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At least 109 records · Page 6

Cellulose synthase gene expression profiling of Physcomitrella patens

Abstract The cellulose synthase ( CESA ) gene family of seed plants comprises six clades that encode isoforms with conserved expression patterns and distinct functions in cellulose synthesis complex ( CSC ) formation and primary and secondary cell wall synthesis. In mosses, which have rosette CSC s like those of seed plants but lack lignified secondary cell walls, the CESA gene family diversified independently and includes no members of the six functionally distinct seed plant clades. There are seven CESA isoforms encoded in the genome of the moss Physcomitrella patens . However, only Pp CESA 5 has been characterised functionally, and little information is available on the expression of other Pp CESA family members. We have profiled Pp CESA expression through quantitative RT ‐ PCR , analysis of promoter‐reporter lines, and cluster analysis of public microarray data in an effort to identify expression and co‐expression patterns that could help reveal the functions of Pp CESA isoforms in protein complex formation and development of specific tissues. In contrast to the tissue‐specific expression observed for seed plant CESA s, each of the Pp CESA s was broadly expressed throughout most developing tissues. Although a few statistically significant differences in expression of Pp CESA s were noted when some tissues and hormone treatments were compared, no strong co‐expression patterns were observed. Along with CESA phylogenies and lack of single Pp CESA mutant phenotypes reported elsewhere, broad overlapping expression of the Pp CESA s indicates a high degree of inter‐changeability and is consistent with a different pattern of functional specialisation in the evolution of the seed plant and moss CESA families.

Tran, M. L.↗

Numerical Simulation of Vibrational Sum Frequency Generation Intensity for Non-Centrosymmetric Domains Interspersed in an Amorphous Matrix: A Case Study for Cellulose in Plant Cell Wall

Vibrational sum frequency generation (SFG) spectroscopy can specifically probe molecular species non-centrosymmetrically arranged in a centrosymmetric or isotropic medium. This capability has been extensively utilized to detect and study molecular species present at the two-dimensional (2D) interface at which the centrosymmetry or isotropy of bulk phases is naturally broken. The same principle has been demonstrated to be very effective for the selective detection of non-centrosymmetric crystalline nanodomains interspersed in three-dimensional (3D) amorphous phases. However, the full spectral interpretation of SFG features has been difficult due to the complexity associated with the theoretical calculation of SFG responses of such 3D systems. This paper describes a numerical method to predict the relative SFG intensities of non-centrosymmetric nanodomains in 3D systems as functions of their size and concentration as well as their assembly patterns, i.e., the distributions of tilt, azimuth, and rotation angles with respect to the lab coordinate. We applied the developed method to predict changes in the CH and OH stretch modes characteristic to crystalline cellulose microfibrils distributed with various orders, which are relevant to plant cell wall structures. As a result, the same algorithm can also be applied to any SFG-active nanodomains interspersed in 3D amorphous matrices.

36 MATERIALS SCIENCE↗

Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanol in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.

Carbon Support↗

Enhanced Ion Conductivity through Hydrated, Polyelectrolyte-Grafted Cellulose Nanocrystal Films

Here,iIonically conductive, hydrated polyelectrolyte nanocomposites are prepared from iodomethane-treated poly(2-vinylpyridine) (mPV)-grafted cellulose nanocrystals (MxG-CNC-g-mPV). These polyelectrolyte-grafted nanoparticle (PEGN) films exhibit an order-of-magnitude higher iodide ion conductivity relative to mPV films and a high in-plane/through-plane anisotropy. The PEGN architecture prevents CNC aggregation, maximizing the CNC/polyelectrolyte interface. PEGN films were prepared with varying polymer graft density (0.03-0.12 chains/nm 2 ) and molecular weight (7k-30k g/mol). The greatest ion conductivity enhancement is observed with lower molecular weight, higher density grafts: ca. 89 ± 6 mS/cm (140 ±10 mS/cm accounting for the volume of the CNC) versus 3.3 ± 0.4 mS/cm for ungrafted mPV. Poly(styrene-block-2-vinylpyridine)-grafted CNCs were prepared in which the insulating polystyrene block or the conducting mPV block was directly attached to the CNCs; only the films with the mPV block closest to the CNCs exhibited an enhancement in conductivity relative to mPV. Together, these data point to beneficial CNC/polyelectrolyte interfacial effects, resulting in significant ionic conductivity enhancement along the length of the CNCs in these films.

