CHAPTER 18: Carbohydrates Photosynthesis

The Study of Living Things • Process in which plants produce

carbohydrates using carbon dioxide,
• Biochemistry: Study of the chemical
water, and solar energy
substances found in living organisms
and the chemical interactions of
these substances with each other
Functions of Carbohydrates in the
• Biochemical substance: Chemical
Human Body
substance found within a living
organism • Carbohydrate oxidation provides
• Types of biochemical substances: energy
- Bioinorganic substances - Water and
• Carbohydrate storage, in the form of
inorganic salts
glycogen, provides a short-term
- Bioorganic substances -
energy reserve
Carbohydrates, lipids, proteins, and
nucleic acids • Carbohydrates supply carbon atoms
Bioinorganic and Bioorganic for the synthesis of other
Substances biochemical substances (proteins,
lipids, and nucleic acids)
• As isolated compounds, bioinorganic
and bioorganic substances have no • Carbohydrates form part of the
life in and of themselves structural framework of DNA and
RNA molecules
– When these substances are
gathered together in a cell, • Carbohydrates linked to lipids are
their chemical interactions structural components of cell
can sustain life membranes
Plants and Carbohydrates • Carbohydrates linked to proteins
function in a variety of cell–cell and
• It is estimated that more than half
cell–molecule recognition processes
of all organic carbon atoms are
found in the carbohydrate materials • Empirical formula of simple
of plants carbohydrates –
• Human uses for carbohydrates of - CnH2nOn or Cn(H2O)n (hydrate of C)
the plant kingdom extend beyond • n is the number of
food atoms
– Carbohydrates in the form of • Carbohydrate: Polyhydroxy
cotton and linen are used as aldehyde, ketone, or a compound
clothing that produces such substances upon
hydrolysis.
– Carbohydrates in the form of
wood are used for shelter
and heating and in making
paper

Carbohydrates

• Most of the matter in plants, except

water, is carbohydrate material

• Carbohydrates account for 75% of

dry plant material and are produced
Classifications of Carbohydrates
by photosynthesis

– Cellulose - Structural element 1. Monosaccharides

- Contain a single polyhydroxy
– Starch/glycogen - Energy aldehyde or ketone unit
reservoir
 - Cannot be broken down into simpler • Most molecules that possess
substances by hydrolysis reactions “handedness” exist in two forms:

- Contain 3–7 C atoms – “Left-handed” form

- 5 and 6 carbon species are more – “Right-handed” form

common
• Related in the same
- Pure monosaccharides - Water manner as two hands
soluble white, crystalline solids that are “mirror
images” of each other
- Monosaccharides - Glucose and
fructose Mirror Images
2. Disaccharides • Mirror image: Reflection of an
- Contain 2 monosaccharide units object in a mirror.
covalently bonded to each other
• Classes of objects based on mirror
- Crystalline and water-soluble images -
substances
– Superimposable mirror
- Common disaccharides - Table sugar images: Images that
(sucrose) and milk sugar (lactose) coincide at all points when
- Upon hydrolysis, they produce 2 the images are laid upon
monosaccharide units each other

3. Oligosaccharides • Achiral molecule

- Contain three to ten monosaccharide – Nonsuperimposable
units covalently bonded to each mirror images: Images
other where not all points coincide
when the images are laid
- Free oligosaccharides are seldom
encountered in biochemical systems upon each other

• Chiral molecule
- Usually found associated with
proteins and lipids in complex (handedness)
molecules Chirality
o Serve structural and • Chiral center: C atom attached to
regulatory functions 4 different groups
4. Polysaccharides • A molecule with a chiral center is
- Contain many monosaccharide said to be chiral
units covalently bonded
• A C atom must have four different
- Number of monosaccharide units groups attached to it to be a chiral
varies from a few 100 units to center
50,000 units
• A chiral C is usually denoted by *
- Examples:
- Cellulose - Paper, cotton, wood • Bromochloroiodomethane is a chiral
- Starch - Bread, pasta, potatoes, organic molecule
rice, corn, beans, and peas

Chirality and Handedness

Objects and Handedness

• Most biological molecules, including

carbohydrates, exhibit the property
of “handedness” (a form of
isomerism)
Responses of Left and Right-Handed tetrahedral geometry governed by
Forms of a Molecule in a Human Body the following conventions:

