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CARBOHYDRATE

Key words
Carbohydrate- definition Aldose, ketose Classification Enantiomer, Diastreomer, Epimer Fischer projection, Haworth projection

Carbohydrates
Carbohydrate: most abundant biomolecules (other biomolecules protein, lipid, nucleic acid) Suffix ose indicates the molecule is a carbohydrate - glucose, fructose, maltose, sucrose, cellulose Major role in energy metabolism and structural component

Why Carbohydrates?
Play a number of important roles in biochemistry:
Major energy sources Play a key role of processes that take place on the surfaces of cells. eg. cell-cell interactions Essential structural components of several classes organisms.

Carbohydrates
Definition: a polyhydroxyaldehyde or polyhydroxyketone, or a substance that gives these compounds on hydrolysis

Carbohydrate
Three level number of sugar/saccharide unit
1. Monosaccharide simplest 2. Oligosaccharide consist more than 1 monosaccharide > disaccharide has 2 monosaccharide 3. Polysaccharide has large number of monosaccharide

CARBOHYDRATE

MONOSACCHARIDE

Monosaccharides
Monosaccharide: simplest carbohydrate, sometimes referred as sugar / saccharide Building blocks of all carbohydrates
They have the general formula CnH2nOn, where n varies from 3 to 8 Aldose: a monosaccharide containing an aldehyde group Ketose: a monosaccharide containing a ketone group

Monosaccharides
Monosaccharides are classified by their number of carbon atoms - 3 C = triose - 4 C = tetrose - 5 C = pentose - 6 C = hexose - 7 C = heptose

Trioses are simplest carbohydrate monosaccharides

Aldose: containing an aldehyde group

Ketose: containing a ketone group

D-Glucose

This is a Fischer Formula 6C monomeric molecule Is an aldohexose D to denote the OH on C5 is on the right side of the C chain

Fischer Projections and Haworth Projections

Fischer Projections
Fischer projection: bonds are written in a two dimensional representation showing the configuration of tetrahedral stereocenters
horizontal lines represent bonds projecting forward vertical lines represent bonds projecting to the rear the carbon atom at the intersection of the horizontal and vertical lines is not shown

Comparison of the Fischer and Haworth Representations

Monosaccharides
Glyceraldehyde contains a stereocenter and exists as a pair of enantiomers

Mirror-images stereoisomers are called enantiomers

Stereochemistry of monosacharides
Anomers :- (carbonyl becomes a new chiral; C1)
Epimers :- ( excluding the anomeric carbon )

Enantiomers :- Molecules that are superimposible mirror images of one another.


Isomers : Isomers are molecules with the same molecular formula, but different arrangements of atoms.

Stereoisomers : molecules that differ from each other only in their configuration ( three dimensional shapes )also called optical isomers. Glucose n Galactose. Diastereomers :non superimposable,non mirror image stereoisomers. ( L- Threose with both D n L erythrose. )

Stereoisomer
Stereoisomer that are nonsuperimposable mirror images of each other = enantiomer
Chiral carbon/centre = carbon atom connected to 4 different groups
mirror Chiral carbon

Chiral molecule

Stereoisomer D,L Monosaccharides


What is D and L?
D = dextrorotary, L = levorotary

Are stereoisomers, due to the rotated direction of plane polarized light of solution Enantiomers: stereoisomers that are mirror images
example: D-erythrose and L-erythrose are enantiomers

D,L MonosaccharidesFischer Projections


According to the conventions proposed by Fischer
D-monosaccharide: a monosaccharide that, when written as a Fischer projection, has the -OH on its penultimate carbon on the right L-monosaccharide: a REMEMBER: D,L= enantiomers monosaccharide that, when written as a Fischer projection, has the -OH on its penultimate carbon on the left

D,L MonosaccharidesFischer Projections


According to the conventions proposed by Fischer
D-monosaccharide: has the -OH on its penultimate carbon on the right L-monosaccharide: has the -OH on its penultimate carbon on the left

REMEMBER: D,L= enantiomers

Diastereomers
Diastereomers: stereoisomers that are not mirror images, non-superimposable
example: D-erythrose and D-threose are diastereomers Epimers-diastereomer differ at only one chiral carbon

The aldotetroses have two chiral C ; C2 and C-3. Therefore, the stereoisomers of aldotetroses are 22, or four possible stereoisomers. Diastereoisomers that differ from each other at only one chiral C are known as epimers. D-erythrose and D-threose are epimers.

Fig. 16-3, p.437

Diastereomers - example

Epimers - example
D-mannose and D-galactose differ stereochemically from D-glucose at only 1 chiral D-mannose and Dcenter galactose are
EPIMERS of glucose
D-galactose is a C-4 Epimer of D-glucose

D-mannose is a C-2 Epimer of D-glucose

Fructose

Epimers of D-fructose
Enantiomers of D-fructose Diastrereomer of D-fructose

Fructose

Which structure represents D-Fructose?

