Periodate Oxidation of Cellulose for Functional Derivatization : セルロ―スの過ヨウ素酸酸化による機能性材料の開發

다국어 초록 (Multilingual Abstract)

The author wishes to express sincere appreciation to Professor Shigenori KUGA, the supervisor of my study, Division of Structural Biopolymer Science, the University of Tokyo, for his constant guidance, constructive criticism and continuous encouragement throughout the progress of this study.
The author is very thankful to the former Professor Takeshi OKANO for supervising, advising and encouraging me for the master course part of this study.
The author thanks to Dr. Masahisa WADA for teaching TEM and X-ray techniques and giving much valuable advices, Dr. Tetsuo KONDO, Forestry and Forest Products Research Institute, for solid-state NMR analysis and kind advices, and Professor Akira ISOGAI, Division of Paper Science, the University of Tokyo, for solution NMR analysis and kind advices.
Also the author thanks Dr. Yoshiharu NISHIYAMA, Dr. Dae-Young KIM and students in the laboratory of Structural Biopolymer Science for useful suggestion and kind assistant during my study. The author thanks Ms. Hiroko NAITO, Graduate School of Agricultural and Life Sciences, the University of Tokyo, for elemental analysis and Nitto Boseki Co. for gift of polyallylamine sample.
The author would like to thank Professor Hee-Suck JUNG, Jun-Jae LEE, Hak-Lae LEE and Hyun-Joong KIM, Seoul National University in Korea, for kind advice and encouragement.
The author wishes to express my sincere gratitude to my mother in heaven, my father and my wife’s parents for their spiritual support.
Finally the author is grateful to my wife, Young-Soon SUCK, for supporting my study, and never forget my wife’s love.

목차 (Table of Contents)

