- 學位論文
TTDA-NP，TTDA-TMBS及 TTDA-TIPBS配位子之合成及TTDA-NP 釓金屬錯合物、物化特性研究
Synthesis of TTDA-NP, TTDA-TMBS and TTDA-TIPBS and Physicochemical Characterization of the TTDA-NP Complex with Gadolinium (III) Ion
摘要
本研究主要合成TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triaza-do decanedioic acid)衍生物，2,3,5,6-tetramethylbenenylsulfonyl-methyl -3,6,10-tris(methoxycarbonyl)-3,6,10-triazado-decanedioic acid (TTDA-TMBS) 2,4,6-triisopropylbenenylsulfonyl-3,6,10-tris(methoxy -carbonyl)-3,6,10-triazado-decanedioic acid(TTDA-TIPBS)及2-methyl -4-nitrophenol-3,6,10-tris(methoxycarbonyl)-3,6,10-triazado-decane dioic acid (TTDA-NP)。質子化常數方面，TTDA-NP 的ΣpKa為29.98，較TTDA (ΣpKa = 27.44)與DTPA(pKa = 26.01)高，而[Gd(TTDA-NP)]2?{之穩定常數 (pKa ＝ 22.89)，高於[Gd(TTDA)]2?{ ?n(pKa ＝ 18.96)，與[Gd(DTPA)]2?{ (pKa ＝ 22.46) 類似。利用螢光光譜儀測定[Eu(TTDA-NP)]2?{錯合物，求出其內層水分子數(q)分別為0.92及075。釓金屬錯合物的弛緩率(r1)受到內層水分子的存在時間(?鄝)及分子轉動相關時間(?酺)的影響。利用400 MHz核磁共振光譜儀，測定釓金屬錯合物的17O弛緩率(1/T1, 1/T2)、化學位移(??)及酸水的17O弛緩率(1/T1A, 1/T2A)和化學位移(?膕)。研究結果顯示[Gd(TTDA-NP)]2?{的水交換速率較[Gd(DTPA)]2?{快，且與[Gd(TTDA)]2?{相近。另外， [Gd(TTDA-NP)]2?{之分子轉動時間(?酺)為145ps，大於[Gd(DTPA)]2?{ (?酺 = 103 ps)及[Gd(TTDA)]2?{ (?酺 = 104 ps)。
並列摘要
The derivative of TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triaza-do decane dioicacid),2,3,5,6-tetramethylbenenylsulfonylmethyl-3,6,10 -tris(methoxycarbonyl)-3,6,10-triazadodecane- dioic acid (TTDA-TMBS) , 2,4,6-triisopropyl-benenylsulfonyl-3,6,10-tris(methoxycarbonyl)-3,6,10 -triazado -decanedioic acid(TTDA-TIPBS) and 2-methyl-4-nitrophenol -3,6,10-tris(methoxycarbonyl) -3,6,10 -triazado -decanedioic acid (TTDA-NP) were designed, synthesized and characterized. Protonation Constants of TTDA-NP(pKa ＝ 29.98) are significantly higher than those of TTDA (pKa ＝ 27.44) and DTPA (pKa ＝ 26.01). Stability Constants of TTDA-NP (pKa ＝ 22.89) are significantly higher than those of TTDA (pKa ＝ 18.96) and similar with DTPA (pKa ＝ 22.46). The number of inner-sphere water (q ≈ 1) of [Eu(TTDA-NP)]2?{ was obtained by chemical-luminescence method. 17O NMR longitudinal and transverse relaxation rates and chemical shifts of aqueous solutions of [Gd(TTDA-NP)]2?{ were measured at variable temperature with 400MHz NMR. The water exchange rate (kex298) value for [Gd(TTDANP)]2?{ (110 ?e 106 s?{1) is significantly higher than those of [Gd(DTPA)]2?{ (4.1 ?e 106 s?{1) and similar with [Gd(TTDA)]2?{?n(131 ?e 106 s?{1). The rotational correlation time (τR) value for [Gd(TTDA-NP)]2?{ (145 ps) is higher than those of [Gd(DTPA)]2?{ (103 ps) and [Gd(TTDA)]2?{ (104 ps).