Kinetically Controlled Stepwise Self-Assembly of Au^I-Metallopeptides in Water

Abstract

The combination of attractive supramolecular interactions of a hydrophobic Au-metallopeptide with the shielding effect of flexible oligoethylene glycol chains provides access to a stepwise self-assembly of a Au-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).

C3‐Symmetrical π‐Scaffolds: Useful Building Blocks to Construct Helical Supramolecular Polymers

“…Finally, the kinetic evolution of the three states 0→I→II has been monitored by registering the kinetic profile of the CD pattern at 35 °C with a temperature ramp of 0.5 K/min. Under these experimental conditions, it is possible to monitor the development of the initial monomeric species into State I in only two minutes, which eventually transforms into the final aggregate species (state II ) after 3–5 hours (Figure d) …”

“…Under these experimental conditions, it is possible to monitor the development of the initial monomeric species into State I in only two minutes, which eventually transforms into the final aggregate species (state II) after 3-5 hours (Figure 12d). [47] The similar sequence of three Phe residues has also been used to synthesize modular triazine units with up to three different side chains. These self-assembling units can be functionalized with three dendritic tris-mannose groups or with two dendritic and one branched tris-tetraethyleneglycol unit decorated with a fluorescent Cy3 dye.…”

Twisting Ultrathin Au Nanowires into Double Helices

“…Besides those structures assembled with chiral molecules like the DNA molecules or using them as templates, there are only a few cases of double helical nanowires. Physical confinement can sometimes induce formation of helical or double helix, and external shear/twist force works for certain polymeric materials as well as carbon nanotubes . In a recent work, ultrathin Au double helix were synthesized from a soft template made of chiral ligand molecules …”

Temperature Control of Sequential Nucleation–Growth Mechanisms in Hierarchical Supramolecular Polymers

“…Efforts from various research groups worldwide are currently showing that supramolecular polymerization can go much further than the simplest isodesmic growth regime, and that it can make use of an umber of more complex kinetic pathways for giving rise to highly cooperative processes and thermalh ystereses. [15][16][17][18] For instance, living supramolecular polymerization [19][20][21][22] and access to supramolecular block copolymers [23][24][25][26][27] have been recently demonstrated by precisely engineering molecular structures of monomers andb yt uning experimental conditions. In addition, the presence of competing kinetic and thermodynamic self-assembly pathwaysh as been shown to potentially biast he expression of supramolecular chirality of unidimensional helical polymers.…”