The molecular origins of twist in cellulose I-beta

Bu, Lintao; Himmel, Michael E.; Crowley, Michael F.

doi:10.1016/j.carbpol.2015.02.023

Cited by 53 publications

(60 citation statements)

References 45 publications

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“…covalent) and van der Waals terms. This observation is in agreement with previous simulation studies that have associated microfibril twist with changes in the intrachain, intra-layer, and inter-layer hydrogen bonding patterns (Paavilainen et al 2011;Bu et al 2015;Conley et al 2016;Kannam et al 2017).…”

Section: Twisting Dynamics and The Hierarchical Chiral Ordersupporting

confidence: 93%

“…All-atom MD simulations have been used to study the properties of cellulose in a broad context. This includes studies on the crystal structure of cellulose microfibrils (Matthews et al 2006;Wada et al 2011;Oehme et al 2015bOehme et al , 2018, and, as mentioned before, various aspects of the microfibril twist (Yui et al 2006;Matthews et al 2006;Yui and Hayashi 2007;Paavilainen et al 2011;Hadden et al 2013;Bu et al 2015;Conley et al 2016;Kannam et al 2017). Other studies have looked at the interactions of microfibrils with water (Yui et al 2006;Bergenstråhle et al 2008;Maurer et al 2013;Kulasinski et al 2015Kulasinski et al , 2017Lindh et al 2016;O'Neill et al 2017), their response to elevated temperatures (Matthews et al 2011(Matthews et al , 2012bZhang et al 2011); their mechanical properties (Paavilainen et al 2012;Saitoh et al 2013;Molnár et al 2018), aggregation and disintegration (Oehme et al 2015a;Paajanen et al 2016;Silveira et al 2016), chemical modification (Wada et al 2011;Paajanen et al 2016), enzymatic degradation (Beckham et al 2011;Orłowski et al 2015), and dissolution in ionic liquids (Gross et al 2011;Uto et al 2018); the pyrolytic degradation of cellulose (Zheng et al 2016;Paajanen and Vaari 2017); and radiation-induced defects…”

Section: Computationalmentioning

confidence: 99%

“…Several molecular-level mechanisms have been proposed as the driving force behind the twisting of single microfibrils. Since the phenomenon was first observed in classical MD simulations (Yui et al 2006;Matthews et al 2006;Yui and Hayashi 2007), it has been attributed, solely or in part, to (1) changes in intra and interlayer hydrogen bonding patterns (Paavilainen et al 2011) (2) attractive, interlayer, van der Waals forces (Hadden et al 2013) (3) torsional forces due to the geometry of the trans-glycosidic hydrogen bonds, especially the HO2-O6' bond (Bu et al 2015;Conley et al 2016), and (4) a joint effect of several mechanisms (Kannam et al 2017). In a related discussion (Zhao et al 2013), it has been speculated that amorphous regions repeating along the length of the fibril would be needed to release stresses involved with the twist, and to keep the cellulose I b structure intact.…”

Section: Introductionmentioning

confidence: 99%

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Chirality and bound water in the hierarchical cellulose structure

et al. 2019

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The origins of the unique properties of natural fibres have remained largely unresolved because of the complex interrelations between structural hierarchy, chirality and bound water. In this paper, analysis of the melting endotherms for bleached hardwood pulps indicates that the amount of nonfreezing bound water (0.21 g/g) is roughly half of the amount of freezing bound water (0.42 g/g). We link this result to the two smallest constitutive units, microfibrils and their bundles, using molecular dynamics simulations at both hierarchical levels. The molecular water layers found in the simulations correspond quite accurately to the measured amount of non-freezing and freezing bound water. Disorder that results from the microfibril twist and amphiphilicity prevents co-crystallisation, leaving routes for water molecules to diffuse inside the microfibril bundle. Moreover, the simulations predict correctly the magnitude of the right-handed twist at different hierarchical levels. Significant changes in hydroxymethyl group conformations are seen during twisting that compare well with existing experimental data. Our findings go beyond earlier modelling studies in predicting the twist and structure of the microfibril bundle.

