OCCURRENCE AND FUNCTIONS OF CABOHYDRATES

• Carbohydrate oxidation - provides energy

• Carbohydrate storage, in the form of glycogen, provides a
short-term energy reserve
• Carbohydrates supply carbon atoms for the synthesis of other
biochemical substances (proteins, lipids, and nucleic acids)
• Carbohydrates form part of the structural framework of DNA
and RNA molecules
• Carbohydrates linked to lipids are structural components of
cell membranes
• Carbohydrates linked to proteins function in a variety of cell–
cell and cell–molecule recognition processes

1
BIOCHEMISTRY| 2020
• Simpler Formula:
• CnH2nOn or Cn(H2O)n (hydrates of C)
• n= number of atoms
• Carbohydrates are polyhydroxy aldehydes or ketones
or compounds that produce such substances upon
hydrolysis
CHO CH2 OH
Aldehyde H OH O Ketone
HO H HO H
H OH H OH
H OH H OH
Polyhydroxy ketone
CH2 OH CH2 OH
Polyhydroxy
aldehyde Glucose Fructose

2
BIOCHEMISTRY| 2020
 Monosaccharide
• Contains single polyhydroxy aldehyde or CHO CH2 OH
ketone unit H OH O
HO H
• They can’t be broken down into simpler H OH HO H
H OH
substances by hydrolysis (reaction with water) H OH H OH
reactions CH2 OH CH2 OH

• Contains 3-7 C atoms Glucose Fructose

Glucose and fructose
• Water soluble white crystalline solids are monosaccharides

3
BIOCHEMISTRY| 2020
Oligosaccharides
• Contain ~2-10 monosaccharide units - covalently
bonded to each other
• Disaccharides (contain 2 monosaccharide units) more
common - crystalline water soluble substances
• Table sugar (sucrose) and milk sugar (lactose)
- are common disaccharides
• Upon hydrolysis they produce monosaccharide
• In human body associated with proteins and lipids for
structural and regulatory functions
4
BIOCHEMISTRY| 2020
 Polysaccharides
• Contain many monosaccharide units
covalently bonded
• Polymers: May contain 100s of 1000s of
monosaccharide units
• Examples:
• Cellulose: Paper, cotton, wood
• Starch: Bread, pasta, potatoes, rice, corn,
beans, peas, etc.

5
BIOCHEMISTRY| 2020
 CHIRALITY: HANDEDNESS IN MOLECULES
Objects and Mirror Images

• Most monosaccharides exist in two forms: a “left handed”

and “right handed” form - same as two hands
• Two types of objects:
- Superimposible on their mirror images: -- images that coincide
at all points when the images are laid upon each other -- a
dinner plate with no design features -- Achiral
- Non-superimposible on their mirror images: Chiral
(handedness)
6
BIOCHEMISTRY| 2020
 Chirality
• Chiral Center: C atom attached to 4 different
groups
• A molecule with chiral center is a chiral
molecule
• Best way to visualize - look at all C atoms
and see if there are at least two H atoms
then that can’t be a chiral center
• C atoms with less than one H atoms are
worth looking at for their chirality.
7
BIOCHEMISTRY| 2020
Practice Exercise

Answers:
a. Not a chiral center
b. Not a chiral center
c. Chiral center
d. Not a chiral center

8
BIOCHEMISTRY| 2020
Responses of Left and Right Handed Forms of a
Molecule in a Human Body

• Both may be active, one may be more active or

one may be active and other non-active
• Example: Right handed hormone epinephrine
is 20 times more active than left handed form
• Almost all monosaccharides are right handed
• Amino acids are almost always left handed

9
BIOCHEMISTRY| 2020
STEREOISOMERISM: ENANTIOMERS AND DIASTERIOISOMERS
Stereoisomers
• Stereoisomers are isomers that have the same
molecular and structural formulas but differ in the
orientation of atoms in space.
• Two types:
• Enantiomers are stereoisomers whose molecules
are nonsuperimposable mirror images of each
other. Molecules with chiral center.
• Diastereomers are stereoisomers whose
molecules are not mirror images of each other.
10
BIOCHEMISTRY| 2020
 Fischer Project Formulas
• Fischer projection formulas - a method for giving molecular
chirality specifications in two dimensions. A Fischer
projection formula is a two-dimensional structural notation
for showing the spatial arrangement of groups about chiral
centers in molecules.
• In a Fischer projection formula a chiral center (Carbon) is
represented as the intersection of vertical and horizontal
lines
• Functional groups of high priority will be written at top
• D and L system used to designate the handedness of
glyceraldehyde enantiomers
11
BIOCHEMISTRY| 2020
 Tetrahedral Arrangements
• The four groups attached to the atom at the chiral center assume a
tetrahedral geometry and it is governed by the following
conventions
• Vertical lines from the chiral center represent bonds to groups
directed into the printed page.
• Horizontal lines from the chiral center represent bonds to groups
directed out of the printed page

