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However, their radiotherapeutic efficacy is limited by hypoxia in deep\u2010seated tumors and short half\u2010lives of reactive oxygen species (ROS). Herein the conjugation of a nitric oxide (NO) donor, S\u2010nitroso\u2010N\u2010acetyl\u2010DL\u2010penicillamine (SNAP), to the Hf\n                    <jats:sub>12<\/jats:sub>\n                    secondary building units (SBUs) of Hf\u20105,5\u2032\u2010di\u2010p\u2010benzoatoporphyrin MOL is reported to afford SNAP\/MOL for enhanced cancer radiotherapy. Under X\u2010ray irradiation, SNAP\/MOL efficiently generates superoxide anion (O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:bold>\n                      <jats:sup>\u2212.<\/jats:sup>\n                    <\/jats:bold>\n                    ) and releases nitric oxide (NO) in a spatio\u2010temporally synchronized fashion. The released NO rapidly reacts with O\n                    <jats:sub>2<\/jats:sub>\n                    <jats:bold>\n                      <jats:sup>\u2212.<\/jats:sup>\n                    <\/jats:bold>\n                    to form long\u2010lived and highly cytotoxic peroxynitrite which diffuses freely to the cell nucleus and efficiently causes DNA double\u2010strand breaks. Meanwhile, the sustained release of NO from SNAP\/MOL in the tumor microenvironment relieves tumor hypoxia to reduce radioresistance of tumor cells. Consequently, SNAP\/MOL plus low\u2010dose X\u2010ray irradiation efficiently inhibits tumor growth and reduces metastasis in colorectal and triple\u2010negative breast cancer models.\n                  <\/jats:p>","DOI":"10.1002\/advs.202413518","type":"journal-article","created":{"date-parts":[[2025,1,1]],"date-time":"2025-01-01T04:38:26Z","timestamp":1735706306000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":44,"title":["Nitric Oxide\u2010Releasing Nanoscale Metal\u2010Organic Layer Overcomes Hypoxia and Reactive Oxygen Species Diffusion Barriers to Enhance Cancer Radiotherapy"],"prefix":"10.1002","volume":"12","author":[{"given":"Yuxuan","family":"Xiong","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinhong","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaomin","family":"Jiang","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenyao","family":"Zhen","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xin","family":"Ma","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7035-7759","authenticated-orcid":false,"given":"Wenbin","family":"Lin","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  Chicago IL 60637 USA"},{"name":"Department of Radiation and Cellular Oncology and the Ludwig Center for Metastasis Research The University of Chicago  Chicago IL 60637 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,1]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/nrc3958"},{"key":"e_1_2_8_1_2","doi-asserted-by":"publisher","DOI":"10.1038\/nrclinonc.2016.211"},{"key":"e_1_2_8_1_3","doi-asserted-by":"publisher","DOI":"10.1038\/s41392-022-01102-y"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41572-019-0064-5"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1089\/ars.2013.5668"},{"key":"e_1_2_8_2_3","doi-asserted-by":"publisher","DOI":"10.1038\/s41571-018-0046-7"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0140-6736(98)05180-0"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1038\/s43586-024-00320-8"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201707819"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1186\/s12645-016-0021-x"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.2217\/fon.12.96"},{"key":"e_1_2_8_5_3","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-018-04703-w"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202208685"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41551-018-0203-4"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201704828"},{"key":"e_1_2_8_7_3","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b11593"},{"key":"e_1_2_8_7_4","doi-asserted-by":"publisher","DOI":"10.1021\/nl504044p"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00313"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.abb5223"},{"key":"e_1_2_8_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202405494"},{"key":"e_1_2_8_8_4","author":"Wang C.","year":"2024","journal-title":"Angew. 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