Wood Chemistry - Fundamentals and Application
Wood Chemistry - Fundamentals and Application
Wood Chemistry - Fundamentals and Application
Crown characteristics
Leaf structure
Stem structure
Root structure
11
11
Douglas- fir
longleaf pine
eastern hemlock
11
11
balsam fir
ponderosa pine
white spruce
white oak
of openDouglasock;
(E)
of openspruce;
Douglashagbark
lock; (E)
e maple.
spruce;
hagbark
r maple.
openouglasck; (E)
spruce;
agbark
maple.
FIGURE 2.1. Variations in the form of opengrown trees. (A) Eastern white pine; (B) Douglasfir; (C) longleaf pine; (D) eastern hemlock; (E)
balsam fir; (F) ponderosa pine; (G) white spruce;
(H) white oak; (I) sweetgum; (J) shagbark
hickory; (K) yellow-poplar; (L) sugar maple.
Photos courtesy St. Regis Paper Co.
STEM FORM
sweetgum
shagbark hickory
yellow-poplar
sugar maple
STEM
FORMin the taper of tree
Much interest has
been shown
Wood Character ()
Wood Character ()
Wood Character ()
Furniture
Fuel
Bark products
Cellulose
Extractives
Rubber, tannins
Lignin products
Naval stores
Pyrolysis products
Pine oil, rosin, turpentine, tall oil, tall oil fatty acids, tall oil rosin
Wood sugar
Earlywood
tracheids
Well-developed
Latewood
Tracheids
Ray
tracheids
are very thick
Storage
Only
Hardwoods
Every plant consists of many different cell types, each with a unique cell
wall that contains not only different ratios of wall components, but
sometimes also qualitative differences in their components.
When thinking about strategies for changing the composition of plant cell walls, whether in terms of abundance of
certain polymers or substitution patterns of specific polymers, one can gain significant insights by looking into
natures laboratory. Certain plant species have evolved
specialized tissues that have unusual wall compositions,
that is, they contain elevated levels of cellulose, hemicellulose, or lignin (for overview see Figure 2).
Specialized cells that make cellulose
of
www.sciencedirect.com
Major challenge in this process is that plants have evolved wall structures that are recalcitrant to biological
degradation. Hence, the biomass must be subjected to such energy-intensive and cost-intensive treatments as steam,
weak acid, or non-aqueous ammonia.
High enzyme loading is required to release fermentable glucose monomers from cellulose because of its tight linkage
with hemicelluloses and lignin in native walls. Therefore, one major research objective of plant scientists is to make
walls more open and accessible to enzymatic degradation: to increase the water solubility of polysaccharides.
Fermentability of the released mono-saccharides.Yeasts used in the ethanol fermentation process utilize only hexoses
such as glucose and mannose. However, the most common hemicellulosic polysaccharides consist mainly of xylose and
arabinose, pentoses that do not ferment so readily. Progress has been made in developing specialized yeast and
bacterial strains that can ferment these pentoses, but they are not yet very efficient. Therefore, one desirable change in
biomass is an increased abundance of hexose-containing polymers such as cellulose or mannans rather than xylans.
This process is hampered by inhibiting components, such as phenolic compounds or aliphatic acids, present to
varying degrees in the degraded biomass. One plant breeding goal should thus be to reduce the abundance of
such compounds to a minimum.
CelluloseMature cotton plants (upper left) produce cotton fibers (lower left), whose secondary walls that are nearly pure
cellulose.tissues
Poplar in
trees
(upper
produce
tension wooda(lower
with polymer.
walls that are also nearly pure cellulose.
of specialized
plants
thatright)
produce
predominantly
singleright)
cell wall
Mature
cotton plants (upper left) plants
produce
cotton
fibers
(lower
left), containing
whose secondary
walls
that(lower
are nearly
pureare
cellulose
(upper
left)
produce
seeds
endosperm
walls
left) that
largely(courtesy of
HemicellulosesFenugreek
Haigler, E. Roberts, and E. Hequet, NC State University). Poplar trees (upper right) produce tension wood (lower right) with walls that are also
galactomannan. Psyllium plants (upper center) produce seeds surrounded by a mucilaginous layer (lower center) with walls
e cellulose (courtesy of Frank Telewski and Jameel Al-Haddad, Michigan State University).
rich in arabinoxylan.