• Both forms may be active, one may – Vertical lines from the chiral
be more active, or one may be center represent bonds to
active and the other non-active groups directed into the
printed page
• Example:
– Horizontal lines from the
– Response of the body to the
chiral center represent bonds
right-handed hormone
to groups directed out of the
epinephrine is 20 times
printed page
greater than responses to
the left-handed form

• Almost all monosaccharides are

right-handed

• Amino acids are always left-handed

Stereoisomers
Fischer Project Formulas
• Isomers that have the same
• L and D system used to designate
molecular and structural formulas
the handedness of glyceraldehyde
but differ in the orientation of atoms
enantiomers are shown below
in space

• Two types:

– Enantiomers:
Stereoisomers whose
molecules are non-
superimposable mirror
images of each other

• Molecules with chiral • We now consider Fischer

center projection formulas for the
– Diastereomers: compound 2,3,4-
Stereoisomers whose trihydroxybutanal, a
molecules are not mirrored monosaccharide with four
images of each other carbons and two chiral centers
– There are four stereoisomers
• Example: Cis-trans
for this compound and two
isomers
pairs of enantiomers
Fischer Project Formula

• Two-dimensional structural notation

for showing the spatial arrangement
of groups about chiral centers in
molecules

• According to this formula, a chiral

center is represented as the • The D, L system used to designate
intersection of vertical and horizontal the handedness of glyceraldehyde
lines enantiomers can be extended to
other monosaccharides with more
• Functional groups of high priority than one chiral center
will be written at the top
– The carbon chain is
Tetrahedral Arrangements numbered starting at the
carbonyl group end of the
• The four groups attached to the
molecule, and the highest-
atom at the chiral center assume a
 numbered chiral center is Figure 18.10 - Vibrational
used to determine D or L Characteristics of Ordinary Light and
configuration Plane-Polarized Light

• Epimers: Diastereomers whose

molecules differ only in the
configuration at one chiral center

Properties of Enantiomers

Constitutional Isomers and Diastereomers

• Constitutional isomers differ in most

chemical and physical properties
Dextrorotary and Levorotatory
– Have different boiling points Compounds
and melting points
• Enantiomers are optically active, i.e.,
• Diastereomers also differ in most they are compounds that rotate the
chemical and physical properties plane of polarized light

– Have different boiling points • Dextrorotatory compound: Chiral

and freezing points compound that rotates light towards
the right (clockwise; +)
• In contrast, nearly all the properties
of a pair of enantiomers are the • Levorotatory compound: Chiral
same compound that rotates light towards
left (counterclockwise; -)
– Two differences:
• There is no correlation between D, L
1. Their interaction with
and +, -
plane-polarized light
– In D and L system, the
2. Their interaction with
structure is viewed
other chiral
substances – + and – can be determined
using a polarimeter
Interaction of Enantiomers with Plane-
Polarized Light Interactions Between Chiral
Compounds
• Properties of light:
• Right- and left-handed baseball
– Ordinary light waves- Vibrate
players cannot use the same glove
in all directions
(chiral) but can use the same hat
– Plane polarized light waves - (achiral)
Vibrate only in one direction
– Two members of the
• Plane-polarized light is rotated enantiomer pair (chiral) react
clockwise (to right) or differently with other chiral
counterclockwise (to left) when molecules
passed through enantiomers
• Enantiomeric pairs have the same
– Direction and extent of solubility in achiral solvents like
rotation will depend upon the ethanol and have different solubility
concentration of the in a chiral solvent like D-2-butanol
enantiomer
• Enantiomers have the same boiling
– Same concentration of two points, melting points, and densities
enantiomers rotates light to
– All these are dependent upon
same extent but in opposite
intermolecular forces,
directions
whereas chirality doesn’t
depend on such forces
 • Our body responds differently to • Six-membered cyclic form
different enantiomers

– One may give higher rate or

one may be inactive

• Example: Body response to D isomer

of hormone epinephrine is 20 times
greater than its response to L isomer

Classifications of Monosaccharides
D-Galactose
Monosaccharides
• Milk sugar
• Classification based on number of
• Synthesized in human beings
carbon atoms:
• Also called brain sugar
– Triose - 3 carbon atoms
– Part of brain and nerve tissue
– Tetrose - 4 carbon atoms
• Used to differentiate between blood
– Pentoses - 5 carbon atoms
types
– Hexoses - 6 carbon atoms
• Six-membered cyclic form
• Classification based on functional
groups:

