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Bpol6010 275 287 PDF
Bpol6010 275 287 PDF
10
Cellulose
2 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.1 Natural Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
2.2 Synthetic Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
5 Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.1 Synthesis of Substrates for the Polymerizing Enzyme . . . . . . . . . . . . . 286
5.2 Polymerizing Enzyme System and Enzymology of Biosynthesis . . . . . . . 287
5.3 Genetic Basis of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
5.4 Regulation of Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
276 10 Cellulose
6 Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
6.1 Intracellular Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
6.2 Extracellular Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
8 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
8.1 Physical and Material Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 293
8.2 Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
13 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
acetylation and deacetylation of cellulose; types of plants often combined with other
these experiments resulted in the concept of biopolymers. Of great scientific importance
polymer-analogous reactions (Staudinger is access to cellulose using enzymatic and
and Daumiller, 1937). According to this chemical methods, respectively, developed
concept, functional groups of macromole- during the last decade.
cules ± in the case of cellulose predomi-
nantly hydroxyl groups ± can undergo the
same kind of reactions as the corresponding
2.1
low-molecular compounds. Further, it was
Natural Sources
observed that the supramolecular structure
of the polymer may play an important role in
The primary occurrence of cellulose is the
determining the rate and final degree of
existing lignocellulosic material in forests,
conversion, as well as the distribution of the
with wood as the most important source.
functional groups, which has been well
Other cellulose-containing materials include
recognized for cellulose.
agriculture residues, water plants, grasses,
and other plant substances. Besides cellu-
lose, they contain hemicelluloses, lignin,
2 and a comparably small amount of extrac-
Occurrence tives (Hon, 1996). Commercial cellulose
production concentrates on harvested sour-
The main source of cellulose is the occur- ces such as wood or on naturally highly pure
rence of this polysaccharide in different sources such as cotton (Table 1).
Hardwood 43 ± 47 25 ± 35 16 ± 24 2±8
Softwood 40 ± 44 25 ± 29 25 ± 31 1±5
Bagasse 40 30 20 10
Coir 32 ± 43 10 ± 20 43 ± 49 4
Corn cobs 45 35 15 5
Corn stalks 35 25 35 5
Cotton 95 2 1 0.4
Flax (retted) 71 21 2 6
Flax (unretted) 63 12 3 13
Hemp 70 22 6 2
Henequen 78 4±8 13 4
Istle 73 4±8 17 2
Jute 71 14 13 2
Kenaf 36 21 18 2
Ramie 76 17 1 6
Sisal 73 14 11 2
Sunn 80 10 6 3
Wheat straw 30 50 15 5
a
Adapted from Hon (1996).
2 Occurrence 279
Tab. 2 Carbohydrate composition and degree of polymerization (DP) of some cellulose samplesa
3.1
Hydrogen Bonding
3.2
Crystal Structure
4
Physiological Function
walls from already dead cells are crucial wall, such as proteins, pectines, and hemi-
functional units of higher plants (xylem). celluloses. For further increasing the stabil-
The main building blocks of the primary ity of plants, lignin is incorporated into the
cell wall of plants consist of different plant architecture. The portion and distribu-
components, e.g., pectins, hemicelluloses, tion of the different components of cell walls
celluloses, and proteins. In the primary cell define the final properties of the plant parts
wall, the non-cellulosic components domi- and tissues. Examples of the role and
nate; on this basis, the mechanical stability structure of hemicelluloses in the plant cell
of the primary cell wall is low. While in later wall system are given by Henriksson et al.
on formed structures of the cell wall and (2000).
units important for plant morphogenesis the Rose et al. (1997) have found that specific
fibrillar structure of cellulose stabilizes the proteins, so-called expansins, are able to
plant organism. The later on formed struc- induce the extension of isolated plant cell
tures of the cell wall and cell units important walls in vitro and to disrupt the non-covalent
for plant morphogenesis were stabilized interactions between hemicelluloses and
by the fibrillar character of cellulose The cellulose microfibrils. Because the primary
primary cell wall swells and forms jelly-like cell wall acts as the main factor for cell
structures. (To the groups of hemicelluloses enlargement, this process may be an integral
belong glucanes of the (1 ! 3)-b as well as part to plant cell expansion. Using expan-
(1 ! 4)-b-, gluco-, and galactomannanes and sins, the role of the different components
mainly xylanes; Sitte et al., 1991) The cellu- within this primary cell wall can be studied.
lose molecules in the primary cell walls have Some of these reactions and substance
high degrees of polymerization between formations will be regulated by ethylene
2000 and 15,000 anhydroglucose units in and other phytohormones.
long, non-branched molecules. The cellulose The microtubule arrays are of high im-
chains are twisted along the axis of the portance because of their involvement in the
glucan chains (1808) and stabilized by hydro- orientation of cellulose microfibrils. The
gen bonds between the chains. As a result, plant interphase tubulins play an important
the rings of the pyranoses lie approximately role in these processes and have influences
in the same level, forming ligaments. The on structuring the microfibrils within the
smaller chains have lengths around 8 mm. cell-wall system (Moore et al., 1997).
