Chemistry 203

Chapter 20

Carbohydrates
 Carbohydrates

• Produced by photosynthesis
in plants.

• The major source of energy

from our diet.

• Composed of the elements C,

H, and O.
Cn(H2O)n

Photosynthesis
6CO2 + 6H2O + energy C6H12O6 + 6O2
Respiration
glucose
 Carbohydrates

- The most abundant organic compounds in nature (50% of the

earth’s biomass).

- 3/4 of the weight of plants.

- 1% of the weight of animals and humans (they do not store).

- 65% of the foods in our diet.

 Carbohydrates

H+ or enzyme
1. Monosaccharide + H2O no hydrolysis

H+ or enzyme
2. Disaccharide + H2O two monosaccharide units

H+ or enzyme
3. Polysaccharide + many H2O many monosaccharide units
 Monosaccharides (Simple Sugar)

A carbohydrate that cannot be split or hydrolyzed into smaller carbohydrates.

Monosaccharides are carbohydrates with:

• The simplest carbohydrates

• 3-9 carbon atoms Cn(H2O)n
• A carbonyl group (aldehyde or ketone) CnH2nOn
• Several hydroxyl groups

O
║
C─H
│
H─ C ─ OH
│
H─ C ─ OH
│
CH2OH
 Monosaccharides - Aldose

Aldose is monosaccharide: O
║
• With an aldehyde group and many 1C─H aldose
hydroxyl (-OH) groups.
│
• triose (3C atoms) H─ C ─ OH
• tetrose (4C atoms) │
• pentose (5 C atoms) H─ C ─ OH
• hexose (6 C atoms) │
CH2OH

“Aldo-” + suffix an aldotetrose

(Erythose)
 Monosaccharides - Ketose

1CH2OH
Ketose is monosaccharide:
│
2 C=O ketose
• With a ketone group and many │
hydroxyl (-OH) groups. H─ C ─ OH
│
• triose (3C atoms) H─ C ─ OH
• tetrose (4C atoms) │
• pentose (5 C atoms)
H─ C ─ OH
• hexose (6 C atoms)
│
CH2OH
“Keto-” + suffix
a ketohexose
(Fructose)
 Monosaccharides (Simple Sugar)

•The simplest aldose is glyceraldehyde.

•The simplest ketose is dihydroxyacetone.

C3H6O3 C3H6O3

Constitutional Isomers
 Some important Monosaccharides

Glucose (Dextrose)

(C6H12O6, aldohexose) – Blood sugar

H O
• The most abundant monosaccharide
C
H C OH
• Is found in fruits, vegetables, HO C H
corn syrup, and honey.
H C OH
• Is found in disaccharides such as H C OH
sucrose, lactose, and maltose.
CH2OH
• Makes up polysaccharides such as
starch, cellulose, and glycogen.
 Some important Monosaccharides

Glucose (Dextrose)

- Normal blood glucose levels are 70-110 mg/dL.

- Excess glucose is stored as the polysaccharide glycogen or as fat.

- Insulin (a protein produced in the pancreas) regulates blood glucose

levels by stimulating the uptake of glucose into tissues or the
formation of glycogen.

- Patients with diabetes produce insufficient insulin to adequately

regulate blood sugar levels, so they must monitor their diet and/or
inject insulin daily.
 Some important Monosaccharides

Fructose

(C6H12O6, ketohexose), CH2OH

C O
• Is the sweetest of the carbohydrates.
HO C H
• Is found in fruit juices and honey (fruit sugar).
H C OH
• In bloodstream, it is converted to its isomer, H C OH
glucose.
CH2OH
• Is bonded to glucose in sucrose (a
disaccharide known as table sugar).
 Some important Monosaccharides

Galactose

(C6H12O6, aldohexose), H O
C
• Has a similar structure to glucose
except for the –OH on Carbon 4. H C OH
HO C H
• Cannot find in the free form in nature.
HO C H
• Exist in the cellular membranes of the H C OH
brain and nervous system.
CH2OH
• Combines with glucose in lactose (a
disaccharide and a sugar in milk).
 Disease - Galactosemia

Galactosemia

missing the enzyme that convert galactose to glucose.

Accumulation of galactose in the blood and tissues.

Mental retardation and cataract

Solution: removing the galactose from food: no milk.