74 ATOMIC AND MOLECULAR PHYSICS↗

Effects of Plant Cell Wall Matrix Polysaccharides on Bacterial Cellulose Structure Studied with Vibrational Sum Frequency Generation Spectroscopy and X-ray Diffraction

The crystallinity, allomorph content, and mesoscale ordering of cellulose produced by Gluconacetobacter xylinus cultured with different plant cell wall matrix polysaccharides were studied with vibrational sum frequency generation (SFG) spectroscopy and X-ray diffraction (XRD).

biofuels (including algae and biomass), bio-inspir↗

A Thermophilic Ionic Liquid-Tolerant Cellulase Cocktail for the Production of Cellulosic Biofuels

Generation of biofuels from sugars in lignocellulosic biomass is a promising alternative to liquid fossil fuels, but efficient and inexpensive bioprocessing configurations must be developed to make this technology commercially viable. One of the major barriers to commercialization is the recalcitrance of plant cell wall polysaccharides to enzymatic hydrolysis. Biomass pretreatment with ionic liquids (ILs) enables efficient saccharification of biomass, but residual ILs inhibit both saccharification and microbial fuel production, requiring extensive washing after IL pretreatment. Pretreatment itself can also produce biomass-derived inhibitory compounds that reduce microbial fuel production. Therefore, there are multiple points in the process from biomass to biofuel production that must be interrogated and optimized to maximize fuel production. Here, we report the development of an IL-tolerant cellulase cocktail by combining thermophilic bacterial glycoside hydrolases produced by a mixed consortia with recombinant glycoside hydrolases. This enzymatic cocktail saccharifies IL-pretreated biomass at higher temperatures and in the presence of much higher IL concentrations than commercial fungal cocktails. Sugars obtained from saccharification of IL-pretreated switchgrass using this cocktail can be converted into biodiesel (fatty acid ethyl-esters or FAEEs) by a metabolically engineered strain of E. coli . During these studies, we found that this biodiesel-producing E. coli strain was sensitive to ILs and inhibitors released by saccharification. This cocktail will enable the development of novel biomass to biofuel bioprocessing configurations that may overcome some of the barriers to production of inexpensive cellulosic biofuels.

09 BIOMASS FUELS↗

Effects of Surface Modifications of Kraft Wood Pulp Cellulose Fibres on Improving the Mechanical Properties of Cellulose Fibre/Latex Composites

In this work, three composites with different contents (5, 10, and 15% w/w) of kraft pulp fibre were produced as reinforcing elements for natural latex matrix and the mechanical properties were evaluated. In order to improve the interfacial adhesion between the matrix and the reinforcing element, chemical modifications were carried out on the surface of the fibres using octanoyl and benzoyl chlorides as modifying agents. The extension of chemical modification of the fibres was visualized by the presence of absorption bands in the spectroscopy analyzes of the modified fibre in relation to the crude fibre (ester carbonyl 1700–1740 cm{sup −1}); in addition, the hydroxyl band was preserved, which indicates a modification of surface character. The modified fibres became more hydrophobic due to the decrease in surface energy and the change in the dispersive and polar components. An increase in the storage modulus was observed for the composites with surface-modified fibres, which agrees with the improved dispersion between the surface-modified fibres and the matrix verified by means of scanning electron microscopy images. The incorporation of fibres did not cause changes in the thermal properties of the composites.

36 MATERIALS SCIENCE↗