ABSTRACT
Molecular structure............................................... 21
1.1.2
Glucose chemistry.................................................. 23
1.1.3
Related di-and polysaccharides ........................... 25
.................................................... 30
........................................................................ 31
..................................................................... 33
..................................... 34
2.2.1
Classification of green plants ............................... 34
2.2.2
Plant cells ............................................................... 36
.............................................. 38
2.3.1
From genes to proteins......................................... 38
2.3.2
DNA cloning and PCR............................................ 41
........................................................ 41
....... 46
2.5.1
Cellulose synthase substrate................................. 46
2.5.2
Cellulose synthases................................................ 47
2.5.3
Polymerization models ......................................... 51
2.5.4
Polymerization of cellulose in
Acetobacter xylinum
......................................... 54
2.5.5
Polymerization of cellulose in plants ................... 58
................................. 68
2.6.1
Chain assembly in
Acetobacter xylinum
.............. 69
2.6.2
Chain assembly in plants....................................... 70
.................. 75
2.7.1
In vitro synthesis .................................................... 75
2.7.2
Chemical synthesis................................................. 79
........................................................................ 80
..................................................................... 87
............................................. 88
3.2.1
Crystallinity of cellulose materials........................ 88
3.2.2
Crystal polymorphs................................................ 89
3.2.3
Coordinate system................................................. 90
3.2.4
Cellulose I............................................................... 90
3.2.5
Cellulose II.............................................................. 101
3.2.6
Cellulose III and IV................................................. 105
3.2.7
Soda celluloses....................................................... 107
3.2.8
Summary of crystal structures .............................. 108
............................................... 109
3.3.1
Introduction........................................................... 109
3.3.4 Bacterial cellulose.................................................. 127
3.4 Properties ......................................................................... 130
3.4.1 Mechanical properties .......................................... 130
3.4.2 Physical properties and liquid crystals ................. 132
3.4.3 Environmental properties ..................................... 137
3.4.4 Nanocomposites .................................................... 138
4.1 Introduction ..................................................................... 147
4.2.1 Water ..................................................................... 148
4.2.2 Organic liquids ...................................................... 156
4.3.1 Alkali metal hydroxides ........................................ 159
4.3.2 Inorganic acids and salts ....................................... 167
4.3.3 Amines ................................................................... 170
4.3.4 Ammonia ............................................................... 173
4.3.5 Hydrazine............................................................... 175
4.4 Dissolution ....................................................................... 175
4.4.1 Non-derivatizing solvents ..................................... 176
4.4.2 Derivatizing solvents............................................. 194
5.1 Introduction ..................................................................... 209
5.2.1 Organism source.................................................... 210
5.2.2 Endo-and exo-action............................................ 210
5.2.3 Modular structure ................................................. 211
5.2.4 Mechanism............................................................. 217
5.2.5 Nomenclature........................................................ 218
5.3.1 Solubilization of native cellulose ......................... 219
5.3.4 Kinetics and activity .............................................. 232
5.3.5 Synergism............................................................... 233
5.4 Multienzyme complexes ............................................... 234
5.4.1 The cellulosome concept ...................................... 234
5.4.2 Types of cellulosome ............................................. 234
5.4.3 Scaffoldin carbohydrate-binding modules .......... 235
5.4.4 Cohesin-dockerin interaction ............................... 236
5.4.6 Designer cellulosomes........................................... 247
6.1 Introduction ..................................................................... 257
6.2 Acid hydrolysis ................................................................ 258
6.2.1 Mechanism and kinetics........................................ 258
6.3 Alkaline degradation ..................................................... 260
6.3.1 Action of alkalis on monosaccharides.................. 260
6.3.2 Action of alkalis on cellulose................................ 261
6.4 Oxidative degradation .................................................. 263
6.4.1 Oxidation by sodium hypochlorite....................... 264
6.4.2 Oxidation by atmospheric oxygen and by hydrogen peroxide ................................... 265
6.5 Thermal degradation ..................................................... 266
6.6 Mechanical and radiation degradation ..................... 268
6.6.1 Mechanical degradation....................................... 268
6.6.2 Radiation degradation.......................................... 270
7.1 Introduction ..................................................................... 275
7.2.1 Inorganic cellulose esters ...................................... 277
7.2.2 Organic cellulose esters ........................................ 282
7.2.3 Summary ................................................................ 287
7.3 Etherification ................................................................... 287
7.3.1 Alkyl ethers of cellulose........................................ 288
7.3.2 Carboxymethylcellulose ........................................ 289
7.3.3 Hydroxyalkyl ethers of cellulose........................... 290
7.3.4 Cyanoethylcellulose .............................................. 293
7.3.5 Other ethers of cellulose ...................................... 293
7.3.6 Summary ................................................................ 294
7.4 Crosslinking of cellulose ............................................... 295
7.4.1 Chemical finishing of textiles and paper ............. 295
7.4.2 Crosslinking agents ............................................... 296
7.5 Grafting of cellulose ...................................................... 298
8.1.1 Biomass .................................................................. 303
8.1.2 Biorefinery and global warming .......................... 304
8.1.3 Bioethanol and biodiesel ...................................... 305
8.1.4 Conversion pathways ............................................ 306
8.2 Biochemical conversion of cellulosic biomass .......... 307
8.2.1 Enzymatic hydrolysis ............................................. 308
8.2.2 Acid hydrolysis ....................................................... 312 Dilute acid hydrolysis .................................................... 312
8.3.1 Primary routes for thermochemical conversion .. 315
8.3.2 Gasification............................................................ 316
8.3.3 Fast pyrolysis .......................................................... 321
8.3.4 Hydrothermal upgrading...................................... 322
8.4 Integrated biorefineries ................................................ 323
9.1 Cellulosic Biomass: the petroleum of the future? ... 327
9.1.1 Planned reductions in greenhouse gas (GHG) emissions................................................................ 327
9.1.2 Global biofuel production .................................... 329
9.1.3 Bioethanol costs and yields .................................. 330
9.1.4 Cellulosic biomass conversion technologies ........ 331
9.2 Biosynthesis of cellulose ............................................... 333
9.3 Cellulose nanofibers ...................................................... 334
9.4 Ionic liquids as new cellulose solvents ...................... 335
