Complexation of AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride) with cucurbit[7]uril enhances the yield of AAPH-derived radicals

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dc.article.number122840
dc.catalogadorgjm
dc.contributor.authorForero Girón, Angie
dc.contributor.authorFuentealba Patiño, Denis Alberto
dc.contributor.authorMariño Ocampo, Nory Johana
dc.contributor.authorGutiérrez Oliva, Soledad
dc.contributor.authorHerrera Pisani, Bárbara Andrea
dc.contributor.authorToro Labbé, Alejandro
dc.contributor.authorFuentes Lemus, Eduardo
dc.contributor.authorDavies, Michael J.
dc.contributor.authorAliaga Miranda, Margarita Elly
dc.contributor.authorLópez Alarcón, Camilo Ignacio
dc.date.accessioned2023-08-17T17:40:12Z
dc.date.available2023-08-17T17:40:12Z
dc.date.issued2023
dc.description.abstractAAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride), a water-soluble azo compound is widely employed to produce peroxyl radicals for chemical and biological studies. This compound is shown herein to form a stable inclusion complex with cucurbit[7]uril (CB7), a well-established supramolecular host. Competitive binding assays using berberine dye, isothermal titration calorimetry (ITC), and nuclear magnetic resonance (1H-NMR) experiments, provided evidence for the inclusion of AAPH inside the CB7 cavity with a binding constant of 2.5 ± 0.8 x 105 L mol-1 (determined by ITC). Computational analysis at B3LYP-D3BJ/6-311G(d,p) of the complex (AAPH@CB7) showed interactions of the positively-charged amino groups of AAPH with carbonyl functions at the CB7 entrances. Photolysis of AAPH@CB7 by illumination at 365 nm, gave a higher yield of carbon-centered radicals when compared to the absence of CB7, as evidenced by electron paramagnetic resonance spin trapping using α-phenyl-N-t-butylnitrone. Enhanced radical formation was corroborated by increased consumption of pyrogallol red, free Trp and Trp-containing peptides when these were exposed to AAPH@CB7 in the presence of light. The increased yield of radicals generated by AAPH@CB7 is believed to arise from a pull effect of CB7 portals on initial AAPH-derived carbon-centered radicals generated by photolysis. It is proposed that these radicals are exposed and released to the bulk solution and react with O2 to give peroxyl radicals. These results suggest that the AAPH@CB7 complex can be used to generate high yields of peroxyl radicals for their use in studying these species in material, environmental and biomedical sciences amongst others.
dc.fechaingreso.objetodigital2023-08-17
dc.format.extent28 páginas
dc.fuente.origenORCID
dc.identifier.doi10.1016/j.molliq.2023.122840
dc.identifier.urihttps://doi.org/10.1016/j.molliq.2023.122840
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/74416
dc.information.autorucEscuela de Química; Forero Girón, Angie; 0000-0001-9557-6501; 1050653
dc.information.autorucEscuela de Química; Fuentealba Patiño, Denis Alberto; 0000-0003-4798-7204; 160255
dc.information.autorucEscuela de Química; Mariño Ocampo, Nory Johana; 0000-0003-2013-9790; 1059618
dc.information.autorucEscuela de Química; Gutiérrez Oliva, Soledad; 0000-0002-3436-1985; 1004064
dc.information.autorucEscuela de Química; Herrera Pisani, Bárbara Andrea; 0000-0003-1911-4473; 4439
dc.information.autorucEscuela de Química; Toro Labbé, Alejandro; 0000-0001-9906-2153; 99827
dc.information.autorucEscuela de Química; Aliaga Miranda, Margarita Elly; 0000-0002-4143-0301; 13361
dc.information.autorucEscuela de Química; López Alarcón, Camilo Ignacio; 0000-0002-0174-8972; 1004308
dc.language.isoen
dc.nota.accesoContenido parcial
dc.revistaJournal of Molecular Liquids
dc.rightsacceso restringido
dc.subjectSupramolecular radical chemistry
dc.subjectCucurbit[7]uril complexes
dc.subjectPeroxyl radicals
dc.subjectAzocompounds
dc.subjectAAPH
dc.subject.ddc510
dc.subject.deweyMatemática física y químicaes_ES
dc.titleComplexation of AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride) with cucurbit[7]uril enhances the yield of AAPH-derived radicals
dc.typepreprint
sipa.codpersvinculados1050653
sipa.codpersvinculados160255
sipa.codpersvinculados1059618
sipa.codpersvinculados1004064
sipa.codpersvinculados4439
sipa.codpersvinculados99827
sipa.codpersvinculados13361
sipa.codpersvinculados1004308
sipa.trazabilidadORCID;2023-08-16
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