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crystalline forms
CHEM-E2140
Eero Kontturi
Cellobiose
OH
• Reducing end group is in equilibrium HO OH
O
with a cyclic hemiacetal O
OH
Molecular vs. supramolecular structure
Molecular structure Supramolecular structure
OH
Anhydroglucose
OH O
HO O
O O
HO n /2
O OH
OH
Cellobiose
Heat treatment
• X-ray diffraction
• Solid state Nuclear Magnetic Resonance (NMR) spectroscopy
specifically: cross-polarization magic angle spinning (CP-MAS) 13C NMR
• Electron diffraction
• Neutron scattering
• IR spectroscopy
• Raman spectroscopy
Native cellulose:
Cellulose Iα
Cellulose Iβ
Cellulose I crystal
Cellulose chains form sheets which are connected with each other
Radial cross section of a cellulose Iβ crystallite:
Cross sectional image taken from: Gross and Chu J. Phys. Chem. B 2010, 114, 13333.
Cellulose I: main hydrogen bonding
patterns
Main hydrogen bonds:
Sheet in cellulose I
• 3→5 intramolecular bond
1 lends rigidity to the cellulose
2 chain
5
Crystallographic details in 1Å
resolution (cellulose Iα ja Iβ):
Nishiyama et al.
J. Am. Chem. Soc. 2002, 124, 9074.
J. Am. Chem. Soc. 2003, 125, 14300.
Cellulose
(a) cellulose II Cellulose
(b) cellulose IIII
1
2 2
5 6
3
3 3
6 6 3
4
5 5 5
5 2
6
6 3
Cellulose I Cellulose II
Parallel Anti-parallel
Distinction between cellulose I and II
Cellulose II
Preparation by: - dissolving the cellulose / regeneration
- swelling in concentrated alkali
Cellulose I Cellulose II
swelling
Parallel Anti-parallel
Distinction between cellulose I and II
• Cellulose crystals in parallel microfibrils run in opposite direction
• NaOH swells the crystals
• Anti-parallel arrangement is thermodynamically more favourable than
parallel arrangement
→ HYPOTHESIS:
Cellulose chains in parallel microfibrils intermingle and form new
antiparallel crystals
Cellulose I Cellulose II
swelling
Parallel Anti-parallel
Evidence for antiparallel cellulose II
Single cellulose I microfibril
CELLULOSE I
CELLULOSE II
Au
→ Forced parallel orientation
Yokota et al. Adv. Mater. 2007, 19, 3368.
Cellulose III
Conversion into cellulose III
NATIVE
FORM Regeneration or
alkali treatment
Cellulose Iα
Cellulose II
Cellulose Iβ
IRREVERSIBLE
Ammonia-cellulose I complex
NH3 (l)
NH3 removal
(e.g. evaporation)
Cellulose Iα
Cellulose II
Cellulose Iβ
Hydrothermal treatment
at ~160°C
or
Thermal treatment at >200°C
Liquid NH3 or
diamine treatment
Heat treatment in
glycerol at 260°C
• Native cellulose I is decidedly stiffer and stronger than the “man-made” forms
Hydrolysis of
cellulose II is much
faster and proceeds
to a greater extent
than that of
cellulose I.
3×5 nm
3.8 nm
Ding and Himmel J. Agric. Food Chem. 2006, 54, 597. Sugiyama et al. Macromolecules 1991, 24, 4168.
Terminological note:
• In many species, the microfibrils are larger but they are multiplicates of
the elementary fibrils
Proposition:
cellulose runs through alternating
crystalline and “ amorphous” regions.
Fringed-fibrillar model of native cellulose
microfibrils
Not just one model
HCl HYDROLYSIS
5OC
18OC
40OC
80OC
LODP
LODP
H+
H+
H+ H+
H+
RESULT:
cellulose nanocrystals
LODP
Reduced accessibility
Suchy et al.
Biomacromolecules 2010, 11, 515.
Summary
• Cellulose exists in several crystalline allomorphs:
- cellulose Iα and Iβ (native forms)
- cellulose II (prepared regeneration or alkaline treatment)
- cellulose IIII and IIIII (prepared by liquid ammonia treatment)