Lesson outcome
Draw from Fischer to Haworth Reaction of monosaccharide Members of disaccharide Disaccharide formation

What Happens if a Sugar Forms a Cyclic Molecule?


Cyclization of sugars takes place due to interaction between functional groups on distant carbons, C1 to C5, to make a cyclic hemiacetal - aldose

Cyclization using C2 to C5 results in hemiketal formation.- ketose In both cases, the carbonyl carbon is new chiral center and becomes an anomeric carbon

Formation of a Cyclic Hemiacetal

Cyclic Structure via Haworth Projections


Monosaccharides have -OH and C=O groups in the same molecule and exist almost entirely as five- and six-membered cyclic hemiacetals
anomeric carbon: the new stereocenter resulting from cyclic hemiacetal formation anomers: carbohydrates that differ in configuration only at their anomeric carbons

Haworth Projections
Haworth projections
five- and six-membered hemiacetals are represented as planar pentagons or hexagons, as the case may be, viewed through the edge most commonly written with the anomeric carbon on the right and the hemiacetal oxygen to the back right the designation -means that -OH on the anomeric carbon is cis to the terminal -CH2OH; - means that it is trans

Haworth Projections
A six-membered hemiacetal ring is shown by the infix -pyran- (pyranose) A five-membered hemiacetal ring is shown by the infix -furan- (furanose)

CONVERTING A FISCHER PROJECTION TO A HAWORTH


Carbon 1 will be the anomeric carbon UP These groups are up in the Haworth

CHO OH HO OH OH CH2OH

DOWN These groups are down in the Haworth

This is the -anomer because the anomeric OH is cis to -CH2OH

This -OH determines D- or LThis group, which is carbon 6, will be up in the Haworth if D- and down if L-

D- 6

CH2OH
5 4

O
up

OH
1 2

cis

OH OH
3

down

OH

down

Reaction of Monosaccharides
1. Oxidation-reduction
i. ii. iii. iv. Oxidation of aldoses to acid Reduction of ribose to deoxyribose Reduction of L-galactose to L-fucose (L-6deoxygalactose) Reduction of carbonyl group to hydroxyl group forming sugar alcohol/alditols

2.
i.

Esterification
Formation of phosphate esters-intermediate in energy metabolism

Oxidation
Reducing sugar: a sugar that has a free carbonyl group (anomeric carbon) one that can reduces an oxidizing agent Tollens reagent oxidizing agent

Reduction

Reduction to sugar alcohol/alditols

ribose to deoxyribose

Esterification Phosphoric Esters


Phosphoric esters are particularly important in the metabolism of sugars to provide energy
phosphoric esters are frequently formed by transfer of a phosphate group from ATP

Monosaccharide derivatives

Amino sugars

The most abundance monosaccharide in nature.

CARBOHYDRATE

DISACCHARIDE

Glycosidic Bond Formation


Glycosidic bond: form between the hemiacetal of
monosaccharide (saccharide) and the hydroxyl group of organic compound such as alcohol. A substance containing a glycosidic bond is a glycoside
Glycosidic bond due to dehydration/condensation

Disaccharide: glycosidic bond formation between the


hemiacetal of monosaccharide and hydroxyl group from another hemiacetal

Glycosidic Bond Formation

Type of bond: O-glycosidic bond

Two Different Disaccharides of -D-Glucose


Glycosidic linkages can take various forms; the anomeric carbon of one sugar to any of the -OH groups of another sugar to form an - or glycosidic linkage
Type of bond: O-glycosidic bond

Disaccharides
Sucrose
Table sugar; obtained from the juice of sugar cane and sugar beet One unit of D-glucose and one unit of D-fructose joined by an -1,2glycosidic bond

Lactose
Made up of D-galactose and one unit of D-glucose joined by a -1,4glycosidic bond Galactose is a C-4 epimer of glucose

Maltose
Two units of D-glucose joined by an -1,4-glycosidic bond Formed from the hydrolysis of starch

Cellobiose
Two units of D-glucose joined by an -1,4-glycosidic bond Formed from the hydrolysis of cellulose

Reducing & Non Reducing Sugar


Sugars exist in solution as an equilibrium mixture of openchain and closed-ring (or cyclic) structures. In the open-chain form, the carbon atom that contains the C=O bond is called the carbonyl carbon. Sugars that can be oxidised by mild oxidising agents such as Benedict's Solution, Fehling's Solution,and Tollen's Reagen are called reducing sugars because the oxidising agent is reduced in the reaction. Reducing sugar: one that has a free aldehyde group and this aldehyde is easily oxidized.

Tollens agent

Being reduced

+ Ag (NH3)2

Haworth Projections

Anomeric carbon

If OH is free at the anomeric carbon = the monosaccharide is reducing sugar

Sucrose
Anomeric carbons of glucose carbon C1 in configuration is linked to the anomeric carbon of fructose C2 in configuration anomeric carbon is tied into a glycosidic bond and none of it able to form an open chain containing free aldehyde and ketone sucrose is NOT a reducing sugar

Lactose
Galactose in a (1-4) linkage with glucose
Principal sugar present in milk Galactose is converted by the body to glucose and glucose used for energy Reducing sugar?