– Aldoses: Monosaccharides
with one aldehyde group

– Ketoses: Monosaccharides
with one ketone group

– Combined number of C
atoms and functional group D-Fructose
– Examples: • Ketohexose
– Aldohexose - Monosaccharide • Sweetest tasting of all sugars
with aldehyde group and 6 C
atoms – Found in many fruits and in
honey
– Ketopentose -
Monosaccharide with ketone • Good dietary sugar due to
group and 5 C atoms higher sweetness
Biochemically Important • Five-membered cyclic form
Monosaccharides

D-Glucose

• Most abundant in nature

• Most important source of human

nutrition

• Grape fruit and ripe fruits are good

sources of glucose (20–30% by D-Ribose
mass)
• Part of a variety of complex
– Also named grape sugar molecules which include:
• Other names – RNA
– Dextrose – ATP
– Blood sugar (70–100 mg/dL) – DNA
 • Five-membered cyclic form Anomers

• Cyclic monosaccharides that differ

only in the position of the
substituents on the anomeric
carbon atom

Cyclic forms of Monosaccharides

Cyclic Hemiacetal Forms of D-Glucose • Intramolecular cyclic hemiacetal

formation and the equilibrium
• Dominant forms of monosaccharides
between various forms are not
with 5 or more C atoms
restricted to glucose
– Cyclic structures are in
• All aldoses with five or more carbon
equilibrium with open chain
atoms establish similar equilibria,
forms
but with different percentages of the
• Cyclic structures are formed by the alpha, beta, and open-chain forms
reaction of carbonyl group (C=O)
• Fructose and other ketoses with a
with hydroxyl (–OH) group on
sufficient number of carbon atoms
carbon 5
also cyclize
Figure 18.17 - The Cyclic Hemiacetal
Pyranose and Furanose
Forms of D-Glucose
• Pyranose - Cyclic monosaccharide
containing a six-atom ring

• Furanose - Cyclic monosaccharide

containing a five-atom ring

• Their ring structures resemble the

ring structures in the cyclic ethers
pyran and furan, respectively

Haworth projection formula:

• 2 forms of D-Glucose:
Two-dimensional structural notation that
– α-form where the –OH of C1
specifies the three-dimensional structure of
and CH2OH of C5 are on
a cyclic form of a monosaccharide
opposite sides

– β-form where the –OH of C1

and CH2OH of C5 are on the
same side

α and β Configuration

• Determined by the position of the –

OH group on C1 relative to the –
 CH2OH group that determines D or L • Other aldoses, as well as ketoses,
series undergo similar reactions

– In a β configuration, both of Oxidation to Produce Acidic Sugars

these groups point in the
• The redox chemistry of
same direction
monosaccharides is closely linked to
– In an α configuration, the the alcohol and aldehyde functional
two groups point in opposite groups
directions
• Oxidation can yield three different
types of acidic sugars depending on
the type of oxidizing agent used

– Aldonic acid - Formed when

weak oxidizing agents such
as Tollens and Benedict’s
solutions oxidize the
aldehyde end
–OH Group Position – Reducing sugar:
• The specific identity of a Carbohydrate that gives a
monosaccharide is determined by positive test with Tollens and
the positioning of the other –OH Benedict’s solutions
groups in the Haworth projection • Strong oxidizing agents can oxidize
formula both ends of a monosaccharide at
– Any –OH group at a chiral the same time (the carbonyl group
center that is to the right in a and the terminal primary alcohol
Fischer projection formula group) to produce a dicarboxylic
points down in the Haworth acid
projection formula – Such polyhydroxy
– Any –OH group to the left in dicarboxylic acids are known
a Fischer projection formula as aldaric acids
points up in the Haworth • In biochemical systems, enzymes
projection formula can oxidize the primary alcohol end
of an aldose such as glucose,
without oxidation of the aldehyde
group, to produce an alduronic acid

