pH-Responsive Gelation in Metallo-Supramolecular Polymers Based on the Protic Pyridinedicarboxamide Ligand
نویسندگان
چکیده
Pyridinedicarboxamide (PDCA) ligands have been widely integrated into different polymer chemistries and provided promising self-healing properties in bulk upon adding specific metal ions. However, their application the development of synthetic hydrogels is limited due to lack clear kinetics thermodynamic data. To fill this gap, we study dynamics formed by condensation linear poly(ethylene glycol) (PEG) precursors PDCA ligand, followed complexation with ions at various pH values. Rheological studies reveal an unprecedented ability Co2+/3+ Ni2+ elevated values, but contrast former reports, not Fe3+ Zn2+. Moreover, gels demonstrate lower equilibrium constants resulting faster more efficient compared those made Ni2+. Spectroscopic UV Fourier transform infrared (FTIR) also suggest structural modifications presence gel-forming others. explain these results, employ static periodic density functional theory (DFT) simulations. Static DFT indeed reveals that binding interaction clearly stronger for Co Ni, Fe shows poorest values far. The most stable complex geometry octahedral, which central pyridyl, one lateral deprotonated amide, carbonyl participate coordination. calculations unveil overstabilization effect noncovalent interactions between PEG segments, results torsion formation a helicoidal-like structure.
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ژورنال
عنوان ژورنال: Chemistry of Materials
سال: 2022
ISSN: ['1520-5002', '0897-4756']
DOI: https://doi.org/10.1021/acs.chemmater.2c01346