Configuration same as that of Dglyceraldehyde are designated D isomers

Same configuration as Lglyceraldehyde are L isomers

A molecule with n chiral centers can have 2n stereoisomers Most of the hexoses of living organisms are D isomers except Arabinose which is found in L configuration

D-isomer

L-isomer

Epimers:
Two sugars that differ only in the configuration around one carbon atom are called epimers.

Cyclic structure of monosaccharides

Aldotetroses and all monosaccharides with five or more carbon atoms in the backbone occur in cyclic form in aqueous solutions.

The formation of ring structures: general reaction between alcohols and aldehydes or ketones to form derivatives called hemiacetals or hemiketals.

Formation of Cyclic structure

Reaction between the aldehyde group at C-1 and the hydroxyl group at C-5 forms a hemiacetal linkage.

Hemiacetals & hemiketals contain an additional asymmetric carbon atom

Pyranose & Furanose

Aldohexoses exist in cyclic forms having six membered rings called pyranose, resembles pyran. Aldopentoses and ketohexoses exist in cyclic forms having five membered rings: resemble furan, are called furanoses.

Anomers
Isomeric forms of monosaccharides differ in configuration about hemiacetal or hemiketal carbon atom : Anomers Hemiacetal (or carbonyl) carbon atom is called anomeric carbon

Mutarotation
The inter-conversion of -D-glucose and -D-glucose is called as mutarotation

Mixture of -D-glucose and -D-glucose form equilibrium with identical optical property. Its consists of 1/3rd -D-glucose, 2/3rd -D-glucose and very small amounts of linear form. Specific rotation [] 20D =+52.7 (equilibrium value)

Specific rotation
is proportional to the concentration of the sample and the length of the sample tube:
[]t = l x c

- angle of rotation measured in degrees t - temperature - wavelength of light l - length of sample cell c - concentration in grams of substance contained in 1 mL of solution

Monosaccharides as reducing agents

Some monosaccharides can reduce Ferric(Fe3+) or Cupric (Cu2+) ions (Fehlings reaction) The anomeric carbon takes part in reduction reaction.

Different forms of conformational isomers

Monosaccharide derivatives
Amino Sugars Hydroxyl group at C-2 is replaced by amino group This amino group is nearly always condensed with acetic acid

Conti Deoxy sugars Absence of OH at C-6 Sugar Phosphates Presence of phosphates. eg:- D glucose 6 Phosphate

Oxidation: Mild oxidation results in aldehyde group convert to carboxylic group and yield Aldonic acid (gluconic acid). It internally esterifies.

Specific oxidation of alcohol group yields Uronic acid (D-glucuronic acid, D-galactouronic acid, and D-mannuronic acid).

Oligosaccharides:
Contains 2-10 monosaccharide units. Categorised as: Disaccharides

Trisaccharides
Tetrasaccharides

Pentasaccharides
Hexasaccharides

Glycosidic Bonds
Formed when a hydroxyl group of one sugar reacts with the anomeric carbon of the other

Disaccharide:
Maltose, a cleavage product of starch. Disaccharide with an (1 4) glycosidic linkage between C1 hydroxyl of one glucose and the C4 hydroxyl of a second glucose

Lactose: Occurs naturally on milk. Yields D-Galactose and D-glucose on hydrolysis, The anomeric carbon of the glucose residue is available for oxidation. Thus it is a reducing disaccharide. Gal (1 -4)Glc

Sucrose (table sugar) is a disaccharide of glucose and fructose. It is formed by plants but not by animals. Has no free anomeric carbon atom. Both the anomeric carbons are involved in the glycosidic bond. It is therefore a non reducing sugar

Reducing end
The end of a chain with a free anomeric carbon :reducing end. The sugar containing reducing end is called reducing sugar.

Non reducing sugar

Anomeric carbon is involved in glycosidic bond :non reducing sugar It cannot take linear form.

Polysaccharides
Also called as glycans.

Made up of more than 10 monomer

units joined by glycosidic bond.

Have no definite molecular weight.

Enzymes are involved in the synthesis. No specific stop points. No defined sequence or length.

Two Types:
HOMOPOLYSACCHARIDE Contains single monomeric species Storage Forms (fuel) Starch Glycogen Structural form Cellulose Chitin HETEROPOLYSACCHARIDE
Contain 2 or more kinds of monomeric units. Provide extracellular support for organisms of all kingdoms. Glycosaminoglycans Peptidoglycans

STARCH
Storage sugar in plant cells. Intracellular large clusters or granules. Heavily hydrated : many exposed hydroxyl groups. Storage as starch reduces intracellular osmotic pressure.

Starch has two types of

glucose polymer:amylose and amylopectin. The amylose consists of long, unbranched chains of D-glucose residues connected by (1 4) linkages. Amylopectin is branched, the glucose residues are joined by (14) & (16) linkages; Note: the branch points (occurring every 24 to 30 residues)

GLYCOGEN
Storage sugar in animal cells. Intracellularly as large clusters or granules. Heavily hydrated just as starch. Similar to amylopectin. Difference: glycogen is extensively branched.

CELLULOSE
Is linear, unbranched homopolysaccharide, consisting of 10,000 to 15,000 D-glucose units. The glucose residues are linked by (14) glycosidic bonds. Cannot be catabolised by animals:Lack cellulase. Termites digest cellulose: contains endosymbiont (contains cellulase) Trichonympha as

Can also be catabolised by wood rot fungi & bacteria

CHITIN:
Exoskeleton of invertebrates: crustaceans , arthropods and spiders. Cell wall constituents of most fungi and many algae. ~10
14

kg produced annually : in oceans.

