1.
Horii, F.; Hirai, A.; Kitamaru, R., Solid-state high-resolution 13C-NMR studies of
regenerated cellulose samples with different crystallinities. Polymer Bulletin 1982, 8 (2-4).
2.
Atalla, R. H.; Vanderhart, D. L., Native cellulose: a composite of two distinct crystalline
forms. Science 1984, 223 (4633), 283-5.
3.
Newman, R. H.; Hemmingson, J. A., Determination of the Degree of Cellulose
Crystallinity in Wood by Carbon-13 Nuclear Magnetic Resonance Spectroscopy.
Holzforschung 1990, 44 (5), 351-356.
4.
Kono, H.; Yunoki, S.; Shikano, T.; Fujiwara, M.; Erata, T.; Takai, M., CP/MAS (13)C
NMR study of cellulose and cellulose derivatives. 1. Complete assignment of the CP/MAS
(13)C NMR spectrum of the native cellulose. J Am Chem Soc 2002, 124 (25), 7506-11.
5.
Vietor, R. J.; Newman, R. H.; Ha, M. A.; Apperley, D. C.; Jarvis, M. C., Conformational
features of crystal-surface cellulose from higher plants. Plant J 2002, 30 (6), 721-31.
6.
Phyo, P.; Wang, T.; Yang, Y.; O'Neill, H.; Hong, M., Direct Determination of
Hydroxymethyl Conformations of Plant Cell Wall Cellulose Using (1)H Polarization Transfer
Solid-State NMR. Biomacromolecules 2018, 19 (5), 1485-1497.
126
Appendix Cross-polarization dynamics and conformational study of variously sized cellulose crystallites
using solid-state 13C NMR
7.
Earl, W. L.; VanderHart, D. L., Observations by high-resolution carbon-13 nuclear
magnetic resonance of cellulose I related to morphology and crystal structure. Macromolecules
1981, 14 (3), 570-574.
8.
Larsson, P. T.; Wickholm, K.; Iversen, T., A CP/MAS13C NMR investigation of
molecular ordering in celluloses. Carbohydrate Research 1997, 302 (1-2), 19-25.
9.
Hill, D. J. T.; Le, T. T.; Whittaker, A. K., A technique for the quantitative measurements
of signal intensities in cellulose-based transformer insulators by13C CPMAS NMR. Cellulose
1994, 1 (4), 237-247.
10.
Heux, L.; Dinand, E.; Vignon, M. R., Structural aspects in ultrathin cellulose
microfibrils followed by 13C CP-MAS NMR. Carbohyd Polym 1999, 40 (2), 115-124.
11.
Daicho, K.; Kobayashi, K.; Fujisawa, S.; Saito, T., Crystallinity-Independent yet
Modification-Dependent True Density of Nanocellulose. Biomacromolecules 2020, 21 (2),
939-945.
12.
Daicho, K.; Saito, T.; Fujisawa, S.; Isogai, A., The Crystallinity of Nanocellulose:
Dispersion-Induced Disordering of the Grain Boundary in Biologically Structured Cellulose.
Acs Applied Nano Materials 2018, 1 (10), 5774-5785.
13.
Okita, Y.; Saito, T.; Isogai, A., Entire surface oxidation of various cellulose microfibrils
by TEMPO-mediated oxidation. Biomacromolecules 2010, 11 (6), 1696-700.
14.
Nemoto, J.; Saito, T.; Isogai, A., Simple Freeze-Drying Procedure for Producing
Nanocellulose Aerogel-Containing, High-Performance Air Filters. ACS Appl Mater Interfaces
2015, 7 (35), 19809-19815.
15.
Terenzi, C.; Prakobna, K.; Berglund, L. A.; Furo, I., Nanostructural effects on polymer
and water dynamics in cellulose biocomposites: (2)h and (13)c NMR relaxometry.
Biomacromolecules 2015, 16 (5), 1506-15.
16.
Sparrman, T.; Svenningsson, L.; Sahlin-Sjovold, K.; Nordstierna, L.; Westman, G.;
Bernin, D., A revised solid-state NMR method to assess the crystallinity of cellulose. Cellulose
2019, 26 (17), 8993-9003.
17.
Funahashi, R.; Okita, Y.; Hondo, H.; Zhao, M.; Saito, T.; Isogai, A., Different
Conformations of Surface Cellulose Molecules in Native Cellulose Microfibrils Revealed by
Layer-by-Layer Peeling. Biomacromolecules 2017, 18 (11), 3687-3694.
127
Appendix Cross-polarization dynamics and conformational study of variously sized cellulose crystallites
using solid-state 13C NMR
18.
