Molecular Food Biochemistry

Carbohydrates

Copyright © 1999-2008 by Joyce J. Diwan.

All rights reserved.
 Carbon Chemistry
• Carbon atoms can form single, double or triple bonds
with other carbon atoms.
• Carbon can form up to 4 bonds
• This allows carbon atoms to form long chains, almost
unlimited in length.
 Macromolecules
• “GIANT MOLECULES”
• Made up of numerous of little molecules.
• Formed from a process known as
polymerization, in which large molecules are
produced by joining small ones together.
• The small units (monomers), join together to
form large units (polymers)
 Where Do Carbohydrates Come From?

• Plants take in
• Carbon dioxide (CO2)
and water (H2O) +
heat from the sun and
make glucose.
• C6H12O6
 Carbohydrates
• As the name implies, consist of carbon, hydrogen,
and oxygen.
• Hydrate=(water) hydrogen and oxygen.
• The basic formula for carbohydrates is C-H2O,
meaning that there is one carbon atom, two
hydrogen atoms, and one oxygen atom as the ratio
in the structure of carbohydrates
• What would be the formula for a carbohydrate that
has 3 carbons.
• C3H6O3
 Carbohydrate
• Fancy way of saying sugar.
• Carbohydrates are energy packed compounds,
that can be broken down quickly by organisms
to give them energy.
• However, the energy supplied by
carbohydrates does not last long, and that is
why you get hungry every 4 hours.
• Carbohydrates are also used for structure.
 Saccharides
• Scientist use the word saccharides to describe
sugars.
• If there is only one sugar molecule it is known
as a monosaccharide
• If there are two it is a disaccharide
• When there are a whole bunch, it is a
polysaccharide.
 Glucose is a monosaccharide
• Notice there is only
one sugar molecule.
• Glucose is the main
fuel for all living cells.
• Cells use glucose to do
work.
 Disaccharide
Maltose
• Maltose is an example
of a disaccharide
• Notice it is two sugar
molecules together.
• Glucose + Glucose =
Maltose
 The most common disaccharide is
Sucrose
• Sucrose is glucose +
fructose and is known
as common table
sugar.
 Polysaccharide
• Polysaccharides are a
whole bunch or
monosaccharides
linked together.
• An example of a
polysaccharide is
starch.
 Polysaccharide

• Polysaccharides are a
whole bunch or
monosaccharides
linked together.
• An example of a
polysaccharide is
starch.
 Polysaccharide

• 90% of the considerable carbohydrate mass in nature is in

the form of polysaccharides.
• Polysaccharides can be either linear or branched.
• The general scientific term for polysaccharides is glycans.
• Homoglycan & Hetroglycan
• Homoglycan: glycosyl units are of the same sugar type.
Eg., Cellulose and Starch amylose (linear)
* Starch amylopectin (branched)
• Hetroglycan:

two or more different monosaccharide units

* Diheteroglycans:
 Most of the names of carbohydrates end
in -ose
• Glucose-What plants make
• Maltose- used in making beer (disaccharide)
• Fructose – found in fruit (monosaccharide)
• Sucrose- Table sugar (disaccharide)
• Lactose – In milk (disaccharide)
 Isomers
• Glucose • Fructose
• C6H12O6 • C6H12O6
• Fructose sweeter than
glucose because of its
structure.
Glucose can be found in a ring structure or
linear structure
• In Water
 Dehydration Synthesis
• Sounds technical but all it
really means is taking out
the water and making some
thing new.
• Dehydration is what
happens to you when you
don’t drink enough water.
• Synthesis means “making
some thing new”
• In this case we are taking Fructose
out water and connecting
glucose with fructose to
make sucrose (table sugar)

Sucrose
 Hydrolysis
Hydro=water lysis= break apart
• Hydrolysis breaks down a
disaccharide molecule into
its original
monosaccharides.
• Hydrolysis, it means that
water splits a compound.
• When sucrose is added to
water, it splits apart into
glucose and fructose.
• It is just the opposite of
dehydration
 What do we do with all the sugar?

