Gubarev Alexander S, Lezov Alexey A, Mikusheva Nina G, Perevyazko Igor, Senchukova Anna S, Lezova Alexandra A, Podsevalnikova Anna N, Rogozhin Vyacheslav B, Enke Marcel, Winter Andreas, Schubert Ulrich S, Tsvetkov Nikolai V
Department of Molecular Biophysics and Polymer Physics, St. Petersburg University, Universitetskaya Nab. 7/9, 199034 Saint-Petersburg, Russia.
Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany.
Polymers (Basel). 2022 Apr 27;14(9):1776. doi: 10.3390/polym14091776.
Nowadays, the study of metallopolymers is one of the fastest growing areas of polymer science. Metallopolymers have great potential for application in multiple technological and various biomedical processes. The macromolecules with the possibility of varying the number and type of metal ions along the entire length of the polymer chain are of particular interest. In this regard, this study presents results on two successfully synthesized homopolymers, random and block copolymers based on PMMA, containing ferrocene and terpyridine moieties in the side chain. Different architectures of copolymers may attribute interesting properties when creating complexes with various metal ions. A detailed hydrodynamic study of these structures was carried out, the consistency of hydrodynamic data was established using the concept of a hydrodynamic invariant, the absolute values of the molar masses of the studied objects were calculated, and the conformational parameters of macromolecules were determined. Using the Fixman-Stockmayer theory, the equilibrium rigidities of the studied systems were calculated and the relationship between the chemical structure and conformational characteristics was established. The studied copolymers can be attributed to the class of flexible-chain macromolecules. An increase in the equilibrium rigidity value with an increase of the side chain, which is characteristic of comb-shaped polymers, was determined.
如今，金属聚合物的研究是聚合物科学中发展最快的领域之一。金属聚合物在多种技术和各种生物医学过程中具有巨大的应用潜力。沿着聚合物链的整个长度改变金属离子数量和类型的大分子尤其令人感兴趣。在这方面，本研究展示了两种成功合成的均聚物、基于聚甲基丙烯酸甲酯（PMMA）的无规共聚物和嵌段共聚物的研究结果，这些聚合物在侧链中含有二茂铁和三联吡啶部分。当与各种金属离子形成配合物时，共聚物的不同结构可能赋予其有趣的性质。对这些结构进行了详细的流体动力学研究，利用流体动力学不变量的概念确定了流体动力学数据的一致性，计算了所研究对象的摩尔质量绝对值，并确定了大分子的构象参数。利用菲克斯曼 - 斯托克迈耶理论，计算了所研究体系的平衡刚性，并建立了化学结构与构象特征之间的关系。所研究的共聚物可归类为柔性链大分子。确定了平衡刚性值随侧链增加而增加，这是梳状聚合物的特征。
