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Mechanism for the depolymerization of cellulose under alkaline conditions

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Abstract

The mechanism for the hydroxyl-radical-induced depolymerization of cellulose under alkaline conditions in air was investigated using density functional theory at the B3LYP/6-31+G(d,p) level as well as electron transfer theory. The pathway for the depolymerization of cellulose was obtained theoretically and H abstraction from the C(3) atom of the pyran ring during the cleavage of the glucosidic bond was found to be the rate-limiting step due to its high energy barrier (16.81 kcal/mol) and low reaction rate constant (4.623 × 104 mol L−1 s−1). Calculations of the electron transfer between O2 and the saccharide radical performed with the HARLEM software package revealed that following the H abstraction, the oxygen molecule approaches C(2) on the saccharide radical and obtains an electron from the radical, even though no bond forms between the oxygen molecule and the radical. The rate constant for electron transfer could be as high as 1.572 × 1011 s−1. Furthermore, an enol intermediate is obtained during the final stage of the depolymerization.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant no. 21272171) and the Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase) under grant no. U1501501.

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Authors and Affiliations

  1. Key Laboratory of Industrial Fermentation Microbiology (Tianjin University of Science & Technology), Ministry of Education, College of Biotechnology, Tianjin University of Science and Technology, Tianjin, 300457, China

    Chunfu Shao, Kunpeng Shi, Qingyuan Hua, Liming Zhang, Yujie Dai, Yang Liu & Chaozheng Zhang

  2. Tasly Academy, Tasly Group, Tianjin, 300410, China

    Chunfu Shao, Wei You, Yang Liu & Changwen Li

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  1. Chunfu Shao
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  2. Kunpeng Shi
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  3. Qingyuan Hua
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  4. Liming Zhang
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  5. Yujie Dai
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  9. Chaozheng Zhang
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Correspondence to Yujie Dai.

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Shao, C., Shi, K., Hua, Q. et al. Mechanism for the depolymerization of cellulose under alkaline conditions. J Mol Model 24, 124 (2018). https://doi.org/10.1007/s00894-018-3654-3

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  • DOI: https://doi.org/10.1007/s00894-018-3654-3

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