Nasturtium
plants (upper
produce
seeds where
the(lower
cotyledon
(lower
right)galactomannan.
have a wall that Psyllium plants
osesFenugreek
plants (upper
left) produce
seedsright)
containing
endosperm
walls
left) cells
that are
largely
nter) produce
seeds
surrounded
by
a
mucilaginous
layer
(lower
center)
with
walls
rich
in
arabinoxylan.
Nasturtium
plants (upper right)
is largely xyloglucan.
eeds where the cotyledon cells (lower right) have a wall that is largely xyloglucan (courtesy of Marlene Cameron, Curtis Wilkerson, Michigan
LigninPine trees (upper panel) produce compression wood (lower panel) that is enriched in lignin with a different
versity).
composition
fromproduce
normal wood.
ne trees
(upper panel)
compression wood (lower panel) that is enriched in lignin with a different composition from normal wood
of Frank Telewski and Jameel Al-Haddad, Michigan State University).
Wood Ultrastructure
The
Elementary
0.1 m
1(earlywood) - 5 (latewood) m
0.2-0.3 m
Cell corner
0.1-0.2 m
0.2-1.0 m
Middle lamella
Located between the cells and serves
the function of binding the cells
together
At an early stage of the growth, it is
mainly composed of pectin substances,
but it eventually becomes highly
lignified.
Primary wall
PW is a thin layer consisting of
cellulose, hemicellulose, pectin, and
completely embedded in lignin.
Primary wall
In the presence of reagents which induce strong swelling
the primary wall is peeled off and the belts around the
fibers expand.
Compound middle lamella
The middle lamella together with the primary wall on
both sides, is often referred to as the compound middle
lamella.
Its lignin content is high (concentration is the highest), but
because the layer is thin, only 20-25% of the total lignin in
wood is located in this layer.
S1 layer
S1 contains 3-4 lamellae where the
microfibrils from either a Z helix or S
helix.
The microfibril angle of the crossed
fibrillar varies between 50 and 70 with
respect to the fiber axis.
S2 layer
S2 forms the main portion of the cell
wall.
Its thickness is softwood tracheids
varies between 1 m (earlywood) and
5 m (latewood).
It may contain 30-40 lamellae or more
than 150 lamellae.
S2 layer
The microfibrillar angle varies between
5-10 (latewood) and 20-30
(earlywood).
The characteristic of the S2
layer (thickness, microfibrillar
angle) have a decisive
influence on the fiber stiffness
and other paper making
properties.
Electron micrograph of a delignified secondary wall (S2) of Pinus sylvestris
S3
S3 is a thin layer consisting of several
lamellae which contain microfibrils in
both Z helix and S helix (50-90
angle).
Great variations are noted among
different wood species.
W layer
Warty layer is a thin amorous membrane
located in the inner surface of wall in all
confers and in some hardwoods.
The composition of warty layer deposits
is still unknown.
Each species has its own, characteristic
warty layer.
Reaction wood
Compression wood
Compression wood
Tension wood
Tension wood
G
Tension wood differs from normal wood formed in the absence of stimulus,
and from opposite wood located on the lower side of the inclined stem, in a
number of biochemical, anatomical and mechanical characteristics.
Research review
Review
of
pposite
fibres
ondary
all; SW,
r.
on of tension
(Nelson
studies
this model
will lead wood;
to the (b)
identification
(a)wood
Fibres
in wood
areaon
opposite
to tension
tension and
pression of the gene coding
characterization of specific genes involved in the definition
oxylate oxidase, responsible
of particular mechanical properties of wood.
wood G-fibres with an additional thick layer in the secondary cell
gly induced during tension
Genomics studies on reaction wood have already been
son-Gunners et al., 2003).
initiated with loblolly pine (Whetten et al., 2001) and poplar.
