Review on catalytic cleavage of C-C inter-unit linkages in lignin model compounds: Towards lignin depolymerisation

Lignin depolymerisation has received considerable attention recently due to the pressing need to find sustainable alternatives to fossil fuel feedstock to produce chemicals and fuels. Two types of interunit linkages (C–C and C–O linkages) link several aromatic units in the structure of lignin. Between these two inter-unit linkages, the bond energies of C–C linkages are higher than that of C–O linkages, making them harder to break. However, for an efficient lignin depolymerisation, both types of inter-unit linkages have to be broken. This is more relevant because of the fact that many delignification processes tend to result in the formation of additional C–C inter-unit bonds. Here we review the strategies reported for the cleavage of C–C inter-unit linkages in lignin model compounds and lignin. Although a number of articles are available on the cleavage of C–O inter-unit linkages, reports on the selective cleavage of C–C inter-unit linkages are relatively less. Oxidative cleavage, hydrogenolysis, two-step redox-neutral process, microwave assisted cleavage, biocatalytic and photocatalytic methods have been reported for the breaking of C–C inter-unit linkages in lignin. Here we review all these methods in detail, focused only on the breaking of C–C linkages. The objective of this review is to motivate researchers to design new strategies to break this strong C–C inter-unit bonds to valorise lignins, technical lignins in particular

Heterogeneously catalyzed lignin depolymerization

Biomass offers a unique resource for the sustainable production of bio-derived chemical and fuels as drop-in replacements for the current fossil fuel products. Lignin represents a major component of lignocellulosic biomass, but is particularly recalcitrant for valorization by existing chemical technologies due to its complex cross-linking polymeric network. Here, we highlight a range of catalytic approaches to lignin depolymerisation for the production of aromatic bio-oil and monomeric oxygenates

Investigation of lichens using molecular techniques and associated mineral accumulations on a basaltic flow in a Mediterranean environment

The role of lichens in the breakdown of rocks in various environments is well documented. We investigated the formation of secondary minerals under 13 different fungal species growing on a basaltic flow in Sanliurfa (Turkey) to understand the influence of lichen species on the transformation of minerals in a Mediterranean environment. We used molecular technique (rDNA sequence) to identify 13 different species of lichens (7 crustose, 5 foliose and 1 pathogenic). X-ray diffraction and scanning electron microscopy were used to determine the composition of mineral accumulations. The formation of quartz and 2:1 phyllosilicates in various layers (top, brown and white) of the weathered basaltic flows under all the lichen colonies may be the result of precipitated silica alone (quartz) or in combination with aluminum (2:1 clays) released as a by-product during the breakdown/weathering of primary silicate minerals present in the basalt. However, aeolian deposition may also be a possible source of these mineral species. Whewellite, a calcium oxalate mineral, accumulates in the weathered basalt underneath all the species of lichens. We believe that the formation of whewellite was due to organic acids excreted by fungal hyphae to dissolve primary minerals (e.g., olivine and feldspars); this lichen-mediated process released enough calcium and generated oxalate necessary for the formation of whewellite. © 2006 Elsevier B.V. All rights reserved.Natural Sciences and Engineering Research Council of Canada Canada Research ChairsFunding for this work was provided by the Natural Science and Engineering Research Council grants to J.M. Arocena and R.W. Thring, and the Canada Research Chair Program grant to JMA