structures is a powerful approach toward the development of new materials and nanoscale devices. As a novel class of self-assembled materials, Organogels have received considerable attention in recent years because they can organize into regular nanoarchitectures through specific noncovalent interactions including hydrogen bonds, hydrophobic interactions, QUOTE interactions and Van der Waals forces. In this dissertation, one serie of azobenzene moiety contained gelator was designed and synthesized. The morphology, mechanism of the gel formation and the packing fashion in the gel state were studied in details.
A new low molecular mass organic gelator (LMOG) bearing hydrazide and azobenzene groups , namely N-(3,4,5-octanoxyphenyl)-N’-4-[(4-hydroxyphenyl)azophenyl] benzohydrazide (BNB-t8), was designed and synthesized. The organgelator has shown great ability to gel a variety of organic solvents to form stable organogels with the critical gelation concentration as low as 0.5 mg/mL. Both left- and right-hand helical structure were observed in xerogels from DMSO/H2O. Xerogels from chloroform exhibited entangled and dense fibrous aggregates with the diameters of 20-30nm. The organogel showed photoinduced gel-to-precipitate transition under the irradiation by 365 nm UV-light, which was attributed to trans-BNB-t8 to cis-BNB-t8 photoisomerization. The trans-cis isomeriz
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