Bioinspired Mechanically Responsive Hydrogel upon Redox Mediated by Dynamic Coordination between Telluroether and Platinum Ions

Abstract

Inspired by natural lives, materials with switchable mechanical properties have been constructed by virtue of the development of dynamic chemistry. However, the limited dynamic reactions are hampering their further development. The progress in organotellurium chemistry brings opportunity to open new frontiers of dynamic reactions for fabrication of mechanically responsive materials. Herein, a bioinspired mechanically responsive hydrogel upon redox mediated by dynamic coordination between telluroether and platinum ions is reported. The low electronegativity and superior σ electron-donating capability of telluroether facilitate its coordination with Pt ions. Remarkably, the coordination interaction is highly redox-active. Telluroether can dissociate from Pt ions upon oxidation (e.g., H 2 O 2 ) because the effect of the polar solvent dramatically reduces the thermodynamic activity of oxidized telluroether. In turn, the coordination interaction is easily regenerated via reduction (e.g., vitamin C) of oxidized telluroether. When the coordination system is introduced into the polymer network of a hydrogel via copolymerization of telluroether containing a monomer and Nhydroxyethylacrylamide, the hydrogel exhibits a switchable and regulatable microporous structure and mechanical strength upon redox stimuli by virtue of the dynamic coordination interaction between telluroether and Pt ions. This work provides a new set of dynamic coordination chemistry and a new strategy to prepare mechanically responsive hydrogel.

Supramolecular Self‐Assembled DNA Nanosystem for Synergistic Chemical and Gene Regulations on Cancer Cells

“…To explore the coordination capability of TeEG 2 with Mn II , the 1 H NMR spectra of the mixtures of TeEG 2 and Mn II in methanol‐D4 were collected (Figure S2). When the molar ratio of Mn II to TeEG 2 was increased from 1/8 to 1, the signal peak of Te gradually down‐shifted from ppm 2.55–2.65 to ppm 2.75–2.90, and a total shift was observed when the molar ratio increased to 1:1, verifying the coordination interaction of TeEG 2 with Mn II [14] . X‐ray photoelectron spectroscopy (XPS) analysis also demonstrated that, in the presence of Mn II (stoichiometry ratio of TeEG 2 to Mn II was set as 2:1), the binding energy of most Te3d in TeEG 2 up‐shifted from 584.17 eV and 573.84 eV to 585.96 eV and 575.48 eV, respectively; meanwhile, binding energy of most Mn2p down‐shifted from 654.10 eV and 642.03 eV to 653.32 eV and 641.38 eV, respectively, revealing the coordination interaction of TeEG 2 with Mn II (Figure S3A and Figure S3B).…”

Supramolecular Self‐Assembled DNA Nanosystem for Synergistic Chemical and Gene Regulations on Cancer Cells

“…When the molar ratio of Mn II to Te EG 2 was increased from 1/8 to 1, the signal peak of Te gradually downshifted from ppm 2.55-2.65 to ppm 2.75-2.90, and atotal shift was observed when the molar ratio increased to 1:1, verifying the coordination interaction of TeEG 2 with Mn II . [14] X-ray photoelectron spectroscopy (XPS) analysis also demonstrated that, in the presence of Mn II (stoichiometry ratio of TeEG 2 to Mn II was set as 2:1), the binding energy of most Te 3d in Te EG 2 up-shifted from 584.17 eV and 573.84 eV to 585.96 eV and 575.48 eV,r espectively;m eanwhile,b inding energy of most Mn2p down-shifted from 654.10 eV and 642.03 eV to 653.32 eV and 641.38 eV,r espectively,r evealing the coordination interaction of Te EG 2 with Mn II (Figure S3A and Figure S3B).…”

Smart and Functionalized Development of Nucleic Acid‐Based Hydrogels: Assembly Strategies, Recent Advances, and Challenges

“…[ 2 , 157 ] The most commonly‐applied triggers primarily include temperature, pH, light, metal ions, enzymes, and small molecules. [ 30 , 158 , 159 , 160 ] Recently, new stimuli, such as redox, [ 71 , 161 ] magnetic fields, [ 9 , 10 , 84 ] electric fields, [ 159 ] and near‐infrared radiation [ 162 ] are gradually being used to regulate the properties of hydrogels. [ 2 ] In smart DNA‐based hydrogels, these stimuli are provided by FNAs, small molecules, and polymers with unique features.…”