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Structure and Morphology of Cellulose in Wheat Straw

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DOI: 10.1007/s10570-004-0955-8

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Cellulose 12: 25–34, 2005. 25

-1

Structure and morphology of cellulose in wheat straw

Ruigang Liu1, Hui Yu1 and Yong Huang1,2,*

1
State Key Laboratory of Polymer Physics and Chemistry, Chinese Academy of Sciences, Beijing 100080,
China; 2Laboratory of Cellulose and Lignocellulosics Chemistry, Guangzhou Institute of Chemistry, Chinese
Academy of Sciences, Guangzhou 510650, China; *Author for correspondence (e-mail: yhuang@cashq.ac.cn)

Received 12 March 2003; accepted in revised form 16 February 2004

Springer 2005

Key words: Cellulose, Crystallinity, FTIR, Orientation, Morphology, Wheat straw

Abstract

The structure and morphology of cellulose extracted from wheat were studied. It was found that the
extraction process is effective and hemicelluloses and lignin can be extracted completely. Cellulose in wheat
straw was identified as cellulose I allomorph with low crystallinity and the crystallinity of cellulose from
different parts of the wheat straw has little difference. There was no metastable cellulose Ia crystalline
modification found in wheat straw; only the more stable cellulose Ib crystalline modification existed.
Cellulose chains in the epidermis of wheat straw were observed with their orientation along the growth
direction of wheat straw, while those in parenchyma were observed with almost no preferred orientation.
There are two kinds of morphologies on the surface of wheat straw. One is the fiber structure with fibrils of
about 5 lm diameter, and the other is the fiber structure with serration morphology at the edge of the fiber,
with which the fibers are connected together. The diameter of the latter one is about 10 lm. The vascular
bundles consist of circular rings while spiral structure cellulose backbones covered with thin cellulose film
were also observed.

