Title: 對二價銅離子具專一選擇性的芘-甲酯之螢光化學劑量器
Pyren-1-ylmethyl acetate as a Cu2+ Selective Fluorescent Chemodosimeter
Authors: 黃毓玲
Huang, Yu-Ling
鍾文聖
Chung, Wen-Sheng
理學院應用科技學程
Keywords: 芘、脂基、二價銅、化學劑量器;Pyrene,Ester,Copper(II),Chemodosimeter
Issue Date: 2011
Abstract: 第一部份的研究中,合成出含芘甲酯控制化合物34及下緣修飾芘甲酯單取代芳杯35及雙取代芳杯36。上述三個化合物於乙腈中與17種過氯酸鹽金屬離子混合,從螢光光譜發現化合物34只會與二價銅離子產生芘之激態雙體,而化合物35只顯示芘之單體螢光放射,且二價銅離子造成其螢光淬熄;另外除了二價銅離子會造成化合物36螢光淬熄外, Pb2+、Cr3+及Fe2+也有相同的螢光淬熄效果,因此我們沒有對化合物35及36進行詳細探討。
我們也發現雖然芘甲酯衍生物34、41及45的螢光光譜對於二價銅離子有高選擇性,但是卻無法從它們的螢光變化之Job Plots得到錯合比例。化合物34及化合物45只有過氯酸銅的乙腈溶液條件下,才會有激態雙體的放射,在甲醇及乙腈:甲醇 (1:1) 的混溶劑及不同鹽類的條件下不會有螢光雙體之放射。控制化合物34 (1 mM) 在常溫下加入Cu2+離子 (10 mM),48小時之後我們可以經由管柱層析純化得到產物40及46;化合物45加入Cu2+離子後經由管柱分離也可得到化合物40。由此確認芘甲酯控制化合物34及45在乙腈中,可以與二價銅離子發生化學反應。
第二部分的研究主要在於探討醯胺-硼酯-芳杯衍生物之合成。我們成功的合成出芳杯下緣單醯胺基-硼酯取代37、雙醯胺基-硼酯取代38,及芳杯上緣雙丙烯基下緣修飾雙醯胺基-硼酯取代化合物39。
In the first part, pyrenylmethyl acetate control compound 34 and its derivatives of calix[4]arenes at the lower-rim with mono- (35) and distal-disubstituted pendants (36). These three compounds were dissolved in acetonitrile and screened with 17 different metal perchlorates using fluorescence spectroscopy. Compound 34 only showed excimer emission in the presence of Cu2+ but not by other metal ions. In contrast, compound 35 showed only monomer (no excimer) emission of the pyrenylmethyl group and its emission was quenched by Cu2+. Furthermore, the monomer emission of compound 36 was quenched by Cu2+, Pb2+, Cr3+, and Fe2+. Since compounds 35 and 36 did not show specific recognition to metal ions, we did not do further studies on them.
Although pyrenylmethyl derivatives 34, 41, and 45 showed specific responses toward Cu2+, we were unable to determine their binding ratios from their Job plots. Compounds 34 and 45 will show excimer emissions only in the presence of both Cu2+ and in acetonitrile solution; they will not show excimer emission in methanol or acetonitrile/methanol (v/v, 1:1) cosolvent, neither would they show excimer emission in the presence of other metal ions. When compound 34 (1 mM) was treated with Cu2+ (10 mM ) for 48 h, we were able to isolate two products 40 and 46 from the reaction mixture; similarly, product 40 was isolated from the reaction mixture of 45 with Cu2+. These results confirmed that the pyrenylmethyl derivatives 34 and 45 could react with Cu2+ in acetonitrile solution.
The second part of the thesis was to develop synthetic methods for the synthesis of amido-boronic ester-calixarene derivatives. We were able to synthesize lower-rim mono- and bis-amido-boronic ester-calixarene derivatives 37 and 38 and compound 39 where the upper-rim of 38 was further modified with 5,17-bis-ally groups.
URI: http://140.113.39.130/cdrfb3/record/nctu/#GT079873615
http://hdl.handle.net/11536/48798
Appears in Collections:Thesis