Reduction to Produce Sugar Alcohols

• The carbonyl group in a

Reactions of Monosaccharides monosaccharide (either an aldose or
a ketose) is reduced to a hydroxyl
• Five important reactions of group using hydrogen as the
monosaccharides: reducing agent
– Oxidation to acidic sugars – The product is the
– Reduction to sugar alcohols corresponding polyhydroxy
alcohol called sugar alcohol
– Glycoside formation or alditol
– Phosphate ester formation – Sorbitol - Used as a
moisturizing agent in foods
– Amino sugar formation
and cosmetics and as a
• Glucose will be used as the sweetening agent in chewing
monosaccharide reactant gum
Glycloside Formation • Digested easily by humans because
of an enzyme that can break
• Glycoside: Acetal formed from a
α(1🡪4) linkages
cyclic monosaccharide by
replacement of the hemiacetal • Baby foods are rich in maltose
carbon –OH group with an –OR
group

– Glucoside - Glycoside
produced from glucose

– Galactoside - Glycoside
produced from galactose

– Exist in both α and β forms

Cellobiose
Phosphate Ester Formation
• Produced as an intermediate in the
• Hydroxyl groups of a hydrolysis of the polysaccharide
monosaccharide can react with cellulose
inorganic oxyacids to form inorganic
– Contains two D-glucose
esters
monosaccharide units, one of
• Phosphate esters of various which must have a β
monosaccharides are stable in configuration, linked through
aqueous solution and play important a β(1🡪4) glycosidic linkage
roles in the metabolism of
• Cannot be digested by humans
carbohydrates

Amino Sugar Formation

• Amino sugar - Formed when one of

the hydroxyl groups of a
monosaccharide is replaced with an
amino group

• In naturally occurring amino sugars,

the C2 hydroxyl group is replaced by Lactose
an amino group
• Made up of β-D-galactose unit and a
• Amino sugars and their N-acetyl D-glucose unit joined by a β(1🡪4)
derivatives are important building glycosidic linkage
blocks of polysaccharides such as
chitin and hyaluronic acid • Milk is rich in the disaccharide
lactose
Diasaccharides
• Lactase hydrolyzes β(1🡪4)
• Two monosaccharides can react to glycosidic linkages
form a disaccharide

– One monosaccharide acts as

a hemiacetal and the other
as an alcohol

– Resulting ether bond is a

glycosidic linkage

Maltose (Malt Sugar)

• Structurally made of 2 D-glucose

units, one of which must be α-D-
glucose, linked via an α(1🡪4)
glycosidic linkage
Lactose Intolerance or Lactase Persistence – Raffinose - Made of 1
galactose, 1 glucose, and 1
• Lactose is the principal carbohydrate
fructose
in milk
– Stachyose - Made of 2
– Human mother’s milk - 7%–
galactose, 1 glucose, and 1
8% lactose
fructose units
– Cow’s milk - 4%–5% lactose
• Commonly found in onions,
• Lactose intolerance is a condition in cabbage, broccoli, and whole wheat
which people lack the enzyme
Blood Types and Oligosaccharides
lactase needed to hydrolyze lactose
to galactose and glucose • Human blood is classified into four
types
• Deficiency of lactase can be caused
by a genetic defect, physiological – A, B, AB, and O
decline with age, or by injuries to
– The basis for the difference
intestinal mucosa
is the type of sugars
• When lactose is undigested, it (oligosaccharides) present
attracts water causing fullness,
– Blood of one type cannot be
discomfort, cramping, nausea, and
given to a recipient with
diarrhea
blood of another type
• Bacterial fermentation of the lactose
– A transfusion of wrong blood
further along the intestinal tract
type can cause the blood
produces acid (lactic acid) and gas,
cells to form clumps, a
adding to the discomfort
potentially fatal reaction
Sucrose (Table Sugar)
– People with type O blood are
• The most abundant of all universal donors, and those
disaccharides and found in plants with type AB blood are
universal recipients
• Produced commercially from the
juice of sugar cane and sugar beets • In the United States, type O blood is
the most common and type A the
– Sugar cane contains up to
second most common
20% by mass sucrose
• The biochemical basis for the
– Sugar beets contain up to
various blood types involves
17% by mass sucrose
oligosaccharides present on plasma
membranes of red blood cells

• The oligosaccharides responsible for

blood groups are D-galactose and its
derivatives

Other Oligosaccharides

• Solanine, a potato plant toxin, is a

oligosaccharide found in association
with an alkaloid
Oligosaccharides
– Bitter taste of potatoes is due
• Carbohydrates that contain 3–10
to relatively higher levels of
monosaccharide units bonded to
solanine
each other via glycosidic linkages

