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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
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
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
Monosaccharides
Glyceraldehyde contains a stereocenter and exists as a pair of enantiomers
Stereochemistry of monosacharides
Anomers :- (carbonyl becomes a new chiral; C1)
Epimers :- ( excluding the anomeric carbon )
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
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
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.
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
Fructose
Epimers of D-fructose
Enantiomers of D-fructose Diastrereomer of D-fructose
Fructose
Lesson outcome
Draw from Fischer to Haworth Reaction of monosaccharide Members of disaccharide Disaccharide formation
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
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)
CHO OH HO OH OH 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
ribose to deoxyribose
Monosaccharide derivatives
Amino sugars
CARBOHYDRATE
DISACCHARIDE
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
Tollens agent
Being reduced
+ Ag (NH3)2
Haworth Projections
Anomeric carbon
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
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
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
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.