Abstract
We describe the synthesis of highly amphiphilic cellulose nanocrystals (CNCs) and their assembly into ultrathin smooth monolayers and multilayers by the Langmuir–Blodgett technique. The amphiphilicity of the CNCs and hence their solubility in chloroform was tuned by controlling the extent of surface functionalization with hydrophobic –C8 groups and the concentration of the carboxylic acid groups at the reducing end. For the most amphiphilic CNCs, a well-defined LB isotherm with three distinct phases was observed without the use of any additives. The assembled monolayers were exceptionally stable at the air/water interface for over 3 h, allowing their facile transfer to both hydrophilic and hydrophobic substrates, resulting in smooth films. A monolayer of amphiphilic CNCs deposited by the upstroke on a hydrophilic substrate showed good alignment along the substrate, while random orientation was observed on a hydrophobic substrate. Atomic force microscopy study of the monolayer transferred at a surface pressure of 15–20 mN/m showed complete monolayer coverage. Smooth multilayers were also fabricated by the sequential deposition of up to six monolayers. The excellent control over film formation afforded by the combination of the amphiphilicity of the CNCs, LB assembly, and the use of organic solvent make this methodology useful for emerging optical and electronic applications of CNCs.
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Acknowledgements
This work was supported by the University of Wisconsin-Madison, Office of the Vice Chancellor for Research and Graduate Education with funding from the Wisconsin Alumni Research Foundation. The authors gratefully acknowledge the use of facilities and instrumentation at the University of Wisconsin-Madison Wisconsin Centers for Nanoscale Technology partially supported by the NSF through the University of Wisconsin Materials Research Science and Engineering Center (DMR1720415). The NMR instrumentation in the Paul Bender Chemistry Instrumentation Center was supported by a generous gift from Paul J. and Margaret M. Bender and UW2020. NT was funded by a Science Achievement Scholarship of Thailand. We gratefully acknowledge the CNC samples from Forest Product Laboratories, in Madison, WI, from Dr. Junyong (J.Y.) Zhu.
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HK synthesized, characterized, and assembled the CNCs. JS assisted with LB assembly, characterization and analysis of the data. NT assisted in the optimization of LB studies. CMC provided expertise on 13C NMR characterization. JHD contributed toward substrate preparation. All authors contributed toward writing the manuscript.
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Kar, H., Sun, J., Clewett, C.F.M. et al. Uniform amphiphilic cellulose nanocrystal films. Polym J 54, 539–550 (2022). https://doi.org/10.1038/s41428-021-00611-x
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DOI: https://doi.org/10.1038/s41428-021-00611-x