Dynamics in supramolecular nanomaterials

Abstract

The self-assembly of amphiphilic small molecules in water leads to nanostructures with customizable structure-property relationships arising from their tunable chemistries. Characterization of these assemblies is generally limited to their static...

Structure and Dynamics of Supramolecular Polymers: Wait and See

“…The amino acid sequences in proteins that lack a secondary structure show more fluctuations in space than amino acid sequences contained in α-helices or β-sheets. − Similarly, the amphiphilic phospholipids in the cell membrane are limited in their lateral diffusion when tightly packed, for example when they are assembled into lipid rafts. − The structure, dynamics, and function of those assemblies are influenced by the order within the assemblies: the tighter the packing of the molecules, the less dynamic they are. Likewise, synthetic supramolecular assemblies made from small amphiphiles can show different structures − and dynamics depending on the packing of the monomers. Gaining control over the order within supramolecular assemblies will help to gain control over their properties.…”

“… 4 − 6 The structure, dynamics, and function of those assemblies are influenced by the order within the assemblies: the tighter the packing of the molecules, the less dynamic they are. Likewise, synthetic supramolecular assemblies made from small amphiphiles can show different structures 7 − 9 and dynamics 10 depending on the packing of the monomers. Gaining control over the order within supramolecular assemblies will help to gain control over their properties.…”

“…These properties of the supramolecular polymers are generally studied over a short time period, as these polymers are assumed to reach thermodynamic equilibrium in a reasonably short period of time. 10 , 23 , 28 , 35 , 36 Surprisingly, hydrogen/deuterium exchange experiments used to elucidate the exchange dynamics of BTAs indicate that some monomer exchange processes occur within minutes, while others occur over longer time scales, even in the range of weeks. 37 This broad spectrum of dynamics is even observed in the same sample.…”

“… Supramolecular monomers can easily be modified, and even the smallest modifications can result in supramolecular polymers with drastically different properties. ,,− A major challenge lies in the ability to predict how small changes in the chemical structure of the monomers affect molecular packing, the overall structure, and the exchange dynamics of the supramolecular polymers. These properties of the supramolecular polymers are generally studied over a short time period, as these polymers are assumed to reach thermodynamic equilibrium in a reasonably short period of time. ,,,, Surprisingly, hydrogen/deuterium exchange experiments used to elucidate the exchange dynamics of BTAs indicate that some monomer exchange processes occur within minutes, while others occur over longer time scales, even in the range of weeks . This broad spectrum of dynamics is even observed in the same sample.…”

Antifouling Surface Coatings from Self‐Assembled Zwitterionic Aramid Amphiphile Nanoribbons

“…Amphiphilic selfassembly produces internally organized nanostructures with surface presentations, chemistries, and dynamics that are tunable through molecular design. [36][37][38][39][40] Importantly, nanomaterials constructed through the self-assembly of zwitterionic small molecule amphiphiles offer extremely high surface densities of zwitterionic moieties that are resistant to biofouling. To this end, we propose that several criteria should be met to form effective antifouling surface coatings from small molecule supramolecular assemblies: 1) the molecular assemblies should be sufficiently stable to maintain their structure upon drying for application; 2) the nanostructures should take on an appropriate geometry for substrate coating and aspect-ratio to provide dense surface coverage; and 3) the surface should produce a substantial hydration layer that is protective against biofouling.…”