Abstract
BackgroundBesides classical utilization of wood and paper, lignocellulosic biomass has become increasingly important with regard to biorefinery, biofuel production and novel biomaterials. For these new applications the macromolecular assembly of cell walls is of utmost importance and therefore further insights into the arrangement of the molecules on the nanolevel have to be gained. Cell wall recalcitrance against enzymatic degradation is one of the key issues, since an efficient degradation of lignocellulosic plant material is probably the most crucial step in plant conversion to energy. A limiting factor for in-depth analysis is that high resolution characterization techniques provide structural but hardly chemical information (e.g. Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM)), while chemical characterization leads to a disassembly of the cell wall components or does not reach the required nanoscale resolution (Fourier Tranform Infrared Spectroscopy (FT-IR), Raman Spectroscopy).ResultsHere we use for the first time Scanning Near-Field Optical Microscopy (SNOM in reflection mode) on secondary plant cell walls and reveal a segmented circumferential nanostructure. This pattern in the 100 nm range was found in the secondary cell walls of a softwood (spruce), a hardwood (beech) and a grass (bamboo) and is thus concluded to be consistent among various plant species. As the nanostructural pattern is not visible in classical AFM height and phase images it is proven that the contrast is not due to changes in surfaces topography, but due to differences in the molecular structure.ConclusionsComparative analysis of model substances of casted cellulose nanocrystals and spin coated lignin indicate, that the SNOM signal is clearly influenced by changes in lignin distribution or composition. Therefore and based on the known interaction of lignin and visible light (e.g. fluorescence and resonance effects), we assume the elucidated nanoscale structure to reflect variations in lignification within the secondary cell wall.
Highlights
Besides classical utilization of wood and paper, lignocellulosic biomass has become increasingly important with regard to biorefinery, biofuel production and novel biomaterials
Scanning Near-Field Optical Microscopy (SNOM) images of cross sections of beech (Figure 2a), spruce (2b) and bamboo (2c) cell walls indicate that the circumferential segmentation in light and dark batches is a common feature for different dicot and monocot species, despite differences in cell organization and chemical composition
To gain a deeper understanding of the SNOM signal origin in secondary cell wall analysis, we conducted a comparative investigation on a bilayer of cellulose nanocrystals and spin coated Dehydrogenation Polymers (DHP) (DeHydrogenation-Polymer)lignin on top
Summary
Besides classical utilization of wood and paper, lignocellulosic biomass has become increasingly important with regard to biorefinery, biofuel production and novel biomaterials For these new applications the macromolecular assembly of cell walls is of utmost importance and further insights into the arrangement of the molecules on the nanolevel have to be gained. The micellar theory of Nägeli [7] (developed in the 19th century) refers to a spatial distribution of the macromolecules in a concentric lamellae structure due to alternating circumferential layers of higher cellulose and higher lignin content This theory has been supported in various studies based on visible/ ultraviolet microscopy, the delamination behavior of wood fibers, the distribution and form of pores after selective removal of lignin as well as electron microscopy and atomic force microscopy studies [8,9,10,11]. Electron microscopy and atomic force microscopy (AFM) studies supported a random texture without any structured arrangement of the wood components [15,16]
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