Biochemistry I

• BSC 211

Thomson Sanudi, PhD

Basic Sciences Department
LUANAR
Carbohydrates

• Most abundant biomolecule produced through photosynthesis.

• Carbohydrate oxidation is the main process of yielding energy (ATP) in

most non photosynthesizing organisms.

• Structural and protective elements in bacteria, plants & animals.

• Useful in signal transduction and immune responses.

• Storage molecules as either glycogen or starch.

Carbohydrates

• Carbohydrates are aldehydes of ketones or any substance that yield such

compounds upon hydrolysis.

• Carbohydrates of four of more carbons tend to be cyclic.

Carbohydrates
Chiral carbon

• An asymmetric carbon has four different types of atoms or

different groups

• The maximum possible number of stereoisomers can be

calculated as 2n where n is the number of asymmetric carbon
atoms.

• A chiral molecule has non superimposable mirror image.

Carbohydrates

• Monosaccharide are simple sugars consisting of a single polyhydroxy

aldehyde or ketone unit. (CH2O)n where n = 3 - 6.

• Oligosaccharide consists of short chains of 2 - 20 monosaccharide units

joined by characteristic glycosidic bonds.

• Polysaccharide contain a chain of not less than 20 monosaccharide

units.
Carbohydrates
Monosaccharides

• Have one aldehyde (aldose) or ketone (ketone) unit and a

number of hydroxyl groups.

• The carbon atom to which the hydroxyl groups are

attached are chiral centers which give rise to many sugar
stereoisomers.

• All monosaccharides except dihydroxyacetone contain

one or more asymmetric carbon atoms.
Carbohydrates
Trioses

• There are two important three

carbon sugars collectively referred
to as trioses - aldotriose and
ketotriose.

• Have one chiral carbon, have two stereoisomer (D- and L-). However,
only the D- form are dominant in living organisms.

• The designation of either D- or L- depends on the chiral carbon with

the highest number.
Carbohydrates
Tetroses

• Four carbon sugars have two

chiral carbons.

Pentoses

• Five carbon sugars

have three chiral
carbons.
Carbohydrates
Hexoses

• Stereoisomers which differ at only one chiral carbon are called epimers.
• Glucose and galactose are epimers of each other as they differ at C4.
• Glucose and mannose differ at C2.
Carbohydrates
Ketoses
Carbohydrates
Monosaccharide

• In cyclic structures, the carbonyl group forms a covalent bond

with the oxygen of the hydroxyl group along the chain.

• The formation of these ring structures is the result of a general

reaction between alcohols and aldehydes or ketones to form
derivatives called hemiacetals or hemiketals resulting in a five or
six member ring if the -OH and carbonyl groups are from the
same molecule.
Carbohydrates
Monosaccharide

• Full acetal of metal is formed by the addition of the second molecule of alcohol to
form a glycosidic bond.
• The reaction with the first molecule of alcohol creates an addition chiral center at the
carbonyl carbon because the alcohol can add in either of two ways attaching either the
front or the back of the carbonyl carbon to produce either of the two stereoisomeric
configuration denoted alpha or beta.
• Isomeric forms that differ only in their configuration about the hemiacetal or hemiketal
carbon atom are enantiomers and the carbonyl carbon atom is called anomeric.
• Both the 5 and 6 carbon monosaccharides can form hemiacetals
through intramolecular reactions.

• In ketohexose, when C2 reacts with C5 a five membered ring called a

furan is formed but when the C2 reacts with a C6 a pyran is formed.

• In aldohexose, when C1 reacts with C5 a six membered ring called

pyran is formed.
 Carbohydrates
Ring formation

• The most oxidized carbon (C1

which is attached to 2 Oxygen
atoms is anomeric.

• A new chiral centre on C1 is

created after ring formation.

• The OH group could either be

pointing up or down.
Carbohydrates
Ring form

• Aldoses and ketoses equilibrate between cyclic and open forms.

• In cyclic both alpha and beta structures exist.
• The ring forms, however, are not planar due to the tentahendral geometry of
carbon atoms.

