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Chemistry of the wood constituents

1. Carbohydrates
Cellulose is the world's most abundant and
important biopolymer.
It has been estimated that globally 1 a 11
tons of this macromolecular substance are
synthesized and destroyed each year.
Although the technical utilization of cellulose
has a long history, the understanding of its
chemistry and structure is relatively new.
Today, the chemical structure of cellulose has been
clarified in detail, but its supramolecular state and
its polymer properties are not yet fully
understood.
Cellulose is a polydispersed linear
homopolysaccharide consisting of beta-D-
glucopyranose moieties (in 4C
1
conformation)
linked together by (1-4)-glycosidic bonds .


The degree of pOlymerization (DP) of native
wood cellulose is of the order of 10 000 and
lower than that of cotton cellulose (about 15
000).
These DP values correspond to molecular masses
of 1.6 and 2.4 million Da and to molecular lengths
of 5.2 and 7.7um, respectively.
In technical processes, such as chemical pulping,
the OP of cellulose can decrease to 500-2 000.
The polydispersity (Mw/Mn)of cellulose is rather
low <2), indicating that the weight average
molecular mass (Mw) and the number average
molecular mass (Mn) do not deviate much from
each other.

Because of the strong tendency for intra- and
intermolecular hydrogen bonding, bundles of
cellulose molecules aggregate to microfibrils,
which form either highly ordered (crystalline) or
less ordered (amorphous) regions. These
microfibrils pass through several crystalline
regions (about 60 nm in length).
As a result of further aggregation of microfibrils,
"fiber wall cellulose" with a high degree of
crystallinity (60%-75%) is formed.
This also means that cellulose is relatively inert
during chemical treatments but also that it is
soluble only in a few solvents. The most common
cellulose solvents are cupriethylenediamine
(CEO) and cadmiumethylenediamine (Cadoxen).

Besides cellulose, the other major naturally
occurring carbohydrate based polymers,
hemicelluloses, are heteropolysaccharides and are
clearly less welldefined than cellulose.
Their building units are hexoses (D-glucose, D-
mannose, and D-galactose), pentoses (0- xylose,
L-arabinose, and 0- arabinose), or deoxyhexoses
(L-rhamnose or 6-deoxy-Lman nose and rare L-
fucose or 6-deoxy-L-galactose).
Softwoods and hardwoods differ not only in the
content of total hemicelluloses but also in the
percentages of individual hemicellulose
constituents.


Lignin

Lignin is an amorphous polymer with a chemical structure
that distinctly differs from the other macromolecular
constituents of wood.
It is also characteristic that, unlike wood carbohydrates, the
chemical structure of lignin is irregular in the sense that
different structural elements (phenylpropane units) are not
linked to each other in any systematical order.
In general, lignins are roughly classified into three major
groups: softwood, hardwood, and grass lignins.
There are several industrially based technical lignins that
are byproducts of the chemical pulping.
Kraft lignin (or sulfate lignin), alkali lignin (or soda lignin),
and lignosulfonates are derived from kraft, soda-AQ, and
sulfite pulping of wood, respectively. It is also known that
there are many characteristic differences between all these
lignins.
However, in the following, the chemical structure of
lignins present in intact softwood and hardwood will
be emphasized.
According to a widely accepted concept confirmed
originally by numerous studies of lignin labeled with
radioactive carbon (14C), lignin can be defined as a
polyphenolic material arising primarily from enzymic
dehydrogenative polymerization of three phenyl-
propanoid units (p-hydroxycinnamyl alcohols).
This biosynthesis process comprises various oxidative
coupling reactions of the resonance stabilized phenoxy
radicals obtained from these precursors leading to the
formation of a randomly cross-linked macromolecule.
Although the precursors of the p-hydroxycinnamyl
alcohol type are practically the only building units of all
lignins.

trans-Coniferyl alcohol
trans-Sinapyl alcohol
trans-p-Coumaryl alcohol
The structural building blocks of lignin are joined
together by ether linkages (C-OC) and carbon-
carbon bonds (C-C).
Of these inter-unit linkages, the former ones
dominate with the most prominent type in both
softwood and hardwood lignins.
Detailed knowledge about the characteristics of
these linkages is of great theoretical interest, for
example, for a better understanding of the
degradation reactions of lignin in technical
processes, such as delignification.
In addition, numerous miscellaneous linkages and
minor structures are known. It is also evident that
the frequency of these groups can vary according
to the morphological location of lignin.

