Carbohydrates-Classification

Dr.M.K.Mehta
ANN-211
 Carbohydrates
Importance
Make up 60% to 70% of diet
Major source of energy
1. Microbes
Energy for microbes
Metabolism, Growth, Protein synthesis
2. Animal
End products of the fermentation
Digestible CHOC escaping the rumen
Classification
Nonstructural (NSC)
Cell contents - storage
Structural (SC)
Cell walls
Chemistry of Feed Dry Matter
1. Organic
 Carbohydrates
Fiber
− Cellulose, hemicellulose
Soluble fiber
 Pectin, fructans, β-glucans
Starch
Free sugars
 Lignin and other phenolics
 Proteins
 Lipids
1. Inorganic
 Plant Carbohydrates

Cell Content Cell Wall

Organic acids Pectins
Sugars β-glucans
Starches Hemicelluloses
Fructans Cellulose

Mammalian enzymes will digest starch and

sucrose (limited in ruminants)
Microbes digest the plant polysaccharides
 Plant Cell Walls
Many plant cells have a primary cell wall, which accommodates the cell as it
grows, and a secondary cell wall that develops inside the primary wall after
the cell has stopped growing. The primary cell wall is thinner and more pliant
than the secondary cell wall.

A specialized region of
the cell walls of plants is
the middle lamella. Rich
in pectins, the middle
lamella is shared by
neighboring cells and
cements them firmly
together.
Secondary cell wall would develop
The main chemical components of the primary cell wall include cellulose and
two groups of branched polysaccharides, the pectins and cross-linking glycans
(hemicellulose). The secondary plant cell wall, which is often deposited inside
the primary cell wall as a cell matures, contains lignin in addition to cellulose,
but less hemicellulose and pectin.
 Carbohydrates
1. Monosaccharides - one sugar molecule
 Hexoses - 6 carbons
Glucose Fructose Galactose Mannose

Pentoses - 5 carbons
o Arabinose Xylose Ribose
1. Disaccharides - two sugar molecules
 Maltose = glucose + glucose

Cellobiose = glucose + glucose

Sucrose = glucose + fructose
 Lactose = glucose + galactose
 Carbohydrates - Continued
3. Polysaccharides - polymers of sugar molecules
- Starch - polymer of glucose (plants)
o Alpha 1- 4 linkages, branch at alpha 1-6
o Amylose (unbranched) 20 to 30% of starch in
grain
o Amylopectin (branched) 70 to 80% of starch in
grain
- Glycogen - polymer of glucose (animals)
o Alpha 1- 4 linkages, branch at alpha 1- 6
- Cellulose - polymer of glucose (plants)
o Beta 1- 4 linkages
 Cellulose
Cellulose: A polymer of glucose units in β – 1,4 linkages.
Cellulose is a linear molecule consisting of 1,000 to 10,000 β-D-
glucose residues with no branching. Neighboring cellulose chains
may form hydrogen bonds leading to the formation of microfibrils with
partially crystalline parts. Hydrogen bonding among microfibrils can
form microfibers and microfibers react to form cellulose fibers.
Cellulose fibers usually consist of over 500,000 cellulose molecules.

β-1,4 linkage
 Starch
Starch: A polymer of α-D-glucose in α-1, 4 linkages. Starch consists
of two types of molecules, amylose and amylopectin. Amylose is a
single chain of glucose units whereas in amylopectin at about every
twenty glucose units there is a branch with an α-1, 6 linkage. The
relative proportions of amylose to amylopectin depend on the source
of the starch, e.g. normal corn contains over 50% amylose whereas
'waxy' corn has almost none (~3%). Amylose has lower molecular
weight with a relatively extended shape, whereas amylopectin has
large but compact molecules.

Partial structure of amylose Partial structure of amylopectin

Starch, Cellulose and Glycogen
 Starch

Amylose molecules consist of single mostly-unbranched chains with

500-20,000 α-(1, 4)-D-glucose units with a few α-1, 6 branches.
Amylose can form an extended shape. Hydrogen bonding occurs
between aligned chains. The aligned chains may form double stranded
crystallites that are resistant to amylases.