• Pyranose can adopt two different conformations

• CHAIR (more stable due to lack of steric hindrances from 6’ carbons)
• BOAT (less stable due to steric hinderances).
• ENVELOPE (for the furanose, is most stable approximately coplanar)
Pentoses such as D-ribose and 2-deoxy-D-ribose form two
very important furganose rings that we will encounter in the
structures of DNA and RNA molecules.
Carbohydrates
Derivatives of monosaccharides

• Sugar phosphates - metabolized as phosphate esters.

• Deoxy sugars - hydrogen atoms replace hydroxyl group at
C2. Used in nucleic acids.

• Amino sugars - amino group (NH2-) substituted for -OH

group

• Sugar alcohols - replace carbonyl oxygen to form

polyhydroxyl alcohols e.g. glycerol - glyceraldehyde.
Carbohydrates
Derivatives of monosaccharides

Sugar acids - these are obtained by oxidation of carbonyl

carbon or highest carbon

Glucose - gluconate or glucuronate.

Ascorbic acids - derived from D- glucuronate.

Carbohydrates
Monosaccharide

• Six member ring compounds are called pyranoses

because they resemble six member ring compound pyran.

• In ketohexoses, the hydroxyl group at C-5 or C-6 may

react with the keto group at C-2 forming a furganose or
pyranose ring containing a hemiacetal bond.
Carbohydrates
Monosaccharides

• Cyclic sugar structures are more accurately represented in Haworth

Perspective formula than win the fisher projections commonly used
for linear sugar structures.

• The hydroxyl group may be replaced with other substituents or a

carbon atom is oxidized to a carbonyl group.

• In glucosamine, galactosamine and mannosamine, the hydroxyl at

C-2 is replaced with an amine group.
Carbohydrates
Disaccharides

• Disaccharides consists of two monosaccharides joined

covalently by O-gylcosidic bond which forms when a hydroxyl
group of one sugar molecule reacts with anomeric carbon of
the other.

• N-glycosyl bonds are formed when the anomeric carbon of a

sugar is joined to a nitrogen atom in glycoproteins.
Carbohydrates
Polysaccharides

• Polymers of medium to high molecular weigh also called glycans.

• They differ from each other in the identity of their recurring monosaccharide
units, length of the chain, type of bonds linking the units and degree of
branching.

• Homopolysaccharide contain a single type of monosaccharide while

heteropolysaccharide contain two or more types of monosaccharides in the
chain.
Carbohydrates
Polysaccharide - Starch

• Starch has two types of glucose polymer; amylose and

amylopectin

• Amylose contain long unbranched chains of D-glucose

residues connected by @1-4 linkages while amylopectin
is branched and the bond joining successive glucose
residues are @1-4 while the linkages in the branches are
@1-6.
Carbohydrates
Polysaccharide - Glycogen

• The main storage polysaccharide of animal cells.

• Like amylopectin, glycogen is a polymer of @1-4 linked
subunits of glucose with @1-6 linked branches.

• Glycogen is more branched than starch.

Carbohydrates
Polysaccharide - Dextrans

Dextrans are bacterial and yeast polysaccharides made up of

@1-6 linked poly D-glucose and all branches have @1-3
branches and some also have @1-2 or @1-4 branches.
Carbohydrates
Polysaccharides - Cellulose

• Like amylose, cellulose is a linear, unbranched homopolysaccharide.

• Differ from starch because the glucose residues have beta
configuration where as amylose, the glucose is in the alpha
configuration.

• The glucose residues in cellulose are linked by @1-4 glycosidic

bond.
Carbohydrates
Polysaccharides - Cellulose

• Glycogen and starch ingested in diet are hydrolyses by alpha

amylases and glycosides that break @1-4 glycosidic bonds between
glucose units.

• Most vertebrate animals cannot use cellulose because they lack an

enzyme to hydrolyze the beta1-4 bonds.

• Termites can digest cellulose only because their intestine tract has
symbiotic trichonymph that secretes cellulases.
Carbohydrates
Polysaccharides - chitin

• Chitin is a linear homopolysaccharide composed of N-

acetyl glusosammine residues with beta1-4 linkage.

• The hydroxyl group at C-2 is replaced with an acetylated

amino group.