Domain-selective thermal decomposition within supramolecular nanoribbons

Abstract

Self-assembly of small molecules in water provides a powerful route to nanostructures with pristine molecular organization and small dimensions (<10 nm). Such assemblies represent emerging high surface area nanomaterials, customizable for biomedical and energy applications. However, to exploit self-assembly, the constituent molecules must be sufficiently amphiphilic and satisfy prescribed packing criteria, dramatically limiting the range of surface chemistries achievable. Here, we design supramolecular nanoribbons that contain: (1) inert and stable internal domains, and (2) sacrificial surface groups that are thermally labile, and we demonstrate complete thermal decomposition of the nanoribbon surfaces. After heating, the remainder of each constituent molecule is kinetically trapped, nanoribbon morphology and internal organization are maintained, and the nanoribbons are fully hydrophobic. This approach represents a pathway to form nanostructures that circumvent amphiphilicity and packing parameter constraints and generates structures that are not achievable by self-assembly alone, nor top-down approaches, broadening the utility of molecular nanomaterials for new targets.

Geometric Transformations Afforded by Rotational Freedom in Aramid Amphiphile Nanostructures

“…These uniform intermolecular distances represent an extended hydrogen bonding network along the nanoribbons, which has been confirmed in other selfassembling AA nanostructures. 22 Based on the X-ray scattering results, we speculate that the hydrogen bonding network among aramid domains of D-AAs is activated only at high concentrations. When the concentration is low, the D-AAs are packed in a distinct way.…”

Antifouling Surface Coatings from Self‐Assembled Zwitterionic Aramid Amphiphile Nanoribbons

“…These coatings harness the thermal stability of ZAA nanoribbons, which has been previously demonstrated up to 250 °C. [ 42 ] We find with scanning electron microscopy (SEM) that the nanoribbons maintain their 3D architecture, aggregate into bundles, and form a dense mesh ( Figure a). 250 µL of a 1 mg mL –1 nanoribbon solution is observed as the minimum volume needed to fully disperse across 15 mm diameter circular glass discs, which fit the bottom of a 24‐well plate.…”

Unsupervised Data-Driven Reconstruction of Molecular Motifs in Simple to Complex Dynamic Micelles

“…1−5 Recent studies suggest that the mobility of building blocks and the formation of dynamically diverse domains within the assemblies may significantly impact their properties, in a similar way as they do in natural systems. 3,6,7 This is the case, for example, of supramolecular polymers where the intrinsic reshuffling dynamics of their monomers occurring on defected domains controls directly how fastly/slowly the polymeric fiber can reorganize its structure in response to a specific stimulus. 8 In general, the possibility to create a certain degree of disorder (i.e., defects) in soft supramolecular assemblies is key for tuning and modulating fluid-like domains, 9,10 controlling their stability, 11 triggering stimuli-responsive attitude, 12 and speeding-up chemical reactions.…”

“…Understanding the structural environments which characterize soft supramolecular assemblies and their intrinsic dynamics is of prime importance toward the rational design of self-assembling materials with controllable dynamic properties. − Recent studies suggest that the mobility of building blocks and the formation of dynamically diverse domains within the assemblies may significantly impact their properties, in a similar way as they do in natural systems. ,, This is the case, for example, of supramolecular polymers where the intrinsic reshuffling dynamics of their monomers occurring on defected domains controls directly how fastly/slowly the polymeric fiber can reorganize its structure in response to a specific stimulus …”

“… 1 − 5 Recent studies suggest that the mobility of building blocks and the formation of dynamically diverse domains within the assemblies may significantly impact their properties, in a similar way as they do in natural systems. 3 , 6 , 7 This is the case, for example, of supramolecular polymers where the intrinsic reshuffling dynamics of their monomers occurring on defected domains controls directly how fastly/slowly the polymeric fiber can reorganize its structure in response to a specific stimulus. 8 …”