Kovács Attila, Varga Zoltán
European Commission, Joint Research Centre (JRC), 76125 Karlsruhe, Germany.
Department of Chemistry, Chemical Theory Center, Minnesota Supercomputer Institute, University of Minnesota, Minneapolis, MN 55455, USA.
Molecules. 2024 Sep 4;29(17):4198. doi: 10.3390/molecules29174198.
The Pb and Pb lead radioisotopes are attracting growing interest as they can aid in the development of personalized, targeted radionuclide treatment for advanced and currently untreatable cancers. In the present study, the bonding interactions of Pb with twelve macrocyclic ligands, having an octa and nona coordination, were assessed using Density Functional Theory (DFT) calculations. The molecular structures in an aqueous solution were computed utilizing the polarized continuum model. The preference for the twisted square antiprismatic (TSAP) structure was confirmed for ten out of the eleven cyclen-based complexes. The characteristics of the bonding were assessed using a Natural Energy Decomposition Analysis (NEDA). The analysis revealed a strong electrostatic character of the bonding in the complexes, with minor variations in electrical terms. The charge transfer (CT) had a comparable energetic contribution only in the case of neutral ligands, while in general, it showed notable variations regarding the various donor groups. Our data confirmed the general superiority of the carboxylate O and aromatic N donors. The combination of the selected efficient pendant arms pointed out the superiority of the acetate pendant arms and the lack of significant cooperation between the different pendant arms in the probed ligands. Altogether, the combination led only to a marginal enhancement in the total CTs in the complexes.
铅和铅的放射性同位素正吸引着越来越多的关注，因为它们有助于开发针对晚期及目前无法治疗的癌症的个性化、靶向放射性核素治疗方法。在本研究中，使用密度泛函理论（DFT）计算评估了铅与十二个具有八配位和九配位的大环配体的键合相互作用。利用极化连续介质模型计算了水溶液中的分子结构。在十一种基于环糊精的配合物中，有十种证实了对扭曲四方反棱柱（TSAP）结构的偏好。使用自然能量分解分析（NEDA）评估了键合的特征。分析表明配合物中键合具有很强的静电性质，电学方面的变化较小。仅在中性配体的情况下，电荷转移（CT）具有相当的能量贡献，而总体而言，它在各种供体基团方面表现出显著差异。我们的数据证实了羧酸根氧供体和芳香氮供体的总体优势。所选有效侧链臂的组合指出了乙酸酯侧链臂的优势以及所研究配体中不同侧链臂之间缺乏显著协同作用。总之，这种组合仅导致配合物中总电荷转移略有增强。