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Section: Twisting Dynamics and The Hierarchical Chiral Ordersupporting

confidence: 93%

Section: Computationalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chirality and bound water in the hierarchical cellulose structure

et al. 2019

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“…Despite the recent attention, twist is a much debated property of cellulose microfibrils with conjecture as to whether it exists and if so, what drives its formation [6,7,8]. In general, experiments performed on cellulose fibers of micrometer length and with a diameter of 20-50 nm have found that 180 • twist occurs over a length of a few hundred nanometers to a few micrometers [9,10,11,12].…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Hydrogen bonds and twist in cellulose microfibrils

Kannam

Oehme

Doblin

et al. 2017

Carbohydrate Polymers

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There is increasing experimental and computational evidence that cellulose microfibrils can exist in a stable twisted form. In this study, atomistic molecular dynamics (MD) simulations are performed to investigate the importance of intrachain hydrogen bonds on the twist in cellulose microfibrils. We systematically enforce or block the formation of these intrachain hydrogen bonds by either constraining dihedral angles or manipulating charges. For the majority of simulations a consistent right handed twist is observed. The exceptions are two sets of simulations that block the O2-O6' intrachain hydrogen bond, where no consistent twist is observed in multiple independent simulations suggesting that the O2-O6' hydrogen bond can drive twist. However, in a further simulation where exocyclic group rotation is also blocked, right-handed twist still develops suggesting that intrachain hydrogen bonds are not necessary to drive twist in cellulose microfibrils.

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“…The microfibrils can achieve width from 2-3 nm in the primary wall and 5-10 nm for secondary wall. The microfibrils may have some twisted regions (BU;CROWLEY, 2015;CONLEY et al, 2016). The amorphous regions occurs in a periodic distribution as show by ramie fibers studies (NISHIYAMA et al, 2003a).…”

Section: -Cellulosementioning

confidence: 99%

Nanostructure variability of cellulose from plants and the impact on cellulose nanocrystals production

Oliveira¹

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For last four years, I dedicate myself in the construction, performing and developing this thesis. This thesis is a result of several years of work and dedication in researching. This is a dream comes true, from a shy child, that has dream to become a scientist. This thesis would not be possible without the help of a lot of people, I work with. So, I want to acknowledge their contributions in this work. Firstly, I am gratefully to professor Antonio Aprigio da Silva Curvelo for the opportunity to develop this thesis in his group, for all the guidance, during the work, not only in academic's subjects but also in life. I want to acknowledge Carlos Driemeier for being my advisor along these years. He was the first person to give me a chance in research during the undergrad, he was the person that present to me the world of research. So, I am very grateful to Carlos for all his done, and because of that was an honor been his student. For both I want to say thanks for everything, I veary gratefful for all the things and for all these years. Also, I want to acknowledge the professors Mohamed Naceur Belgacem and Julien Bras for receiving me at their group in Grenoble. The time I spent at Naceur and Julien laboratory, was enlightening as researcher. Both help me to seek new heights as a researcher and as person. I want to thank all the technicians from CTBE, IQSC, Pagora, LNNano and from the Department of Materials Engineering USP-São Carlos for their help, teaching, and patience. To my colleagues from laboratory, those gave me advice, to perform experiments, new points of view and friendship all these years. For the teaching all the things, techniques, procedures, and theory that I can use. For those I develop friendship, that goes beyond the laboratory. I want to thank my roommates and friends, for their support at happy and sad moments. They were help in times of need motivation and support to continue this work. For them is difficult to express my gratitude and express my feelings to them are beyond the words. Their friendship was, reward for all the sad moments, and especially at the happy moments, that I will never forget. I want to thank the "Laboratório de Ciência e Tecnologia do Bioetanol" (CTBE) and the "Centro Nacional de Pesquisa em Energia e Materiais" (CNPEM) for allow me to perform experiments in their facility.

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The molecular origins of twist in cellulose I-beta

Cited by 53 publications

References 45 publications

Chirality and bound water in the hierarchical cellulose structure

Chirality and bound water in the hierarchical cellulose structure

Hydrogen bonds and twist in cellulose microfibrils

Nanostructure variability of cellulose from plants and the impact on cellulose nanocrystals production

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