Oehme, D. P.; Downton, M. T.; Doblin, M. S.; Wagner, J.; Gidley, M. J.; Bacic, A.,
Unique aspects of the structure and dynamics of elementary Ibeta cellulose microfibrils
revealed by computational simulations. Plant Physiol 2015, 168 (1), 3-17.
19.
Wickholm, K.; Larsson, P. T.; Iversen, T., Assignment of non-crystalline forms in
cellulose I by CP/MAS 13C NMR spectroscopy. Carbohydrate Research 1998, 312 (3), 123129.
20.
Isogai, A.; Atalla, R. H., Amorphous celluloses stable in aqueous media: Regeneration
from SO2–amine solvent systems. Journal of Polymer Science Part A: Polymer Chemistry
1991, 29 (1), 113-119.
21.
Saito, T.; Hirota, M.; Tamura, N.; Kimura, S.; Fukuzumi, H.; Heux, L.; Isogai, A.,
Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using
TEMPO catalyst under neutral conditions. Biomacromolecules 2009, 10 (7), 1992-6.
22.
Horii, F.; Hirai, A.; Kitamaru, R., Solid-state 13C-NMR study of conformations of
oligosaccharides and cellulose. Polymer Bulletin 1983, 10 (7-8), 357-361.
23.
Montanari, S.; Roumani, M.; Heux, L.; Vignon, M. R., Topochemistry of Carboxylated
Cellulose Nanocrystals Resulting from TEMPO-Mediated Oxidation. Macromolecules 2005,
38 (5), 1665-1671.
24.
Horii, F.; Hirai, A.; Kitamaru, R., CP/MAS Carbon-13 NMR Study of Spin Relaxation
Phenomena of Cellulose Containing Crystalline and Noncrystalline Components. Journal of
Carbohydrate Chemistry 2006, 3 (4), 641-662.
25.
Yang, H.; Wang, T.; Oehme, D.; Petridis, L.; Hong, M.; Kubicki, J. D., Structural factors
affecting 13C NMR chemical shifts of cellulose: a computational study. Cellulose 2017, 25 (1),
23-36.
128
Acknowledgments
Acknowledgments
This thesis is a compilation of studies carried out from April 2016 to March 2021 under
my supervisor, Associate Professor Saito Tsuguyuki at the University of Tokyo. I would like
to express my deepest respect and appreciation to Associate Professor Saito Tsuguyuki for his
generous guidance and continuous encouragement throughout this research.
I am grateful to Professor Isogai Akira, Assistant Professor Fujisawa Shuji, and
Kobayashi Kayoko for their continuous encouragement and advice. I thank Dr. Ono Yuko, Dr.
Kimura Minoru, Dr. Isobe Noriyuki, Dr. Tanaka Reina, Dr. Sun Zhifang, Dr. Soeta Hiroto, Dr.
Ning Ruizhi, Dr. Zhou Yaxin, Dr. Goi Yosuke, Dr. Nemoto Junji, Dr. Takeuchi Miyuki, Dr.
Lavoine Nathalie, Mr. Mengchen Zhao, Mr. Sakuma Wataru, Mr. Ishioka Shun, Mr. Nakamura
Yasutaka, Mr. Kubo Ryuji, Mr. Yamasaki Syunsuke, Mr. Ochiai Yu, Mr. Kaku Yuto, Mr.
Kotsuka Junki, Mr. Ishida Suguru, Mr. Ito Tomoki, Mr. Yagita Yasuhito, Mr. Iijima Takumi,
Mr. Tamura Naoki, Mr. Doi Yoshinori, Ms. Sato Yuriko, and the other members of the Pulp &
Paper Science laboratory for their kind cooperation and advice.
Dr. Nishiyama Yoshiharu provided useful suggestions and advice about the XRD
measurement and crystal structure of cellulose. Discussions on the microfibril structure with
Dr. Pan Chen in KTH were very insightful. I would like to thank Dr. Furihata Kazuo and Dr.
Ashida Jun for their technical support and the valuable suggestions of solid-state NMR. I
sincerely thank Dr. Ishida Yasuhiro and Dr. Sano Koki for the SAXS measurements and fruitful
discussions. I also thank Associate Professor Koga Hirotaka for the measurement of the
electrical properties and insightful discussions. Professor Berglund Lars, Dr. Rojass Ramiro,
and Dr. Willhammer Tom gave me precious opportunities to discuss with researchers and
showed me gracious hospitality during my visit to Stockholm. I would like to express my
gratitude to them for their favors. I would like to thank Associate Professor Kontturi Eero, Dr.
