About Making Lignin Great Again-Some Lessons From the Past.

Lignin, the second most abundant biopolymer on the planet, serves land-plants as bonding agent in juvenile cell tissues and as stiffening (modulus-building) agent in mature cell walls. The chemical structure analysis of cell wall lignins from two partially delignified wood species representing between 6 and 65% of total wood lignin has revealed that cell wall-bound lignins are virtually invariable in terms of inter-unit linkages, and resemble the native state. Variability is recognized as the result of isolation procedure.

Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(-)-MS/MS.

The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative-ion mode electrospray ionization tandem mass spectrometry (ESI(-)-MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C(15), catechin).

Surface-initiated dehydrogenative polymerization of monolignols: a quartz crystal microbalance with dissipation monitoring and atomic force microscopy study.

This work highlights a real-time and label-free method to monitor the dehydrogenative polymerization of monolignols initiated by horseradish peroxidase (HRP) physically immobilized on surfaces using a quartz crystal microbalance with dissipation monitoring (QCM-D). The dehydrogenative polymer (DHP) films are expected to provide good model substrates for studying ligninolytic enzymes. The HRP was adsorbed onto gold or silica surfaces or onto and within porous desulfated nanocrystalline cellulose films from an aqueous solution.

Surface plasmon resonance studies of pullulan and pullulan cinnamate adsorption onto cellulose.

Surface plasmon resonance studies showed pullulan cinnamates (PCs) with varying degrees of substitution (DS) adsorbed onto regenerated cellulose surfaces from aqueous solutions below their critical aggregation concentrations. Results on cellulose were compared to PC adsorption onto hydrophilic and hydrophobic self-assembled thiol monolayers (SAMs) on gold to probe how different interactions affected PC adsorption. PC adsorbed onto methyl-terminated SAMs (SAM-CH(3)) > cellulose > hydroxyl-terminated SAMs (SAM-OH) for high DS and increased with DS for each surface.

Determination of the surface coverage of adsorbed dextran and beta-cyclodextrin derivatives on gold by surface titration.

The self-assembly of thiophene-containing dextran and cyclodextrin derivatives on gold surfaces was investigated. Morphological studies (AFM) and the elemental characterization (XPS) of the surfaces show that the carbohydrate derivatives form either aggregates or uniform films depending on the structure and the solvent used. The real coverage of the surface, and hence the amount of unmodified free gold, was examined by a "titration" of the surface with a carboxyl-terminated SAM (11-mercaptoundecanoic acid, MUA) and with Mn-12, a manganese oxocluster.