Functional groups of native lignin
Functional group Softwood lignin Hardwood lignin
Phenolic hydroxyl 20-30 10-20
Aliphatic hydroxyla 115-120 110-115
Methoxyl 90-95 140-160
Carbonyl 20 15
Lignin-hemicellulose bonds


The close association between lignin and
carbohydrate components in wood strongly
suggests the existence of chemical linkages
between these constituents.
This question has been a subject of much debate
and many intensive studies.
It has been evident for a long time that physical
and chemical interactions (i.e., hydrogen bonds,
van der Waals' forces, and chemical bonding)
occur between lignin and carbohydrates.
But it has been difficult to definitively verify the
precise type and amount of chemical linkages
The nature of the different bonds between lignin
and carbohydrates is highly complex and far from
being completely understood.
However, it is now generally accepted that lignin is
chemically linked at least with a part of wood
hemicelluloses, although there are even indications
of lignin and cellulose bonds.
The terms "lignin-polysaccharide complex" (LPC) or
"lignin-carbohydrate complex" (LCC) are generally
used for describing the covalently bonded
aggregates of lignin and hemicelluloses.
Although the more accurate term "lignin-
hemicellulose complex" (LHC) can be used as well.
Chemical bonds have been reported between lignin
and practically all the hemicellulose constituents.
BENZYL ETHERS
Softwoods Softwoods
BENZYL ESTERS
PHENYL GL YCOSIDES
Softwoods and hardwoods
Softwoods and hardwoods
Extractives
Extractives comprise an extraordinarily large
number of diverse substances (i.e., several
thousands of individual compounds), mainly with
low molecular masses.
By a broad definition, these extractives are either
soluble in neutral organic solvents [e.g., diethyl
ether, methyl tert-butyl ether, petroleum ether,
dichloromethane, acetone, ethanol, methanol,
hexane, toluene, and tetrahydrofuran (THF)] or
water.
Thus, these substances may be both lipophilic and
hydrophilic and are regarded as nonstructural
wood constituents.
The term "resin" is often used as a collective
name for the lipophilic extractives (with the
exception of phenolic substances), which can
be extracted from a wood sample by nonpolar
organic solvents but are insoluble in water.
The extractives impart color, odor, and taste
to wood, and some of them can be the energy
source (fats and waxes) of the biological
functions in the wood cells.
Most resin components protect the wood
against microbiological damage or insect
attacks.

The composition of extractives varies widely
from species to species, and the total amount
of extractives in a given species depends on
growth conditions.
For example, the typical content of
extractives in Scots pine Norway spruce and
silver birch is, respectively, in the range of 2.5
to 4.5, 1.0 to 2.0, and 1.0 to 3.5% of the wood
dry solids.

Classification of organic extractives in woods
Aliphatic and alicyclic compounds Phenolic compounds Other compounds
Terpenes and terpenoids Simple phenols Sugars
(including resin acids and Stilbenes Cyclitols
steroids) Lignans Tropolones
Esters of fatty acids Isoflavones Amino acids
(fats and waxes) Condensed tannins Alkaloids
Fatty acids and alcohols Flavonoids Coumarins
Alkanes Hydrolyzable tannins Quinones
Terpenes and their derivatives (more than 4000
have been isolated and identified) comprise a
broad class of compounds with widespread
appearance in the plant kingdom.
Their basic structural unit is isoprene (2-methyl-1
,3-butadiene; molecular formula C
5
H
S) and they
can be divided into subgroups according to the
number of isoprene units linked in a terpene .
In woody tissues there are also present, although
as rare components, some hemi(C
5
H
s
), sester-
(C
25
H
40
), and tetraterpenes (C
4o
H
64
), and their
derivatives. In addition, some polyterpenes such
as cis-1 ,4-polyisoprene (i.e., rubber, the exudates
of Hevea species such as Hevea braziliensis) are
of great industrial importance.