Introduction source for glucose and ethanol production, and as

Cellulose is one of the most important natural
polymers in terms of its annual production and in
its industrial applications. Several industrial sec-
tors, such as the paper, textile and composite
industries are making persistent, and ever
increasing demands for cellulose fiber materials
(Focher et al. 2001). The straw and other agricul-
tural residues existing in the waste streams from
commercial crop processing plants have little
inherent value and have traditionally constituted a
disposal problem. Actually, these residues repre-
sent an abundant, inexpensive, and readily avail-
able source of renewable lignocellulosic biomass.
However, their utilization as a carbohydrate
a metabolic energy source in ruminant feeds, has
been severely hampered by the low efficiency with
which organisms and enzymes are able to convert
the polysaccharide portion of the residue into
monomeric sugars, which is attributed to the lignin
component of the cell wall and its association with
other cell wall polysaccharides (Gould 1989; Sun
et al. 2000).
In China, the annual yield of main crop straw
and stalk is about 604 million tons, including
115.4 and 139.6 million tons of wheat and rice
straw, respectively. About 50% of this biomass
source is burned for cooking and heating and left
or combusted directly on the land, so that a lot of
crop straw and stalk resources are lost and serious
26
environmental pollution occurs. Meanwhile, in-
creased awareness of global deforestation has
raised the demand of alternatives to wood as a raw
material for pulp and paper. Therefore, it is nec-
essary to find different methods of disposal or use
of wheat straw. Rather than destroy this valuable
raw material, using it for pulp and paper produc-
tion as well as for producing chemical materials
would be more environmentally and economically
beneficial. Moreover, the unique physical structure
of wheat straw makes it an excellent candidate for
fibers and fillers in structural composites (Hornsby
et al. 1997a, b) and many works have been carried
out on the preparation of bio- or nano-composites
by using materials from wheat straw (Avella et al.
1993, 2000; Helbert et al. 1996; Dufresne et al.
1997, 1999; Hornsby et al. 1997b; Dufresne and
Vignon 1998; Dubief et al. 1999; Patil et al. 2000).
For wheat straw tissues the changes in cell wall
structure and composition accompanying pro-
cessing dictate the end use performance. The
ability to accurately monitor these changes,
therefore, is vital. In this paper, the structure and
morphology of cellulose in wheat straw was stud-
ied and described.
Materials and methods
Extraction of cellulose from wheat straw
Mature wheat straw was harvested from east
China, one of the main resources of wheat straw in
China, in early June 2002.
The isolation of cellulose from wheat straw was
carried out according to the following procedure.
The wheat straw was cut into small pieces (about
5 mm in length) and washed with distilled water.
Then it was immersed in chloroform–ethanol (1:1,
v/v) overnight and then transferred into acetone to
replace the residual chloroform and ethanol. After
acetone was replaced by distilled water, the sample
was subjected to water extraction at 90 C for 6 h.
Then the sample was treated with 0.5% ammo-
nium oxalate at 70 C for another 6 h. It was then
extracted twice with 0.3% dodecyl sulfate for 12 h
and with an aqueous solution of 50% urea for
another 12 h at room temperature. Then, the
wheat straw was subjected to bleaching at 80 C
for 4 h in a 0.3% NaClO2 aqueous solution buf-
fered with acetic acid at pH 4.9. Then it was
immersed overnight in 5% KOH at room tem-
perature. The wood sections were then disen-
crusted thoroughly with a multiple combination of
two purification methods for the primary wall
(Chanzy et al. 1978) and the wood secondary wall
(Wada et al. 1994) to completely remove pectin,
polysaccharides, lignin, and other noncellulosic
substances. The samples were finally washed
thoroughly with distilled water and freeze-dried
with tert-butyl alcohol. All treatments described
above were achieved by gentle shaking of samples
in each solution.
X-ray photoelectron spectroscopy
The X-ray photoelectron spectroscopy (XPS)
measurements were performed on a VG ESCA-
LAB 220i-XL spectrometer (VG Scientific Ltd.,
East Grinstead, UK) using monochromatic AlKa
radiation (1486.7 eV) as the X-ray source. The
survey spectra were recorded with pass energy of
100 eV with an energy resolution of
1.0 eV. The
detection angle was 90 with respect to the plane of
the sample. O/C ratios were taken from the survey
spectra using linear background subtraction.
Wide-angle X-ray diffraction
X-ray photoelectron spectroscopy (WAXD) spec-
tra of samples from different parts of treated wheat
straw, i.e. epidermis, parenchyma, node, and leaf
sheath, were recorded by using Ni-filtered CuKa
radiation (k = 0.1542 nm) from a Rigaku D/
Max-rB X-ray diffractometer. The operating
voltage and current were 40 kV and 60 mA,
respectively. The crystallinity was calculated from
the diffraction intensity data. A two-phase struc-
ture (crystalline–amorphous) was assumed and an
arbitrary background to the diffraction trace was
obtained by a line between the intensity minima,
thus separating an arbitrary crystalline phase from
an arbitrary amorphous phase. The crystallinity Xc
was calculated by:
Acr
Xc ¼  100
Acr þ Am
where Acr and Aam are the integrated area of the
crystalline and amorphous phases, respectively
(Alexander 1969).
 27

Microscopy

Polarized optical microscopy (POM) was per-

formed by using an Olympus BH-2 polarized
optical microscope.
Scanning electron microscopy (SEM) analysis
was performed using a Hitachi S-570 SEM, oper-
ated at 25 kV. The samples were coated with gold
with an Eiko IB-3 Incoater.

Fourier transform infrared spectra

Fourier transform infrared (FTIR) measurement

Figure 1. POM photograph of a cross section of wheat straw.
was carried out on a Bruker IFS-113V FTIR
spectrometer with a resolution of 2 cm1. The
FTIR dichroism measurements of the samples
from epidermis and parenchyma were recorded
with a Bruker IFS-113V FTIR spectrometer with a
Perkin-Elmer gold wire grid polarizer at a resolu-
tion of 2 cm1.

