Chapter 7: Carbohydrates Two major structural features that generate

stereoisomerism:
Classification of carbohydrates: ● The presence of a chiral center in a
Monosaccharides molecule
● Is a carbohydrate that contains a single ● The presence of “structural rigidity” in a
polyhydroxy aldehyde or polykydroxy molecule
ketone unit (Structural rigidity-caused by restricted
● Cannot be broken down into simpler units rotation about chemical bonds, cis-trans
● Examples: glucose and fructose isomerism)
Disaccharides
● Is a carbohydrate that contains two Enantiomers
monosaccharide units covalently bonded ● Stereoisomers that are nonsuperimposable
● Examples: sucrose (glucose-fructose), mirror images of each other
lactose (galactose-glucose), and maltose ● Handedness (D and L forms) is determined
(glucose-glucose) by the configuration at high-numbered
Oligosaccharides chiral center
● Is a carbohydrate that contains three to ten
monosaccharide units covalently bonded
● Example: Raffinose
(galactose-glucose-fructose)
● Complete hydrolysis of an oligosaccharide
produces monosaccharides
Polysaccharides
● Is a polymeric carbohydrate that contains
many monosaccharide units covalently Diastereomers
bonded ● Stereoisomers that are not mirror images of
● Examples: cellulose and starch each other
● Cis-trans isomers
Property of handedness
Most monosaccharides exist in two forms:
“left-handed” and “right-handed”
Two types of objects:
● Superimposable mirror images- images that
coincide at all points
● Non-superimposable mirror images- images
where not all points coincide ● Opposite configurations at some chirality
centers
Chirality
Any organic molecule that contains a carbon
atom with four different groups attached to it in
a tetrahedral orientation possesses handedness
● Chiral molecule is a molecule whose mirror
images are not superimposable
● Achiral molecule is a molecule whose mirror
images are superimposable, does not
possess handedness Designating handedness using Fischer
Projections
Stereoisomerism: Enantiomers and
Diastereomers Fischer Projection Formula
Stereoisomers are isomers that have the same A two-dimensional structural notation for
molecular and structural formulas but differ in showing the spatial arrangement of groups
the orientation of atoms in space about chiral centers in molecules
● The carbon chain is always vertical
● The carbonyl group is at or near the top
 In the cyclic hemiacetals of glucose, C1 is the
chiral center (anomeric atom)
2 anomeric forms of D-glucose:
● Alpha-form: C1 and C5 are on opposite sides
● Beta-form: C1 and C5 are on the same sides
Anomers: cyclic monosaccharides that differ
only in the position of the substituents on the
anomeric carbon atom

