Quantum mechanical modeling of the structures, energetics and spectral properties of Iα and Iβ cellulose
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Periodic planewave and molecular cluster density functional theory (DFT) calculations were performed on Iα and Iβ cellulose in four different conformations each. The results are consistent with the previous interpretation of experimental X-ray and neutron diffraction data that both Iα and Iβ cellulose are dominantly found in the tg conformation of the hydroxymethyl group with a H-bonding conformation termed “Network A”. Structural and energetic results of the periodic DFT calculations with dispersion corrections (DFT-D2) are consistent with observation suggesting that this methodology is accurate to within a few percent for modeling cellulose. The structural and energetic results were confirmed by comparison of calculated vibrational frequencies against observed infrared and Raman frequencies of Iα and Iβ cellulose. Structures extracted from the periodic DFT-D2 energy minimizations were used to calculate the 13C nuclear magnetic resonance chemical shifts (δ13C), and the tg/Network A conformations of both Iα and Iβ cellulose produced excellent correlations with observed δ13C values.
KeywordsCellulose Infrared Raman NMR DFT
This work was supported by the U.S. Department of Energy grant for the Energy Frontier Research Center in Lignocellulose Structure and Formation (CLSF) from the Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001090. The authors also thank Ilana Bar Ben Gurion University of the Negev for providing IR and Raman frequencies of crystalline cellobiose and Yoshiharu Nishiyama for suggesting DFT-D2 calculations as a methodology for modeling cellulose. Computational support was provided by the Research Computation and Cyberinfrastructure group at The Pennsylvania State University.
- Cirtog M, Alikhani ME, Madebène B, Soulard P, Asselin P, Tremblay B (2011) Bonding nature and vibrational signatures of oxirane: (water) n = 1-3. Assessment of the performance of the dispersion-corrected DFT methods compared to the ab initio results and Fourier transform infrared experimental data. J Phys Chem A 115(24):6688-6701CrossRefGoogle Scholar
- Eck B (2012) wxDragon. Retrieved from www.wxdragon.de
- Erata T, Shikano T, Yunoki S, Takai M (1997) The complete assignment of the 13C CP/MAS NMR spectrum of native cellulose by using 13C labeled glucose. Cellul Commun 4:128-131Google Scholar
- Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr et al (2009) Gaussian 09 Revision B.01. Gaussian, Inc, Wallingford, CTGoogle Scholar
- Harris DM, Corbin K, Wang T, Gutierrez R, Bertolo AL, Carloalberto P, Smilgies D-M et al (2012) Cellulose microfibril crystallinity is reduced by mutating C-terminal transmembrane region residues CESA1A903 V and CESA3T942I of cellulose synthase. Proc Natl Acad Sci USA 109(11):4098-4103CrossRefGoogle Scholar
- Hesse-Ertelt S, Witter R, Ulrich AS, Kondo T, Heinze T (2008) Spectral assignments and anisotropy data of cellulose Iα: 13C-NMR chemical shift data of cellulose Iα determined by INADEQUATE and RAI techniques applied to uniformly 13C-labeled bacterial celluloses of different Gluconacetobacter xylinus strains. Magn Reson Chem 46:1030-1036CrossRefGoogle Scholar
- Lee CM, Park YB, Mohamed MNA, Kubicki JD, Roberts E, Cosgrove et al (2012) Structural understanding of cellulose from sum-frequency-generation (SFG) spectroscopy analyses. In: 243rd American chemical society national meeting and exposition. American Chemical Society, San DiegoGoogle Scholar
- Lovas F, Belov S, Tretyakov M, Stahl W, Suenram RD (1995) The a-Type K = 0 microwave spectrum of the methanol dimer. J Mol Spectrosc 170:478-492. Retrieved from http://www.sciencedirect.com/science/article/pii/S0022285285710867
- Payen A (1838) Memoir on the composition of the tissue of plants and of woody material. CR Biol 7:1052-1056Google Scholar
- Tormo J, Lamed R, Chirino AJ, Morag E, Bayer EA, Shoham Y, Steitz TA (1996) Crystal structure of a bacterial family-III cellulose-binding domain: a general mechanism for attachment to cellulose. J Eur Mol Biol Organ (EMBO) 5:5739-5751Google Scholar
- Zhao Y, Schultz NE, Truhlar DG (2006) Design of density functionals by combining the method of constraint satisfaction with parametrization for thermochemistry, thermochemical kinetics, and noncovalent interactions. Design 2:364-382Google Scholar
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