Chemiluminescence in the reaction of 1,2,4,5-tetraoxanes with ferrous ions in the presence of xanthene dyes: fundamentals and perspectives of analytical applications.

The reaction of biologically active bridged 1,2,4,5-tetraoxanes and diperoxide of trifluoroacetone with ferrous ions in the presence of xanthenes, methylene blue and methylene green is accompanied by bright chemiluminescence (CL) caused by the emission from electronically-excited dyes. The promising perspectives for the employment of the CL method for the analytical detection of tetraoxanes were demonstrated. The most convenient CL system was found to be their reaction with ferrous gluconate in the presence of rhodamine 3B, which allowed the detection of up to 10-9 M of diperoxides. The discovered CL-probe is selective towards tetraoxanes over reactive oxygen species such as singlet oxygen, hydroxyl radicals, hydrogen peroxide, hypochlorite and superoxide ions. It is suggested that electronically-excited states may be involved in biological activities of cyclic organic peroxides.

A novel chemiluminescence from the reaction of singlet oxygen with ß-diketonates of europium(III), neodymium(III) and ytterbium(III).

Decomposition of 1,4-dimethylnaphthalene endoperoxide, which is the source of singlet oxygen, in the presence of ß-diketonates of europium(III), neodymium(III) and ytterbium(III) is accompanied by bright chemiluminescence (CL) in visible and near infra-red spectral region due to characteristic emission from the lanthanides at λmax = 615 and 710 nm ((5)D0→(7)F2 and (5)D0→(7)F4 transitions of Eu(3+)), 900 nm ((4)F3/2→(4)I9/2 transition of Nd(3+)) and 1000 nm ((2)F5/2→(2)F7/2 transition of Yb(3+)). Singlet oxygen is the key intermediate responsible for the observed CL, which is presumably generated by the reaction of (1)O2 with ligands of the complexes. The CL phenomenon discovered herein paves the way towards the development of lanthanide-based CL probe for (1)O2.