12
BIOCHEMISTRY| 2020
 Fischer Project Formulas
• D and L system used to designate the handedness of
glyceraldehyde enantiomers (see figure below)

CHO CHO
H OH HO H
CH2OH CH2OH
D-Glyceroldehyde L-Glyceroldehyde
(-OH on right side) (-OH on left side)

13
BIOCHEMISTRY| 2020
 Fischer Project Formulas
• We now consider Fischer projection formulas for the compound 2,3,4-
trihydroxybutanal - a monosaccharide with four carbons and two chiral
centers
• There are four stereoisomers for this compound—two pairs of enantiomers

14
BIOCHEMISTRY| 2020
 Fischer Project Formulas
• The D,L system used to designate the handedness of
glyceraldehyde enantiomers can be extended to other
monosaccharides with more than one chiral center
• The carbon chain is numbered starting at the carbonyl
group end of the molecule, and the highest-numbered
chiral center is used to determine D or L configuration
• Epimers are diastereomers whose molecules differ only
in the configuration at one chiral center

15
BIOCHEMISTRY| 2020
Exercise

16
BIOCHEMISTRY| 2020
 PROPERTIES OF ENANTIOMERS
Constitutional Isomers and Diastereomers
• Constitutional isomers differ in most chemical and
physical properties. For example, constitutional isomers
have different boiling points and melting points.
• Diastereomers also differ in most chemical and physical
properties. They also have different boiling points and
freezing points.
• In contrast, nearly all the properties of a pair of
enantiomers are the same
• Two differences:
1. Their interaction with plane polarized light
2. Their interaction with other chiral substances
17
BIOCHEMISTRY| 2020
 Dextrorotary and Levorotatory
Compounds
• Enantiomers are optically active: Compounds that rotate plane
polarized light
• Two Types:
• Dextrorotatory:
• Chiral compound that rotates light towards right
(clockwise; +)
• Levorotatory:
• Chiral compound that rotates light towards left
(counterclockwise; -)
• There is no correlation between D, L and +, -
• In D and L you need to look at the structure
• + and - are determined by using a polarimeter
18
BIOCHEMISTRY| 2020
 Interactions Between Chiral Compounds
• Right and Left handed baseball players can’t use same glove
(chiral) but can use same hat (achiral)
• Two members of enantiomer pair (chiral) react differently with
other chiral molecules
• Enantiomeric pairs have same solubility in achiral solvents
like ethanol and have different solubility in chiral solvent like
D-2-butanol
• Enantiomers have same boiling points, melting points and
densities - all these are dependent upon intermolecular
forces and chirality doesn’t depend on them
19
BIOCHEMISTRY| 2020
 CLASSIFICATION OF MONOSACCHARIDES
Monosaccharides
• Triose --- 3 carbon atoms
• Tetrose -- 4 carbon atoms
• Pentoses – 5 carbon atoms
• Hexoses -- 6 carbon atoms
• Aldoses: Monosaccharides with one aldehyde group
• Ketoses: Monosaccharides with one ketone group
• Combined # of C atoms and functional group:
• Example: Aldohexose: Monosaccharide with aldehyde
group and 6 C atoms
20
BIOCHEMISTRY| 2020
Most Common Monosaccharides
• Example: CHO CH2OH
• Aldohexose:
H OH O
Monosaccharide with
aldehyde group and 6 C HO H HO H
atoms – D-glucose
H OH H OH
• Ketohexose:
Monosaccharide with H OH H OH

aldehyde group and 6 C CH2OH CH2OH

atoms – D-fructose
D-Glucose D-Fructose
(aldohexose) (ketohexose)