These chains associate to elementary fibrils
having a diameter of about 5 ± 30 nm. In the
secondary cell walls, the fibrils associate to 5
microfibrils with diameters of about 5 ± Biosynthesis
30 nm. These microfibrils have an organ-
ization in crystal lattices, bringing a high The biosynthesis of cellulose is not yet
stability into the cell walls of plants. These completely elucidated. Moreover, contrary
associated cellulose fibrils bring the main results have been described and discussed in
contribution to the high mechanical many papers. During the last few years, the
strength of the plant cell walls. The tensile numbers of patents in this field has in-
strength of plant cell walls has a basis not creased because of the interesting possibility
only in the association of the chains by to increase the cellulose content of plants
hydrogen bonds but also in sticking together and to construct new and more efficient
with other components of the primary cell plants. Because of the ability of some
286 10 Cellulose
bacterial strains to form cellulose and be- feeding modified glucoses to bacteria (Glu-
cause of the similarity of the biosynthetic conacetobacter xylinum), as well as to plant
apparatus in some aspects, much of the cells or cell extracts, no significant formation
research was done using these bacteria. of modified celluloses could be detected
Results obtained with the bacterium Gluco- (Schmauder, unpublished; Brown, personal
nacetobacter xylinum as a model organism communication).
are discussed in Volume 5 of Biopolymers, Another possible source for UDP-glucose
Chapter 3. Table 5 contains a summarization could be sucrose synthase, an enzyme
of different relevant publications, which will associated with the plasma membrane,
not be discussed in detail, while Table 6 e.g., of cotton fibers. Because of this location,
shows a selection of interesting patents. a direct channeling of the substrate UDP-
glucose to the polymerizing enzyme is
5.1 possible. But the regulation, control, and
Synthesis of Substrates for the Polymerizing targeting of this process is unknown in wide
Enzyme areas. Other possible sources for the stabi-
lizing and transport of the substrate are
The only substrate for cellulose biosynthesis annexin-like molecules, which are able to
is UDP-glucose. The biosynthesis of this bind UDP-glucose, e.g., a 170-kDa polypep-
energy-rich compound follows the normal tide was co-purified with the cellulose
biosynthetic pathways in the cells, starting synthase. This protein shows some homol-
from glucose (Figure 7). The enzyme cellu- ogies to the yeast b-1,3-glucan synthase (see
lose synthase accepts only UDP-glucose as a also Brown, 1999; Delmer, 1997, 1999a,b,
substrate; moreover, it was noticed that by 2000a,b).
Role of callose synthase and other (1,3)-b-glucan synthase in cellulose Him et al., 2000
biosynthesis; enhancing of cellulose synthesis by cellobioses
Effect of retardants on cellulose biosynthesis in cotton; effects on fibers and Akhunov et al., 2000
seedlings
Review about genes and proteins involved in cellulose synthesis in plants; role Delmer et al., 2000
of the sucrose synthase for substrate formation; orientation of the microfibril
deposition; role of membrane-associated cellulase in biosynthesis process
Cellulose structure elucidation using atomic force microscopy Baker et al., 2000
Estimation of the relations between Cellulose Ia and Ib in wood; application of Newman, 1999
13
C-NMR
Supramolecular architecture; fibril formation and its regulation Kataoka and Kondo,
1999a,b
Cellulose biosynthesis as a binding factor for CO2 Hayashi et al., 1998b
Reviews on cellulose biosynthesis; comparison of synthesis by microorganisms Brown, 1996; Brown
and by plants et al., 1996; Kudlicka
and Brown, 1996
General reviews concerning cellulose biosynthesis by bacteria, fungi, and plants Blanton and Haigler,
1996
5 Biosynthesis 287
Overexpression of cellulose synthase genes for modulating expression of Taylor and Turner, 2000
enzymes involved in synthesis of plant cell walls
Polynucleotides encoding cellulose synthase for acceleration of plant growth Carraway et al., 2000
and up-regulation of cellulose synthase level; modifying of lignin biosynthesis
Cellulose synthase gene from poplar; application for altering cellulose and Chiang et al., 2000
lignin composition
New genes encodes maize cellulose synthase polypeptides; modulation of Bowen et al., 2000
expression of cellulose synthase in plants; production of transgenic plants
expressing the new protein
Genes for cellulose synthase; application of these genes for improving plant Dhugga et al., 2000
stalk quality; increase of cellulose in stalks etc.
Transgenic plant expressing cell-wall modulating proteins as a basis for, e.g., Shani et al., 1999
altered morphology, increased growth, modified fiber lengths, increased
cellulose and starch content
Isolated genes encoding polypeptides involved in cellulose biosynthesis, Arioli et al., 1999
transgenic plants, expressed in sense or anti-sense orientation, ribozxymes, co-
suppression, gene-targeting molecules
Fig. 7 Intracellular activation of glucose as the precursor for cellulose biosynthesis. 1: Glucokinase; 2:
Phosphoglucomutase; 3: UDP-glucose-pyrophosphorylase; UDP uridine 5'-diphopsphate; glc glucose;
glc-6-P glucose-6-phosphate; glc-1-P glucose-1-phosphate; Pi inorganic phosphate.
Summarizing those effects, Brett (2000) Brown and Saxena (2000) and Delmer
states that UDP-glucose on the one hand or (1999b) describe that the cellulose-synthase
sucrose on the other, as well as further complex has a rosette structure character-
soluble intermediates from these pathways, ized by ultrastructural investigations. This
could serve as possible precursors. structure is highly symmetrically arranged
(about six-fold) and contains transmem-
5.2 brane particle subunits. From these sub-
Polymerizing Enzyme System and Enzymology units, the crystalline cellulose I will be
of Biosynthesis generated. In this review, the historical data
for this finding are discussed in detail. The
Different data are described for the cellulose catalytic subunit is a transmembrane protein
synthase as the active enzyme system in with some transmembrane regions.
cellulose formation. Carpita and Vergara Brown and Saxena (2000) discuss four
(1998) discuss the polypeptide formed as a different models for cellulose synthesis:
result of the CelA gene family (cotton), with
a size of about 110 kD, and the existence of 1) The most acceptable model, model 1,
eight transmembrane domains. works with the assumption that the