Component Analysis of the Fluorescence Spectra of a Lignin Model Compound

In order to test whether lignin fluorescence originates from discrete fluorophores, fluorescence emission spectra of the lignin model dehydrogenative polymer (DHP) were analyzed by the band deconvolution method and time-resolved analysis of both the excitation and emission spectra. Two series of 22 fluorescence emission spectra of DHP in chloroform/methanol (3:1, v/v) solution, and as a solid suspension in water, were deconvoluted into three fluorescence and one Raman Gaussian components. Emission spectra were obtained by stepwise variation of the excitation wavelength from 360 to 465 nm. Deconvolution was performed by nonlinear fitting of all three Gaussian parameters: area, width and position. Position of all components in a series was treated as a random variable and its approximate probability distribution (APD) calculated from a series of histograms with increasing number of abscissa intervals. A five peak multimodal APD profile was obtained for both series of DHP emission spectra. The mean fluorescence lifetime varied with wavelength both in the emission and the excitation decay-associated spectra (DAS), where four kinetic components were resolved. The shapes of the excitation spectra of the four components were quite different and gradually shifted bathochromically. The multicomponent nature of the DHP emission spectra along with the changes in the mean fluorescence lifetime and the form of the excitation DAS of the four components give evidence of the heterogeneous origin of fluorescent species emitting in the visible.