Tekla Tammelin, and Assistant Professor Stefan Spirk for instructive discussions and great
opportunities in a summer school in Finland in 2018. I gratefully acknowledge Dr. Alfred
French, Professor Kim Seong, Dr. Laurent Heux, Professor Nogi Masaya, Professor Lennart
Bergstrom, and other researchers for their valuable advice and sincere encouragement.
129
Acknowledgments
My supervisor in my undergraduate course, Professor Sawatari Chie, introduced me to
the field of cellulose science. I would like to express my gratitude to her for her support and
encouragement.
Special thanks are extended to Professor Tadahisa Iwata, Professor Kiyohiko Igarashi,
Professor Saito Yukie, and Professor Masahisa Wada for their careful review of this thesis and
valuable suggestions and comments.
I have been a research assistant as part of the JST-Mirai R&D Program from 2018 to
2020, and the Japan Society for Promotion of Science from 2020 to 2021. I would like to express
my gratitude to all the people mentioned above. I would like to acknowledge the financial
support from the JST-Mirai R&D Program and the Research Fellowship for Young Scientists
from the Japan Society for the Promotion of Science, PHOENIX Grant-in-Aid, and Research
Program for Next Generation Young Scientists of Dynamic Alliance for Open Innovation
Bridging Human, Environment, and Materials in Network Joint Research Center for Materials
and Devices.
Last but not least, I thank my family for their sincere support and encouragement.
March 19, 2021
Kazuho Daicho
大長 一帆
130
Publications
Publications
Peer-reviewed journal articles
1. Daicho, K., Saito, T., Fujisawa, S., Isogai, A., The Crystallinity of Nanocellulose:
Dispersion-Induced Disordering of the Grain Boundary in Biologically Structured
Cellulose. ACS Applied Nano Materials 2018, 1 , 5774-5785.
2. Daicho, K., Kobayashi, K., Fujisawa, S., Saito, T., Crystallinity-Independent yet
Modification-Dependent True Density of Nanocellulose. Biomacromolecules 2020,
21 , 939-945.
3. Daicho, K., Fujisawa, S., Kobayashi, K., Saito, T., Ashida, J., Cross-polarization
dynamics and conformational study of variously sized cellulose crystallites using
solid-state 13C NMR. Journal of Wood Science 2020, 66 , 62.
4. Medina, L., Nishiyama, Y., Daicho, K., Saito, T., Yan, M., Berglund, L. A.,
Nanostructure and Properties of Nacre-Inspired Clay/Cellulose Nanocomposites—
Synchrotron X-ray Scattering Analysis. Macromolecules 2019, 52 , 3131-3140.
5. Yamasaki, S., Sakuma, W., Yasui, H., Daicho, K., Saito, T., Fujisawa, S., Isogai, A.,
Kanamori, K., Nanocellulose Xerogels With High Porosities and Large Specific
Surface Areas. Frontiers in chemistry 2019, 7, 316.
6. Hirano, T., Mitsuzawa, K., Ishioka, S., Daicho, K., Soeta, H., Zhao, M., Takeda, M.,
Takai, Y., Fujisawa, S., Saito, T., Anisotropic Thermal Expansion of Transparent
Cellulose Nanopapers. Frontiers in chemistry 2020, 8, 68.
7. Willhammar, T., Daicho, K., Johnstone, D., Kobayashi, K., Liu, Y., Midgley, P.,
Bergström, L., Saito, T., Local Crystallinity in Twisted Cellulose Nanofibers. ACS
Nano, 2020, 15, 2, 2730-2737.
8. Adachi K., Daicho, K., Furuta K., Shiga, T., Saito, T., Kodama T. , Thermal
conduction through individual cellulose nanofibers, Appl. Phys. Lett., 2021, 118,
053701.
131
Publications
Reviews
1. 大長一帆, 齋藤継之, ナノセルロースの結晶性解析, ナノセルロースジャパン 研
究最前線シリーズ , 2020
2. 大長一帆, 齋藤継之, ナノセルロースの真密度, ナノセルロースジャパン 研究最
前線シリーズ , 2020
3. 大長一帆, 齋藤継之, セルロースナノファイバーの結晶性解析, Cellulose
Communications 2020, 27, 3, 85-90
International conference
Oral presentation (Peer-reviewed)
1. Daicho, K., Saito, T., Fujisawa, S., Isogai, A., Dispersion-induced Disordering of the
Grain Boundary in Wood Cellulose Governs the Crystallinity of Nanocellulose. 2018
SWST/JWRS International Convention, Nagoya, Japan, 2018.
2. Daicho, K., Saito, T., Fujisawa, S., Isogai, A., Crystallinity of nanocellulose:
Dispersion-induced disordering of the grain boundary in biologically structured
cellulose. 257th ACS National Meeting & Exposition, Orlando, 2019.
