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Herein, we report a therapeutic peptide\u2010programmed liquid\u2010crystalline depot in which the Vpr\u2010derived antitumor peptide (VDAP) functions simultaneously as an immunotherapeutic effector and a supramolecular topology regulator. At physiological pH, cationic \u03b1\u2010helical VDAP was electrostatically anchored by oleic acid\u2010containing lipid domains, reinforcing a compact inverse hexagonal (\n                    <jats:italic>H<\/jats:italic>\n                    <jats:sub>II<\/jats:sub>\n                    ) topology associated with reduced peptide diffusion. In the acidic postoperative tumor microenvironment, protonation of oleic acid could disrupt anionic anchoring, whereas histidine protonation within VDAP amplified intrachannel electrostatic repulsion. This cooperative peptide\u2013lipid charge reprogramming could drive graded liquid\u2010crystalline topology remodeling from a diffusion\u2010restrictive\n                    <jats:italic>H<\/jats:italic>\n                    <jats:sub>II<\/jats:sub>\n                    organization to a more interconnected bicontinuous cubic\n                    <jats:italic>Im<\/jats:italic>\n                    3\u0304\n                    <jats:italic>m<\/jats:italic>\n                    network, consistent with increased pH\u2010responsive peptide release. In an orthotopic incomplete\u2010resection breast tumor model, the depot induced immunogenic tumor destruction, enhanced damage\u2010associated molecular pattern release, promoted dendritic cell maturation and CD8\n                    <jats:sup>+<\/jats:sup>\n                    T cell infiltration, and reshaped the immunosuppressive surgical bed. These results demonstrate that electrostatic\u2010topology\u2010gated VDAP\u2010enabled supramolecular topology switching provides effective adaptive local cancer immunotherapy, effectively suppressing postoperative tumor recurrence and attenuating pulmonary metastasis.\n                  <\/jats:p>","DOI":"10.1002\/advs.78360","type":"journal-article","created":{"date-parts":[[2026,10,18]],"date-time":"2026-10-18T15:08:29Z","timestamp":1792336109000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Therapeutic Peptide\u2010Programmed Liquid\u2010Crystalline Topology Switching for pH\u2010Gated Postoperative Cancer Immunotherapy"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0002-2019-9996","authenticated-orcid":false,"given":"Yan","family":"Yan","sequence":"first","affiliation":[{"name":"School of Pharmacy and Laboratory of Drug Discovery from Natural Resources and Industrialization Macau University of Science and Technology  Macau China"},{"name":"Livzon Pharmaceutical Group Inc. 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