Quantum-chemical insights into chemiluminescence from carbonyls

Organisms undergoing oxidative metabolism or stress chemically generate electronically excited species through dioxetane and tetroxide pathways. Consequently, luminescence is emitted which could be exploited for non-invasive label-free monitoring of oxidative stress. Spectral analysis of this endogenous chemiluminescence can serve as a tool for identification of the emitters as products of oxidation. Here we employ quantum mechanical calculations (Gaussian software package) and sensitive experimental photon counting methods to obtain deeper understanding of the emitter molecules both from theoretical and experimental perspective. We focused on the analysis of excited carbonyl groups of simple model species (formaldehyde, acetone, etc.) and carbonyls formed by fragmentation of linoleic acid since they are common product of oxidation and also potential emitters of endogenous chemiluminescence.