3. Daicho, K., Kobayashi, K., Fujisawa, S., Saito, T., Crystallinity-Independent yet
Modification-Dependent True Density of Nanocellulose. The 6th EPNOE
International Polysaccharide Conference, Aveiro, 2019.
Oral presentation
1. Daicho, K., Saito, T., Isogai, A., The dispersion-induced disordering of the fibril
interfaces in biologically-structured cellulose determines the crystallinity of cellulose
nanofibers. Nanocellulose seminar, Stockholm, 2017.
2. Daicho, K., Saito, T., Isogai, A., Crystallinity index of cellulose nanofibers: The
assembly and dispersion of cellulose microfibrils as a dominant factor to determine
their surface molecular conformation. UT-RIKEN Soft Matter Joint Seminar, Saitama,
2017.
132
Publications
3. Daicho, K., Kobayashi, K., Fujisawa, S., Saito, T., Crystallinity-Independent yet
Modification-Dependent, True Density of Nanocellulose. The 2nd RIKEN-UT joint
seminar, Tokyo, 2019.
Poster presentation (Peer-reviewed)
1. Daicho, K., Saito, T., Fujisawa, S., Isogai, A., The crystallinity of nanocellulose:
Assembly-induced ordering and dispersion-induced disordering of the grain boundary
in biologically structured cellulose. MoDeSt2018, Tokyo, 2018.
2. Daicho, K., Saito, T., Fujisawa, S., Isogai, A., Dispersion-Induced Disordering of the
Grain Boundary in Wood Cellulose. TAPPI Nano 2019, Chiba, 2019.
Domestic conference
Oral presentation
1. 大長一帆, 小野祐子, 齋藤継之, 磯貝明, 木材パルプ及びセルロースナノファイ
バーの結晶性評価. 第 67 回日本木材学会大会, 福岡, 2017 年.
2. 大長一帆, 小野祐子, 齋藤継之, 磯貝明, セルロースナノファイバーの結晶性解
析. 平成 29 年度繊維学会年次大会, 東京, 2017
3. 大長一帆, 小野祐子, 齋藤継之, 磯貝明, セルロースナノファイバーの結晶性評
価(III). 第 68 回日本木材学会大会, 京都, 2018.
4. 大長一帆, 齋藤継之, 藤澤秀次, 磯貝明, ナノセルロースの結晶性:分散と会合
が支配する界面構造. セルロース学会第 25 回年次学会, 京都, 2018.
5. 大長一帆, CNF 素材の結晶性. JFlex 2019, 東京, 2019.
6. 大長一帆, 齋藤継之, 藤澤秀次, 磯貝明., セルロースナノファイバーの真密度 ―
結晶性および表面改質との相関分析. 第 86 回紙パルプ研究発表会, 東京, 2019.
7. 大長一帆, ナノセルロースの結晶性解析. セルロース学会関東支部ミニシンポ
ジウム, 東京, 2019.
8. 大長一帆, セルロースナノファイバーの結晶性:分散と会合が支配する界面構
造. 第一工業製薬 若手研究者スキルアップセミナー, 東京, 2020.
133
Publications
9. 大長一帆, 小林加代子, 藤澤秀次, 齋藤継之, CNF 間相互作用が結晶性を回復さ
せる. 第 71 回日本木材学会大会, 東京, 2020.
Poster presentation
1. 大長一帆, 小野祐子, 齋藤継之, 磯貝明, 澤渡千枝, セルロースナノファイバーの
結晶性評価(II). セルロース学会第 24 回年次学会, 岐阜, 2017.
2. 大長一帆, 齋藤継之, 藤澤秀次, 磯貝明., ナノセルロースの結晶性:会合と分散
が支配する界面構造. 第 9 回 島津 新素材セミナー2018, 東京, 2018.
3. 大長一帆, 齋藤継之, 小林加代子, 藤澤秀次, 磯貝明, ナノセルロースの真密度:
結晶性と表面改質の寄与. 第 69 回日本木材学会大会, 函館, 2019.
4. 大長一帆, 齋藤継之, 小林加代子, 藤澤秀次, 磯貝明, 結晶性に依存せず表⾯改質
に依存するナノセルロースの真密度, セルロース学会第 26 回年次学会, 福岡,
2019.
5. 大長一帆, 齋藤継之, 藤澤秀次, 磯貝 明, 小林加代子, ナノセルロースの結晶性操
作. 第 70 回日本木材学会大会, 鳥取, 2020.
Awards
1. 第 69 回 日本木材学会大会, 優秀ポスター賞
2. 2019 年度 日本木材学会 優秀女子学生賞
3. 令和2年度 農学生命科学研究科 研究科長賞
134
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