Tertiary amines chemiluminescence

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. ... 

Holeman, J.A. Danielson, N.D. Microbore liquid chromatography of tertiary amine anticholinergic pharmaceuticals with tris(2,2 -bipyridine)ruthenium(III) chemiluminescence detection. J.Chromatogr. ScL, 1995, 33, 297-302... 

Knight AW, Greenway GM (1996) Relationship between structural attributes and observed electrogenerated chemiluminescence (ECL) activity of tertiary amines as potential analytes for the tris(2,2-bipyridine)mthenium(II) ECL reaction a review. Analyst 121(11) 101R— 106R... 

Knight AW, Greenway GM (1995) Indirect, ion-annihilation electrogenerated chemiluminescence and its application to the determination of aromatic tertiary-amines. Analyst 120(4) 1077-1082. doi 10.1039/an9952001077... 

Wightman RM, Forty SP, Mans R, Badocco D, Pastore P (2004) Rate-Determining Step in the Electrogenerated Chemiluminescence from Tertiary Amines with Tris(2,2 -bipyridyl)mthenium(II). J Phy Chem B 108(50) 19119-19125. doi 10.1021/jp0360341... 

A flow injection analysis method for determining low parts per million levels of an amine ethoxylate was based on the chemiluminescence reaction of tertiary amines with hypochlorite ion (129). Because of the low intensity of the chemiluminescence, Rhodamine B is added as a sensitizer. 

The chemiluminescence intensity from the reaction of amines with tris(2,2 -bipyridyl)ruthenium(III) is generally in the order tertiary > secondary > primary, but no definitive mechanisms have been elucidated. Derivatives of tris(2,2 -bipyridyl)ruthenium(II) have been introduced as labels for immunoassay or DNA probes (e.g., (13)). The use of chemiluminescent labels is clearly advantageous due to their nonradio-active nature and they can be quantified at sub-pi-comolar levels via oxidation in the presence of tripropylamine. 

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