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Polysaccharides

• Also called glycans, differ from eachother in

o the identity of their recurring monosaccharide units

o Chain length

o Types of bonds linking the units

o Degree of branching

• Homopolysaccharides can serve as

o storage forms of monosaccharides that are used as fuels

 Ex.) starch and glycogen

o Structural elements in plant cell walls and animal cytoskeletons

 Ex.) cellulose and chitin

• Heteropolysaccharides provide extracellular support for organisms of all


kingdoms

o Ex.) the rigid layer of the bacterial cell envelope, forms matrices in
extracellular space in animal tissue.

o Also provides protection, shape, and support to cells, tissues, and


organs

• Generally do not have defining molecular weights

• Fuel Storage

o Most important are starch and cellulose

 Occur intracellularly as large clusters or granules

 Heavily hydrated b/c they have many exposed hydroxyl groups


available to hydrogen bond with water

o Starch contains 2 types of glucose polymer

 Amylose which consists of long, unbranched chains of D-glucose


residues connected by (a 1 4) linkages (as in maltose)

 Amylopectin is highly branched.


• The glycosidic linkages joining successive glucose
residues are (a14)

• The branch points(occur every 24-30 residues) are


(a16) linkages

o Glycogen is the main storage polysaccharide of animal cells

 Polymer of (a14) linked subunits of glucose, with (a16)


linked branches

 Branched every 8-12 residues and more compact than starch

 Very abundant in liver (about 7% of wet weight) also present in


skeletal muscle

 In hepatocytes, found in large granules composed of smaller


granules of single highly branched glycogen molecules

• Glycogen molecules also contain the enzymes responsible


for the synthesis and degradation of glycogen

 Each glycogen branch ends with a nonreducing sugar unit so a


glycogen with n branches has n+1 nonreducing ends but only 1
reducing end

 When used as an energy source, glucose units are removed one


at a time from nonreducing ends

o Dextrans are bacterial and yeast polysaccharides made up of (a16)


linked poly-D-glucose

 All have (a13) branches and some also have (a12) or


(a14) branches

• Homopolysaccharide Structural Roles

o Like amylose, cellulose is a linear, unbranched homopoly. Consisting of


10-15,000 D-glucose units.

 In cellulose, glucose residues are in B configuration where as in


amylose they’re in the A configuration

 In cellulose, glucose residues are linked by (B14) glycosidic


bonds
o Glycogen and starch ingested in the diet are hydrolyzed by a-amylases
and glycosidases

 Enzymes in saliva and intestines that break (a14) glycosidic


bonds

 Termites readily digest cellulose bc of trichonympha parasite in


their intestines that secrete cellulose which can break the
(B14) linkages.

o Chitin is a linear homopoly. Composed of N-acetylglucosamine residues


in (B14) linkages

 Its only difference from cellulose is the replacement of the OH


group at C-2 with an acetylated amino group

 Chitin forms extended fibers likce cellulose and cannot be


digested by vertebrates

 Principle component of exoskeletons and is probably the 2nd


most abundant polysaccharide behind cellulose in nature

o Steric Factors and Hydrogen Bonding Influence Homopolysaccharide


Folding

 Same basic folding principles of polypeptides

 H-bonding has especially important influence on folding b/c of all


of the OH groups Glycogen, Starch, and cellulose are composed
of pyranoside subunits(6 membered ring, as are the
oligosaccharides of glycoproteins and glycolipids

• These molecules can be represented as a series of


pyranose rings connected by an oxygen atom bridging 2
carbon atoms(the glycosidic bond)

o In principle, there is free rotation about bot C-O


bonds linking the residues, but its limited by steric
hindrance of substituents

• 3D-structure can be described in terms of dihedral angles


about the glycosidic bond.

• The most stable 3D structure for the (a14) linked chains


of starch and glycogen is a tightly coiled helix
o In amylose this structure is regular enough to allow
crystallization and thus determination of the
structure by x-ray diffraction.

 The average plane of each residue forms a


60o angle with the average plane of the
preceding residue, so there are 6 residues
per turn

 The core of the amylose helix is the right


dimensions to accommodate iodine as
complex ions (I3- and I5-) giving an intensely
blue complex

• For cellulose, the most stable conformation is where each


chair is turned 180o relative to its neighbors, yielding a
straight, extended chain

• All OH groups are available for H bonding with


neighboring chains