{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T01:15:50Z","timestamp":1791422150064,"version":"4.3.3"},"reference-count":47,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2009,3,16]],"date-time":"2009-03-16T00:00:00Z","timestamp":1237161600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,4,27]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:bold>Kept in the dark<\/jats:bold>: The non\u2010photocatalytic generation of free radicals from fine and ultrafine TiO<jats:sub>2<\/jats:sub> particles has been studied by means of a spin\u2010trapping\/ESR spectroscopy technique (see figure). The amount and kind of free radicals generated depends on the crystalline structure, but not on the particle dimensions.<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text><\/jats:p><jats:p>Titania is generally considered to be an inert and safe material. Several studies, however, have reported that nanosized TiO<jats:sub>2<\/jats:sub> may elicit toxic effects. In some cases the observed adverse effects have been related to free radicals. Although new studies mainly concern irradiated titania, the role and the mechanisms of the generation of free radicals by TiO<jats:sub>2<\/jats:sub> in the absence of UV irradiation are not well known. The purpose of the present study is to investigate the free\u2010radical\u2010generation mechanisms by nano\u2010 and micronsized anatase or rutile powders under normal laboratory illumination or in the dark by means of a spin\u2010trapping\/ESR spectroscopy technique. This technique is used to identify the nature and the amount of free radicals released in solution, and in the solid\u2010state to characterise the paramagnetic centres at the surface of particles that may participate in the reactions. The following radical\u2010generating mechanisms have been considered: 1)\u2005the generation of oxygenated free radicals (HO<jats:sub>2<\/jats:sub><jats:sup>.<\/jats:sup>, O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup>, HO<jats:sup>.<\/jats:sup>) following the reaction of TiO<jats:sub>2<\/jats:sub> with oxygen, water or H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> and 2)\u2005the generation of carbon\u2010centred radicals following the cleavage of the C\uf8ffH bond in a model molecule. Although no free radicals were detected in a simply buffered solution, anatase and rutile generated O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup> and HO<jats:sup>.<\/jats:sup>, respectively, in the presence of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub>. Both polymorphs were also active in the cleavage of the C\uf8ffH bond. Although the formation of O<jats:sub>2<\/jats:sub><jats:sup>.\u2212<\/jats:sup> appears to be related to exposure to sunlight, the generation of HO<jats:sup>.<\/jats:sup> and carbon\u2010centred free radicals also occurs in the dark. When samples of equal surface area were tested, micron\u2010 and nanosized anatase was found to react in the same way indicating that a reduction in diameter does not generate new kinds of reactive sites. The data presented herein may have implications in the assessment of the health risk associated with the exposure to TiO<jats:sub>2<\/jats:sub> nanoparticles and in the ecotoxicological impact following their possible leakage into the environment.<\/jats:p>","DOI":"10.1002\/chem.200802542","type":"journal-article","created":{"date-parts":[[2009,3,16]],"date-time":"2009-03-16T09:45:25Z","timestamp":1237196725000},"page":"4614-4621","source":"Crossref","is-referenced-by-count":178,"title":["Non\u2010UV\u2010Induced Radical Reactions at the Surface of TiO<sub>2<\/sub> Nanoparticles That May Trigger Toxic Responses"],"prefix":"10.1002","volume":"15","author":[{"given":"Ivana","family":"Fenoglio","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giovanna","family":"Greco","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stefano","family":"Livraghi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bice","family":"Fubini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,4,17]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1093\/annhyg\/41.1.37"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1080\/01902140260426742"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1289\/ehp.7339"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1007\/s10646-008-0214-0"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1097\/01.jom.0000058338.05741.45"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1023\/B:CACO.0000036188.23970.22"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1093\/annhyg\/mei012"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1470-2045(06)70651-9"},{"key":"e_1_2_7_9_2","unstructured":"IARC monograph on the evaluation of carcinogenic risk to humans Vol.\u200593 Carbon black titanium dioxide talc. 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