Results and discussion

The cellulose, hemicellulose, and lignin contents of

wheat straw are 34–40%, 30–35%, and 14–15%,
respectively (Lawther et al. 1996; Sun et al. 1998).
Macroscopically, a wheat straw stem comprises
internodes separated by nodes, which are hard
points at which the leaves are attached to the stem.
The internodes are formed as concentric rings
leaving a void or lumen in the center (Figure 1).
The outermost ring is a cellulose-rich dense layer
(termed the epidermis), which has a concentration
of silica on the surface. Beneath the epidermis is a
loose layer containing parenchyma and vascular Figure 2. XPS survey spectra for the surface of wheat straw
bundles (Hornsby et al. 1997a). The silica in the epidermis, (a) after dewaxing, and (b) after extraction.
epidermis surface of wheat straw is about 1%,
which is calculated by XPS. It shows that there are that the content of lignin on the surface of the
two small peaks of Si2s and Si2p in the XPS survey epidermis was decreased during the extraction
spectrum of the epidermis of wheat straw before procedure (Gustafsson et al. 2003).
extraction (Figure 2a). After extraction, these Figure 3 shows the WAXD curves of cellulose
two small peaks of Si2s and Si2p disappeared samples from different parts, i.e. leaf sheath, epi-
(Figure 2b). XPS results indicate that a small dermis, parenchyma, and node of the wheat straw
amount of silica in the epidermis surface was after the extraction of lignin and hemicelluloses.
extracted by the extraction method. The O/C ratio The samples from different parts were prepared by
in the surface of the epidermis, which was taken carefully cutting certain tissues in wheat straw and
from the survey spectra using linear background extracting lignin and hemicelluloses by the stan-
subtraction, was about 0.11 after dewaxing and dard procedure presented in the Experimental part.
changed to 0.48 after extraction. This indicates The WAXD curves of all the cellulose samples
28
Figure 3. WAXD curves of cellulose from wheat straw.
from the wheat straw show typical X-ray diffrac-
tion patterns of semi-crystalline cellulose I allo-
morph with low crystallinity. The diffraction peaks
of the (101) and (10 1) planes merged together,
while the diffraction peak (040) is very weak.
Moreover, the crystallinities of cellulose from dif-
ferent parts of wheat straw are little different and
fairly low, about 40% (Table 1). This means that
the cellulose from wheat straw is a suitable parent
polymer for the preparation of cellulose derivatives
(Helbert et al. 1997). The structure of cellulose in
wheat straw is similar to that of the native crys-
talline cellulose in the cell wall of Oomycota (fun-
gal-like protista that have motile cells, cellulose cell
walls and chromosome structure which distin-
guishes them from the kingdom fungi) (Helbert
et al. 1997) and those from Crambe abyssinica
(crucifer family, an annual herbaceous plant) hull
(Gastaldi et al. 1998). The results indicate that the
native cellulose crystalline polymorphism was not
destroyed during the chemical treatment procedure.
When the cellulose from wheat straw was hydro-
lyzed by 60% H2SO4 aqueous solution at 70 C for
10 h, during which the amorphous part of cellulose
is hydrolyzed, the crystallinity of cellulose obtained
increased to 77.2% and the crystals of cellulose I
became more perfect. The diffraction peaks of the
(101) and (10 1) planes can be resolved in the
WAXD curve and the diffraction peak of the (040)
plane appeared (Figure 3e). This result indicates
that wheat straw is a potential resource for pro-
ducing cellulose microfibrils and cellulose whiskers,
Table 1. Crystallinity index of cellulose from different parts of
wheat straw.
Sample Crystallinity (%)
Leaf sheath 47.4
Epidermis 44.4
Parenchyma 44.3
Node 43.2
Hydrolyzed for 10 h 77.2
which are useful in the field of biodegradable
composites (Dufresne and Vignon 1998; Dufresne
et al. 2000) or nanocomposites (Dufresne et al.
1997; Dubief et al. 1999; Angles and Dufresne 2000,
2001; Mathew and Dufresne 2002), respectively.
The FTIR spectrum of cellulose extracted from
the wheat straw is shown in Figure 4. It is shown
that the peculiar hemicelluloses band at
1735 cm1 (Chen et al. 1997; Gastaldi et al. 1998)
in the FTIR spectrum is not discernible, which
indicates that hemicelluloses were extracted
completely by the procedure applied. Meanwhile,
the typical lignin bands at 1650–1250 and 1200–
900 cm1 are also not discernible, and the pecu-
liar absorbances of lignin at 1595 cm1 (Revol
1982; Stewart et al. 1995), associated with an
aromatic ring stretch that is strongly associated
with the aromatic C–O stretching mode, and at
1510 cm1 (Revol 1982; Stewart et al. 1995) are
absent in the FTIR spectrum. The results indicate
that lignin was extracted completely by the used
method. The absorption band at 1640 cm1 is

