Regulating HS release from self-assembled peptide HS-donor conjugates using cysteine derivatives.

Self-assembled peptides provide a modular and diverse platform for drug delivery, and innovative delivery methods are needed for delivery of hydrogen sulfide (HS), an endogenous signaling molecule (gasotransmitter) with significant therapeutic potential. Of the available types of HS donors, peptide/protein HS donor conjugates (PHDCs) offer significant versatility. Here we discuss the design, synthesis, and in-depth study of a PHDC containing three covalently linked components: a thiol-triggered HS donor based on an -aroylthiooxime (SATO), a GFFF tetrapeptide, and a tetraethylene glycol (TEG) dendron.

Impact of sample history and solvent effects on pathway control in the supramolecular polymerisation of Au(i)-metallopeptide amphiphiles.

We investigate the kinetics of the supramolecular polymerisation of an Au(i)-metallopeptide amphiphile that assembles into exceptionally long and rigid nanofibers. We developed a precise preparation protocol to measure the concentration dependent assembly kinetics which elucidated a nucleation-elongation dominated supramolecular polymerisation process. We show striking differences in the assembly behavior and morphology in aqueous media, even at organic solvent contents as low as 1 vol%, compared to pure buffer.

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 (C ) and a terpyridine-functionalized (C ) C -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).