21
BIOCHEMISTRY| 2020
Exercise

22
BIOCHEMISTRY| 2020
BIOCHEMICALLY IMPORTANT MONOSACCHARIDES
CHO
Glucose and Fructose
H
1. Most abundant in nature
OH

HO H
2. Nutritionally most important
3. Grape fruit good source of glucose (20 - 30%
H OH
by mass) -- also named grape sugar, dextrose
H OH and blood sugar (70 - 100 mg/100 mL of blood)

4. Six membered cyclic form

CH2OH
D-Glucose
(aldohexose)

CH2OH

O 1. Ketohexose
HO H
2. Sweetest tasting of all sugars
H OH
3. Found in many fruits and in honey
H OH
4. Good dietary sugar-- due to higher sweetness
CH2OH
5. Five membered cyclic form
D-Fructose
(ketohexose)

23
BIOCHEMISTRY| 2020
 Galactose and Ribose
CHO
H OH
1. Milk sugar
HO H
2. Synthesize in human
HO H
3. Also called brain sugar-- part of brain and
H OH
CH2 OH
nerve tissue
4. Used to differentiate between blood types
D-Galactose
5. Six membered cyclic form
(aldohexose)
CHO
H OH
H OH
1. Part of RNA
H OH
2. Part of ATP
CH2 OH
3. Part of DNA
D-Ribose
4. Five membered cyclic form
(aldopentose)

24
BIOCHEMISTRY| 2020
 Cyclic Hemiacetal Forms of D-Glucose
• Dominant form of monosaccharides
with 5 or more C atoms is cyclic -
cyclic forms are in equilibrium with
open chain form
• Cyclic forms are formed by the
reaction of carbonyl group (C=O)
with hydroxyl (-OH) group on carbon
5

25
BIOCHEMISTRY| 2020
 Cyclic Hemiacetal Forms of D-Glucose
• 2 forms of D-glucose:
• Alpha-form: -OH of C1 and CH2OH of C5 are on opposite sides
• Beta-form: -OH of C1 and CH2OH of C5 are on same sides

6 6
CH2 OH CH 2OH

O O OH
5 5
4 1 4
OH OH
1
2 OH 2
OH OH
3 3
OH OH
-D-Glucose -D-Glucose

26
BIOCHEMISTRY| 2020
 Cyclic Hemiacetal Forms of
Monosaccharides
• Intramolecular cyclic hemiacetal formation and the
equilibrium between various forms are not restricted to
glucose.
• All aldoses with five or more carbon atoms establish
similar equilibria, but with different percentages of the
alpha, beta, and open-chain forms.
• Fructose and other ketoses with a sufficient number of
carbon atoms also cyclize.

27
BIOCHEMISTRY| 2020
 Pyranose and Furanose
• A cyclic monosaccharide containing a six-atom ring is
called a pyranose, and one containing a five-atom ring is
called furanose because their ring structures resemble
the ring structures in the cyclic ethers pyran and furan
respectively.
Pyran Furan
O
O

CH2 OH

OH CH2 OH CH2 OH CH2OH

O
O
OH OH
OH
OH
-D-Glucose OH
OH
OH OH
OH
Pyranose Furanoses
 -D-Fructose  -D-Ribose
28
BIOCHEMISTRY| 2020
 HAWORTH PROJECTION FORMULAS
• A Haworth projection formula is a two-dimensional
structural notation that specifies the three-
dimensional structure of a cyclic form of a
monosaccharide.
CH2 OH

O CH2 OH
CH2 OH CH2 OH
O O
OH
OH
OH OH
OH OH
OH OH OH
OH
-D-Glucose  -D-Fructose  -D-Ribose

29
BIOCHEMISTRY| 2020
 Alpha and Beta Configuration
• Alpha or Beta configuration is determined by the position of the —OH group on
C1 relative to the CH2OH group that determines D or L series.
• In a Beta configuration, both of these groups point in the same direction
• In an Alpha configuration, the two groups point in opposite directions.

