Stable Organic Radicals in Lignin: A Review

Abstract Lignin and the quest for the origin of stable organic radicals in it have seen numerous developments. Although there have been various speculations over the years on the formation of these stable radicals, researchers have not been able to arrive at a solid, unequivocal hypothesis that applies to all treatments and types of lignin. The extreme complexity of lignin and its highly aromatic, cross‐linked, branched, and rigid structure has made such efforts rather cumbersome. Since the early 1950s, researchers in this field have dedicated their efforts to the establishment of methods for the detection and determination of spin content, theoretical simulations, and reactions on model compounds and spin‐trapping studies. Although a significant amount of published research is available on lignin or its model compounds and the reactive intermediates involved during various chemical treatments (pulping, bleaching, extractions, chemical modifications, etc.), the literature provides a limited view on the origin, nature, and stability of such radicals. Consequently, this review is focused on examining the origin of such species in lignin, factors affecting their presence, reactions involved in their formation, and methods for their detection.