Type I and Type II Photosensitized Oxidation Reactions: Guidelines and Mechanistic Pathways.

Abstract:

:Here, 10 guidelines are presented for a standardized definition of type I and type II photosensitized oxidation reactions. Because of varied notions of reactions mediated by photosensitizers, a checklist of recommendations is provided for their definitions. Type I and type II photoreactions are oxygen-dependent and involve unstable species such as the initial formation of radical cation or neutral radicals from the substrates and/or singlet oxygen (1 O21 ∆g ) by energy transfer to molecular oxygen. In addition, superoxide anion radical (O2·-) can be generated by a charge-transfer reaction involving O2 or more likely indirectly as the result of O2 -mediated oxidation of the radical anion of type I photosensitizers. In subsequent reactions, O2·- may add and/or reduce a few highly oxidizing radicals that arise from the deprotonation of the radical cations of key biological targets. O2·- can also undergo dismutation into H2 O2 , the precursor of the highly reactive hydroxyl radical (·OH) that may induce delayed oxidation reactions in cells. In the second part, several examples of type I and type II photosensitized oxidation reactions are provided to illustrate the complexity and the diversity of the degradation pathways of mostly relevant biomolecules upon one-electron oxidation and singlet oxygen reactions.

journal_name

Photochem Photobiol

authors

Baptista MS,Cadet J,Di Mascio P,Ghogare AA,Greer A,Hamblin MR,Lorente C,Nunez SC,Ribeiro MS,Thomas AH,Vignoni M,Yoshimura TM

doi

10.1111/php.12716

subject

Has Abstract

pub_date

2017-07-01 00:00:00

pages

912-919

issue

4

eissn

0031-8655

issn

1751-1097

journal_volume

93

pub_type

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