Gregorić Tomislav, Makarević Janja, Štefanić Zoran, Žinić Mladen, Frkanec Leo
Laboratory of Supramolecular Chemistry, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, 10000 Zagreb, Croatia.
Laboratory for Chemical and Biological Crystallography, Division of Physical Chemistry, Ruđer Bošković Institute, 10000 Zagreb, Croatia.
Polymers (Basel). 2022 Jan 5;14(1):214. doi: 10.3390/polym14010214.
Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide ( and ) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators' self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide ( and ) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative was determined.
通过外部刺激来控制超分子自组装的聚合反应，对于响应性软材料的开发以及纳米级别的操控具有巨大潜力。已发现双（亮氨酸或缬氨酸）富马酰胺的乙烯基酯（和）是多种有机溶剂的凝胶剂，并将其应用于本研究中，以考察有机凝胶剂的自组装对γ射线和紫外线辐射诱导的固态聚合反应的影响。在此，我们报告了对双（氨基酸乙烯基酯）富马酰胺的自组装对γ射线和紫外线诱导的聚合反应影响的研究。凝胶剂分子通过非共价相互作用自组装，主要是通过酰胺基（CONH）和羧基（COO）之间的氢键，从而形成凝胶网络。利用核磁共振（NMR）和傅里叶变换红外光谱（FTIR）来研究和表征超分子凝胶。使用透射电子显微镜（TEM）和扫描电子显微镜（SEM）来研究凝胶和聚合物的形态。形态学研究表明，凝胶包含纳米尺寸的丝状结构，该结构在三维网络中是详尽无遗的。所制备的衍生物含有适合在所选凝胶的超分子聚集体中进行由γ射线或紫外线辐射引发的聚合反应的反应性烷基。发现聚合反应仅在凝胶网络中发生，并且取决于聚集体的结构或凝胶网络中双键的接近程度和取向。通过将凝胶暴露于甲苯中的γ射线和紫外线辐射，以及将水/二甲基甲酰胺（DMF）凝胶的凝胶结构转录为聚合物，从而形成聚合物。该聚合材料能够通过溶胀固定各种溶剂。此外，合成了双（亮氨酸和缬氨酸）富马酰胺的甲酯（和）；这些化合物不显示凝胶化性质，并且测定了缬氨酸衍生物的晶体结构。
