title: Structural analysis of lignin by resonance Raman spectroscopy.
abstract: Resonance Raman (RR) spectroscopy, combined with Kerr gated fluorescence rejection in the time domain, has recently elucidated lignin structure with unique sensitivity and selectivity. This promises structural studies of fluorescent natural macromolecules, such as lignin, which were previously not possible. Such studies rely on an improved understanding of the RR spectral behavior of lignin, which is today scarcely understood. We explain for the first time this behavior by a semi-empirical theory, and observe its pertinent features for lignin in vascular plants. We have used well-defined oxidative treatments as means of probing lignin structural elements, and show that RR sensitivity and selectivity depend crucially on excitation wavelength. Through the theory we relate these results to basic structural aspects of lignin. Spectra obtained by blue light laser excitation (400 nm) are dominated by low redox potential syringyl lignin groups, whereas lower photon energy (500 nm) decreases the selectivity markedly. RR bands depend on molecular structure but also on molecular environment. Thus charge transfer donor-acceptor interactions within lignin reduce the intensity of bands associated with electron rich moieties. New possibilities for basic and selective structural information on fluorescent natural materials, such as lignin, have thus appeared.
authors.affiliation: Forest and Landscape, The Royal Veterinary and Agricultural University, Højbakkegård Allé 1, DK-2630 Taastrup, Denmark. sbar@kvl.dk
authors.forename: Søren
authors.initials: S
authors.lastname: Barsberg
authors.forename: Pavel
authors.initials: P
authors.lastname: Matousek
authors.forename: Mike
authors.initials: M
authors.lastname: Towrie
mesh_terms: D008031:Lignin / Q000737:chemistry*; D015394:Molecular Structure; D013059:Spectrum Analysis, Raman / Q000379:methods
chemical_list: D008031:Lignin