CAJ | 학술논문

合成3个多氨-多酰氨配体l,12-二(α-羟甲基)苯基)-2,5,8,11-四氮杂十二烷-1,12-二酮(L1),1,13-二((α-羟甲基)苯基)-2,5,9,12-四氮杂十三烷-1,13-二酮(L2),1,15-二(α-羟甲基)苯基)2,5,8,11,14-五氮杂十五烷-1,15-二酮(L3).利用pH滴定分别在5.0℃,15.0℃,25.0℃,35.0℃测定了铜(Ⅱ)与这3种配体在二氧六环/水(V/V,15/85)混合溶剂中配位的稳定常数,得到了热力学参数△Hmθ.和△Smθ.其结果显示了配体的质子化和金属配合物的形成受到焓变化的控制.此外,在25.0℃测定了铜(Ⅱ),配体L和氨基酸(AA)三元配合物的稳定常数,其中L=L1,L2和L3,AA=L-脯氨酸(Pro),L-异亮氨酸(Ile),L-缬氨酸(Val),甘氨酸(Gly),L-丝氨酸(Ser).观察到在三元体系中存在着直线自由能关系(LFER).
합성3개다안-다선안배체l,12-이(α-간갑기)분기)-2,5,8,11-사담잡십이완-1,12-이동(L1),1,13-이((α-간갑기)분기)-2,5,9,12-사담잡십삼완-1,13-이동(L2),1,15-이(α-간갑기)분기)2,5,8,11,14-오담잡십오완-1,15-이동(L3).이용pH적정분별재5.0℃,15.0℃,25.0℃,35.0℃측정료동(Ⅱ)여저3충배체재이양륙배/수(V/V,15/85)혼합용제중배위적은정상수,득도료열역학삼수△Hmθ.화△Smθ.기결과현시료배체적질자화화금속배합물적형성수도함변화적공제.차외,재25.0℃측정료동(Ⅱ),배체L화안기산(AA)삼원배합물적은정상수,기중L=L1,L2화L3,AA=L-포안산(Pro),L-이량안산(Ile),L-힐안산(Val),감안산(Gly),L-사안산(Ser).관찰도재삼원체계중존재착직선자유능관계(LFER).
Three polyamino-polyamide ligands 1,12-bis((α-hydroxylmethyl)phenyl)-2,5,8,11-tetraazadodecane-1,12-dione(L1), 1,13-bis ((α-hydroxylmethyl)phenyl)-2,5,9,12-tetraazatridecane- 1,13- dione (L2), 1,15-bis ((α-hydroxylmethyl)phenyl)-2,5,8,11,14-pentaazapentadecane-1,15-dione (L3) have been synthesized. The stability constants of complexation of Cu(Ⅱ) with these three ligands in dioxane/water (V/V, 15/85) mixed solvent have been determined by pH titrations at 5.0 ℃, 15.0 ℃, 25.0 ℃ and 35.0 ℃ respectively. The thermodynamic parameters △Hmθ. and △Smθ. were obtained. The result shows that both the protonation of the ligands and the formation of metal complexes are controlled by the change of enthalpy. In addition, the stability constants of ternary complexes of Cu(Ⅱ), L and α-amino-acid (AA) have been determined at 25.0 ℃, where L = L1, L2 and L3, AA = L-proline (Pro), L-isoleucine (Ile), L-valine (Val), glycine (Gly), L-serine (Ser), respectively. It is observed that linear free energy relationship (LFER) exists in the ternary systems.