論文

査読有り 本文へのリンクあり
2018年7月31日

DFT Optimization of Isolated Molecular Chain Sheet Models Constituting Native Cellulose Crystal Structures

ACS Omega
  • Takuya Uto
  • ,
  • Toshifumi Yui

3
7
開始ページ
8050
終了ページ
8058
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acsomega.8b00834

© 2018 American Chemical Society. Because of high crystallinity and natural abundance, the crystal structures of the native cellulose allomorphs have been theoretically investigated to elucidate the cellulose chain packing schemes. Here, we report systematic structure optimization of cellulose chain sheet models isolated from the cellulose Iα and Iβ crystals by density functional theory (DFT). For each allomorph, the three-dimensional chain packing structure was partitioned along each of the three main crystal planes to construct either a flat chain sheet model or two stacked chain sheet models, each consisting of four cello-octamers. Various combinations of the basis set and DFT functional were investigated. The flat chain sheet models constituting the cellulose Iα (110) and Iβ (100) planes, where the cellulose chains are mainly linked by intermolecular hydrogen bonds, exhibit a right-handed twist. More uniform and symmetrical sheet twists are observed when the flat chain sheet models are optimized using a basis set with diffuse functions (6-31+G(d,p)). The intermolecular interactions are more stable when the chain sheet models are optimized with the two hybrid functionals CAM-B3LYP and M06-2X. Optimization of the two stacked chain sheet models, where van der Waals interactions predominated between adjacent chains, gave differing results; those retaining the initial structures and those losing the sheet appearance, corresponding to the cellulose Iα/Iβ (010)/(110) and (100)/(110) chain sheet models, respectively. The cellulose Iβ (110) chain sheet model is more stable using the M06-2X functional than using the CAM-B3LYP functional.

リンク情報
DOI
https://doi.org/10.1021/acsomega.8b00834
Scopus
https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85050388583&origin=inward 本文へのリンクあり
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ID情報
  • DOI : 10.1021/acsomega.8b00834
  • eISSN : 2470-1343
  • SCOPUS ID : 85050388583

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