BIO 203 Biochemistry I

by
Seyhun YURDUGÜL,Ph.D.

Lecture 6
Carbohydrates
 Content Outline
• Definition
• Monosaccharides
• Disaccharides
• Polysaccharides
 Introduction

– Carbohydrates:
– carbon compounds that contain large
quantities of hydroxyl groups.
– simplest carbohydrates:
– also contain either an aldehyde moiety (these
are termed polyhydroxyaldehydes)
– or a ketone moiety (polyhydroxyketones).
 Carbohydrates:

– All carbohydrates can be classified as:

– either monosaccharides,
– oligosaccharides,
– or polysaccharides.
 Monosaccharides:
• Simple carbohydrates:
• consist of a single polyhydroxyaldehyde or
ketone unit.

• e.g. Glucose(simplest sugar)

• e.g. Fructose(sugar from honey origin)
• e.g. Galactose(a sugar in milk and yogurt)
Glucose
Two forms of monosaccharides:

• Aldose sugar

• Ketose sugar
 Aldose
• If the carbonyl group:
• at an end of the carbon chain:
• monosaccharide is aldehyde and called
aldose.
• e.g. glyceraldehyde
D-glyceraldehyde
 Ketose

• If the carbonyl group:

• at any other position, monosaccharide is
ketone and called ‘ketose’
• e.g. dihydroxyacetone
(2) Dihydroxyacetone
 Other monosaccharides:
• Tetroses (4 carbon)
• Pentoses (5 carbon)
• Hexoses (6 carbon)
• Heptoses (7 carbon)
 Disaccharides:
• Made up by combination of simple sugars:
• e.g. Maltose: glucose + glucose
(Sugar of malt)
• e.g. Lactose: glucose + galactose
(milk sugar)
• e.g. Sucrose: glucose + fructose
(table sugar)
 Oligosaccharides and
polysaccharides

– Anywhere from two to ten monosaccharide

units, linked by glycosidic bonds:
– make up an oligosaccharide(includes
disaccharides).
– Polysaccharides :
– much larger, containing hundreds of
monosaccharide units.
 Structure of carbohydrates:
• The presence of the hydroxyl groups:
• allows carbohydrates to interact with
the aqueous environment,
• and to participate in hydrogen bonding,
both within and between chains.
 Structure of carbohydrates:
• Derivatives of the carbohydrates can
contain:
• nitrogens,
• phosphates
• and sulfur compounds.
• Carbohydrates also can combine with
lipid to form glycolipids;
• or with protein to form glycoproteins.
Carbohydrate nomenclature:

• The predominant carbohydrates encountered in

the body:
• structurally related to the aldotriose
glyceraldehyde;
• and to the ketotriose, dihydroxyacetone.
• All carbohydrates contain at least one
asymmetrical (chiral) carbon,
• and are, therefore, optically active.
Carbohydrate nomenclature
• In addition, carbohydrates can exist:
• in either of two conformations,
• as determined by the orientation of the
hydroxyl group about the asymmetric carbon
farthest from the carbonyl.
• With a few exceptions, exist in the D-
conformation.
• The mirror-image conformations, called
enantiomers, are in the L-conformation.
 Asymmetry
• All the monosaccharides except
dihydroxyacetone:
• contain one or more asymmetric(chiral) C-
atoms
• Glyceraldehyde: 2 optical isomers or
enantiomers
• A molecule with ‘n’ chiral centers, have 2n
stereoisomers
 D- and L- isomers of
carbohydrates:
• D: Dextrorotatory L: Levorotatory
• Structures of Glyceraldehyde
enantiomers
Structure of carbohydrates:

• The aldehyde and ketone moieties of the

carbohydrates with five and six carbons:
• spontaneously react with alcohol groups present in
neighboring carbons,
• to produce intramolecular hemiacetals;
• or hemiketals, respectively.
Structure of carbohydrates:
• This results in the formation of five-
• or six-membered rings.
• As five-membered ring structure resembles the
organic molecule furan,
• derivatives with this structure are termed
furanoses.
Structure of carbohydrates:

• Those with six-membered rings resemble the

organic molecule pyran,
• and are termed pyranoses.
• Such structures can be depicted by either
Fischer or Haworth style diagrams.
Structure of carbohydrates:

• The numbering of the carbons in

carbohydrates:
• proceeds from the carbonyl carbon, for
aldoses;
• or the carbon nearest the carbonyl, for ketoses.
• Cyclic Fischer projection of alpha-D-
Glucose
Haworth projection of α-D-
glucose:
♨The rings can open and re-close,
♨allowing rotation to occur about the carbon
bearing the reactive carbonyl yielding:
 Epimers
• When two sugars differ only in the
configuration around one carbon atom:
• called ‘epimers’ or ‘diastereoisomers’ of
each other:
• e.g. D-glucose and D- mannose,
• or D-erythrose and D-threose.
Examples of epimers
 Anomers
• The carbon about which this rotation in the
carbonyl carbon occurs:
• is the anomeric carbon,
• and the two forms: termed anomers.
 Anomers:

• Carbohydrates can change

spontaneously between the α and β
configurations:
• a process known as mutarotation.
 Anomers
• When drawn in the Fischer projection;
• the α configuration places the hydroxyl
attached to the anomeric carbon to the
right, towards the ring.
• When drawn in the Haworth projection,
the α configuration:
• places the hydroxyl downward.
Conformations of carbohydrates in
the space:
• The spatial relationships of the atoms of
the furanose and pyranose ring structures,
• more correctly described by the two
conformations identified:
• as the ‘chair’ form
• and the ‘boat’ form.
Conformations of carbohydrates in
the space
• The chair form:
• the more stable of the two.
• Constituents of the ring that project
above or below the plane of the ring are
axial
• and those that project parallel to the
plane are equatorial.
Conformations of carbohydrates in
the space:

• In the chair conformation:

• the orientation of the hydroxyl group
about the anomeric carbon of α-D-
glucose: axial
• and equatorial in β-D-glucose.
• Chair form of α-D-glucose
 Disaccharides:

• Covalent bonds between the anomeric hydroxyl of

a cyclic sugar;
• and the hydroxyl of a second sugar (or another
alcohol containing compound):
• termed as ‘glycosidic’ bonds,
• and the resultant molecules: ‘glycosides’.
 Disaccharides:
• The linkage of two monosaccharides to form
disaccharides:
• involves a glycosidic bond.
• Several physiologically important disaccharide
examples:
• sucrose,
• lactose
• and maltose.
Structure of sucrose:
 prevalent in sugar cane
and sugar beets,
 is composed of glucose
and fructose
 by linkage through an α-
(1,2)-β-glycosidic bond.
Demonstration of sucrose:
• Lactose:
• found exclusively in
the milk of mammals.
• consists of galactose
and glucose in a β-
(1,4) glycosidic bond
• Maltose:
• the major degradation product of starch,
• composed of two glucose monomers in an
α-(1,4) glycosidic bond.
 Polysaccharides

• Most of the carbohydrates found in nature:

• occur in the form of high molecular weight
polymers;
• called polysaccharides.
• The monomeric building blocks used to generate
polysaccharides:
• varied; in all cases,
• however, the predominant monosaccharide
found in polysaccharides:
• D-glucose.
 Polysaccharides
• When composed of a single
monosaccharide building block:
• they are termed ‘homopolysaccharides’.
• Polysaccharides composed of more than
one type of monosaccharide:
• termed as ‘heteropolysaccharides’.
 Glycogen

• the major form of stored carbohydrate in

animals.
• a homopolymer of glucose in α-(1,4)
linkage; it is also highly branched, with α-
(1,6) branch linkages occurring every 8-10
residues.
 Glycogen

• has a very compact structure;

• that results from the coiling of the polymer
chains.
• This compactness allows large amounts of
carbon energy to be stored in a small
volume;
• with little effect on cellular osmolarity.
 Starch

• the major form of stored carbohydrate in

plant cells.
• Structure: identical to glycogen,
• except for a much lower degree of
branching (about every 20-30 residues).
• Unbranched starch: amylose;
• branched starch: called amylopectin.
Structure of amylose
Structure of amylopectin
Structural polysaccharides in living
organisms:
• e.g. Cellulose:
• present in the cell walls of plants, stems,
stalks, trunks
• linear, unbranched
homopolysaccharide(10000 to 15000 D-
glucose units)
• resembles amylose and the main chains of
glycogen
Structure
Structural polysaccharides in living
organisms:
• Chitin
• Principal component of the hard
exoskeletons of nearly a million species of
arthropods(insects, lobsters and crabs)
Chitin structure:
 LITERATURE CITED
• Devlin,T.M. Textbook of Biochemistry with Clinical
Correlations,Fifth Edition,Wiley-Liss Publications,New
York, USA, 2002.
• Lehninger, A. Principles of Biochemistry, Second edition,
Worth Publishers Co., New York, USA, 1993.
• Matthews, C.K. and van Holde, K.E., Biochemistry,
Second edition, Benjamin / Cummings Publishing
Company Inc., San Francisco, 1996.