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Synthesis of 1,2‐Dioxetanes as Thermochemiluminescent Labels for Ultrasensitive Bioassays: Rational Prediction of Olefin Photooxygenation Outcome by Using a Chemometric Approach
Author(s) -
Andronico Luca A.,
Quintavalla Arianna,
Lombardo Marco,
Mirasoli Mara,
Guardigli Massimo,
Trombini Claudio,
Roda Aldo
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603765
Subject(s) - photooxygenation , dioxetane , singlet oxygen , chemistry , photochemistry , steric effects , quantum yield , combinatorial chemistry , singlet state , molecular descriptor , olefin fiber , yield (engineering) , molecule , fluorescence , computational chemistry , quantitative structure–activity relationship , organic chemistry , stereochemistry , materials science , excited state , catalysis , oxygen , chemiluminescence , physics , quantum mechanics , nuclear physics , metallurgy
Great interest in new thermochemiluminescent (TCL) molecules, for example, in bioanalytical assays, has prompted the design and synthesis of a small library of more than 30 olefins to be subjected to photooxygenation, with the aim of obtaining new 1,2‐dioxetane‐based TCL labels with optimized properties. Fluorine atoms on the acridan system remarkably stabilize 1,2‐dioxetanes when they are located in the 3‐ and/or 6‐position ( 4 h and 4 i ). On the other hand, 2,7‐difluorinated acridan dioxetane ( 4 j ) showed a significantly enhanced fluorescence quantum yield with respect to the unsubstituted dioxetane ( 4 a ). Some of the synthesized olefins did not undergo singlet oxygen addition and a rationale was sought to ease the photooxygenation step, leading to the TCL dioxetanes. A chemometric approach has been adopted to exploit principal component analysis and linear discriminant analysis of the structural and electronic molecular descriptors obtained by DFT optimizations of olefins 3 . This approach allows the steric and electronic parameters that govern dioxetane formation to be revealed.