{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,18]],"date-time":"2026-07-18T00:51:31Z","timestamp":1784335891961,"version":"3.55.0"},"reference-count":40,"publisher":"Wiley","issue":"54","license":[{"start":{"date-parts":[[2025,8,17]],"date-time":"2025-08-17T00:00:00Z","timestamp":1755388800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100021856","name":"Ministero dell'Universit\u00e0 e della Ricerca","doi-asserted-by":"publisher","award":["2022WZ8LME"],"award-info":[{"award-number":["2022WZ8LME"]}],"id":[{"id":"10.13039\/501100021856","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100002803","name":"Fondazione Cariplo","doi-asserted-by":"publisher","award":["2022\u20100437"],"award-info":[{"award-number":["2022\u20100437"]}],"id":[{"id":"10.13039\/501100002803","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2025,9,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>N<\/jats:italic>\u2010Fmoc\u2010pentafluoro\u2010<jats:italic>L<\/jats:italic>\u2010phenylalanine (<jats:bold>F<jats:sub>5<\/jats:sub><\/jats:bold>) forms stable supramolecular hydrogels, mainly through \u03c0\u2010\u03c0 stacking of its aromatic groups. Hydrogen bonding\u2010driven co\u2010assembly of <jats:bold>F<jats:sub>5<\/jats:sub><\/jats:bold> with suitable partner molecules has been reported to affect the gel's properties, in accordance with what is observed in their corresponding co\u2010crystal structures. Herein, we extended this hydrogel modulation strategy to halogen bonding (XB) interactions by introducing an XB\u2010donating iodine atom in the <jats:italic>para<\/jats:italic>\u2010position of the <jats:bold>F<jats:sub>5<\/jats:sub><\/jats:bold> phenyl ring. Under conditions mimicking biological environments, both crystal packing and hydrogelation of the resulting <jats:italic>N<\/jats:italic>\u2010Fmoc\u20104\u2010iodo\u2010tetrafluoro\u2010phenylalanine (<jats:bold>IF<jats:sub>4<\/jats:sub><\/jats:bold>), were significantly affected by iodine\u2010\u03c0 interactions. Slower fibril formation kinetics and reduced strength of <jats:bold>IF<jats:sub>4<\/jats:sub><\/jats:bold> hydrogels in phosphate buffer solution, compared to <jats:bold>F<jats:sub>5<\/jats:sub><\/jats:bold>, mirrored iodine\u2010induced changes in Fmoc stacking in the solid state. Notably, the addition of strong XB\u2010acceptors \u2013 such as iodide anions or pyridine\u2010containing substrates, like vitamin B<jats:sub>3<\/jats:sub> \u2013 induced a significant increase in gel stiffness. These findings suggest the possibility of exploiting properly tailored Fmoc\u2010amino acids as \u201cXB\u2010responsive\u201d hydrogelators, useful for anion sensing applications or for trapping bioactive molecules.<\/jats:p>","DOI":"10.1002\/chem.202501476","type":"journal-article","created":{"date-parts":[[2025,8,18]],"date-time":"2025-08-18T06:56:40Z","timestamp":1755500200000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Halogen Bond\u2010Tuning of Responsive Supramolecular Amino Acid Hydrogels"],"prefix":"10.1002","volume":"31","author":[{"given":"Eleonora","family":"Veronese","sequence":"first","affiliation":[{"name":"Laboratory of Supramolecular and Bio\u2010Nanomaterials (SBNLab) Department of Chemistry Materials and Chemical Engineering \u201cGiulio Natta\u201d Politecnico di Milano  Via L. Mancinelli 7 Milan 20131 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrea","family":"Pizzi","sequence":"additional","affiliation":[{"name":"Laboratory of Supramolecular and Bio\u2010Nanomaterials (SBNLab) Department of Chemistry Materials and Chemical Engineering \u201cGiulio Natta\u201d Politecnico di Milano  Via L. Mancinelli 7 Milan 20131 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicola","family":"Demitri","sequence":"additional","affiliation":[{"name":"Elettra Sincrotrone Trieste  S.S. 14, km 163.5, in Area Science Park Basovizza\u2010Trieste 34149 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Greta","family":"Bergamaschi","sequence":"additional","affiliation":[{"name":"Istituto di Scienze e Tecnologie Chimiche National Research Council of Italy (SCITEC\u2010CNR)  Via M. Bianco 9 Milan 20131 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giancarlo","family":"Terraneo","sequence":"additional","affiliation":[{"name":"Laboratory of Supramolecular and Bio\u2010Nanomaterials (SBNLab) Department of Chemistry Materials and Chemical Engineering \u201cGiulio Natta\u201d Politecnico di Milano  Via L. Mancinelli 7 Milan 20131 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7945-099X","authenticated-orcid":false,"given":"Pierangelo","family":"Metrangolo","sequence":"additional","affiliation":[{"name":"Laboratory of Supramolecular and Bio\u2010Nanomaterials (SBNLab) Department of Chemistry Materials and Chemical Engineering \u201cGiulio Natta\u201d Politecnico di Milano  Via L. 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These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service. Crystals of theF5\u00b7Nasalt were also obtained from dimethylsulfoxide (DMSO deposition number 2354251) and showed a different unit cell but similar interaction patterns (see Supporting Information for details). 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