• Generally present in association with

other complex molecules
General Characteristics of Types of Polysaccharides Isolated from
Polysaccharides Starch

The Polymer Chain • Amylose

• Polysaccharides are polymers of – Unbranched-chain polymer

many monosaccharide units bonded and accounts for 15%–20%
with glycosidic linkages of the starch

• Two types: – Has α(1🡪4) glycosidic bonds

– Homopolysaccharide • Amylopectin

– Heteropolysaccharide – Branched chain polymer and

accounts for 80%–85% of
Figure 18.26 - The Polymer Chains of a
the starch
Polysaccharide
– Has α(1🡪4) and α(1🡪6)
glycosidic bonds

– Up to 100,000 glucose units

are present

– Amylopectin is digested more

readily by humans (can
hydrolyze α linkages but not
β linkages)

Glycogen

• Glucose storage polysaccharide in

• Polysaccharides are not sweet and humans and animals
do not show positive tests with
Tollen’s and Benedict’s solutions, • Contains only glucose units
whereas monosaccharides are sweet • Branched chain polymer with
and show positive tests α(1🡪4) glycosidic bonds in straight
• Limited water solubility chains and α(1🡪6) in branches

• Examples: • Three times more highly branched

than amylopectin in starch
– Cellulose and glycogen -
Storage polysaccharides • Contains up to 1,000,000 glucose
units
– Chitin - Structural
polysaccharide • Excess glucose in blood is stored in
the form of glycogen
– Hyaluronic acid - Acidic
polysaccharide Structural Polysaccharides

Storage Polysaccharides Cellulose

Starch • Linear homopolysaccharide with

β(1🡪4) glycosidic bond
• Storage polysaccharide:
Polysaccharide that is a storage form • Contains up to 5000 glucose units
for monosaccharides and used as an with molecular mass of 900,000 amu
energy source in cells – Cotton has 95% cellulose
• Starch and wood 50% cellulose

– Glucose is the monomeric • Humans do not have enzymes that

unit hydrolyze β(1🡪4) linkages and so
they cannot digest cellulose
– Storage polysaccharide in
plants – Animals also lack these
enzymes, but they can digest
 cellulose due to the presence – Heparin
of cellulase-producing
Hyaluronic Acid
bacteria
• Alternating residues of N-acetyl- β-
• It serves as dietary fiber in food and
D-glucosamine and D-glucuronate
readily absorbs water resulting in
softer stools • Highly viscous and serve as
lubricants in the fluid of joints as
– 20–35 g of dietary fiber is
well as vitreous humor of the eye
desired everyday

Heparin

• Polysaccharide with 15–90

Chitin disaccharide residues per chain

• Similar to cellulose structurally and • Blood anticoagulant

functionally

• Linear polymer with all β(1🡪4)

glycosidic linkages

– It has an N-acetyl amino

derivative of glucose

• Function is to give rigidity to the

exoskeletons of crabs, lobsters,
shrimp, insects, and other Dietary Considerations and
arthropods Carbohydrates

Figure 18.32(b) - The Structure of Nutrition

Chitin
• Food’s high in carbohydrate content
constitute over 50% of the diet of
most people of the world

– Corn in South America

– Rice in Asia

– Starchy root vegetables in

parts of Africa

– Potato and wheat in North

America
Acidic polysaccharides
– Balanced dietary food should
• Polysaccharides with a repeating contain about 60% of
disaccharide unit containing an carbohydrate
amino sugar and a sugar with a
negative charge due to a sulfate or a Classes of Dietary Carbohydrates
carboxyl group
• Simple carbohydrates: Dietary
• They are heteropolysaccharides, i.e., monosaccharides or disaccharides
different monosaccharides exist in
– Sweet to taste and
an altering pattern
commonly referred to as
• Examples: sugars

– Hyaluronic acid
 – Constitute 20% of the energy
in the US diet

• Complex carbohydrates: Dietary

polysaccharides

– Include starch and cellulose,

which are normally not sweet
to taste

Glycolipids and Glycoproteins: Cell

Recognition

• Glycolipid: Lipid molecule that has

one or more carbohydrate (or
carbohydrate derivative) units
covalently bonded to it

• Glycoprotein: Protein molecule that

has one or more carbohydrate (or
carbohydrate derivative) units
covalently bonded to it

– Such carbohydrate
complexes are very
important in cellular
functions such as cell
recognition