Lecture 9

Carbohydrates: Polysaccharides and Glycocojugates

Sugar acids
Oxidation of carbonyl group generate aldonic acids while C-6 oxidation results in alduronic acids. glucose  gluconate or glucuronate

D-gluconate cyclizes to D-glucono-δ-lactone

β-D-glucuronate

Number 1 2 3 4 5 6 7 8 9 10 11 20 12 13 14 15 16 17 18 19

Monosaccharide or derivatives Ribose 2-Deoxyribose Fructose Galactose Fucose (6-Deoxy-L-galactose) Galactosamine N-Acetylgalactosamine Glucose Glucosamine N-Acetylglucosamine Glucuronic acid Iduronic acid Mannose Xylose Ribose Ribulose Ribose 5-phosphate Muramic acid Neuraminic acid Rhamnose

abbreviations Rib dRib Fru Gal Fuc GalN GalNAc Glc GlcN GlcNAc GlcUA/ GlcA IdoA Man Xyl Rib Ribulo (or Rul) Rib5P Mur Neu Rha

Reducing and non-reducing Oligosaccharides

Polysaccharides
1) homoglycans - homopolysaccharides composed on one monosaccharide 2) Heteroglycans heteropolysaccharides made of more than one type of monosaccharide According to their biological role
•Storage Starch and glycogen •Structural Chitin and cellulose •Recognition Cell surface polysaccharides

Starch
• A plant storage polysaccharide • Two forms: amylose and amylopectin • Most starch is 10-30% amylose and 70-90% amylopectin • Average amylose chain length 100 to 1000 residues polymerized by a1->4 links, one reducing end. • Amylopectin is a branched polymer a-(1--> 6) branches of residues in an a-(1 --> 4) linkage; overall between 300-6000 glucose residues, with branches once every 25 residues; side chains are 15-25 residues long. Many non-reducing ends and one reducing.

Amylose and Amylopectin

Starch
• Amylose is poorly soluble in water, but forms micellar suspensions • In these suspensions, amylose is helical • Amylose reacts with iodine to give dark blue complex. While amylopectine gives a red-violet color with complex.

Starch hydrolysis
• α-amylase is an endoglycosidase (act on internal a-(1 --> 4) glycosidic linkage). found in human saliva and also plants. hydrolyzes the a (1--> 4) bond of amylose and amylopectin randomly. • β-amylase is an exoglycosidase (act on terminal a-(1 --> 4) glycosidic linkage). Found in higher plants that hydrolyzes maltose residues from non-reducing ends of amylopectin.

Amylase enzymes

Glycogen
• Glycogen is stored energy for animals • Glycogen constitutes up to 10% of liver mass and 1-2% of muscle mass • Only difference from amylopictine: number of branches residues. Alpha(1,6) branches every 8-12 residues containing as many as 50,000 glucose. • Like amylopectin, glycogen gives a red-violet color with iodine

glycogen

Cellulose
• • • • Cellulose is the most abundant natural polymer on earth Cellulose is the principal strength and support of trees and plants Cellulose can also be soft and fuzzy - in cotton straight chain homoglycan of glucose with β-(1--> 4) linkages. ranges in size from 300-15,000 glucose residues. • β -linkages results extended conformation in which each glucose residue is rotated 180° relative to its neighbors. • Extensive H-bonding within and between cellulose chains. Makes bundles or fibrils ---> rigid. • Cellulose hydrolysis is catalysed by cellulase (β -glucosidase) enzyme that is not present in human and other mammals. ruminant (sheep and cows) have microorganisms in their rumen that produce β -glucosidase, therefore they can obtain glucose from cellulose rich grass and other plants.

Cellulose

Cellulose
•β-(1--> 4) linkages. •Alternate residue rotation 180° relative to its neighbors •Intrachain and Interchain Hbonding allows multi-chain interactions. Forms cable like structures

Cellulose vs Amylose
amylose

cellulose

Glucose units rotated 180o relative to next residue

Chitin
• Exoskeletons of crustaceans, insects and spiders, and cell walls of fungi • similar to cellulose, but instead of glucose uses N-acetyl glucosamine (C-2s are N-acetyl instead of –OH) • β-1->4 linked N-acetylglucosamine units • cellulose strands are parallel, chitins can be parallell or antiparallel
CH2OH OH OH H H O H H NH C CH3 O OH

Chitin

Chitin vs Cellulose

Dextrans
• If you change the main linkages between glucose from alpha(1,4) to alpha(1,6), you get a new family of polysaccharides - dextrans • Branches can be (1,2), (1,3), or (1,4) • Dextrans formed by bacteria are components of dental plaque • Cross-linked dextrans are used as "Sephadex" gels in column chromatography

Dextrans

1) Proteoglycans • Complexes of polysaccharides called glycosaminoglycans and core proteins. • Found in extracellular matrix of connective tissues. • Glycosaminoglycans are unbranched heteroglycans of repeating disaccharide units. e.g. hyaluronic acid Found in cartilage and synovial fluid = GlcNac + GlcA ß-(1-3)linkage. • 1) Amino sugar, usually D-galactosamine or D-glucosamine with acetyl group some times, • 2) Alduronic acid such as glucuronic acid and iduronic acid. *Specific hydroxyl and amino groups of many glycosaminoglycans are sulphated. SO3- and COO- of alduronic acid make

Heteroglycans = Glycoconjugates

glycosaminoglycans polyionic. highly hydrated

glycosaminoglycans
= GlcNac + GlcA ß-(1-3)linkage

Every unit is composed of uronic acid (D-GlcA or L-IdoA) and amino sugar (D-GalNAc or DGlcNH2). R, H or SO3- ; R', H, COCH3 or SO3-.

Glycosaminoglycan chains covalently bound by a glycosidic linkage to the OH oxygen of ser residue

Proteoglycans

2) Peptidoglycans
Found in cell wall of bacteria = hetroglycan linked cvalently to peptides • The hetroglycan component Composed of alternating residues of N-acetylglucosamine and Nacetylmuramic acid joined by ß-(1--> 4) linkages. • N-acetylmuramic is 9C sugar specific to bacteria = lactate (3C) joined by ether linkage to C3 of GlcNAc. • The peptide component varies among bacteria

Peptidoglycans

*Compare between structures of heteroglycan component of the peptidoglycans and chitin .

3) Glycoproteins
• Proteins with covalently oligosaccharides attached. • Carbohydrate chains are from 1-30 residues in length. and account 80% of total mass of the molecule. • Extraordinteroarily groupe of proteins that could be enzymes, hormones, structural proteins, transport proteins. • Oligosacharide chaines exhibt great variability in composition (unlike glycosaminoglycan) • Found in eucaryotic cells. • Can be attached to proteins with one of two configurations:
– O-linked - carbohydrate bonded to -OH of serine or threonine – N-linked - carbohydrate (usually N-acetylglucosamine) linked to asparagines.