• Plants store glucose in • Animals store glucose

the form of in the from of a
polysaccharides known polysaccharide known
as starch in their roots . as glycogen in our liver
and muscle cells.
 Cellulose

• The most abundant

organic molecule on
earth.
• Gives trees and plants
structure and strength.
• Most animals can not
break the glucose linkage
by normal means of
hydrolysis. Need special
enzymes.
• We need cellulose (fiber)
to keep our digestive
tracts clean and healthy.
 Chitin
Polysaccharides are used in the shell
of crustaceans like crabs and lobsters.
 Carbohydrates also serve as structural
elements.
• The chains sticking out of the proteins in the
cell membrane are polysaccharides known as
cell markers(glycoproteins).
 How Sweet It Is
• The human tongue has four
basic taste qualities.
• Bitter
• Salty
• Sour
• Sweet
• We perceive taste qualities
when receptors on our
tongue send a message to
our brain.
Its all about how tightly the molecules fit
into the receptors on the tongue.
• The chemical structure of a compound
determines its shape, which in turn will
determine how well it will fit into a receptor.
• Compounds that bind more tightly to “sweet”
taste receptors send stronger “sweet”
messages to the brain.
 TASTE
• Taste buds: mostly on tongue
• Two types
– Fungiform papillae (small, on entire surface of tongue)
– Circumvallate papillae (inverted “V” near back of tongue)

26
• Taste buds of 50-100
epithelial cells each
• Taste receptor cells
(gustatory cells)
• Microvilli through pore,
bathed in saliva
• Disolved molecules bind
& induce receptor cells
to generate impulses in
sensory nerve fibers
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Carbohydrate Structure
 Carbohydrates
• Cx(H2O)y
• 70-80% human energy needs
• >90% dry matter of plants
• Monomers and polymers
• Functional properties
– Sweetness
– Chemical reactivity
– Polymer functionality
 Simple Sugars
• Cannot be broken down by mild acid
hydrolysis
• C3-9 (esp. 5 and 6)
• Polyalcohols with aldehyde or ketone
functional group
• Many chiral compounds
• C has tetrahedral bond angles
Nomenclature: Classification of Carbohydrates
Functional group

Ketone Aldehyde
4 Tetrose Tetrulose
5 Pentose Pentulose
Number of carbons

6 Hexose Hexulose
7 Heptose Heptulose
8 Octose Octulose
9 Nanose Nanolose
Table 1
 Chiral Carbons
• A carbon is chiral if it has four different groups
• A chiral carbon atom is one that can exist in two
different spatial arrangements (configurations).
• Chiral compounds have the same composition but
are not superimposable (two different arrangements of the four groups in space
(configurations) are nonsuperimposable mirror images of each other)

• Display in Fisher projection

CHO CHO
H OH HO H
CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde

ENANTIOMERS
 Glucose
• Fisher projection C-1
H O
• D-series sugars are built on D-
glyceraldehyde H OH C-2

• 3 additional chiral carbons HO H C-3

• 23 D-series hexosulose sugars C-4
(based on D-glyceraldehyde) H OH
• 23 L-series based on L- H OH C-5
glyceraldehyde
H OH C-6
• D-Glucose is the most
abundant carbohydrate H

Original D-glyceraldehyde carbon

 D-Fructose
• A ketose sugar found
H2C CH3
abundantly in natural foods
• One less chiral carbon than O
the corresponding aldose HO CH
(only 3) HC OH
• Sweetest known sugar
HC OH
• 55% of high-fructose corn
syrup C OH
H2
• and about 40% of honey
Carbohydrates (glycans) have the following
basic composition: I
(CH2O)n or H - C - OH
I
 Monosaccharides - simple sugars with multiple OH
groups. Based on number of carbons (3, 4, 5, 6), a
monosaccharide is a triose, tetrose, pentose or
hexose.
 Disaccharides - 2 monosaccharides covalently linked.
 Oligosaccharides - a few monosaccharides covalently
linked.
 Polysaccharides - polymers consisting of chains of
monosaccharide or disaccharide units.
 Monosaccharides
Aldoses (e.g., glucose) have an Ketoses (e.g., fructose) have
aldehyde group at one end. a keto group, usually at C2.
H O
C CH2OH

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH

D-glucose D-fructose
 D vs L configuration

CHO CHO
D & L designations are
H C OH HO C H
based on the
configuration about CH2OH CH2OH
the single asymmetric D-glyceraldehyde L-glyceraldehyde
C in glyceraldehyde.
CHO CHO
The lower H C OH HO C H
representations are
CH2OH CH2OH
Fischer Projections.
D-glyceraldehyde L-glyceraldehyde
 Sugar Nomenclature

For sugars with more O H O H

than one chiral center, C C
D or L refers to the H – C – OH HO – C – H
asymmetric C farthest HO – C – H H – C – OH
from the aldehyde or H – C – OH HO – C – H
keto group. H – C – OH HO – C – H
Most naturally CH2OH CH2OH
occurring sugars are D D-glucose L-glucose

isomers.
D & L sugars are mirror O H O H
images of one another. C C
They have the same H – C – OH HO – C – H
name, e.g., D-glucose HO – C – H H – C – OH
& L-glucose. H – C – OH HO – C – H
Other stereoisomers H – C – OH HO – C – H
have unique names, CH2OH CH2OH
e.g., glucose, mannose, D-glucose L-glucose
galactose, etc.

