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Controlling the Assembly of Ureido-Pyrimidinone Supramolecular Monomers by Tuning the Hydrophilic-Hydrophobic Balance

Title: Controlling the Assembly of Ureido-Pyrimidinone Supramolecular Monomers by Tuning the Hydrophilic-Hydrophobic Balance
Authors: Bellan, Riccardo; Cardellini, Annalisa; Perego, Claudio; Paffen, Lars J.M.M.; Rijns, Laura; Pavan, Giovanni M.; Dankers, Patricia Y.W.
Source: Bellan, R, Cardellini, A, Perego, C, Paffen, L J M M, Rijns, L, Pavan, G M & Dankers, P Y W 2026, 'Controlling the Assembly of Ureido-Pyrimidinone Supramolecular Monomers by Tuning the Hydrophilic-Hydrophobic Balance', Journal of Polymer Science, vol. 64, no. 3, pp. 682-690. https://doi.org/10.1002/pol.20250943
Publication Year: 2026
Subject Terms: cryoTEM; molecular dynamics simulations; self-assembly; supramolecular polymers; ureido-pyrimidinone
Description: Understanding the self-assembly of supramolecular monomers in water is essential to develop responsive and bioactive biomaterials. In this work, a series of water-compatible ureido-pyrimidinone (UPy) derivatives differing in the length of the oligo(ethylene glycol) chain and of the alkyl-urea spacer are prepared. The self-assembly behavior of each monomer is elucidated in water by means of experimental techniques and computational molecular modeling, unveiling the importance of the monomer hydrophilic-hydrophobic balance in the self-assembly properties and morphology of the resulting supramolecular polymers. Even though the increasing size of the alkyl-urea spacer is shown to foster both the UPy dimerization and the π–π stacking of the dimers, molecular dynamics simulations highlight a competitive intramolecular interaction between the UPy core and the lateral urea moiety, leading to the formation of sheet-like structures rather than one-dimensional supramolecular polymers in water. The findings of this work highlight the importance of monomer design on the self-assembly properties of UPy systems, paving the way towards the development of novel supramolecular biomaterials with tuneable properties.
Document Type: article in journal/newspaper
File Description: application/pdf
Language: English
ISSN: 2642-4150; 2642-4169
Relation: info:eu-repo/semantics/altIdentifier/pissn/2642-4150; info:eu-repo/semantics/altIdentifier/eissn/2642-4169
DOI: 10.1002/pol.20250943
Availability: https://research.tue.nl/en/publications/b3eca113-4841-4518-8dcb-b9fd7ee0aaf1; https://doi.org/10.1002/pol.20250943; https://pure.tue.nl/ws/files/379864398/Journal_of_Polymer_Science_-_2025_-_Bellan_-_Controlling_the_Assembly_of_Ureido_Pyrimidinone_Supramolecular_Monomers_by.pdf; https://www.scopus.com/pages/publications/105022615362
Rights: info:eu-repo/semantics/openAccess ; http://creativecommons.org/licenses/by/4.0/
Accession Number: edsbas.2CF11BA9
Database: BASE