在本文中，疏水2,2,6,6-四甲基-1-哌啶氧自由基（TEMPO）-氧化纖維素奈米纖維膜通過三種方法，其是醯胺化，離子絡合烷基胺，和用甲醇甲基化製備。
通過傅立葉轉換紅外光譜、紫外線可見光透射率、拉伸強度、水氣吸附、接觸角和在水中的穩定性來確認膜的改性、光學性質、機械性質和疏水性。由於長烷基側鏈相互作用，膜的透射率從87％降低至41％，斷裂應力降低了約50％。然而接觸角從56°增加到93°，並且水氣吸附從630mg降低到184mg，表明疏水性增加且該膜在水中變得非常穩定。因此，這些結果表明成功地合成耐水性和疏水性的纖維素膜。

In the thesis, the hydrophobic 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO)-oxidized cellulose nanofibers films were prepared by three methods, which are amidation, amine complexation with alkylamines, and methylation with methanol.
The modification, optical property, mechanical property, and hydrophobicity of the films were confirmed with Fourier transform infrared absorption, ultraviolet-visible transmittance, tensile strength, vapor adsorption, contact angle, stability in water.
The long alkyl side chain interaction caused transmittance decreased from 87% to 41% and the breaking stress decreased by approximately 50%. However, the contact angle of films increased from 56 to 93, and the vapor adsorption of the film decreased from 630 mg to 184 mg, indicating the increase of the hydrophobicity. Then, the film became very stable in water. Thus, these results indicate water resistance and hydrophobic cellulose film successfully synthesize.

[1] D. M. Updegraff, "SEMIMICRO DETERMINATION OF CELLULOSE IN BIOLOGICAL MATERIALS," (in English), Analytical Biochemistry, Article vol. 32, no. 3, pp. 420-+, 1969.
[2] H. Wondraczek and T. Heinze, "Cellulosic Biomaterials," in Polysaccharides: Bioactivity and Biotechnology, K. G. Ramawat and J.-M. Mérillon, Eds. Cham: Springer International Publishing, 2015, pp. 289-328.
[3] Y. Habibi, L. A. Lucia, and O. J. Rojas, "Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications," (in English), Chemical Reviews, Review vol. 110, no. 6, pp. 3479-3500, Jun 2010.
[4] F. W. Herrick, R. L. Casebier, J. K. Hamilton, and K. R. Sandberg, "Microfibrillated cellulose: morphology and accessibility," in J. Appl. Polym. Sci.: Appl. Polym. Symp.;(United States), 1983, vol. 37, no. CONF-8205234-Vol. 2: ITT Rayonier Inc., Shelton, WA.
[5] X. M. Dong, J. F. Revol, and D. G. Gray, "Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose," (in English), Cellulose, Article vol. 5, no. 1, pp. 19-32, Mar 1998.
[6] M. Henriksson, G. Henriksson, L. A. Berglund, and T. Lindstrom, "An environmentally friendly method for enzyme-assisted preparation of microfibrillated cellulose (MFC) nanofibers," (in English), European Polymer Journal, Article vol. 43, no. 8, pp. 3434-3441, Aug 2007.
[7] L. Wagberg, G. Decher, M. Norgren, T. Lindstrom, M. Ankerfors, and K. Axnas, "The build-up of polyelectrolyte multilayers of microfibrillated cellulose and cationic polyelectrolytes," (in English), Langmuir, Article vol. 24, no. 3, pp. 784-795, Feb 2008.
[8] A. Isogai, T. Saito, and H. J. n. Fukuzumi, "TEMPO-oxidized cellulose nanofibers," vol. 3, no. 1, pp. 71-85, 2011.
[9] F. Rol, M. N. Belgacem, A. Gandini, and J. Bras, "Recent advances in surface-modified cellulose nanofibrils," (in English), Progress in Polymer Science, Review vol. 88, pp. 241-264, Jan 2019.
[10] C. H. Xue, S. T. Jia, J. Zhang, and J. Z. Ma, "Large-area fabrication of superhydrophobic surfaces for practical applications: an overview," (in English), Science and Technology of Advanced Materials, Review vol. 11, no. 3, p. 15, Jun 2010, Art. no. 033002.
[11] W. Barthlott and C. Neinhuis, "Purity of the sacred lotus, or escape from contamination in biological surfaces," (in English), Planta, Article vol. 202, no. 1, pp. 1-8, May 1997.
[12] R. S. Hebbar, A. M. Isloor, and A. F. Ismail, "Chapter 12 - Contact Angle Measurements," in Membrane Characterization, N. Hilal, A. F. Ismail, T. Matsuura, and D. Oatley-Radcliffe, Eds.: Elsevier, 2017, pp. 219-255.
[13] W. Thielicke, "Computer graphic of a lotus leaf surface," 2007.
[14] J. Wang, "Lotus Leaf: Lotus Effect," in Encyclopedia of Tribology, Q. J. Wang and Y.-W. Chung, Eds. Boston, MA: Springer US, 2013, pp. 2010-2016.
[15] R. A. Fleming and M. Zou, "Silica nanoparticle-based films on titanium substrates with long-term superhydrophilic and superhydrophobic stability," (in English), Applied Surface Science, Article vol. 280, pp. 820-827, Sep 2013.
[16] G. Momen and M. Farzaneh, "A ZnO-based nanocomposite coating with ultra water repellent properties," (in English), Applied Surface Science, Article vol. 258, no. 15, pp. 5723-5728, May 2012.
