Supplement Information
Probing crystallinity of never-dried wood cellulose with
Raman spectroscopy
Umesh P. Agarwala,*, Sally A. Ralpha, Richard S. Reinera, Carlos Baeza
a
Fiber and Chemical Sciences Research, USDA FS, Forest Products Laboratory, 1 Gifford
Pinchot Drive Madison, WI 53726-2398.
*
To whom correspondence should be addressed. Email: uagarwal@fs.fed.us
Fiber and Chemical Sciences Research, USDA FS, Forest Products Laboratory, 1 Gifford Pinchot Drive
Madison, WI 53726-2398
Ph: 608-231-9441
uagarwal@fs.fed.us
Table SI1: % O6s that are D2O accessible under various models of crystalline cellulose
Crystal model*
Surface
Interior
N = Ratio of
N/2 = D2O
% O6s D2O
chains
chains
surface-to-total
accessible O6s accessible
chains
36 chain, square
20
16
0.56
0.28
28
cross section
30 chain, rectangular 18
12
0.60
0.30
30
cross section (6 x 5)
24 chain rectangular 16
8
0.67
0.33
33
cross section (6 x 4)
18 chain rectangular 14
4
0.78
0.39
39
cross section (6 x 3)
* A microfibril arises from a rosette of six particles on the plasma membrane. Therefore, it is
reasonable to assume that a microfibril comprises of a multiple of six cellulose chains.
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Fig. SI1(a): Raman spectra of SA2-ND in D2O and H2O, 850 – 1550 cm-1 region.
Fig. SI1(b): Raman spectra of SA7-ND in D2O and H2O, 850 – 1550 cm-1 region.
2
Fig. SI1(c): Raman spectra of SA18 in D2O and H2O, 850 – 1550 cm-1 region.
Fig. SI1(d): Raman spectra of SA19 in D2O and H2O, 850 – 1550 cm-1 region.
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Fig. SI2: Plot showing increase in intensity at 1380 cm-1 is related to presence of Raman
contribution in the O-D stretch region. OD = oven dried from D2O; FD – free dried from D2O.
Fig. SI3: A 6 x6 cellulose crystal model with square cross sectional shape. The model consists
of 16 interior (green in [200]) and 20 surface chains.
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Fig. SI4: Low frequency Raman spectra of various celluloses that produced cellulose
nanocrystals upon acid hydrolysis.
Fig. SI5: XRD full width at half maximum (FWHM) of various samples
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Fig. SI 6: Variation of 2θ for [200] diffraction peak
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