Figure 4. FTIR of cellulose from wheat straw.
attributed to the absorbed water in the cellulose
(Chen et al. 1997; Gastaldi et al. 1998).
It is known that there are two crystalline mod-
ifications of native cellulose, Ia and Ib (Atalla and
VanderHart 1984; VanderHart and Atalla 1984,
1987), which have a triclinic and monoclinic unit
cell, respectively (Sugiyama et al. 1991b). The Ia
phase of cellulose is metastable and could be
converted readily into the thermodynamically
stable Ib phase following a hydrothermal anneal-
ing treatment (Horii et al. 1987; Yamamoto et al.
1989; Yamamoto and Horii 1993). According to
Sujiyama et al. (1991a), the absorption bands at
750 and 710 cm1 in FTIR spectra of cellulose
were assigned to the Ia and Ib phases, respectively.
In the FTIR spectra of cellulose extracted from
wheat straw (Figure 4), the absorption band at
750 cm1 was not detectable, which indicates that
there is no cellulose Ia crystalline polymorphism in
wheat straw. There is only the absorption band at
710 cm1, which indicates that only cellulose Ib
crystalline polymorphism exists in the wheat straw.
Figure 5 shows the polarized FTIR spectra of
cellulose from epidermis and parenchyma. The
cellulose related absorbances in the FTIR spec-
trum are seen at 1162, 1130, 1098, and 900 cm1
(Agarwal and Atalla 1986; Atalla et al. 1992;
Gilbert et al. 1993) in cellulose samples from both
epidermis and parenchyma. The absorbance at
900 cm1 is associated with the antisymmetric
out-of-plane ring stretch of amorphous cellulose
(Michell 1990). The remaining absorbances are
associated with the C–H (1500–1300 cm1) and
C–O (1300–900 cm1) vibrations of cellulose
(Stewart et al. 1995). The assignment of the
absorption bands and the IR dichroic ratios
29
Figure 5. Polarized FTIR of cellulose from wheat straw. (a)
Cellulose from epidermis, (b) cellulose from parenchyma.
R = A||/A^ are listed in Table 2, where A|| and A^
are the absorbances for IR radiation polarized
parallel and perpendicular to the growth direction
of wheat straw. The results show that the intensities
of the absorption bands for the epidermis in par-
allel and perpendicular to the growth directions are
different (Figure 5a). The IR dichroic ratio of the
antisymmetric out-of-plane ring stretch of amor-
phous cellulose, which is perpendicular to the cel-
lulose chains, is less than 1, whereas the IR dichroic
ratios of ring stretching, C–C, and C–O stretching
at 1115–1120 cm1, the mainly antisymmetric
stretching (mas) C–O–C glycoside at 1162 cm1, and
the symmetric stretching (ms) C–O–C glycoside at
1205 cm1, which are parallel to cellulose chains,
are larger than 1. Moreover, the IR dichroic ratios
of absorption bands at 1280–1430 cm1, and the
in-plane bending of O–H, which is contributed by
both the O–H deformation and C–O stretching
absorption along the cellulose chains (Bellamy
1954), are larger than 1. The FTIR dichroism
indicates that cellulose chains are parallel to the
growth direction of wheat straw in the epidermis.
By contrast, there is no IR dichroism of cellulose
from parenchyma (Figure 5b and Table 2). The
30

Table 2. The assignment of FTIR absorption bands of cellulose and their dichroic ratios.

Wavenumber (cm1) Assignment A||/A^

Epidermis Parenchyma

900 Antisymmetric out-of-plane ring stretch of amorphous cellulose <1 1

1115–1120 Ring stretch, CC and CO stretching >1
1162 Mainly antisymmetric stretching (mas) C–O–C glycoside >1 1
1205 Symmetric stretching (ms) C–O–C glycoside >1 1
1230 C–H bending >1 1
1280 O–H in-plane bending (b) >1 1
1315 b(O–H()) of C–O–H alcohol groups >1 1
1335 b(O–H()) of C–O–H alcohol groups >1 1
1370 C–H bending >1 1
1430 b(O–H()) of C–O–H alcohol groups 1 1
1640 Absorbed water H2O 1 1

Figure 6. SEM photograph of cellulose morphology in the cell wall of epidermis of wheat straw after extraction of lignin and
hemicelluloses, (a) long fibers; (b) outer surface; (c) fibers in outer surface; and (d) fibers with serrations at the edge.

original FTIR spectra of IR radiation polarized spectrum of IR radiation polarized parallel to the
parallel and perpendicular to the growth direction growth direction of wheat straw was shifted par-
of wheat straw overlapped each other. The FTIR allel along the absorption intensity axis in order to

