Thermochemiluminescence as a fast method to detect and characterize hydroperoxide moieties in novel 3-hydroperoxyisothiazole 1,1-dioxides

Gilbert, Matthias; Zakharova, Valeria M.; Ramenda, Anna; Jebsen, Christian; Schulze, B.; Wilhelm, Christian

doi:10.1016/j.tet.2012.05.100

Cited by 3 publications

(1 citation statement)

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“…If these chemiluminophores are chemically modified to be stable at room temperature, their decomposition can be induced by heating or by application of mechanical force, and the respective phenomena are referred to as thermo- and mechanochemiluminescence. It was demonstrated recently that mechanochemiluminescent polymers can be prepared by incorporating mechanoluminophores in their polymer backbone 5,6 , and thermochemiluminescence was also accomplished by heating of deposited nanoparticles 7–9 and microcrystalline powder 10 . Chemiluminescence in the pure macroscopic solid state, however, was deemed unfeasible due to the very limited ability of molecules for diffusion required for their reaction and the anticipated low quantum yields.…”

Section: Introductionmentioning

confidence: 99%

Thermochemiluminescent peroxide crystals

Schramm¹,

Karothu²,

Lui³

et al. 2019

Nat Commun

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Chemiluminescence, a process of transduction of energy stored within chemical bonds of ground-state reactants into light via high-energy excited intermediates, is known in solution, but has remained undetected in macroscopic crystalline solids. By detecting thermally induced chemiluminescence from centimeter-size crystals of an organic peroxide here we demonstrate direct transduction of heat into light by thermochemiluminescence of bulk crystals. Heating of crystals of lophine hydroperoxide to ~115 °C results in detectable emission of blue-green light with maximum at 530 nm with low chemiluminescent quantum yield [(2.1 ± 0.1) × 10 ‒7 E mol ‒1 ]. Spectral comparison of the thermochemiluminescence in the solid state and in solution revealed that the solid-state thermochemiluminescence of lophine peroxide is due to emission from deprotonated lophine. With selected 1,2-dioxetane, endoperoxide and aroyl peroxide we also establish that the thermochemiluminescence is common for crystalline peroxides, with the color of the emitted light varying from blue to green to red.

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Section: Introductionmentioning

confidence: 99%

Thermochemiluminescent peroxide crystals

Schramm¹,

Karothu²,

Lui³

et al. 2019

Nat Commun

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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

Andronico

Quintavalla

Lombardo

et al. 2016

Chemistry A European J

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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.

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