The number of stereoisomers is 2n, where n is the number of asymmetric centers.

The 6-C aldoses have 4 asymmetric centers.
Thus there are 16 stereoisomers (8 D-sugars and 8 L-sugars).
 Hemiacetal & hemiketal formation

H H
An aldehyde can
C O + R' OH R' O C OH
react with an
alcohol to form R R
a hemiacetal. aldehyde alcohol hemiacetal

R R
A ketone can
react with an C O + "R OH "R O C OH
alcohol to form R' R'
a hemiketal. ketone alcohol hemiketal
 CHO
Pentoses and 1

hexoses can cyclize H

2
C OH

as the ketone or HO
3
C H D-glucose
aldehyde reacts H C OH (linear form)
with a distal OH. 4
H C OH
Glucose forms an 5

intra-molecular 6
CH2OH

hemiacetal, as the 6 CH2OH 6 CH2OH

C1 aldehyde & C5 5 O 5 O
H H H OH
OH react, to form H H
a 6-member 4 OH H 1 4 OH H 1

pyranose ring, OH
3 2
OH OH
3 2
H
named after pyran. H OH H OH
-D-glucose -D-glucose

These representations of the cyclic sugars are called

Haworth projections.
 1
CH2OH

2C O

HO C H
1 CH2OH
3 HOH2C 6 O
H C OH HO
4 5 H 2

H C OH H 4 3 OH
5
OH H
6
CH2OH

D-fructose (linear) -D-fructofuranose

Fructose forms either

 a 6-member pyranose ring, by reaction of the C2 keto
group with the OH on C6, or
 a 5-member furanose ring, by reaction of the C2 keto
group with the OH on C5.
 6 CH 2 OH 6 CH 2 OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D-glucose -D -glucose

Cyclization of glucose produces a new asymmetric center

at C1. The 2 stereoisomers are called anomers,  & .
Haworth projections represent the cyclic sugars as having
essentially planar rings, with the OH at the anomeric C1:
 (OH below the ring)
  (OH above the ring).
 H OH H OH
4 6 H O H O
HO 5 HO
HO 2 H HO OH
3 H OH 1 H OH
H OH H H

-D-glucopyranose -D -glucopyranose

Because of the tetrahedral nature of carbon bonds,

pyranose sugars actually assume a "chair" or "boat"
configuration, depending on the sugar.
The representation above reflects the chair
configuration of the glucopyranose ring more accurately
than the Haworth projection.
 Sugar derivatives
COOH CHO
CH2OH
H C OH H C OH
H C OH
HO C H HO C H
H C OH
H C OH H C OH
H C OH
H C OH H C OH
CH2OH
CH2OH COOH
D-ribitol
D-gluconic acid D-glucuronic acid

 sugar alcohol - lacks an aldehyde or ketone; e.g., ribitol.

 sugar acid - the aldehyde at C1, or OH at C6, is oxidized
to a carboxylic acid; e.g., gluconic acid, glucuronic acid.
 Sugar derivatives
CH 2OH CH 2OH

H O H H O H
H H
OH H OH H

OH OH OH O OH
H NH 2 H N C CH 3
H
-D-glucosamine -D-N-acetylglucosamine

amino sugar - an amino group substitutes for a hydroxyl.

An example is glucosamine.
The amino group may be acetylated, as in N-
acetylglucosamine.
 O H

H3C C NH O COO
R HC OH
H H R=
HC OH
H OH
CH2OH
OH H
N-acetylneuraminate (sialic acid)

N-acetylneuraminate (N-acetylneuraminic acid, also

called sialic acid) is often found as a terminal residue
of oligosaccharide chains of glycoproteins.
Sialic acid imparts negative charge to glycoproteins,
because its carboxyl group tends to dissociate a proton
at physiological pH, as shown here.