Department of Earth, Life and Environment Sciences, University of Urbino, Località Crocicchia, 61029 Urbino, Italy.
Phys Chem Chem Phys. 2014 Jan 14;16(2):685-94. doi: 10.1039/c3cp54005g.
The structure of copper(II) complexes formed with triethanolamine (TEA) core poly(amidoamine) (PAMAM) dendrimers from generation 0 (G0) to 4 (G4) were investigated by the electron paramagnetic resonance (EPR) technique and molecular simulations. Different square planar coordination modes were detected as a function of copper(II) concentration, whose dynamic evolution relates to the high structural flexibility peculiar to this dendrimer family. Modulated by generation and solvation effects, copper(II) complexation begins at the dendrimer core and progresses to the dendrimer periphery. Differently from the ethylenediamine (EDA) core PAMAM dendrimers, the copper complexes involving the TEA core showed high mobility and saturation of the internal sites above the 1 : 1 molar ratio between the dendrimers and the ions. Therefore, by combining EPR and molecular simulations for the first time, ultimately we obtained unique information on structure, dynamics and copper interacting ability of these dendrimers which could be successfully exploited in biomedical applications.
采用电子顺磁共振（EPR）技术和分子模拟研究了从第 0 代（G0）到第 4 代（G4）的三乙醇胺（TEA）核聚酰胺-胺（PAMAM）树枝状大分子形成的铜（II）配合物的结构。检测到不同的正方形平面配位模式，作为铜（II）浓度的函数，其动态演变与这种树枝状大分子家族的高结构灵活性有关。受代和溶剂化效应的调节，铜（II）配合物从树枝状大分子核心开始，并向树枝状大分子外围发展。与乙二胺（EDA）核 PAMAM 树枝状大分子不同，涉及 TEA 核的铜配合物在树枝状大分子与离子之间的摩尔比为 1 ：1 以上时表现出高迁移率和内部位的饱和。因此，通过首次将 EPR 和分子模拟相结合，我们最终获得了有关这些树枝状大分子的结构、动力学和与铜相互作用能力的独特信息，这些信息可成功地应用于生物医学应用。
