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Herein, we report the first comprehensive chemical and immunological characterization of LPS from\n                    <jats:italic>Segatella copri<\/jats:italic>\n                    DSM 18205, a prominent member of the human oral and intestinal microbiota. This LPS features a unique chemical architecture, including a mannose\u2010 and glucose\u2010rich oligosaccharide (OS) and a highly heterogeneous, hypo\u2010acylated lipid A domain, as elucidated by advanced mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy. Functionally,\n                    <jats:italic>S. copri<\/jats:italic>\n                    LPS displayed attenuated TLR4 activation and weak pro\u2010inflammatory activity. Strikingly, high\u2010dimensional cytometry by time\u2010of\u2010flight (CyTOF) revealed a selective preservation of CD14\n                    <jats:sup>+<\/jats:sup>\n                    CD16\n                    <jats:sup>+<\/jats:sup>\n                    monocytes, immune subsets typically depleted by canonical enterobacterial LPSs. These findings identify\n                    <jats:italic>S. copri<\/jats:italic>\n                    LPS as a chemically and functionally distinct microbial signature, offering new insights into host\u2010microbiota immune crosstalk and highlighting its potential for microbiome\u2010informed immunomodulatory strategies.\n                  <\/jats:p>","DOI":"10.1002\/anie.202512947","type":"journal-article","created":{"date-parts":[[2025,9,30]],"date-time":"2025-09-30T07:45:38Z","timestamp":1759218338000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Decoding a Gut Commensal Signal: Structural and Immunological Profiling of\n                    <i>Segatella Copri<\/i>\n                    Lipopolysaccharide"],"prefix":"10.1002","volume":"64","author":[{"given":"Luca","family":"De Simone Carone","sequence":"first","affiliation":[{"name":"Department of Chemical Sciences University of Naples Federico II  via Cinthia, 4 Naples 80126 Italy"},{"name":"CEINGE\u2010Biotecnologie Avanzate Franco Salvatore  Via Gaetano Salvatore 486 Naples 80145 Italy"},{"name":"Department of Biology University of Naples Federico II  via Cinthia, 4 Naples 80126 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giusi","family":"Barra","sequence":"additional","affiliation":[{"name":"Bio\u2010Organic Chemistry Unit Institute of Biomolecular Chemistry CNR  Via Campi Flegrei 34 Naples 80078 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Roberta","family":"Cirella","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences University of Naples Federico II  via Cinthia, 4 Naples 80126 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marcello","family":"Ziaco","sequence":"additional","affiliation":[{"name":"Bio\u2010Organic Chemistry Unit Institute of Biomolecular Chemistry CNR  Via Campi Flegrei 34 Naples 80078 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