Seed-Induced Living Two-Dimensional (2D) Supramolecular Polymerization in Water: Implications on Protein Adsorption and Enzyme Inhibition.

In biological systems, programmable supramolecular frameworks characterized by coordinated directional non-covalent interactions are widespread. However, only a small number of reports involve pure water-based dynamic supramolecular assembly of artificial π-amphiphiles, primarily due to the formidable challenge of counteracting the strong hydrophobic dominance of the π-surface in water, leading to undesired kinetic traps. This study reveals the pathway complexity in hydrogen-bonding-mediated supramolecular polymerization of an amide-functionalized naphthalene monoimide (NMI) building block with a hydrophilic oligo-oxyethylene (OE) wedge. O-NMI-2 initially produced entropically driven, collapsed spherical particles in water (Agg-1); however, over a span of 72 h, these metastable Agg-1 gradually transformed into two-dimensional (2D) nanosheets (Agg-2), favoured by both entropy and enthalpy contributions. The intricate self-assembly pathways in O-NMI-2 enable us to explore seed-induced living supramolecular polymerization (LSP) in water for controlled synthesis of monolayered 2D assemblies. Furthermore, we demonstrated the nonspecific surface adsorption of a model enzyme, serine protease α-Chymotrypsin (α-ChT), and consequently the enzyme activity, which could be regulated by controlling the morphological transformation of O-NMI-2 from Agg-1 to Agg-2. We delve into the thermodynamic aspects of such shape-dependent protein-surface interactions and unravel the impact of seed-induced LSP on temporally controlling the catalytic activity of α-ChT.

Pathway Complexity in Supramolecular Copolymerization and Blocky Star Copolymers by a Hetero-Seeding Effect.

This study unravels the intricate kinetic and thermodynamic pathways involved in the supramolecular copolymerization of the two chiral dipolar naphthalene monoimide (NMI) building blocks (O-NMI and S-NMI), differing merely by a single heteroatom (oxygen vs sulfur). O-NMI exhibits distinct supramolecular polymerization features as compared to S-NMI in terms of its pathway complexity, hierarchical organization, and chiroptical properties. Two distinct self-assembly pathways in O-NMI occur due to the interplay between the competing dipolar interactions among the NMI chromophores and amide-amide hydrogen (H)-bonding that engenders distinct nanotapes and helical fibers, from its antiparallel and parallel stacking modes, respectively. In contrast, the propensity of S-NMI to form only a stable spherical assembly is ascribed to its much stronger amide-amide H-bonding, which outperforms other competing interactions. Under the thermodynamic route, an equimolar mixture of the two monomers generates a temporally controlled chiral statistical supramolecular copolymer that autocatalytically evolves from an initially formed metastable spherical heterostructure. In contrast, the sequence-controlled addition of the two monomers leads to the kinetically driven hetero-seeded block copolymerization. The ability to trap O-NMI in a metastable state allows its secondary nucleation from the surface of the thermodynamically stable S-NMI spherical "seed", which leads to the core-multiarmed "star" copolymer with reversibly and temporally controllable length of the growing O-NMI "arms" from the S-NMI "core". Unlike the one-dimensional self-assembly of O-NMI and its random co-assembly with S-NMI, which are both chiral, unprecedentedly, the preferred helical bias of the nucleating O-NMI fibers is completely inhibited by the absence of stereoregularity of the S-NMI "seed" in the "star" topology.