Figure 7. Cells in epidermis of wheat straw after extraction of hemicelluloses and lignin.
Figure 8. SEM photograph of cellulose morphology in the cell wall of parenchyma of wheat straw after extraction of lignin and
hemicelluloses.
separate these two spectra. Moreover, the dichroic
ratios of all the specific absorption bands are all
almost equal to 1. The results indicate that cellulose
chains have no preferred orientation along the
growth direction in the parenchyma, even though
the crystallinity index of cellulose in the paren-
chyma of wheat straw is the same as that in the
epidermis (Table 1).
Figure 6 shows the SEM micrographs of cellu-
lose in the epidermis of wheat straw after extrac-
tion of lignin and hemicelluloses. Figure 6a shows
the long cellulose fibers in the epidermis of wheat
straw, which is the most important part to produce
paper, pulp, and composites. In the outer surface
of wheat straw, there are two main kinds of fiber
shaped structures. One is the long fiber with a
diameter of about 5 lm, which is composed of fi-
brils (Figure 6c). The other has a diameter of
10 lm with the serration at the edge and connected
together with the neighboring fibers (Figure 6d).
These structures of wheat straw provide good
strengths in both the longitudinal and lateral
directions of the straw.
The epidermal cells of wheat straw are shown in
Figure 7. Similar to the fiber structure in the outer
surface of the wheat straw (Figure 6d), there is
31
serration structure at the edge of the cells, which
are combined with neighboring cells. The dimen-
sion of the epidermal cells is about 22 lm in width
and 100 lm in length. Among these epidermal
cells, specialized cells, so-called stomata, enable
gas penetration (Figures 7a, b). The dense layers
of epidermal cells give additional mechanical
strength to the stem and inhibit evaporation.
Figure 8 shows the cellulose in the parenchyma, in
which the structure of the cell wall is kept. It is
indicated that cellulose forms the backbone of the
cell. There are also holes in the cellulose wall for
ventilation and metabolism (Figure 8c).
Figure 9 shows SEM micrographs of a cross
section of untreated wheat straw. Corresponding
to POM micrographs of the cross section of un-
treated wheat straw (Figure 1), the epidermis part
of wheat straw is more dense with small lumen,
while the parenchyma part is less dense with large
die cell lumen. In the vascular bundles, there are
annular rings in the vessels (Figure 9b), which act
as the braces of the vessels in wheat straw.
The vascular bundles are the conducting system
in wheat straw and the longitudinal view of vessels
is shown in Figure 10, in which hemicelluloses and
lignin have been extracted. The annular or spiral
32

Figure 9. SEM photograph of a cross section of wheat straw (untreated).

Figure 10. Longitudinal view of vessels in wheat straw after extraction of lignin and hemicelluloses. (a, b) POM photograph of vessels;
(c, d) SEM photograph of protoxylem vessels with annular rings; (e) SEM photograph of protoxylem vessel with spiral shape; and (f)
SEM photograph of metaxylem vessel with simple perforation.

form structures in vessels are quite bright under
POM (Figures 10a and b). Figures 10c–e show
that the protoxylem tracheid cells have dense lig-
nified thickenings in the secondary wall, arranged
as annular rings or in the form of a spiral; thus
they are capable of stretching. The protoxylem
vessels are formed early in the season, but during
growth they are partly broken down and form an
inter-nodal cavity called lacuna. The morphology
of cellulose in vascular protoxylem consists of
annular rings (Figures 10c, d) or spiral form
(Figure 10e) backbones with thin cellulose film
around them. Figure 10f shows the metaxylem,
which is the main conducting system formed by
two large vessel tubes. The vessels have simple
perforation and alternative pitting and are
conspicuously larger than any other cells in the
vascular bundles.
SEM results show that cellulose remained as the
skeleton structures in the wheat straw, even after
chemical extraction of hemicelluloses and lignin.
Conclusions
Hemicelluloses and lignin can be extracted effec-
tively and completely. Cellulose in wheat straw
comprises the cellulose I allomorph with low
crystallinity and only the stable cellulose Ib poly-
morphic crystal structure exists in the wheat straw.
Cellulose from different parts of wheat straw has a
similar crystallinity. Cellulose chains in wheat
straw epidermis are orientated along the growth
direction, while they have almost no preferred
orientation along the growth direction in the
parenchyma part. There are two kinds of mor-
phologies in the outer surface of wheat straw, a
fiber structure consisting of fibrils with diameter
about 5 lm and one with a serration structure at
the edge of the fiber. These serration structures
connect the fibers together. The diameter of the
latter one is about 10 lm. The vascular bundles
consist of circular rings or spiral formed structure
cellulose backbones which are covered with thin
cellulose film.
Acknowledgements
The financial support by the National Natural
Science Foundation of China (Grant no.
33
29925411) and the Key Project of CAS is greatly
appreciated.
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