Programmierbare transiente Thermogele vermittelt durch eine pH- und Redox-regulierte supramolekulare Polymerisation

Transient Hydrogels Mediated by Redox-Switchable Supramolecular Polymerization

Spatial and temporal control in multi-stimuli-responsive materials are critical properties to advance and optimize functional soft matter in order to mimic key features of living systems. In this contribution, I will discuss our methodology in developing non-equilibrium states in supramolecular materials. We have expanded our concept of charge regulated s–sheet self-assembly of alternating hydrophilic and hydrophobic amino acids in order to introduce redox-switchable properties. An interplay of pH- and oxidation-stimuli, promoted by the production of reactive oxygen species (ROS) thus leads to transient supramolecular polymerizations of methionine containing amphiphiles, with tuneable lifet…

Tuneable Transient Thermogels Mediated by a pH- and Redox-Regulated Supramolecular Polymerization.

A multistimuli-responsive transient supramolecular polymerization of β-sheet-encoded dendritic peptide monomers in water is presented. The amphiphiles, which contain glutamic acid and methionine, undergo a glucose oxidase catalyzed, glucose-fueled transient hydrogelation in response to an interplay of pH and oxidation stimuli, promoted by the production of reactive oxygen species (ROS). Adjusting the enzyme and glucose concentration allows tuning of the assembly and the disassembly rates of the supramolecular polymers, which dictate the stiffness and transient stability of the hydrogels. The incorporation of triethylene glycol chains introduces thermoresponsive properties to the materials. …

Kinetic control in the temperature-dependent sequential growth of surface-confined supramolecular copolymers

We report the sequential growth of supramolecular copolymers on gold surfaces, using oppositely charged dendritic peptide amphiphiles. By including water-solubilising thermoresponsive chains in the monomer design, we observed non-linear effects in the temperature-dependent sequential growth. The step-wise copolymerisation process is characterised using temperature dependent SPR and QCM-D measurements. At higher temperatures, dehydration of peripheral oligoethylene glycol chains supports copolymer growth due to more favourable comonomer interactions. Both monomers incorporate methionine amino acids but remarkably, desorption of the copolymers via competing sulphur gold interactions with the …