OH Group
• The specific identity of a monosaccharide is determined by the positioning of the
other —OH groups in the Haworth projection formula.
• Any —OH group at a chiral center that is to the right in a Fischer projection
formula points down in the Haworth projection formula and any —OH group to
the left in a Fischer projection formula points up in the Haworth projection
formula.
30
BIOCHEMISTRY| 2020
 Practice Exercise

• Which of the monosaccharides glucose, fructose, galactose, and ribose

has each of the following structural characteristics? (There may be more
than one correct answer for a given characteristic)
a. It is a pentose.
b. It is a ketose.
c. Its cyclic form has a 6-membered ring.
d. Its cyclic form has two carbon atoms outside the ring.
Answers:
a. Ribose
b. Fructose
c. Glucose, galactose
d. Fructose
31
BIOCHEMISTRY| 2020
 REACTIONS OF MONOSACCHARIDES
• Five important reactions of monosaccharides:
• Oxidation to acidic sugars
• Reduction to sugar alcohols
• Glycoside formation
• Phosphate ester formation
• Amino sugar formation
• These reactions will be considered with respect to
glucose.
• Other aldoses, as well as ketoses, undergo similar
reactions.

32
BIOCHEMISTRY| 2020
 Oxidation
• Oxidation to acidic sugars: The redox chemistry
of monosaccharides is closely linked to the
alcohol and aldehyde functional groups present
in them.
• Oxidation can yield three different types of
acidic sugars depending on the type of oxidizing
agent used:
• Weak oxidizing agents such as Tollens and
Benedict’s solutions oxidize the aldehyde end to
give an aldonic acid.
• A reducing sugar is a carbohydrate that gives a
positive test with Tollens and Benedict’s solutions.
33
BIOCHEMISTRY| 2020
 Oxidizing Agents
• Strong oxidizing agents can oxidize both ends of a
monosaccharide at the same time (the carbonyl group
and the terminal primary alcohol group) to produce a
dicarboxylic acid:
• Such polyhydroxy dicarboxylic acids are known as aldaric
acids.
• In biochemical systems enzymes can oxidize the primary
alcohol end of an aldose such as glucose, without
oxidation of the aldehyde group, to produce an alduronic
acid.

34
BIOCHEMISTRY| 2020
 Sugar Alcohols
• Reduction to sugar alcohols: The carbonyl
group in a monosaccharide (either an aldose or
a ketose) is reduced to a hydroxyl group using
hydrogen as the reducing agent.
• The product is the corresponding polyhydroxy
alcohol - sugar alcohol.
• Sorbitol - used as moisturizing agents in foods and
cosmetics and as a sweetening agent in chewing
gum

35
BIOCHEMISTRY| 2020
 Glycloside
• Glycoside formation: Cyclic forms of monosaccharides are
hemiacetals, they react with alcohols to form acetals:
• Monosaccharide acetals are called glycoside
• A glycoside is an acetal formed from a cyclic monosaccharide
by replacement of the hemiacetal carbon —OH group with an
—OR group:
• A glycoside produced from glucose - glucoside
• A glycoside produced from galactose – galactoside
• Glycosides exist in both Alpha and Beta forms

36
BIOCHEMISTRY| 2020
 Blood Types and Monosaccharides
• Blood Types and Monosaccharides: Human blood is classified into four types:
A, B, AB, and O:
• Blood of one type cannot be given to a recipient with blood of another type.
• A transfusion of wrong blood type can cause the blood cells to form clumps - a
potentially fatal reaction.
• People with type O blood are universal donors, and those with type AB blood are
universal recipients.
• The biochemical basis for the various blood types involves monosaccharides
present on plasma membranes of red blood cells.
• The monosaccharides responsible for blood groups are D-galactose and its
derivatives.
37
BIOCHEMISTRY| 2020
 Phosphate Ester Formation
• Phosphate ester formation: The hydroxyl
groups of a monosaccharide can react
with inorganic oxyacids to form inorganic
esters.
• Phosphate esters of various
monosaccharides are stable in aqueous
solution and play important roles in the
metabolism of carbohydrates.
38
BIOCHEMISTRY| 2020
 Amino Sugar Formation
• Amino sugar formation: An amino sugar - one of the
hydroxyl groups of a monosaccharide is replaced with an
amino group
• In naturally occurring amino sugars the carbon 2 hydroxyl
group is replaced by an amino group
• Amino sugars and their N-acetyl derivatives are important
building blocks of polysaccharides such as chitin

39
BIOCHEMISTRY| 2020
 DISACCHARIDES
• Two monosaccharides can react to form
disaccharide
• One monosaccharide act as a hemiacetal and
other as alcohol

40
BIOCHEMISTRY| 2020
 Cellobiose
• Cellobiose is produced as an intermediate in the
hydrolysis of the polysaccharide cellulose:
• Cellobiose contains two b - D-glucose monosaccharide
units linked through a b (1—4) glycosidic linkage.