Amylopectin is formed by non-random α-1, 6 branching of the

amylose-type α-(1, 4)-D-glucose structure. This branching is
determined by branching enzymes that leave each chain with up to 30
glucose residues. Each amylopectin molecule contains one to two
million residues, about 5% of which form the branch points, in a
compact structure forming granules. The molecules are oriented
radially in the starch granule and as the radius increases so does the
number of branches required to fill the space, resulting in concentric
regions of alternating amorphous and crystalline structure.
Amylopectin

Corn starch

Potato starch
 Carbohydrates - Continued
• Polysaccharides
- Pentosans - polymers of 5-carbon sugars
- Fructans – Water soluble chains of fructose
β-2-6 with β-2-1 branching
Found in temperate grasses
β-2-1 Found in Jerusalem artichokes
- β-Glucans – Soluble chains of glucose
β-1-3 and β-1-4 chains not linear like cellulose
Found in oats & barley
 Carbohydrates - Continued
Mixed polysaccharides
 Hemicellulose
Branched polysaccharides that are structurally homologous
to cellulose because they have a backbone composed of β-
1, 4 linked sugar residues – Most often xylans, no exact
structure
Hemicellulose is abundant in primary walls but is also found
in secondary walls
Various side chains : arabinose, glucuronic acid, manose,
glucose, 4-0-methylglucuronic acid – varies among species
In plant cell walls:
o Close association with lignin – linkages to coumaric and

ferulic acids
o Xylan polymers may be crosslinked to other

hemicellulose backbones
o Bound to cellulose in plant cell wall

o Ratio of cellulose to hemicellulose ranges from 0.8:1 to

1.6:1
• Mixed Polysaccharides - Continued
– Pectins
•Pectins have a complex and not exact structure. Backbone is
most often α-1- 4 linked D-galacturonic acid
• Rhamnose might be interspersed with galacturonic acid with
branch-points resulting in side chains (1 - 20 residues) of
mainly L-arabinose and D-galactose
• Also contain ester linkages with methyl groups and sidechains
containing other residues such as D-xylose, L-frucose, D-
glucuronic acid, D-apiose, 3-deoxy-D-manno-2-octulosonic acid
and 3-deoxy-D-lyxo-2-heptulosonic acid attached to poly-α-(1,
4)-D-galacturonic acid regions
• Proteins called extensins are commonly found associated
with pectin in the cell wall
• Commonly form crosslinkages and entrap other polymers
• Composition varies among plants and parts of plants
o Citrus pulp, beet pulp, soybean hulls have

high concentrations
o Alfalfa intermediate concentrations of pectin

o Grasses low concentrations of pectin

 Structural Carbohydrates in Plants

Pectin Hemicellulose Cellulose

35
30
% Dry matter

25
20
15
10
5
0
Young Young alfalfa Mature alfalfa
Orchardgrass

Pectins less in grass than legumes.

Hemicellulose greater in grass than legumes.
Hemicellulose and cellulose increase with maturity.
 Lignin
Lignin Monomers
Not a carbohydrate – does not
contain sugars
Large phenolic three-dimensional
polymers in secondary cell walls
The monomers are polymerized
phenylpropane units,
predominantly coumaryl alcohol
[with an OH-group in position 4 of
the phenyl ring], coniferyl alcohol
(OH-group in position 4, -OCH3 in
position 3) and sinapyl alcohol
(OH-group in position 4, -OCH3
group in positions 3 and 5).
The side groups of the monomers
are reactive forming poorly
defined structures that are heavily
cross linked.
Attach with hemicellulose and
pectins
Not digested in the rumen
Relation of Lignin to Digestibility of Cell Walls
1. A negative relationship usually observed
• Encrustation of cell wall polysaccharides
• Enzymes can not digest polysaccharides
However lignin content related to maturity
rather than digestibility of cell walls
2. Ratio of monomers varies among plants
• High concentrations of syringyl unit (sinapyl)
less digestible
However ratio of monomers not always
related to digestibility of cell walls
3. Hydroxycinnamic acids (acid forms of monomers)
can form cross links among polysaccarides and
link polysaccarides with lignin
 Lignin and Digestibility of Cell Walls

Cross links
Ferulic acid (acid form of coniferyl alcohol) is first
product synthesized
The ferulates (hydroxycinnamic acids)
1. Can react with polysaccharides of cell wall
• Reduces digestibility of cell wall polysaccharides
2. Can link polysaccharides in cell wall with lignin
• More dramatic reduction in digestibility of cell walls
• Form early in the plant and become diluted with
maturity so negative relationship not always
apparent
 Interaction of Lignin with
Polysaccharides
Core lignin

Non core lignin

THAT’S ALL