wall (G-layer). PW,
cell wall;
secondary
cellKTH-Royal
wall; G,
In primary
Sweden (Ume
PlantSW,
Science
Centre and
Institute of Technology), 5723 ESTs have been produced from a
n wood gelatinous layer. Populus tremula P. tremuloides tension wood cDNA library
have been well studied at the
(Sterky et al., 2004). In another project launched in our instiBefore the commencement
tute (INRA-Orlans), four different cDNA libraries were prew genes involved in xylem
pared from the xylem collected from three P. tremula P. alba
ed and characterized, and
trees, induced to form tension wood on gravitational stimulain lignin biosynthesis (for
tion (for details see Djardin et al., 2004). The first cDNA
2003). This work led to a
library corresponds to genes expressed in the cambial zone
etabolism and, through the
(CZ) which includes cambium and very young xylem cells.
e production of wood with
The second cDNA library was prepared from the differentiating
or paper production (Pilate
xylem collected on the tension wood side (DX-TW); and the
third from the differentiating xylem collected on the opposite
side (DX-OW). The fourth cDNA library corresponds to the
genes expressed in the mature xylem (MX) collected on either
nsion wood
side of the stem. From the clustering, alignment and annotaaken on trees, through EST
tion of more than 10 000 ESTs, it appeared that a number of
d formation in pine (Allona
expressed sequences did not show any homology with the
et al., 1998). Since then a
sequences present in the public databases, suggesting that
projects have been initiated
they may be specific to trees. The 11 consensus containing more
ree tissues. In addition to
than 10 ESTs, whose sequences gave no hit in the Swiss-Prot,
n regular wood formation,
EMBL, GenBank, DDBJ and PDB databases, are listed in
he use of tension wood as a
Table 1. However, using more specific motif searches, four
consensus sequences (Table 1, italics) had similarities with
asily be induced by a stem
arabinogalactan proteins (AGPs), a class of hydroxyprolinewith tension wood) and the
rich proteins with poorly defined functions in cell wall formad) of the bent stem can be
tion. Nonetheless, these 11 sequences are likely to correspond
ssion profiling. With such
to tree- or taxon-specific genes.
fy genes linked to G-layerFunctional genomics approaches, using bioinformatics motif
lignin content, its increased
searches, expression studies and characterization of transgenic
ed MFA. We anticipate that
poplars altered in the expression of these genes, will help
hytologist.org
65
Cellulose + Hemicellulose
Starch
Pectic
substances
Water-soluble
polysaccharides: Arabinogalactans
Lignin 20 - 30%
Extractives 5 - 10%
Pectin
A mixture
ion.
Preparing
Extraneous materials
Soluble in neutral
solvents
Resins
Fatty materials
Alcohol
Phenolic substances
Lignin
Polysaccharides
Cellulose
Hemicellulose
Mineral constituents
Proteinaceous matter
Pectic substances
D-glocose
Pentose
D-Xylose
L-Arabinose
Hexoses
D-Glucose
D-mannose
D-Galatose
Uronic acid
Acetic acid
Uronic acid
Methoxy uronic acid
Separation of Lignin
Extractives
Generally refer to compounds extractable with
organic solvents
Extractives
Extractive-free wood
or
Soluble in organic
solvents
Soluble in water
Not hydrolyzed by
acid
Delignification
Holocellulose
Lignin
-cellulose
Hemicellulose
Determination of sugar and
or
uronic acid units by
hydrolysis and
chromatography
Extractives-free wood
Separation of Polysaccharides
Holocellulose
Wood powder
Extractives-free wood
Benzene EtOH extraction
Delignin with chloride
Holocellulose (Cross-Bovan cellulose)
17.5% NaOH
Insoluble portion
-Cellulose
Soluble portion
Neutralization with CH3COOH
-Cellulose
-Cellulose
-, -, - Cellulose
Degree of Polymerization
- Cellulose
1000-3000
- Cellulose
10-100
- Cellulose
10
Hemicellulose
Hardwood
Extractives
Carbohydrates
Higher mannan
content (10-15%)
Lower xylan content
(<10%)
Higher (23-33%)
16-25%
Higher methoxy
content
Lignin
Heartwood
Extractives
Less
More
Cellulose
More
Higher acetyl content
Less
Less acetyl content
Lignin
More
Less
lignin
Less
cellulose
The
Tension
More
wood (hardwood)
Lignin-free
The