CH2OH
O OH
CH2OH  (1-4)
H
O OH
O
OH
OH
OH
OH
Cellobiose

41
BIOCHEMISTRY| 2020
 Maltose
• Maltose is digested easily by humans because we have
enzymes that can break a (1-4) linkages but not b (1-4)
linkages of cellobiose. Therefore cellobiose cannot be
digested by humans.

CH2 OH CH2 OH

O O

OH OH
O OH
OH

OH
a (1-4) OH

Maltose
42
BIOCHEMISTRY| 2020
 Lactose
• Lactose is made up of b-D-galactose unit and a b-D-
glucose unit joined by a b(1-4) glycosidic linkage

CH2OH
O OH
 (1-4)
CH2OH H
OH
OH O O
OH
OH

OH
Lactose

43
BIOCHEMISTRY| 2020
 Lactose
• Lactose - principal carbohydrate in milk.
• Human - 7%–8% lactose
• cow’s milk - 4%–5% lactose
• Lactose intolerance: a condition in which people lack the enzyme
lactase needed to hydrolyze lactose to galactose and glucose.
• Lactase hydrolyzes b(1-4) glycosidic linkages.
• Deficiency of lactase can be caused by a genetic defect,
physiological decline with age, or by injuries to intestinal mucosa.
• When lactose is undigested it attracts water causing fullness,
discomfort, cramping, nausea, and diarrhea. Bacterial fermentation
of the lactose further along the intestinal tract produces acid (lactic
acid) and gas, adding to the discomfort.
44
BIOCHEMISTRY| 2020
 Sucrose
• Sucrose (table sugar): The CH2 OH

most abundant of all

O

CH2 OH
disaccharides and found in OH
OH
OH
O

plants. OH OH

• It is produced commercially -D-Glucose OH

OH  (1-2)
+
from the juice of sugar cane CH2 OH
O OH
CH2OH
O
O
Linkage

and sugar beets. OH OH

• Sugar cane contains up CH 2OH CH 2OH

to 20% by mass sucrose OH OH

-D-Fructose Sucrose
• Sugar beets contain up
to 17% by mass sucrose

45
BIOCHEMISTRY| 2020
 Practice Exercise
• Which of the monosaccharides maltose, cellobiose, lactose, and sucrose
has each of the following structural or reaction characteristics? (There
may be more than one correct answer for a given characteristic)
a. Two different monosaccharide units are present.
b. Hydrolysis produces only monosaccharides.
c. Its glycosidic linkage is a “head-to-head” linkage.
d. It is not a reducing sugar.
Answers:
a. Lactose, sucrose
b. Maltose, cellobiose, lactose, sucrose
c. Sucrose
d. Sucrose
46
BIOCHEMISTRY| 2020
GENERAL CHARACTERISTICS OF
POLYSACCHARIDES
The Polymer Chain

• Polymers
• Many monosaccharide units bonded
with glycosidic linkages
• Two types:
- Linear and branched, homo- and
hetero-polysaccharides

47
BIOCHEMISTRY| 2020
• Polysaccharides are not sweet and don’t show
positive tests with Tollen’s and Benedict’s
solutions whereas monosaccharides are sweet
and show positive tests
• Limited water solubility
• Examples:
• Cellulose, starch in plants
• Glycogen in animals
• Chitin in arthropods
48
BIOCHEMISTRY| 2020
 Starch
• A storage polysaccharide is a polysaccharide that is
a storage form for monosaccharides and is used as
an energy source in cells.
• Starch:
• Glucose is the monomeric unit
• Storage polysaccharide in plants
• Two types of polysaccharidse isolated from starch:
• Amylose: Straight chain polymer - 15 - 20% of the starch
and has a (1  4) glycosidic bonds
• Molecular Mass: 50,000 (up to 1000 glucose units)

