title: Stable free radicals in insect cuticles: electron spin resonance spectroscopy reveals differences between melanization and sclerotization.
abstract: Insect cuticles (exuviae; cast skins) were examined for the first time by ESR spectroscopy for the presence of stable free radicals, as found in melanins. All cuticles, except those from a locust albino strain, irrespective of the presence of melanin, provided single-line signals of varied g-values and linewidths. The ESR signals of melanins, isolated or in cuticles, were characterized by g-values <2.004 and small linewidths in the range of 4-6G, while sclerotized cuticles, lacking melanin, showed g-values >2.004 and broad linewidths of 5-11 G. The melanin spectra were comparable to those reported for eumelanins with indol-based monomers. Minor signals ascribed to pheomelanins were found in several probes. The 'sclerotin' spectra were broader and displayed unresolved hyperfine structure in some cases. As for melanins, the location and environment of the radicals in cuticles giving rise to the two types of ESR spectra could not be assigned. Changes in the radical environment due to insecticide or solvent treatment can be detected by ESR spectroscopy.
authors.affiliation: Department of Biology I, University of Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany. hartmut.kayser@uni-ulm.de
authors.forename: Hartmut
authors.initials: H
authors.lastname: Kayser
authors.forename: Cornelia G
authors.initials: CG
authors.lastname: Palivan
mesh_terms: D000818:Animals; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D005609:Free Radicals / Q000032:analysis*; D066298:In Vitro Techniques; D019476:Insect Proteins / Q000378:metabolism*; D007313:Insecta / Q000145:classification; D008543:Melanins / Q000032:analysis*; D011506:Proteins / Q000032:analysis*; D012867:Skin / Q000378:metabolism*; D013045:Species Specificity; D014018:Tissue Distribution
chemical_list: D005609:Free Radicals; D019476:Insect Proteins; D008543:Melanins; D011506:Proteins; C047663:cuticle proteins, insects; C013247:sclerotin