title: Synthesis of 1,2-Dioxetanes as Thermochemiluminescent Labels for Ultrasensitive Bioassays: Rational Prediction of Olefin Photooxygenation Outcome by Using a Chemometric Approach.
abstract: 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.
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Luca A
authors: LA
authors: Andronico
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Arianna
authors: A
authors: Quintavalla
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Marco
authors: M
authors: Lombardo
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Mara
authors: M
authors: Mirasoli
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Massimo
authors: M
authors: Guardigli
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Claudio
authors: C
authors: Trombini
authors: Department of Chemistry "G. Ciamician", Alma Mater Studiorum, University of Bologna, Via Selmi 2, 40126, Bologna, Italy.
authors: Aldo
authors: A
authors: Roda
keywords: fluorine; olefination; photooxygenation; substituent effects; thermochemiluminescence