Reversible Self-Assembly of Monosaccharide-Based Nanoparticles With Reversible Fluorescence Modulation

Abstract

Reversible self-assembly of nanoparticles remains challenging due to limited molecular mobility. Moreover, reported successful examples typically rely on inorganic-core nanoparticles that require surface pre-functionalization with specific stimuli-responsive ligands. Here, we demonstrate reversible self-assembly of organic nanoparticles through the selective self-modulation of aliphatic chains, without the need for prior modification with external stimuli-responsive ligands. D-glucose 11-octadecylthioundecanoate (D-Glc-C11S18E) self-assembles into microspheres (3–6 µm) comprising nanospheres (100–300 nm). Within these nanospheres, octadecylthioundecanoyl (C29) groups form interior crystalline domains (C29 lamella) while octadecyl (C18) chains organize at nanosphere interfaces (C18 lamella). Thermal triggering enables selective reversibility: at 50°C, the C18 lamella dissociates into disordered structures while the C29 lamella remains intact; cooling to 20°C regenerates the C18 lamella. In methanol, this process drives reversible microsphere-nanosphere morphological transitions (validated by scanning electron microscopy/dynamic light scattering), accompanied by a reversible fluorescence modulation. Both structural and optical modulations exhibit no apparent fatigue over 10 consecutive cycles. Energy decomposition analysis reveals stronger C29 binding energy (ΔE_int = –29.80 kcal/mol vs. C18's –19.90 kcal/mol), explaining selective reversibility. Density functional theory calculations confirm the distinct highest occupied molecular orbital-lowest unoccupied molecular orbital gaps correlating with emission wavelengths. Leveraging the temperature/wavelength-dependent fluorescence, we constructed a multi-input logic gate. This work establishes a new insight for reversible assembly and enables smart and fatigue-resistant optoelectronic applications.

Keywords

clustering-triggered emission / nanoparticles / nonconventional luminophores / reversible self-assembly

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2025 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.