 Chirality

All carbohydrates have 1 or more chirality centers.

Glyceraldehyde, the simplest aldose, has one chirality center, and

has two possible enantiomers.
 Fischer Projections

- Horizontal lines represent bonds projecting forward from the stereocenter.

- Vertical lines represent bonds projecting to the rear.

- Only the stereocenter (tetrahedral carbon) is in the plane.

CHO Convert to Fischer

CHO
Projection
H C OH H OH
CH2 OH
CH2 OH

3D 2D
 Fischer Projections

1. Carbon with four different groups bonded to it.

2. The chiral carbon furthest from the carbonyl group (-CHO).

CHO CHO
CHO CHO H CHO OH CH2H OHCHOO
H * OH H HO OH
H CHO
CHO
* HOH C=HOOH CHO
CHOO
H
HO * H HO HO H
H
HH * OH OH
OHHO
H HH
HO H HH O
O
H * OH HO HO HH * OH
HO H
H H OH HO
HO H H H
H
OH
H * OH H HO OHH CH
H OH
* OH
H OH H OH HO
HO H CHH
OH
H2
2
CH2 OH CH HOH
H CHOH
D-Glucose
2 2 OH
OH CH 2HOH
H CHOH
OH
D-Galactose
2
D-Glucose D-Galactose CH
D-Glucose
CH 2 OH
D-Fructose
OH CH
D-Galactose
CH22
D - glucose L - glucose
2
D-Glucose
D-Glucose D-Galactose
D-Galactose
Naturally occurring enantiomer
 Cyclic Structure – Haworth Structure

Aldehydes and ketones react with alcohols to form hemiacetals.

Unstable

A hemiacetal contains a hydroxyl group (OH) and an alkoxy group (OR)

on the same carbon.
 Cyclic Structure – Haworth Structure

Cyclic hemiacetals form readily when the hydroxyl and carbonyl groups
are part of the same molecule.

O red raw to show

1 -OH an d -CHO
4
H clos e to each oth er
O-H
4-Hyd roxypentanal 1 H H
4
C
O O O O-H
H A cyclic hemiacetal

Stable
Cyclic Structure – Haworth Structure
1

Anomeric carbon

1
1 1

Alpha (α) Beta ()

More stable form
Anomers
Cyclic Structure – Haworth Structure
 Cyclic Structure – Haworth Structure

CH2OH CH2OH
O
O OH 
1 1
OH OH
OH OH  OH

OH OH
-D-Glucose -D-Glucose

CH 2OH CH 2OH CH 2OH

O O O
OH OH OH
1 1
OH OH OH
OH OH OH

OH OH OH

-D-Galactose -D-Galactose
 1
CH2 O CH 2 OH Structure – Haworth Structure
Cyclic
H HO 2

H OH( )
HO H 1
CH2 OH
1
2
O OH OH ( )
Anomeric carbon
 -D -Fructofuranose C=O HOCH2
( - D -Fructos e) HO H C=O
5 H HO
5 22
H OH H CH2 OH
H 5 OH HO H 1

CH2 OH
D -Fru ctose  - D -Fru ctofu ran os e
(- D -Fructose)
HOCH2
O
O CH2OH O
HOCH2 OH
2 2
H HO HO
H OH H H CH2OH

OH H OH H

-D-fructose -D-fructose
 Cyclic Structure – Haworth Structure

CH2OH CH2OH

O O
OH
1 1
OH OH
OH OH OH

OH
OH
-D-Glucose -D-Glucose

Humans have -amylase (an enzyme) and they can digest starch
products such as pasta (contain -glucose)

Humans do not have β-amylase (an enzyme) and they cannot digest
cellulose such as wood or paper (contain β-glucose)
 Chair Conformation

6
CH2 OH 6
H5 O OH() 4 CH2 OH
H HO O
4 OH 1
H HO 5
HO H 2 OH( )
3 3
2 OH 1
H OH
-D -Glucop yranose  - D -Glucopyranose
(Haw orth p rojection) (ch air con formation)

-D-Glucose -D-Glucose
(Haworth projection) (Chair conformation)
 Mutarotation

Change in specific rotation that accompanies the equilibration

of α and  anomers in aqueous solution.