Classification of the main terpene structural types in woody

tissues
Name Number of Molecular
(C
1o
H
16
) units formula
Monoterpenes 1 C
10
H
1
6
Sesq u ite rpenes 1.5 C
15
H
24

Diterpenes 2 C
2o
H
3
2
Triterpenes 3 C
30
H
48

Polyterpenes >4 > C
4o
H
6
4
Chemical structure of some common terpenes and terpenoids.
MONOTERPENES AND MONOTERPENOIDS
(-)- Limonene
3-Carene
SESQUITERPENES AND SESQUITERPENOIDS
Longifolene
a-Cadinol a-Muurolene
Farnesene
Monoterpenes and monoterpenoids are volatile
compounds and contribute substantially to the odor
of wood.
Wood contains a large variety of aromatic extractives
reaching from simple phenols to complex polyphe-
nols and their related compounds .
It is characteristic for polyphenols that they often
are colored compounds which are accumulated
abundantly in the heartwood of many species and
only small amounts are present in sapwood .
Some of them are probably degradation products of
compounds that can be hydrolyzed during extraction
or steam distillation .
This kind of extractives also has fungicidal properties
and thus protect the tree against microbiological
attack.
Examples of fatty alcohols and fatty acids
in wood

FATTY ALCOHOLS,
Arachinol or eicosanol (C
20
). behenol or docosanol (C
22
). and
lignocerol or tetracosanol (C
24
)
FATTY ACIDS
Saturated acids: lauric or dodecanoic acid (Cd. myristic or
tetradecanoic acid (C
14
). palmitic or hexadecanoic acid (C
16
).
stearic or octadecanoic acid (CIS)' arachidic or eicosanic acid
(C
20
), behenic or docosanoic acid (C
22
), and lignoceric or
tetracosanoic acid (C
24
). and unsaturated acids.' oleic or cis-9-
octadecenoic acid (C
181
(ge)), linoleic or cis. cis-9, 12-
octadecadienoic acid (C
182
(ge 12e))' linolenic or cis.cis.cis-9, 12,
15-octadecatrienoic acid (C
183
(ge.12e15e)), pinolenic or
cis.cis.cis-5,9, 12-octadecatrienoic acid (C
183
(5ege 12e))' and
eicosatrienoic or cis. cis, cis-5, 11, 14-eicosatrienoic acid
(C
203
(5e,11 e14e))

Inorganic components
In woods from temperate zones, elements other than
carbon, hydrogen, oxygen, and nitrogen make up between 0.1
% and 0.5% of the dry solids in wood, whereas those from
tropical and subtropical regions make up even to 5%.
In practice, the total amount of wood inorganics is measured
as ash, which is the residue obtained after the proper
combustion of the organic matter of a wood sample.
The ash contains mainly different metal oxides and average
values for the ash content of commercial softwoods and hard-
woods are generally in the range of 0.3% to 1.5% of the wood
dry solids.
There is also a significant dependence of the ash content and
composition on the environmental conditions (e.g., site
fertility and climate) under which the tree has grown and, on
the other hand, on the location within the tree.
Approximative concentration levels of various elements a in the dry
stemwood of softwoods and hardwoods
Range, Elements
ppm
400-1000 K Ca
100-400 Mg P
10-100 F Na Si S Mn Fe Zn Ba
1-10 B AI Ti Cu Ge Se Rb Sr y Nb
Ru Pd Cd Te P
0.1-1 Cr Ni Br Rh Ag Sn Cs Ta Os
<0.1 Li Sc V Co Ga As Zr Mo In Sb
I Hf ,W Re Ir Au Hg Pb Bi

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