Self-Assembled Homopolymeric Spherulites from Small Molecules in Solution

Abstract

Polymeric spherulites are typically formed by melt crystallization: spherulitic growth in solution is rare and requires complex polymers and dilute solutions. Here, we report the mild and unique formation of luminescent spherulites at room temperature via the simple molecule benzene-1,4-dithiol (BDT). Specifically, BDT polymerized into oligomers (PBDT) via disulfide bonds and assembled into uniform supramolecular nanoparticles in aqueous buffer; these nanoparticles were then dissolved back into PBDT in a good solvent (i.e., dimethylformamide) and underwent chain elongation to form spherulites (rPBDT) in 10 min. The spherulite geometry was modulated by changing the PBDT concentration and reaction time. Due to the step-growth polymerization and reorganization of PBDT, these spherulites not only exhibited robust structure but also showed broad clusterization-triggered emission. The biocompatibility and efficient cellular uptake of the spherulites further underscore their value as traceable drug carriers. This system provides a new pathway for designing versatile superstructures with value for hierarchical assembly of small molecules into a complicated biological system.

Superhydrophobic Surfaces Prepared from Columnar Units by Convenient Electrodeposition with Excellent Mechanical Stability Impact and Corrosion Resistance

“…Figure c illustrates the elemental spectrum of Cu on the surface of CAZ samples. The two peaks observed at 953.6 and 933.6 eV correspond to Cu 2p1/2 and Cu 2p3/2, respectively . Additionally, characteristic satellite peaks at 962 and 943.5 eV correspond to Cu 2p3/2, respectively.…”

“…The two peaks observed at 953.6 and 933.6 eV correspond to Cu 2p1/2 and Cu 2p3/2, respectively. 30 Additionally, characteristic satellite peaks at 962 and 943.5 eV correspond to Cu 2p3/2, respectively. This suggests that Cu is oxidized to generate Cu 2+ during the cross-linking and curing process.…”

Observation of spherulitic covalent triazine frameworks grown from melts

“…The kinetics of 2D polymerization during spherulitic growth over heating time (t) was evaluated by a general form of rate equation (5),…”

“…When fibrous crystallites prefer to noncrystallographic branching and radially grow in all directions, polycrystalline aggregates with spherical geometry, known as spherulites, would result 1 . Spherulites have been discovered in a broad spectrum of crystalline substances including metals 1 , minerals 2 , inorganic materials 3 , polymers 4,5 , natural molecules 6,7 , and proteins 8 . However, the spherulitic structures formed by porous materials are rarely explored possibly because of the limited control over the nucleation, directional growth, and topologic dimension.…”

Improving Powder Performances of d-Ribose through Spherulitic Growth

“…However, the introduced impurities may be affecting the purity of the crystals and are not always effective. It is known that spherical particles significantly improve flowability, mechanical properties, and postprocessing efficiency of crystal, which is an effective way to improve the powder properties of crystalline products. , Recently, Yin et al obtained spherulites of sodium amoxicillin by a high supersaturation, high stirring rate-induced strategy, which improved tap density, flowability, and reduced hygroscopicity . However, since functional sugar is a highly viscous system, no one has yet improved the filterability, tap density, and flowability of functional sugar by forming spherical particles.…”