萘基尿素芳杯衍生物之合成及其離子感測之研究

Abstract

本論文研究的方向有兩部分，分別在芳杯下緣進行萘基尿素基團或萘基硫化尿素基團雙取代的衍生物46-49之合成及其感測研究。 首先，合成出含有萘基尿素基團的芳杯化合物46與47，然後加入不同的金屬陽離子及陰離子進行篩選。由螢光光譜的結果顯示化合物47對F- (Ks = 1.7 x 104 M-1)、Cr3+ (Ks = 4.1 x 104 M-1) 和Cu2+ (Ks = 4.3 x 104 M-1) 具有不錯的錯合能力。而當化合物47加入Ca2+時會使得在358 nm的螢光強度增強而在384 nm的螢光強度下降。經由氫核磁共振光譜滴定實驗得知化合物47可能利用尿素基團羰基上的氧與Ca2+錯合。 其次，發現具有萘基硫化尿素基團的芳杯化合物48與49為Hg2+的化學劑量器。

This thesis reports the syntheses and the binding studies of the two-armed calix[4]arene derivatives 46-49 containing naphthylurea and naphthylthiourea groups. Firstly, naphthylurea calix[4]arenas 46 and 47 were synthesized and then metal ions and anions were added for screening. From fluorescence quenching data, 47 was sensitive to F- (Ks = 1.7 x 104 M-1), Cr3+ (Ks = 1.7 x 104 M-1), Cu2+ (Ks = 1.7 x 104 M-1). When Ca2+ was added to the solution of 47, the emission intensity at 358 nm was enhanced with a concomitant decrease in emission intensity at 384 nm. The 1H-NMR spectroscopy revealed that the compound 47 was binding to Ca2+ through the carbonyl oxygen of urea groups. Secondly, naphthylthiourea calix[4]arenes 48 and 49 were found to be extremely selective toward Hg2+ as chemodosimeters.