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-Dglucopyranose moieties (in 4C1 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, Dmannose, and D-galactose), pentoses (0- xylose, L-arabinose, and 0- arabinose), or deoxyhexoses (L-rhamnose or 6-deoxy-Lman nose and rare Lfucose 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 phenylpropanoid 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 carboncarbon 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 "ligninhemicellulose complex" (LHC) can be used as well. Chemical bonds have been reported between lignin and practically all the hemicellulose constituents.

BENZYL ETHERS

Softwoods

oftwoods

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 C5HS) 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(C5Hs), sester(C25H40), and tetraterpenes (C4oH64), 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

(C1oH16) units

formula

Monoterpenes

C10H16

Sesq u ite rpenes

1.5

C15H24

Diterpenes

C2oH32

Triterpenes

C30H48

Polyterpenes

>4

> C4oH64

Chemical structure of some common terpenes and terpenoids.

MONOTERPENES AND MONOTERPENOIDS

(-)- Limonene

3-Carene

SESQUITERPENES AND SESQUITERPENOIDS

Farnesene

a-Muurolene

a-Cadinol

Longifolene

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 polyphenols 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 (C20). behenol or docosanol (C22). and lignocerol or tetracosanol (C24) FATTY ACIDS Saturated acids: lauric or dodecanoic acid (Cd. myristic or tetradecanoic acid (C14). palmitic or hexadecanoic acid (C16). stearic or octadecanoic acid (CIS)' arachidic or eicosanic acid (C20), behenic or docosanoic acid (C22), and lignoceric or tetracosanoic acid (C24). and unsaturated acids.' oleic or cis-9octadecenoic acid (C181 (ge)), linoleic or cis. cis-9, 12octadecadienoic acid (C182(ge 12e))' linolenic or cis.cis.cis-9, 12, 15-octadecatrienoic acid (C183(ge.12e15e)), pinolenic or cis.cis.cis-5,9, 12-octadecatrienoic acid (C183(5ege 12e))' and eicosatrienoic or cis. cis, cis-5, 11, 14-eicosatrienoic acid (C203(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 hardwoods 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, ppm 400-1000 100-400 10-100 1-10 K Mg F B Ru P Na AI Pd Ni Sc Hf Si S Ti Cu Cd Te Br Rh V Co ,W Re Mn Ge P Ag Ga Ir Sn As Au Cs Zr Hg Ta Mo Pb Os In Bi Sb Fe Se Zn Rb Ba Sr y Nb Ca Elements

0.1-1
<0.1

Cr Li I