Supramolecular Janus Nanocylinders: Solvent-Induced Hydrogen-Bond Modulation Yields Structures under Thermodynamic Equilibrium
Abstract
Janus nanocylinders (JNCs) are anisotropic, non-centrosymmetric colloids composed of two different faces, making them attractive for advanced functional materials. However, their nanometric dimensions and pronounced anisotropy complexify their preparation. Recently, a versatile supramolecular strategy has emerged that enables JNCs to be formed without the need for incompatible polymer arms. It occurs in water via the self-assembly of two polymers end-functionalized with complementary, non-symmetrical, hydrogen-bonding motifs. However, assembly in water is driven by a combination of hydrogen bonds and strong hydrophobic effects, yielding kinetically frozen nanostructures whose amount and dimensions depend on the assembly process. Here, we show that supramolecular assembly in toluene overcomes these limitations. In contrast to aqueous systems, solvophobic effects are negligible in toluene, and supramolecular assembly is predominantly driven by the formation of hydrogen bonds between urea-associating units. Consequently, reorganization of the assemblies is possible in toluene at room temperature and a pathway-independent supramolecular organization can be achieved by modulating intermolecular interactions through heating or by the addition of a moderate hydrogen-bond competitor. These results hint at the formation of supramolecular Janus nanocylinders at thermodynamic equilibrium, which can be formed in a very straightforward direct dispersion approach with repeatable characteristics (length, diameter).
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BibTeX
@article{zguir2026supramolecular,
title = {{Supramolecular Janus Nanocylinders: Solvent-Induced Hydrogen-Bond Modulation Yields Structures under Thermodynamic Equilibrium}},
author = {Rihab Zguir and Mingsheng Ji and Irene Antignano and Bochra Seaali and Jean-Michel Guigner and Christophe Sinturel and Ralf Schweins and Marylene Vayer and Frédérick Niepceron and Sandrine Pensec and Jutta Rieger and Laurent Bouteiller and Erwan Nicol and Olivier Colombani},
journal = {Macromolecules},
year = {2026},
month = sep,
doi = {10.1021/acs.macromol.6c01809},
url = {https://hal.sorbonne-universite.fr/hal-05772417v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Supramolecular Janus Nanocylinders: Solvent-Induced Hydrogen-Bond Modulation Yields Structures under Thermodynamic Equilibrium
AU - Rihab Zguir
AU - Mingsheng Ji
AU - Irene Antignano
AU - Bochra Seaali
AU - Jean-Michel Guigner
AU - Christophe Sinturel
AU - Ralf Schweins
AU - Marylene Vayer
AU - Frédérick Niepceron
AU - Sandrine Pensec
AU - Jutta Rieger
AU - Laurent Bouteiller
AU - Erwan Nicol
AU - Olivier Colombani
PY - 2026
DA - 2026/09/28
JO - Macromolecules
DO - 10.1021/acs.macromol.6c01809
UR - https://hal.sorbonne-universite.fr/hal-05772417v1
AB - Janus nanocylinders (JNCs) are anisotropic, non-centrosymmetric colloids composed of two different faces, making them attractive for advanced functional materials. However, their nanometric dimensions and pronounced anisotropy complexify their preparation. Recently, a versatile supramolecular strategy has emerged that enables JNCs to be formed without the need for incompatible polymer arms. It occurs in water via the self-assembly of two polymers end-functionalized with complementary, non-symmetrical, hydrogen-bonding motifs. However, assembly in water is driven by a combination of hydrogen bonds and strong hydrophobic effects, yielding kinetically frozen nanostructures whose amount and dimensions depend on the assembly process. Here, we show that supramolecular assembly in toluene overcomes these limitations. In contrast to aqueous systems, solvophobic effects are negligible in toluene, and supramolecular assembly is predominantly driven by the formation of hydrogen bonds between urea-associating units. Consequently, reorganization of the assemblies is possible in toluene at room temperature and a pathway-independent supramolecular organization can be achieved by modulating intermolecular interactions through heating or by the addition of a moderate hydrogen-bond competitor. These results hint at the formation of supramolecular Janus nanocylinders at thermodynamic equilibrium, which can be formed in a very straightforward direct dispersion approach with repeatable characteristics (length, diameter).
SN - 0024-9297
SN - 1520-5835
ER -