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dc.contributor.author陳映蓉en_US
dc.contributor.authorChen, Ying-Jungen_US
dc.contributor.author鍾文聖en_US
dc.contributor.authorChung, Wen-Shengen_US
dc.date.accessioned2014-12-12T01:49:56Z-
dc.date.available2014-12-12T01:49:56Z-
dc.date.issued2010en_US
dc.identifier.urihttp://140.113.39.130/cdrfb3/record/nctu/#GT079825530en_US
dc.identifier.urihttp://hdl.handle.net/11536/47619-
dc.description.abstract  本論文成功利用1,3-偶極環化加成方法,在芳杯下緣引入1,2,4-噁二唑蒽基團,成功的合成出針對Fe3+具有高選擇性之螢光化學劑量器45-49。此外,也合成控制化合物50與異咢唑51化合物作為對照組。藉由45與控制化合物50的X-ray單晶繞射可以確認1,2,4-噁二唑蒽基化合物之構造。   由紫外可見光譜與螢光光譜初步篩選實驗可得知,在乙腈溶劑系統下,1,2,4-噁二唑蒽基芳杯化合物45-49、控制化合物50與異咢唑51皆對Fe3+有高度選擇性,具很強的螢光淬熄效果。此外,當加入金屬氧化劑Cu2+,化合物45-47芳杯下緣之羥基亦會被氧化而產生螢光淬熄現象;而化合物48-49、控制化合物50及異咢唑51則僅針對Fe3+有專一性之螢光淬熄現象,且其吸收光譜波形明顯改變。   氫核磁共振滴定光譜實驗數據顯示,化合物46、49與50-51隨著Fe3+的當量逐漸增加,其氫訊號明顯改變,且蒽官能基上的H10訊號消失;藉由Fe2+指示劑我們可以得知含有蒽基噁二唑與異咢唑取代之衍生物與Fe3+在乙腈溶劑下會進行氧化還原反應,而得到Fe2+與其氧化產物。即是當45-51加入Fe3+後,其化學劑量感測模式是藉由Fe3+之氧化力誘使1,2,4-噁二唑蒽基、異咢唑蒽基與芳杯下緣羥基發生氧化反應。   我們藉由合成方式將控制化合物50加入10當量的Fe3+進行氧化還原反應,可單離出氧化產物X1,經由紅外線光譜與碳核磁共振光譜實驗可證實,氧化產物X1其蒽基之C10位置被氧化成羰基,並利用EI-MASS實驗光譜推測可能結構。此外,控制化合物50與Fe3+進行氧化還原反應而得到之副產物63與64也經由X-ray單晶繞射分析鍵定其結構。   將芳杯46加入不同當量的Fe3+進行氧化還原反應,而得到並單離出氧化產物X1與X2-X4,經由紅外線光譜與碳核磁共振光譜實驗可知,氧化產物X3與X4其蒽基之C10位置被氧化成羰基;推測X2為芳杯下緣羥基與Fe3+進行氧化還原反應,所得芳杯上下緣皆被氧化成羰基 (亦即形成對苯醌),而下緣兩個1,2,4-噁二唑蒽基團仍存在之對稱芳杯結構之產物。zh_TW
dc.description.abstract  We report here the design and synthesis of a series of highly selective fluorescent chemodosimeters 45-49 for Fe3+, where 1,2,4-oxadiazoles were introduced to the lower-rim of calix[4]arene by using 1,3-dipolar cycloaddtion of aryl nitrile oxides with nitrile groups. Control compound 50 and isoxazole 51 were also synthesized for comparison. Structures of anthryl-1,2,4-oxadiazolyl cailx[4]arenes 45 and 50 were confirmed by X-ray diffraction analysis.   Anthryl-1,2,4-oxadiazole substituted calix[4]arenes 45-49 all showed a high selectivity and strong fluorescence quenching toward Fe3+ among 17 other metal perchlorate salts in CH3CN. Moreover, in the presence of Cu2+, the metal based oxidant, phenolic-OH of calix[4]arenes 45-47 were oxidized and their fluorescence was turned off.   Results from the 1H NMR titration of 46, 50 and 51 showed that all proton signals were significantly shifted and the anthryl-H10 signal disappeared. Because Fe2+ could be easily detected by ferrozine, the irreversible chemical reaction between anthryl-1,2,4-oxadiazole group and Fe3+ was confirmed to be a redox reaction.   The oxidation of the control compounds 50 led to the formation of products X1, where the anthryl-C10 was found to be oxidized into a carbonyl group. Based on X1 molecular ion from Mass we propose the possible structures of the unknown X1. Two other by-products 63 and 64, resulting from the oxidation of the control compound 50, were confirmed by single crystal X-ray analysis.   Upon addition of different amounts of Fe3+, the oxidation of lower- rim bis-anthryl-1,2,4-oxadiazoly calix[4]arene 46 led to the formation of products X2-X4. From 1H, 13C NMR, and IR spectra of X3-X4, we found that the anthryl-C10 was oxidized into carbonyl group (C=O). Moreover, the lower rim phenol of calix[4]arene was oxidized into carbonyl group (C=O) which formed the oxidation product X2.en_US
dc.language.isozh_TWen_US
dc.subject1,2,4-噁二唑zh_TW
dc.subject芳杯zh_TW
dc.subject螢光化學劑量器zh_TW
dc.subject1,3-偶極環化加成zh_TW
dc.subject1,2,4-oxadiazoleen_US
dc.subjectcalix[4]arenesen_US
dc.subjectFluorescent Chemodosimetersen_US
dc.subject1,3-dipolar cycloaddtionen_US
dc.title含蒽基噁二唑之芳杯衍生物作為對鐵 (III) 離子具高選擇性之螢光化學劑量器zh_TW
dc.titleAnthryl-1,2,4-oxadiazole Substituted Calix[4]arenes as Highly Selective Fluorescent Chemodosimeters for Fe3+ Ionen_US
dc.typeThesisen_US
dc.contributor.department應用化學系碩博士班zh_TW
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