49
BIOCHEMISTRY| 2020
 Amylopectin Stucture
• Amylopectin:
• Branched chain polymer - 80 - 85 % of
the starch a (14) glycosidic bond for
straight chain and a (16) for branch
• Molecular Mass: 300,000 (up to
100,000 glucose units) - higher than
amylose
• Human can hydrolyze alpha linkage
but not beta linkage 50
BIOCHEMISTRY| 2020
 Glycogen
• Humans and animals storage polysaccharide
• Contains only glucose units
• Branched chain polymer – a (14) glycosidic bonds in straight chains
and a (16) in branches
• Molecular Mass: 3,000,000 (up to 1,000,000 glucose units)
• Three times more highly branched than amylopectin in starch
• Excess glucose in blood stored in the form of glycogen

51
BIOCHEMISTRY| 2020
 Cellulose
• Linear homopolysaccharide with b (1  4) glycosidic bond
• Up to 5000 glucose units with molecular mass of 900,000 amu
• Cotton ~95% cellulose and wood ~50% cellulose
• Humans don’t have enzymes that hydrolyze b (1  4) - so humans can not
digest cellulose -- animals also lack these enzymes but they can digest
cellulose because they have bacteria in their guts to hydrolyze cellulose
• It serves as dietary fiber in food-- readily absorbs water and results in softer
stools
• 20 - 35 g of dietary fiber is desired everyday HO

HO O O
OH
HO O O
OH (1-4) OH
HO O O
OH  (1-4)
O O OH
OH (1-4)
O OH

OH
52
BIOCHEMISTRY| 2020
 Chitin
• Similar to cellulose in both function and structure
• Linear polymer with all b (14) glycosidic linkages - it has a N-acetyl
amino derivative of glucose
• Function is to give rigidity to the exoskeleton s of crabs, lobsters,
shrimp, insects, and other arthropods

HO

HO O O
OH
HO O
O
OH HN
N-Acetyl
HO
O O b-D-Glucoseamine
OH HN O
O O
O OH HN O

HN O

53
BIOCHEMISTRY| 2020
 ACIDIC POLYSACCHARIDES
• Acidic polysaccharides - polysaccharides with a repeating
disaccharide unit containing an amino sugar and a sugar with a
negative charge due to a sulfate or a carboxyl group.
• Structural polysaccharide present in connective tissue associated
with joints, cartilage, synovial fluids in animals and humans
• Primary function is lubrication necessary for joint movement
• These are heteropolysaccharides - have more than one type of
monosaccharide monomers is present.
• Examples:
• Hyaluronic acid
• Heparin

54
BIOCHEMISTRY| 2020
 Hyaluronic Acid and Heparin
• Hyaluronic acid:
• Alternating residues of N-
acetyl-b-D-glucosamine and D-
glucuronic acid.
• Highly viscous - serve as
lubricants in the fluid of joints
and part vitreous humor of the
eye.
• Heparin:
• An anticoagulant-prevents
blood clots.
• Polysaccharide with 15–90
disaccharide residues per
chain.

55
BIOCHEMISTRY| 2020
GLYCOLIPIDS AND GLYCOPROTEINS
• A glycolipid is a lipid molecule that has one or more
carbohydrate (or carbohydrate derivative) units covalently
bonded to it.

• A glycoprotein is a protein molecule that has one or more

carbohydrate (or carbohydrate derivative) units covalently
bonded to it.

56
BIOCHEMISTRY| 2020
 Nutrition
• Foods high in carbs content constitute over 50% of the diet of most people of the
world -- a balanced dietary food should contain about 60% of carbohydrate:
• Corn in South America
• Rice in Asia
• Starchy root vegetables in parts of Africa
• Potato and wheat in North America
• Nutritionist divide dietary carbs into two classes:
• Simple carb: dietary monosaccharides or disaccharides - sweet to taste
commonly referred to as sugars - 20 % of the energy in the US die
• Complex carbs: Dietary polysaccharides -- starch and cellulose - normally not
sweet to taste

57
BIOCHEMISTRY| 2020
 Glycemic Foods
• A developing concern about intake of carbohydrates
involves how fast the given dietary carbs are broken
down to glucose within the human body
• Glycemic effect refers to:
• how quickly carbs are digested
• how high blood glucose rise
• how quickly blood glucose levels return to normal
• Glycemic index (GI) has been developed for rating foods

58
BIOCHEMISTRY| 2020