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Previous structural studies suggested that lanthanide ions can replace Ca\n                    <jats:sup>2+<\/jats:sup>\n                    while preserving protein structure, raising the possibility of exploiting paramagnetic lanthanides as NMR probes for studying glycan recognition. Here, we investigated Ca\n                    <jats:sup>2+<\/jats:sup>\n                    \/Ln\n                    <jats:sup>3+<\/jats:sup>\n                    exchange in the immune lectins DC\u2010SIGN and MGL using T\n                    <jats:sub>2<\/jats:sub>\n                    \u2010filtered\n                    <jats:sup>19<\/jats:sup>\n                    F\u2010NMR binding assays with monofluorinated monosaccharides, together with heteronuclear NMR analysis of\n                    <jats:sup>15<\/jats:sup>\n                    N\u2010labeled proteins. Chemical shift perturbations, pseudocontact shifts, and paramagnetic relaxation enhancements showed preferential replacement of the Ca\n                    <jats:sup>2+<\/jats:sup>\n                    ion at the glycan\u2010binding site, while the remaining Ca\n                    <jats:sup>2+<\/jats:sup>\n                    \u2010binding sites were less susceptible to exchange. Unexpectedly, substitution with La\n                    <jats:sup>3+<\/jats:sup>\n                    or Yb\n                    <jats:sup>3+<\/jats:sup>\n                    suppresses carbohydrate binding in both lectins, despite preserving the folded structure of the carbohydrate\u2010recognition domains. Glycan recognition was restored upon EDTA\u2010mediated removal of lanthanides in excess Ca\n                    <jats:sup>2+<\/jats:sup>\n                    , demonstrating the reversibility of the process. These findings show that lanthanides do not necessarily behave as functional Ca\n                    <jats:sup>2+<\/jats:sup>\n                    mimetics in C\u2010type lectins but instead act as reversible disruptors of glycan recognition. Beyond highlighting the need to assess the functional consequences of Ca\n                    <jats:sup>2+<\/jats:sup>\n                    substitution, this work establishes Ca\n                    <jats:sup>2+<\/jats:sup>\n                    \/Ln\n                    <jats:sup>3+<\/jats:sup>\n                    exchange as a strategy for controlled modulation of lectin activity and for developing new tools to investigate C\u2010type lectin\u2010mediated biological processes.\n                  <\/jats:p>","DOI":"10.1002\/cbic.70531","type":"journal-article","created":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T06:50:57Z","timestamp":1789973457000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Reversible Modulation of Glycan Recognition in C\u2010Type Lectins by Calcium\/Lanthanide Exchange"],"prefix":"10.1002","volume":"27","author":[{"given":"Pablo","family":"Valverde","sequence":"first","affiliation":[{"name":"Biomolecular Interactions and Structural Glycobiology Group Institute for Chemical Research (IIQ) CSIC  Seville Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paola","family":"Oquist\u2010Phillips","sequence":"additional","affiliation":[{"name":"Biointeractomics Group Institute for Chemical Research (IIQ) CSIC  Seville Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0542-3080","authenticated-orcid":false,"given":"\u00c1ngeles","family":"Canales","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry Faculty of Chemistry Universidad Complutense de Madrid  Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ana","family":"Diniz","sequence":"additional","affiliation":[{"name":"UCIBIO \u2013 Applied Molecular Biosciences Unit Department of Chemistry NOVA School of Science and Technology NOVA University Lisbon  Caparica Portugal"},{"name":"Associate Laboratory i4HB \u2010 Institute for Health and Bioeconomy NOVA School of Science and Technology NOVA University Lisbon  Caparica Portugal"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5049-8511","authenticated-orcid":false,"given":"Filipa","family":"Marcelo","sequence":"additional","affiliation":[{"name":"UCIBIO \u2013 Applied Molecular Biosciences Unit Department of Chemistry NOVA School of Science and Technology NOVA University Lisbon  Caparica Portugal"},{"name":"Associate Laboratory i4HB \u2010 Institute for Health and Bioeconomy NOVA School of Science and Technology NOVA University Lisbon  Caparica Portugal"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Francisco Javier","family":"Alonso","sequence":"additional","affiliation":[{"name":"Department of Molecular and Cellular Biosciences Centro de Investigaciones Biol\u00f3gicas Margarita Salas CSIC  Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ana","family":"Arda","sequence":"additional","affiliation":[{"name":"CICbioGUNE Bizkaia Science and Technology Park  Bilbao Spain"},{"name":"Ikerbasque Basque Foundation for Science  Bilbao Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5421-8513","authenticated-orcid":false,"given":"Jes\u00fas","family":"Jim\u00e9nez\u2010Barbero","sequence":"additional","affiliation":[{"name":"CICbioGUNE Bizkaia Science and Technology Park  Bilbao Spain"},{"name":"Ikerbasque Basque Foundation for Science  Bilbao Spain"},{"name":"Department of Organic and Inorganic Chemistry EHU  Bilbao Spain"},{"name":"CIBER de Enfermedades Respiratorias (CIBERES) ISCIII  Madrid 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