• Conents = 1
• CHAPTER 1 Introduction = 4
• 1.1 Dedrivatization of cellulose = 5
• 1.1.1 Chemical structure of cellulose = 5
• 1.1.2 Cellulose ester = 5
• 1.1.3 Cellulose ether = 6
• 1.1.4 Oxidized cellulose = 6
• 1.1.5 Crosslinked and grafted cellulose = 6
• 1.2 Oxidation of cellulose = 7
• 1.2.1 Oxidation of primary hydroxyl group = 7
• 1.2.2 Oxidation of secondary hydroxyl group = 8
• 1.3 Periodate oxidation of cellulose = 8
• 1.4 Scope of the Thesis = 11
• CHAPTER 2 Periodate oxidation of crystalline cellulose = 13
• 2.1 Abstracts = 13
• 2.2 Introduction = 14
• 2.3 Experimental = 14
• 2.3.1 Cellulose materials = 14
• 2.3.2 Periodate oxidation = 14
• 2.3.3 Preparation of dicarboxyl cellulose = 15
• 2.3.4 Determination of aldehyde content = 15
• 2.3.5 Chemical stability of dialdehyde cellulose = 15
• 2.3.6 X-ray diffraction = 15
• 2.3.7 FTIR spectroscopy = 15
• 2.3.8 Solid-state 13C NMR = 16
• 2.3.9 Solution-state 13C NMR = 16
• 2.3.10 Transmission electron microscopy = 16
• 2.4 Results and Discussion = 17
• 2.4.1 Time course of peridate oxidation and X-ray analysis of DAC = 17
• 2.4.2 Chemical stability of DAC = 19
• 2.4.3 FTIR and solid-state 13C NMR analysis of DAC = 20
• 2.4.4 Solution-state 13C NMR analysis of DCC = 22
• 2.4.5 TEM observation of DAC-Cladophora = 22
• 2.5 Conclusion = 26
• CHAPTER 3 Thermal decomposition of dialdehyde cellulose and its nitrogen-containing derivatives = 27
• 3.1 Abstracts = 27
• 3.2 Introduction = 28
• 3.3 Experimental = 28
• 3.3.1 Materials = 28
• 3.3.2 Preparation of dialdehyde cellulose = 29
• 3.3.3 Schiffbase reaction = 29
• 3.3.4 X-ray diffraction = 29
• 3.3.5 Thermal analysi = 29
• 3.3.6 Elemental analysis = 30
• 3.4 Results and Discussion = 31
• 3.4.1 Degree of oxidation and conversion to nitrogen-containing derivatives = 31
• 3.4.2 Thermal analysis of dialdehyde cellulose = 32
• 3.4.3 Thermal analysis of nitrogen-containing derivatives = 35
• 3.4.4 Activation energy of decomposition = 38
• 3.5 Conclusion = 39
• CHAPTER 4 Reactive interaction of aromatic amines with dialdehyde cellulose gel = 40
• 4.1 Abstracts = 40
• 4.2 Introduction = 41
• 4.3 Experimental = 41
• 4.3.1 Materials = 41
• 4.3.2 Preparation of dialdehyde cellulose (DAC) gel = 42
• 4.3.3 Determination of aldehyde group = 42
• 4.3.4 Chemical stability of dialdehyde cellulose gel = 42
• 4.3.5 Column packing procedure and evaluation of size exclusion property = 43
• 4.3.6 Gel chromatography = 43
• 4.4 Results and Discussion = 44
• 4.4.1 Degree of oxidation of DAC gel = 44
• 4.4.2 Chemical and mechanical stability of DAC gel = 44
• 4.4.3 Size exclusion property of DAC gel = 44
• 4.4.4 Reactive chromatography on DAC gel = 46
• 4.5 Conclusion = 52
• CHAPTER 5 Ion-exchange chromatography by dicarboxyl cellulose gel = 53
• 5.1 Abstract = 53
• 5.2 Introduction = 54
• 5.3 Experimenal = 55
• 5.3.1 materials = 55
• 5.3.2 Preparation of dialdehyde cellulose (DAC) gel = 55
• 5.3.3 Preparation of dicarboxyl cellulose (DCC) gel = 55
• 5.3.4 Chemical stability of derivatized cellulose gel = 55
• 5.3.5 Column packing procedure and evaluation of size exclusion property = 56
• 5.3.6 Ion-exchange chromatography = 56
• 5.4 Results and Discussion = 57
• 5.4.1 Degree of oxidation and carboxyl cotent of DCC gel = 57
• 5.4.2 Chemical and mechanical stability of DAC and DCC gel = 57
• 5.4.3 Size exclusion property of DCC gel = 58
• 5.4.4 Ion-exchange chromatography of amines = 58
• 5.5 Conclusion = 65
• CHAPTER 6 Polyallylamine-grafted cellulose gel as high-capacity anion exchanger = 66
• 6.1 Abstract = 66
• 6.2 Introduction = 67
• 6.3 Experimenal = 68
• 6.3.1 Materials = 68
• 6.3.2 Preparation of dialdehyde cellulose = 68
• 6.3.3 Preparation of polyallylamine-cellulose gel = 68
• 6.3.4 Column packing procedure and evaluation of size exclusion property = 69
• 6.3.5 Ion-exchange chromatography = 69
• 6.4 Results and Discussion = 70
• 6.4.1 Grafting of polyallylamine onto cellulose via dialdehyde group = 70
• 6.4.2 Chemical and mechanical stability of PAA-cellulose gel = 71
• 6.4.3 Size exclusion property of PAA-cellulose gel = 71
• 6.4.4 Ion-exchange chromatography by PAA-cellulose gel = 72
• 6.5 Conclusion = 75
• CHAPTER 7 Ion-exchange separation of proteins by polyallylamine-grafted cellulose gel = 76
• 7.1 Abstract = 76
• 7.2 Introduction = 77
• 7.3 Experimenal = 77
• 7.3.1 Materials = 77
• 7.3.2 Preparation of dialdehyde cellulose gel = 78
• 7.3.3 Preparation of polyallylamine-grafted cellulose gel = 78
• 7.3.4 Column packing procedure and evaluation of size exclusion property = 78
• 7.3.5 Ion-exchange chromatography = 79
• 7.4 Results and Discussion = 80
• 7.4.1 Grafting of polyallylamine onto periodate-oxidized cellulose = 80
• 7.4.2 Size exclusion property of PAA-cellulose gel = 80
• 7.4.3 Retention behavior of proteins on PAA-cellulose gel = 81
• 7.5 Conclusion = 84
• CHAPTER 8 Summary = 85
• Bibliography = 88
• Publications = 101
• Acknowledgements = 102