臺灣博碩士論文加值系統

本報告首先合成三個直鏈型DTPA-雙醯胺衍生物包括兩種DTPA-bis(N,N-dialkylamide)及一種DTPA-bis(N-monoalkylamide)，即DTPA-BDMA(diethylenetriamine-N,N￠,N2-triacetic-N,N2-bis(dimethyl amide))，DTPA-BDEA (diethylenetriamine - N, N￠, N2-triacetic-N,N2-bis (diethyl amide))及DTPA-BAA(diethylenetriamine-N,N￠,N2-triacetic- N,N2-bis(adamantanamide))與EDTA-雙醯胺衍生物，EDTA-BIPA (ethylenediamine-N,N￠-diacetic-N,N￠-bis(iso-propylamide))及EDTA-BTBA(ethylenediamine-N,N￠-diacetic- N,N￠-bis(tert-butylamide))等有機配位子。在熱力學性質方面，有機配位子之質子化常數乃利用電位滴定法0.10 mol dm-3 Me4NNO3(KCl)求得，同時亦利用NMR-pH滴定法及f值計算確認配位子被質子化的位置及百分率。配位子與釓(III)，鋅(II)，鈣(II)及銅(II)等金屬離子形成金屬錯合物之穩定常數亦由電位滴定法獲得。結果顯示釓金屬錯合物穩定常數大於銅，鋅及鈣。另外配位子之釓金屬錯合物分別與鋅、鈣及銅等金屬離子所形成之金屬錯合物之選擇常數及修飾化選擇常數亦被討論之，利用17O-NMR，求得[Dy(DTPA-BDMA)]與[Dy(DTPA-BDEA)]錯合物各含1.16與1.13個內層水分子，而[Dy(EDTA-BIPA)]+與[Dy(EDTA-BTBA)]+則個含2.42及2.40個內層水分子。另外，在37.0 ± 0.1℃，20 MHz的磁場條件下，研究不同pH值對釓金屬錯合物的自旋-晶格弛緩率(spin-lattice relaxivity，R1)之影響。結果顯示，[Gd(DTPA-BDMA)]，[Gd(DTPA-BDEA)]與[Gd(DTPA-BAA)]的R1值近似或高於DTPA釓金屬錯合物，其理由是具有相同之內層水分子數目及分子量的差異。最後，研究探討改變溫度對R1值的影響，結果發現，R1值隨著溫度改變而呈指數關係下降，換言之[Gd(DTPA-BDMA)]與[Gd(DTPA-BDEA)]其內層弛緩機制為內層水分子與外層水分子間為快速交換。

Two bis(N,N-dialkylamide) derivatives of DTPA (diethylene triamine-N,N,N￠,N2,N2-pentaacetic acid], DTPA-BDMA = the bis (N,N-dimethylamide) and DTPA-BDEA = the bis (N,N-diethylamide), one dis(amide) derivatives of DTPA (diethylene triamine-N,N,N￠,N2,N2-pentaacetic acid], DTPA-BAA = the bis(adamataamide) and two bis (amide) derivatives of EDTA (ethylenediamine-N,N￠-tetraacetic acid), EDTA-BIPA = the bis (iso-propylamide) and EDTA-BTBA = the bis (tert-butylamide) were synthesized. Their protonation constants were determined by potentiometic titration with 0.10 mol dm-3 Me4NNO3(KCl) and by NMR pH titration at 25.0 ± 0.1°C. The stability constants of the complexes of calcium(II), copper(II), zinc(II) and gadolinium(III) were determined by potentiometic titration. The solution 1H-NMR shift was measured for the complexes of Lu3+, Y3+ and Zn2+with EDTA-BIPA. These complexes are hexadentate, possibly of octahedral geometry and various structure isomers. 17O-NMR shifts showed that the inner sphere water of [Dy(DTPA-BDMA)]、[Dy(DTPA-BDEA)]、[Dy(EDTA-BIPA)]+ and [Dy(EDTA-BTBA)]+ are 1.16, 1.13, 2.40 and 2.42 respectively. Spin-lattice relaxivity R1(20MHz, 37.0± 0.1°C) for Gd(III) complexes was also determined at different pH range. Finally, the influence of R1 values at different temperature range was also investigated. A mono exponential decrease of the observed relaxivity upon increaseing the temperature in the range 20-70°C was found. This is characteristic of the first chemical exchange behavior which occurs when the residence lifetime of the co-ordinated water molecular is much shorter than the relaxstion time of the bond water proton.

圖目錄ii
表目錄vii
中文摘要viii
英文摘要x
一、 前言1
二、 儀器及試藥28
三、 實驗方法31
四、 結果與討論42
五、 結論93
六、 參考文獻94
附錄99

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