[17] D. M. Chun, C. V. Ngo, and K. M. Lee, "Fast fabrication of superhydrophobic metallic surface using nanosecond laser texturing and low-temperature annealing," (in English), Cirp Annals-Manufacturing Technology, Article vol. 65, no. 1, pp. 519-522, 2016.
[18] X. J. Liu, Y. Xu, K. Y. Ben, Z. Chen, Y. Wang, and Z. S. Guan, "Transparent, durable and thermally stable PDMS-derived superhydrophobic surfaces Xiaojiang," (in English), Applied Surface Science, Article vol. 339, pp. 94-101, Jun 2015.
[19] Y. Chen, S. G. Chen, F. Yu, W. W. Sun, H. Y. Zhu, and Y. S. Yin, "Fabrication and anti-corrosion property of superhydrophobic hybrid film on copper surface and its formation mechanism," (in English), Surface and Interface Analysis, Article vol. 41, no. 11, pp. 872-877, Nov 2009.
[20] W. S. Jang, S. Y. Kim, J. Lee, J. Park, C. J. Park, and C. J. Lee, "Triangular GaN-BN core-shell nanocables: Synthesis and field emission," (in English), Chemical Physics Letters, Article vol. 422, no. 1-3, pp. 41-45, Apr 2006.
[21] M. Zhou, J. Li, C. X. Wu, X. K. Zhou, and L. Cai, "Fluid drag reduction on superhydrophobic surfaces coated with carbon nanotube forests (CNTs)," (in English), Soft Matter, Article vol. 7, no. 9, pp. 4391-4396, 2011.
[22] J. A. Howarter and J. P. Youngblood, "Self-cleaning and anti-fog surfaces via stimuli-responsive polymer brushes," (in English), Advanced Materials, Article vol. 19, no. 22, pp. 3838-+, Nov 2007.
[23] S. Farhadi, M. Farzaneh, and S. A. Kulinich, "Anti-icing performance of superhydrophobic surfaces," (in English), Applied Surface Science, Article vol. 257, no. 14, pp. 6264-6269, Mar 2011.
[24] J. Li et al., "Stable superhydrophobic coatings from thiol-ligand nanocrystals and their application in oil/water separation," (in English), Journal of Materials Chemistry, Article vol. 22, no. 19, pp. 9774-9781, 2012.
[25] ZDHC Manufacturing Restricted Substance List (ZDHC MRSL) Version 1.1
[26] M. A. Kebede, T. Imae, Sabrina, C. M. Wu, and K. B. Cheng, "Cellulose fibers functionalized by metal nanoparticles stabilized in dendrimer for formaldehyde decomposition and antimicrobial activity," (in English), Chemical Engineering Journal, Article vol. 311, pp. 340-347, Mar 2017.
[27] R. Bendi and T. J. R. A. Imae, "Renewable catalyst with Cu nanoparticles embedded into cellulose nano-fiber film," vol. 3, no. 37, pp. 16279-16282, 2013.
[28] D. D. Perez, S. Montanari, and M. R. Vignon, "TEMPO-mediated oxidation of cellulose III," (in English), Biomacromolecules, Article vol. 4, no. 5, pp. 1417-1425, Sep-Oct 2003.
[29] K. J. Shah and T. Imae, "Photoinduced enzymatic conversion of CO2 gas to solar fuel on functional cellulose nanofiber films," (in English), Journal of Materials Chemistry A, Article vol. 5, no. 20, pp. 9691-9701, May 2017.
[30] E. Lasseuguette, "Grafting onto microfibrils of native cellulose," Cellulose, vol. 15, no. 4, pp. 571-580, 2008/08/01 2008.
[31] H. Fukuzumi, T. Saito, Y. Okita, and A. Isogai, "Thermal stabilization of TEMPO-oxidized cellulose," (in English), Polymer Degradation and Stability, Article vol. 95, no. 9, pp. 1502-1508, Sep 2010.
[32] N. Hashimoto, T. Aoyama, and T. Shioiri, "NEW METHODS AND REAGENTS IN ORGANIC-SYNTHESIS .14. A SIMPLE EFFICIENT PREPARATION OF METHYL-ESTERS WITH TRIMETHYLSILYLDIAZOMETHANE (TMSCHN2) AND ITS APPLICATION TO GAS-CHROMATOGRAPHIC ANALYSIS OF FATTY-ACIDS," (in English), Chemical & Pharmaceutical Bulletin, Note vol. 29, no. 5, pp. 1475-1478, 1981.
[33] V. Kumar and T. Yang, "Analysis of carboxyl content in oxidized celluloses by solid-state C-13 CP/MAS NMR spectroscopy," (in English), International Journal of Pharmaceutics, Article vol. 184, no. 2, pp. 219-226, Jul 1999.
[34] Y. Ono, S. Fukui, R. Funahashi, and A. Isogai, "Relationship of Distribution of Carboxy Groups to Molar Mass Distribution of TEMPO-Oxidized Algal, Cotton, and Wood Cellulose Nanofibrils," (in English), Biomacromolecules, Article vol. 20, no. 10, pp. 4026-4034, Oct 2019.
[35] Y. Okita, T. Saito, and A. Isogai, "Entire Surface Oxidation of Various Cellulose Microfibrils by TEMPO-Mediated Oxidation," (in English), Biomacromolecules, Article vol. 11, no. 6, pp. 1696-1700, Jun 2010.
[36] J. M. Antosiewicz and D. Shugar, "UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 2: selected applications," (in eng), Biophysical reviews, vol. 8, no. 2, pp. 163-177, 2016.