Maltose
Products from hydrolytic breakdown of starch Can be easily digested by humans because of the presence of enzymes catalyzes the hydrolysis of (1-4) glycosidic bonds
Reducing sugar?

Cellobiose
Cellobiose hydrolysis product of cellulose major component of plants Differs from maltose at glycosidic bond Humans do not have the capacity to digest cellobiose or cellulose lack the enzyme cellulase that break (1-4) glycosidic linkages between glucose monomers Ruminants animals can have bacteria in the rumen in gastrointestine tract and secrete cellulase

N-glycosidic bond
The -NH group of amine substitute for hydroxyl groups and react at the anomeric carbon center of carbohydrates. New linkage is called Nglycosidic bond Importance in the construction ATP and in nucleic acids RNA and DNA

ATP

Disaccharides

Formation of glycosidic bond condensation (-H2O)

CARBOHYDRATE

POLYSACCHARIDE

Key words
Definition Function Homopolysaccharide and heteropolysaccharide Cellulose, Chitin, Pectin, Peptidoglycan Starch, glycogen Glycoaminoglycan, glycoprotein

Polysaccharides
Polysaccharide- When many monosaccharides are linked together Divided into 2 type of monosaccharide or function Two main function: energy storage and structure Type of monosaccharide homopolysaccharide and heteropolysaccharide

Structural Polysaccharides
Cellulose Plant cell wall Pectin Chitin component of the exoskeleton of invertebrates and in cell walls of algae, fungi and yeast

Cellulose
the major structural component of plants, especially wood and plant fibers
a linear / unbranched polymer of approximately 2800 -D-glucose units joined by extensive intra- and intermolecular hydrogen bonding between chains-strength Cellobiose is the repeating hydrolysis by cellulase

Cellulose

Cellulose is a Structural polysaccharide

Cellulose

Polymeric Structure of Cellulose

Pectin
Important component of plant cell walls Monomer D-Galacturonic acid, derivative of galactose Commercially importantfood processing industry - as gelling agent in jams and jellies

Chitin
the major structural component of the exoskeletons of invertebrates and crustaceans; and in cell walls of algae, fungi, and yeasts -1,4-glycosidic bonds similar with cellulose

linear polymer, each chain held together by hydrogen bonds composed of units of N-acetyl--Dglucosamine differ with cellulose

Chitin
Differ with glucose

Peptidoglycan
Bacterial cell walls: prokaryotic cell walls are constructed on the framework of the repeating unit NAM-NAG joined by Presence of peptide bond

Storage Polysaccharides
Starch Glycogen

Starch
Starch is used for energy storage in plants
amylose: continuous, unbranched chains of up to 4000 -Dglucose units joined by amylopectin: a highly branched polymer consisting of 24-30 units of D-glucose joined by and branches created by amylases catalyze hydrolysis of -1,4-glycosidic bonds *-amylase is an exoglycosidase and cleaves from the nonreducing end of the polymer *-amylase is an endoglycosidase and hydrolyzes glycosidic linkages anywhere along the chain to produce glucose and maltose debranching enzymes catalyze the hydrolysis of -1,6-glycosidic bonds

Starch

Amylose and Amylopectin

Amylose occurs as a helix


with 6 residues per turn - able to give the dark-blue color complex with iodine.

Glycogen
Glycogen is used for energy storage in animals Has amylose and amylopectin similar to starch Differ with starch the amylopectin is highly branched

- branch point: occur about every 10 residues in starch, about every 25 residues

Polysaccharides
Homopolysaccharide: consists of one type of monosaccharide
Heteropolysaccharide: consists of more than one type of monosaccharide

Polysaccharides

Heteropolysaccharide: Glycosaminoglycans
Glycosaminoglycans: polysaccharides based on a repeating disaccharide where one of the monomers is an amino sugar and the other has a negative charge due to a sulfate or carboxylate group
Heparin: natural anticoagulant Hyaluronic acid: a component of the vitreous humor of the eye and the lubricating fluid of joints Chondroitin sulfate and keratan sulfate: components of connective tissue

Heteropolysaccharide: Glycosaminoglycans

Glycoproteins
Glycoproteins contain carbohydrate units covalently bonded to a polypeptide chain
antibodies are glycoproteins Oligosaccharide portion of glycoproteins act as antigenic determinants Among the first antigenic determinants discovered were the blood group substances In the ABO system, individuals are classified according to four blood types: A, B, AB, and O At the cellular level, the biochemical basis for this classification is a group of relatively small membrane-bound carbohydrates

QUIZ
1. Give two important functions of polysaccharide. 2. Name 2 structural polysaccharide and 2 storage polysaccharide. 3. Give one example of heteropolysaccharide.