Cannot be digested by vertebrates.

Conti

Polymer of (14)-linked subunits of glucose, with (16)-linked branches,

The branch point occurs every 8 to 12 residues and more compact than starch.
Has 1 reducing end & many non-reducing end.

Found in the liver (constitute as much as 7% of the wet Weight)

Also present in skeletal muscle.

Dextrans
Bacterial and yeast polysaccharides. Has (16)-linked poly-D-glucose (13) branches, and some (12) or (14) branches. Dental plaque (bacteria growing on the surface of teeth): rich in dextrans. Synthetic dextrans:(for example, Sephadex) size-exclusion chromatography

Conti.

linear homopolysaccharide.

composed of N-acetylglucosamine residues in (1 4) linkage.

Has acetylated amino gp at C-2 (hydroxyl group in cellulose). the second most abundant polysaccharide, next to cellulose, in nature.

Heteropolysaccharides
Glycosaminoglycans Peptidoglycan

Glycocojugates
Glycoproteins

Proteoglycans
Glycolipids

Peptidoglycan/Murein
Rigid component of bacterial cell walls.
Envelops the entire cell.

Prevents cellular swelling and lysis due to the osmotic entry of water.
Responsible for bacterial virulence. Bacteria can be Gram+ or Gram-.

Alternating (1 4)-linked Nacetylglucosamine (NAG) and Nacetylmuramic acid residues (NAM)

Linear polymer lie side by side in cell wall.

Cross-linked by short peptides (Tetrapeptides).

Pentaglycine in Gram-positive. Lysozymes hydrolyze (1 4) bond.
Peptidoglycan monomer of Staphylococcus aureus

Penicillin: Prevents cross links

GLYCOSAMINOGLYCANS
Present in Extracellular spaces: cartilage. Tendon, skin and blood vessels along with collagen, elastin. Interlocking meshwork of heteropolysacchd. and fibrous protein. These are embedded in a Gel-like matrix: Ground substance. Ground sustance is composed of Glycosaminoglycans :Highly viscous, elastic.

Conti linear polymer with repeating disaccharide units either N-acetylglucosamine or N-acetylgalactosamine; & uronic acid, usually Dglucuronic or L-iduronic acid Some contains sulphur E.g. Hyaluronic acid, Keratan sulphate

Hyaluronate
Essential component of the extracellular matrix of cartilage and tendons:contributes tensile strength and elasticity

High viscosity and elasticity

Hyaluronidase: secreted by some pathogenic bacteria, can hydrolyze the glycosidic linkages of hyaluronate
b-1,3
COO H H OH H H H OH OH H HN O O H H H O H C CH 3 CH 2 OH O O

b-1,4

GlcUA

GlcNAc b-1,3 glycosidic linkage

Condroitin-sulphate :
Tensile strength of cartilage,tendons,ligament and walls of aorta
b-1,3
COO H H OH H H H OH H H HN O
O OSO 3

CH 2 OH O H H O H C CH 3 O

b-1,4

GlcUA

GalNAc

Heparin
Natural anticoagulant
COO H H OH H O

-1,4
O H H

CH 2 OSO 3 O H OH H

-1,4

H O

OSO 3 -

NHSO 3-

GlcUA

GlcNAc

GlcN and GlcUA or IdUA N and O sulfate (C2,6) -1,4 glycosidic linkage

Types Of Glycoconjugate
Glycoconjugate

Proteoglycans

Glycoproteins

Glycolipids

Glycoconjugates
Poylsaccharide attached to protein or lipid

Act as information carriers

Help in
specific cell-cell interactions and interactions between cells and the extracellular matrix

Help in cell migration during development, Plays a role in blood clotting, the immune response, and wound healing

Proteoglycan
Macromolecules of cell surface or extracellular matrix. One or more sulphated glycosaminoglycan chains are joined covalently to membrane proteins. Basic unit has Core Protein with covalently attached glycosaminoglycan(s). Joined by Ser residue and tetrasaccharide bridge

Proteoglycan aggregates
Some form enormous supramolecular assemblies of many core proteins all bound to single molecule of hyaluronan. Aggrecan core protein has multiple chains of chondroitin sulfate and keratan sulfate. They interact strongly with collagen in the extracallular matrix of cartilage Help in development, tensile strenght and resiliency of the connective tissue

Glycoprotein
Eukaryotic protein is covalently attached with carbohydrates glycans smaller, branched. i.e protein is glycosylated.

found on the outer face of the plasma membrane, extracellular matrix, blood.
Also found in Golgi complexes, secretory granules, and lysosomes.

Glycosylation
N-linked NAG is -linked to amide nitrogen of Asn in Asn-X-Ser/ Asn-X-Thr

O-linked
-galactosyl-(1 3)--NAG -linked to the OH of Ser/Thr

Glycoprotein: Role
Has entire spectrum of functions: Enzymes, Transport proteins, hormones, structural proteins. Generally all proteins secreted by cells are glycoprotein.
E.g. Ab, FSH, TSH, Lactalbumin, Ribonuclease

Role of Carbohydrate in glycoproteins

Influences the sequence of polypeptide folding
Helps in forming extended rod like structure Protects proteins from proteolytic attack

Lipopolysaccharides

Glycolipids
Lipid + Oligosaccharide Found on the cell surface hydrophilic head groups are oligosaccharides, which,act as specific sites for recognition by carbohydratebinding proteins E.g. Gangliosides- contain sialic acids