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Emerging Complex Behavior Driven by Self-Organization: Dynamic Covalent Libraries of Acylhydrazones in Water.

Created on 26 Jul 2025

Authors

Ferran Esteve, Zhaozheng Yang, Jean-Marie Lehn

Published in

Journal of the American Chemical Society. Jul 25, 2025. Epub Jul 25, 2025.

Abstract

The generation of self-organized phases drives the emergence of states of matter of higher complexity. Herein, we study in situ generated self-assembled systems based on the condensation between different aldehydes and hydrazides in water. The resulting acylhydrazones can self-organize into turbid hydrogels or bigger microcrystals depending on the component substituents. The generation of the organized phases was investigated by nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-vis) spectroscopy as well as by microscopy, rheology and solid-state X-ray analyses. Polar substituents like imidazole rings, carboxylic acids and alcohols still lead to hydrogels due to the high propensity of the hydrophobic aromatic cores to self-assemble. The microcrystalline gels containing acidic and basic groups displayed pH-responsiveness. Such behavior allowed for adaptive scrambling-sorting transitions and sorting selectivity switching within 1 × 2 dynamic covalent libraries driven by self-organization in response to environmental conditions. Moreover, the generation of hydrophobic microenvironments in the self-assembled three-dimensional (3D)-network promoted selective imine formation made of apolar components as a result of the stabilization and protection of the reversible covalent bond from hydrolysis. Thus, the dynamic systems described here exhibit up to five levels of adaptive behaviors governed by self-organization (see conclusions).

PMID:
40712052
Bibliographic data and abstract were imported from PubMed on 26 Jul 2025.

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