Abstract
The recalcitrance of plant cell wall lignocellulosic biomass to deconstruction is a major hurdle to sustainable biofuel/bioproduct economy. A multitude of interactions stabilize lignocellulosic biomass structure. Among these, tight packing of hemicellulose-cellulose is partly responsible for biomass recalcitrance. Here, unrestrained molecular dynamics simulations are employed to understand the influence of the nature and pattern of naturally-occuring acetyl decorations of the xylan backbone on interactions with the (100) hydrophobic cellulose surface. Periodically O2-acetylated xylan (2AcX) assume twofold helical screw conformations that are stabilized by a combination of multiple hydrophobic contacts and hydrogen bonds with the hydrophobic cellulose surface. In contrast, acetylation at the O3 position in xylan obstructs interactions, thereby adopting threefold helical screw conformations that potentially preferably interact with lignin rather than cellulose. Fully acetylated xylan desorbs from the surface implying a minimum number of unsubstituted residues on the xylan backbone is required for interaction with the surface. The substituted residues must form ~ 20% fewer contacts than the unsubstituted residues to sustain stable twofold helical screw xylan conformations on the cellulose surface. Thus, specific roles of macromolecular conformations of cellulose and hemicellulose in influencing the supramolecular interactions and function of plant cell walls have been determined.
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Acknowledgments
This study was supported by SERB-POWER grant received from Science and Engineering Research Board (SERB), under the Department of Science and Technology (DST) Government of India (Reference No. SPG/2021/002224). This research was supported by the Center for Lignocellulose Structure and Formation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE- SC0001090 and by the Genomic Science Program, Office of Biological and Environmental Research, U. S. Department of Energy (DOE) under Contract FWP ERKP752. This research used resources of the National Energy Research Scientific Computing Center, supported under Contract No. DE-AC02- 05CH11231. Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. This work used resources of the Compute and Data Environment for Science (CADES) at ORNL.
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MG performed all the simulations and analysis and wrote the main manuscript along with preparation of figures and tables. PD, LP and JS provided important inputs to improve the manuscript and reviewed the manuscript.
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Gupta, M., Dupree, P., Petridis, L. et al. Patterns in interactions of variably acetylated xylans with hydrophobic cellulose surfaces. Cellulose 30, 11323–11340 (2023). https://doi.org/10.1007/s10570-023-05584-z
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DOI: https://doi.org/10.1007/s10570-023-05584-z