Chemiluminescence catalyzed peroxide decomposition

Special review articles published since 1968 on these topics are one by E. H. White and D. F. Roswell 2> on hydrazide chemiluminescence M. M. Rauhut 3) on the chemiluminescence of concerted peroxide-decomposition reactions and D. M. Hercules 4 5> on chemiluminescence from electron-transfer reactions. The rapid development in these special fields justifies a further attempt to depict the current status. Results of bioluminescence research will not be included in this article except for a few special cases, e.g. enzyme-catalyzed chemiluminescence of luminol, and firefly bioluminescence 6>. 

Other detection methods have been used in optical MIP sensing systems. An MIP-based chemiluminescent flow-through sensor was developed for the detection of 1,10-phenanthroline (Lin and Yamada 2001). A metal complex was used to catalyze the decomposition of hydrogen peroxide and form the superoxide radical ion that can... 

Like other peroxides, also dioxetanes are sensitive to the presence of metal ions and their complexes, which catalyze the decomposition of the dioxetane molecule. In most cases, this decomposition is dark, i.e. no chemiluminesce is generated in such a catalytic cleavage42. An informative exception, for instance, constitutes the chemiluminescent decomposition of the dioxetane 19 in Scheme 13, initiated by the ruthenium complex Ru(bipy)3Cl243. It has been shown that this chemiexcitation derives from the valence change of the ruthenium ion in the process Ru3+ I e — Ru2+, for which the efficiency of the excited-state generation may be as much as 40%44. Hence, when the radical anion of the carbonyl cleavage fragment from the dioxetane and the Ru3+ ion are formed in... 

Interestingly, the most efficient chemiluminescent reaction so far observed during acene endo-peroxide decomposition has been exhibited by the 1,4-endo-peroxide (41) [38]. However, this very efficient chemiluminescence evidently requires treatment of (41) with acids, and it has been shown [45] that it is not the direct decomposition of the endo-peroxide to yield (43) that produces most of the excitation energy, but the acid catalyzed cleavage of (41) to yield the compounds (44) and (45). The reaction itself had been previously described [46-47]. 

Dioxiranes, three-membered-ring cyclic peroxides, are known as highly efficient and selective oxidants, capable of performing a variety of transformations for synthetic purposes. It is known that some reactions of these peroxides are accompanied by chemiluminescence due to the release of singlet oxygen. For instance, infra-red chemiluminescence (IR-CL) of O2 at A, 1270 nm is emitted in the reaction of tertiary amines and N-oxides with dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFD), as well as during the anion-catalyzed breakdown of the dioxiranes. Furthermore, IR-CL emission is produced in the ketone-catalyzed decomposition of the monoperoxysulfate ion HSOs through the intermediary dioxirane. ... 

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