0000000000328445
AUTHOR
Benedict Kemper
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...
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).
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…
Reversible Covalent and Supramolecular Functionalization of Water-Soluble Gold(I) Complexes.
The ligation of gold(I) metalloamphiphiles with biomolecules is reported, using water-soluble AuI -N-alkynyl substituted maleimide complexes. For this purpose, two different polar ligands were applied: 1) a neutral, dendritic tetraethylene glycol-functionalized phosphane and 2) a charged, sulfonated N-heterocyclic carbene (NHC). The retro Diels-Alder reaction of a furan-protected maleimide gold(I) complex, followed by cycloaddition with a diene-functionalized biotin under mild conditions leads to a novel gold(I) metalloamphiphile. The strong streptavidin-biotin binding affinity in buffered aqueous solution of the resulting biotin alkynyl gold(I) phosphane conjugate remains intact. The cytot…
CCDC 1532063: Experimental Crystal Structure Determination
Related Article: Benedict Kemper, Maximilian von Gröning, Vanessa Lewe, Daniel Spitzer, Tobias Otremba, Natascha Stergiou, Dieter Schollmeyer, Edgar Schmitt, Bart Jan Ravoo, Pol Besenius|2017|Chem.-Eur.J.|23|6048|doi:10.1002/chem.201700588