0000000000224007
AUTHOR
Christian M. Berac
Secondary Structure-Driven Hydrogelation Using Foldable Telechelic Polymer-Peptide Conjugates.
The synthesis of ABA and ABA' triblock polyethylene glycol-and polysarcosine-peptide conjugates is reported. The A/A' peptides are based on phenylalanine(F)-histidine(H) pentapeptide sequences FHFHF, which promote pH-switchable β-sheet self-assembly into nanorods in water. Only parallel β-sheet-driven folding and intermolecular assembly using ABA triblock polymer-peptide conjugates leads to interstrand cross-linking and hydrogelation, highlighting the impact of supramolecular interactions-directed structure formation at the nano- and mesoscopic level.
Modeling Supramolecular Polymerization: The Role of Steric Effects and Hydrophobic Interactions
We present a combined experimental–simulation study of self-assembly into one-dimensional filaments. Experimentally, we study amphiphilic AuI-metallopeptides in neutral aqueous media. Our model foc...
Bridging rigidity and flexibility : modulation of supramolecular hydrogels by metal complexation
The combination of complementary, noncovalent interactions is a key principle for the design of multistimuli responsive hydrogels. In this work, an amphiphilic peptide, supramacromolecular hydrogelator which combines metal-ligand coordination induced gelation and thermoresponsive toughening is reported. Following a modular approach, the incorporation of the triphenylalanine sequence FFF into a structural (C3EG ) and a terpyridine-functionalized (C3Tpy ) C3 -symmetric monomer enables their statistical copolymerization into self-assembled, 1D nanorods in water, as investigated by circular dichroism (CD) spectroscopy and transmission electron microscopy (TEM). In the presence of a terpyridine …
Evaluation of Charge‐Regulated Supramolecular Copolymerization to Tune the Time Scale for Oxidative Disassembly of β‐Sheet Comonomers
A multistimuli-responsive supramolecular copolymerization is reported. The copolymerization is driven by hydrogen bond encoded β-sheet-based charge co-assembly into 1D nanorods in water, using glutamic acid or lysine residues in either of the peptide comonomers. The incorporation of methionine as hydrophobic amino acid supports β-sheet formation, but oxidation of the thioether side-chain to a sulfoxide functional group destabilizes the β-sheet ordered domains and induces disassembly of the supramolecular polymers. Using H2 O2 as reactive oxygen species, the time scale and kinetics of the oxidative disassembly are probed. Compared to the charge neutral homopolymers, it is found that the oxid…
Tuning the life-time of supramolecular hydrogels using ROS-responsive telechelic peptide-polymer conjugates
Abstract The synthesis of multi-stimuli responsive peptide-poly(ethylene glycol) ABA-type conjugates is reported. The β-sheet encoded intramolecular folding and intermolecular self-assembly into 1D nanorods is based on a phenylalanine(F)-methionine(M)-histidine(H) FMHMHF hexapeptide sequence, and the supramolecular nanorods are stabilised by a shielding corona of hydrophilic PEG polymers. Interstrand crosslinking leads to the formation of physical networks and hydrogels at physiological pH and at room temperature. The thioether functional groups integrate oxidation responsive properties in the supramolecular polymer assemblies. We show that the glucose fuelled and glucose oxidase catalysed …