0000000000462053
AUTHOR
Lydia Zengerling
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…
Kinetically Controlled Stepwise Self-Assembly of AuI-Metallopeptides in Water
The combination of attractive supramolecular interactions of a hydrophobic AuI-metallopeptide with the shielding effect of flexible oligoethylene glycol chains provides access to a stepwise self-assembly of a AuI-metalloamphiphile in water. Kinetic control of the supramolecular polymer morphology is achieved using a temperature-dependent assembly protocol, which yields low dispersity supramolecular polymers (metastable state I) or helical bundled nanorods (state II).
Insight into the synthesis of N-methylated polypeptides
The ring-opening polymerization (ROP) of N-carboxy anhydrides (NCAs) is mostly divided into two classes: NCAs of α-substituted amino acids and N-methylated NCAs of α-unsubstituted glycine derivatives (NNCAs). The use of both monomer types offers different mechanistic features and results in a multitude of functional materials. To combine these properties, the synthesis and ROP of α-substituted and N-methylated NCAs (αNNCAs) of several amino acids were investigated. The current study provides insight into the influence of polymerization conditions and the limitations caused by the enhanced steric demand of the amino acid NCA monomers and their N-methylated derivatives. Namely, the effects of…
Synthesis and Structural Stability of α-Helical Gold(I)-Metallopeptidesy
AbstractThe synthesis of hexa- and dodecapeptides functionalized with two Au(I)–phosphine complexes is reported. The high stability of the Au(I)–phosphine bond allowed orthogonal peptide-protecting-group chemistry, even when using hard Lewis acids like boron tribromide. This enabled the preparation of an Fmoc-protected lysine derivative carrying the Au(I) complex in a side chain, which was used in standard Fmoc-based solid-phase peptide synthesis protocols. Alanine and leucine repeats in the metallododecapeptide formed α-helical secondary structures in 2,2,2-trifluoroethanol–H2O and 1,1,1,3,3,3-hexafluoroisopropanol–H2O mixtures with high thermal stability, as shown by temperature-dependent…
CCDC 1976456: Experimental Crystal Structure Determination
Related Article: Christian Muhl, Lydia Zengerling, Jonathan Groß, Paul Eckhardt, Till Opatz, Pol Besenius, Matthias Barz|2020|Polym.Chem.|11|6919|doi:10.1039/D0PY01055C
CCDC 1976455: Experimental Crystal Structure Determination
Related Article: Christian Muhl, Lydia Zengerling, Jonathan Groß, Paul Eckhardt, Till Opatz, Pol Besenius, Matthias Barz|2020|Polym.Chem.|11|6919|doi:10.1039/D0PY01055C