School of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Sichuan, Zigong 643000, PR China.
School of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Sichuan, Zigong 643000, PR China.
J Colloid Interface Sci. 2022 Dec;627:459-468. doi: 10.1016/j.jcis.2022.07.023. Epub 2022 Jul 14.
Four novel long chain-containing tridentate imidazole derivatives (L, n = 1, 2, 3, 4) were synthesized for in situ formation of mononuclear lanthanum(III) complexes as artificial phosphodiesterases. These in-situ formed La(III) complexes (named LaL) were used to catalyze the transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP), a classic RNA model. Critical aggregation concentrations (CAC) were determined for the as-prepared tridentate imidazole derivatives as ligands and corresponding mixtures of equivalent ligand and La ion with a mole rate of 1:1. It denotes that the introduction of La ion increases the CAC values of imidazole derivatives by about 2 to 3 folds. Foaming test shows that the foam height is positively correlated with the length of hydrophobic chain. Transesterification of HPNP mediated by LaL nanoarchitectonics indicates that the introducing of hydrophobic chain benefits rate enhancement, showing excess three orders of magnitude acceleration under physiological conditions (pH 7.0, 25 °C). Moreover, catalytic reactivities of these La(III) complexes increased along with the increase in chain length: LaL < LaL < LaL < LaL, suggesting a positive correlation to hydrophobic chain length.
四种新型长链含三齿咪唑衍生物（L，n=1,2,3,4）被合成用于原位形成单核镧（III）配合物作为人工磷酸二酯酶。这些原位形成的 La(III)配合物（命名为 LaL）被用于催化 2-羟丙基对硝基苯磷酸酯（HPNP）的酯交换反应，HPNP 是一种经典的 RNA 模型。通过预制备的三齿咪唑衍生物作为配体和相应的 La 离子与配体摩尔比为 1:1 的混合物，确定了临界聚集浓度（CAC）。结果表明，La 离子的引入使咪唑衍生物的 CAC 值增加了约 2 到 3 倍。泡沫试验表明，泡沫高度与疏水性链的长度呈正相关。LaL 纳米结构介导的 HPNP 酯交换反应表明，引入疏水性链有利于提高反应速率，在生理条件下（pH 7.0，25°C）表现出超过三个数量级的加速。此外，这些 La(III)配合物的催化反应活性随着链长的增加而增加：LaL<LaL<LaL<LaL，表明与疏水性链长呈正相关。
