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Two-Dimensional Vibrational Spectroscopy II: Correlation of the Absorptions of Lignins in the Mid- and Near-Infrared

Volume 47, Number 11 (Nov. 1993) Page 1920-1925

Barton, F.E.; Himmelsbach, D.S.


Two-dimensional (2D) statistical correlation of mid- and near-infrared spectra was used as a means to assist with qualitative spectral interpretation of the lignin carbohydrate fractions from plant materials. Cross-correlation by least-squares is used to assess changes in both regions that result from changes in the set of sample spectra. The technique has been applied to a set of specially prepared "lignin" samples that differ in lignin content, species of origin, and method of preparation. Dispersive near-infrared (NIR) and Fourier transformed mid-infrared (FT-IR) diffuse reflectance spectra (DRIFTS) were obtained on each of the samples, and point-for-point 2D cross-correlation was obtained. The technique permits the correlation of the combination and overtone bands of the NIR region with the fundamental vibrations in the mid-infrared (MIR) region. The results show a broad correlation of aromatic C-H stretch at 3022 cm−1 in the MIR to 1666-nm location in the NIR region and other locations to a lesser extent all across the NIR from 1400 to 2500 nm. A narrower region of correlation was found for the phenolic O-H stretch in the MIR at 3663 cm−1 to 1428 nm and 1938 nm in the MIR. Multiple narrow correlations occur in the area of the summation bands from 1450 to 1650 cm−1, indicative of substitution patterns and correlated areas of C-H and O-H stretch in the NIR.