High-Temperature Behavior of Cellulose I

Matthews, James F.; Bergenstråhle, Malin; Beckham, Gregg T.; Himmel, Michael E.; Nimlos, Mark R.; Brady, John W.; Crowley, Michael F.

doi:10.1021/jp1106839

Cited by 127 publications

(140 citation statements)

References 119 publications

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“…Similar effects were predicted in hydrated cellulose I b microfibrils with the GLYCAM06 force field, but not the Gromos 45a4 force field (Matthews et al 2012). The unit-cell expansion and structures predicted by the CHARMM and GLYCAM06 force fields are similar to structures in simulations at elevated temperature (Matthews et al 2011) and are consistent with experimental observation of anisotropic thermal expansion (Wada et al 2010). The CVFF (Consistent Valence Force Field) force field (Hagler et al 1979a) is an example of one that is not recognized specifically for study of carbohydrates, but has been used to model the conformation of oligosaccharides (Hardy and Sarko 1993;Hagler et al 1979b;Siebert et al 1992).…”

Section: Introductionsupporting

confidence: 58%

“…These are the same responses as for a tension applied along the chain axis in the CVFF3 model presented here. Molecular dynamics simulations (CHARMM and GLYCAM06 force fields) predict the presence of tilted chains and inter-layer hydrogen bonds in high temperature cellulose I (Matthews et al 2011). Taken together these suggest a mechanistic link between the thermal expansion and Poisson's ratio responses in high temperature cellulose I and kraft cooked cellulose I b , respectively.…”

Section: Discussionmentioning

confidence: 81%

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Modeling of negative Poisson’s ratio (auxetic) crystalline cellulose Iβ

Yao

Alderson²,

Alderson

2016

Cellulose

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Energy minimizations for unstretched and stretched cellulose models using an all-atom empirical force field (molecular mechanics) have been performed to investigate the mechanism for auxetic (negative Poisson's ratio) response in crystalline cellulose I b from kraft cooked Norway spruce. An initial investigation to identify an appropriate force field led to a study of the structure and elastic constants from models employing the CVFF force field. Negative values of on-axis Poisson's ratios m 31 and m 13 in the x 1 -x 3 plane containing the chain direction (x 3 ) were realized in energy minimizations employing a stress perpendicular to the hydrogen-bonded cellobiose sheets to simulate swelling in this direction due to the kraft cooking process. Energy minimizations of structural evolution due to stretching along the x 3 chain direction of the 'swollen' (kraft cooked) model identified chain rotation about the chain axis combined with inextensible secondary bonds as the most likely mechanism for auxetic response.

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Section: Introductionsupporting

confidence: 58%

Section: Discussionmentioning

confidence: 81%

Modeling of negative Poisson’s ratio (auxetic) crystalline cellulose Iβ

Yao

Alderson²,

Alderson

2016

Cellulose

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“…80. The mean helical pitch would probably need to be at least an order of magnitude greater than the resulting column length and would therefore be too long to give rise to small-angle axial scattering features within the q range of our SANS experiments.…”

Section: Discussionmentioning

confidence: 87%

Nanostructure of cellulose microfibrils in spruce wood

Fernandes

Thomas

Altaner

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

627

693

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The structure of cellulose microfibrils in wood is not known in detail, despite the abundance of cellulose in woody biomass and its importance for biology, energy, and engineering. The structure of the microfibrils of spruce wood cellulose was investigated using a range of spectroscopic methods coupled to small-angle neutron and wide-angle X-ray scattering. The scattering data were consistent with 24-chain microfibrils and favored a "rectangular" model with both hydrophobic and hydrophilic surfaces exposed. Disorder in chain packing and hydrogen bonding was shown to increase outwards from the microfibril center. The extent of disorder blurred the distinction between the I alpha and I beta allomorphs. Chains at the surface were distinct in conformation, with high levels of conformational disorder at C-6, less intramolecular hydrogen bonding and more outward-directed hydrogen bonding. Axial disorder could be explained in terms of twisting of the microfibrils, with implications for their biosynthesis.crystallinity | infrared | deuterium exchange | nuclear magnetic resonance | spin diffusion

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“…X-ray contrast depends mainly on local electron density, whereas neutron scattering contrast derives from local elemental composition and density. One advantage of this technique is the very different neutron scattering cross sections of hydrogen and deuterium, which allow for the introduction of contrast through, for example, deuterium exchange in deuterium oxide (D 2 O; Horikawa et al, 2009;Matthews et al, 2011). …”

Section: Microfibril Diameter and Spacing From Small-angle Neutron Scmentioning

confidence: 99%

Structure of Cellulose Microfibrils in Primary Cell Walls from Collenchyma

et al. 2012

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In the primary walls of growing plant cells, the glucose polymer cellulose is assembled into long microfibrils a few nanometers in diameter. The rigidity and orientation of these microfibrils control cell expansion; therefore, cellulose synthesis is a key factor in the growth and morphogenesis of plants. Celery (Apium graveolens) collenchyma is a useful model system for the study of primary wall microfibril structure because its microfibrils are oriented with unusual uniformity, facilitating spectroscopic and diffraction experiments. Using a combination of x-ray and neutron scattering methods with vibrational and nuclear magnetic resonance spectroscopy, we show that celery collenchyma microfibrils were 2.9 to 3.0 nm in mean diameter, with a most probable structure containing 24 chains in cross section, arranged in eight hydrogen-bonded sheets of three chains, with extensive disorder in lateral packing, conformation, and hydrogen bonding. A similar 18-chain structure, and 24-chain structures of different shape, fitted the data less well. Conformational disorder was largely restricted to the surface chains, but disorder in chain packing was not. That is, in position and orientation, the surface chains conformed to the disordered lattice constituting the core of each microfibril. There was evidence that adjacent microfibrils were noncovalently aggregated together over part of their length, suggesting that the need to disrupt these aggregates might be a constraining factor in growth and in the hydrolysis of cellulose for biofuel production.Growth and form in plants are controlled by the precisely oriented expansion of the walls of individual cells. The driving force for cell expansion is osmotic, but the rate and direction of expansion are controlled by the mechanical properties of the cell wall (Szymanski and

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High-Temperature Behavior of Cellulose I

Abstract: Molecular simulations that model cellulose microfibrils at high temperature indicate regions that may be easier to break down, which could lead to more efficient processing of cellulose into biofuel.

Cited by 127 publications

References 119 publications

Modeling of negative Poisson’s ratio (auxetic) crystalline cellulose Iβ

Modeling of negative Poisson’s ratio (auxetic) crystalline cellulose Iβ

Nanostructure of cellulose microfibrils in spruce wood

Structure of Cellulose Microfibrils in Primary Cell Walls from Collenchyma

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