Epimers: diastereomers whose molecules differ Haworth Projection Formulas

only in the configuration at one chiral center -Developed by Walter Norman Haworth
Classification of Monosaccharides -A two dimensional structural notation that
Based on number of carbon atoms: specifies the three-dimensional structure of a
● Triose- 3 carbon atoms cyclic form of a monosaccharide
● Tetrose- 4 carbon atoms - The hemiacetal ring system is viewed “edge
● Pentoses- 5 carbon atoms on” with the oxygen ring atom at the upper
● Hexoses- 6 carbon atoms right or at the top
Based on functional groups:
● Aldoses- with one aldehyde group
● Ketoses-with one ketone group
Combined number of C atoms and functional
group:
● Aldohexose
● Ketopentose
Biochemically important monosaccharides
● D-Glyceraldehyde and Dihydroxyacetone
-the simplest monosaccharides
-important intermediates in the process of
glycolysis
● D-Glucose
-most abundant in nature The D or L form is determined by the position of
-most important source of human nutrition the CH2OH:
-also named grape sugar, dextrose, blood sugar ● D form- positioned above
● D-Galactose ● L form- positioned below
-milk sugar a or B configuration is determined by the
-synthesized in human beings position of the –OH group relative to the
-also called brain sugar CH2OH:
● D-Fructose ● B configuration- same direction
-most important ketohexose ● a configuration- opposite directions
-also known as levulose and fruit sugar
-sweetest among sugars Reactions of Monosaccharides:
● D-Ribose Oxidation- gives three different types of acidic
-pentose sugars depending on the type of the oxidizing
-part of a variety of complex molecules which agent
include: DNA, RNA, ATP ● Weak oxidizing agents like tollens and
Benedict’s solutions oxidize the aldehyde
Hemiacetals- formed from the reaction end to give aldonic reaction (Aldonic acid)
between two functional groups: aldehyde or ● Strong oxidizing agents can oxidize both end
ketone and alcohol of a monosaccharide at the same time to
● Five-membered ring, or furanose ring, produce aldaric acid (Aldaric acid)
derived from parent compound furan ● Enzymes can oxidize the primary alcohol
● Six-membered ring, or pyranose, derived ends of an aldose without oxidation of the
from aren’t compound pyran aldehyde o produce an alduronic acid
(alduronic acid)
Reduction- the carbonyl group in a -souring of milk is caused by the conversion of
monosaccharide is reduced to a hydroxyl group lactose to lactic acid by bacteria in the milk
using hydrogen as the reducing agent -Pasteurization of milk is a quick-heating process
● The Benedict, Barfoed, and Fehling Tests are that kills most of the bacteria and retards the
based on the formation of a brick red souring process
copper (I) oxide precipitate as a positive -Lactose can be hydrolyzed by acid or by the
result while the Tollen’s Testis based on the enzyme lactase.
formation of a silver mirror. ● Sucrose
● The Barfoed Test is more sensitive that it -commonly called table sugar
can distinguish a reducing monosaccharide -nonreducing sugar, no hemiacetal is present.
from a reducing disaccharide. - made up of a-D-glucose and B-D-fructose
Glycoside formation- the cyclic forms of joined by a,B(1—2)glycosidic linkage
monosaccharides, the hemiacetals, react with -sucrase, the enzyme needed to break the
alcohol to form acetals, also called glycosides linkage in sucrose
● Glycoside is an acetal formed from a cyclic -sucrose hydrolysis produces an equimolar
monosaccharide by replacement of the mixture of glucose and fructose called invert
hemiacetal carbon with an –OR group to sugar
form double ether
Phosphate Ester formation- the hydroxyl groups Polysaccharides
of a monosaccharide can react with inorganic -is a polymer containing monosaccharide units
oxyacids to form inorganic esters bonded by glycosidic linkages
Amino sugar formation- one of the hydroxyl -are also alternately called as glycan
group of monosaccharide is replaced with an ● Homopolysaccharides- only contain one
amino group type of monosaccharide repeating unit
Ex. starch, glycogen, cellulose, and chitin
Disaccharides ● Heteropolysaccharide- contain more than
-bond that links the two monosaccharide is one type of monosaccharide repeating unit
glyosidic linkage Ex.Hyaluronic acid and Heparin
-always a carbon-oxygen-carbon Storage Polysaccharides
-a type of polysaccharide that is a storage form
● Maltose for monosaccharides and is used as a energy
-often called malt sugar, produced whenever source in cells
the polysaccharide starch breaks down ● Starch
-made up of two D-glucose -containing only glucose monosaccharide units
-glyosidic linkage between the two glucose units -Energy-storage polysaccharide in plants
id called an a(1—4) linkage. Two different polyglucose polysaccharide can be
-Hydrolysis of D-maltose produces two isolated from most starches:
molecules of D-glucose ● Amylose- accounts for 15%-20% of the
starch, connected by a(1—4) glycosidic
● Cellobiose linkages (300-500 monomer units)
-obtained by enzymatic or acidic hydrolysis of ● Amylopectin- high degree of branching
cellulose in its polyglucose structure, connected
-used as an indicator carbohydrate for Crohn’s by a(1—6) linkages (up to 100,00 units)
disease an malabsorption syndrome -enzyme amylase helps in the hydrolysis of
- made up of two D-glucose starch
-glycosidic linkage is B(1—4) ● Glycogen
-cellubiose cannot be digested by humans or -containing only glucose monosaccharide units
fermented by yeast. -energy-storage polysaccharide in humans and
animals
● Lactose - three times more highly branched than
-made up of a B-D-galactose and a D-glucose amylopectin (up to 1,000,000 glucose units)
unit joined by a B(1—4) glycosidic linkage ● Glycogenesis- glucose to glycogen
-major sugar found in milk thus commonly ● Glycogenolysis- glycogen to glucose
called milk sugar
Structural polysaccharides
-serves as a structural element in plant cell walls Simple Carbohydrates
and animal exoskeletons -a dietary monosaccharide or polysaccharide
● Cellulose - usually sweet to the taste and are commonly
-woody portions of plants referred to as sugars
-unbranched glucose polymer with a Complex Carbohydrates
beta-configuration -a dietary polysaccharide
- contain about 5000 glucose units -the main complex carbohydrates are starch and
-not a source of nutrition for human beings as cellulose, substances not generally sweet to the
we lack enzymes necessary for the hydrolysis of taste
the B(1—4) linkage
-Grazing animals also lack the necessary
enzymes but the intestinal tracts contain the
bacteria cellulose which can hydrolyze cellulose.
● Chitin
-give rigidity to the exoskeletons
-linear polymer with all B(1—4) linkage
-the monosaccharide present is N-acetyl amino

Acidic Polysaccharides
-polysaccharide with a disaccharide repeating
unit in which one of the disaccharide
components is an amino sugar and one or both
components has a negative charge due to
sulfate group or a carboxyl group
Natural sugars
- heteropolysaccharide; two different
-naturally present in whole foods
monosaccharides are present in an alternating
-milk and fresh fruits
pattern
Refined sugars
● Hyaluronic acid
-sugar that has been separated from its plant
-containing alternating residues of N-acetyl
source
glycosamine and glucuronic acid
-sugar beets and sugar cane
-serve as lubricants of joints
● Heparin
Terms:
-an anticoagulant, helps prevent blood clots
Glycemic effect
-contain two negatively charges acidic groups;
Refers to how quickly carbohydrates are
D-glucuronate-2-sulfate and
digested, how high blood glucose levels rise,
N-Sulfo-D-glucosamine-6-sulfate
and how quickly blood glucose levels return to
normal
Difference of glycolipids and glycoproteins
Glycemic index (GI)
A measurement system for rating foods in terms
of their glycemic effect

Dietary considerations and carbohydrates