-D-glucose Open-chain form α-D-glucose

(acyclic)
64% < 0.02% 36%
 Physical properties of Monosaccharides

- Colorless

- Sweet Tasting

- Crystalline solids

- Polar with high melting points (because of OH groups)

- Soluble in water and insoluble in nonpolar solvents

(H-bond because of OH groups)
Chemical properties of Monosaccharides

1. Formation of Glycosides (Acetals)

2. Oxidation

3. Reduction
 Formation of Glycosides (Acetals)

- Exist almost exclusively in cyclic hemiacetal forms.

- They react with an alcohol to give acetals.
- Acetals are stable in water and bases but they are hydrolyzed in acids.

anomeric
CH2 OH carbon
H O OH
+
H H
OH H + CH3 OH
HO -H2 O
H
H OH glycos idic
CH2 OH bond CH2 OH
-D -D-Glucose
-Glu copyran os e
O OCH3 OH
(-D -Glu cose) H H
H H
OH H + OH H
HO H HO OCH3
H OH H OH
Methyl -D -glu copyran os ide Methyl -D -glu copyran os ide
Methyl -D-Glucoside
(Methyl -D -glu coside) (Methylα-D-Glucoside
Methyl -D -glucos ide)
 Oxidation of Monosaccharides

H O OH
H O Aldonic acids
C C
H C OH H C OH
HO C H OH- HO C H + 2Cu+
+ 2Cu2+
H C OH Benedict’s H C OH (Brike red)
Reagent (blue)
H C OH H C OH
CH2OH CH2OH

D - glucose D – gluconic acid

Reducing sugars: reduce another substance.

 Oxidation of Monosaccharides

CH2OH H O
C
C O
H C OH
Rearrangement
HO C H (Tautomerism)
HO C H
H C OH H C OH
H C OH H C OH
CH2OH CH2OH

D-fructose D-glucose
(ketose) (aldose)
 Oxidation of Monosaccharides

primary alcohol at C-6 of a hexose is oxidized to uronic acid

by an enzyme (catalyst).

CHO CHO
enzyme-
H OH catalyzed H OH COO
HO H Enzyme
oxidation HO H
HO
H OH H OH HO
H OH H OH
CH2 OH COOH
D-Glucose D-glucuronic D-Glucuronic
acid acid
D-glucose (a uronic acid)(a uronic acid)

Exist in connective tissue

Detoxifies foreign phenols and alcohols
 Reduction of Monosaccharides

Alditols

Sugars alcohols: sweetners in many sugar-free (diet drinks & sugarless gum).
Problem: diarrhea and cataract
Monitoring Glucose Levels

Glucose
oxidase
O2 H2O2
 Disaccharides

A disaccharide:

• Consists of two monosaccharides linked by a glycosidic bond (when

one –OH group reacts with another –OH group).

Glucose + Glucose Maltose + H2O

Glucose + Galactose Lactose + H2O

Glucose + Fructose Sucrose + H2O

 Disaccharides

Disaccharides have at least one acetal carbon (a carbon atom singly bonded
to two OR (alkoxy) groups.
 Disaccharides

The glycosidic bond joining the two rings can be alpha () or beta ().
 Disaccharides
Maltose:

• Is a disaccharide of two glucose molecules.

• Has a α -1,4-glycosidic bond (between two α-glucoses).
• Is obtained from the breakdown of starches.
• Is used in cereals and candies.
• Is a reducing sugar (carbon 1 can open to give a free aldehyde to oxidize).

CH2OH CH2OH CH2OH

CH2OH
 -1,4-glycosidic
O

O O O
bond OH
OH
1 + 4 1 4 + H2O
OH OH O OH
OH OH OH OH OH
OH OH
OH OH
α-glucose α-glucose
- maltose
 Disaccharides
Lactose:
• Is a disaccharide of galactose and glucose.
• Has a β -1,4-glycosidic bond (between β-galactose and α-gulcose).
• Is found in milk and milk products (almost no sweet).
• Is a reducing sugar (carbon 1 can open to give a free aldehyde to oxidize).

-lactose
 Disaccharides
Sucrose:
• Is found in table sugar (obtained from sugar cane and sugar beets).
• Consists of glucose and fructose.
• Has an α,β-1,2-glycosidic bond (between α-glucose and -fructose).
• Is not a reducing sugar (carbon 1 cannot open to give a free aldehyde
to oxidize).

β-1,2-glycosidic
bond
 Disaccharides

Sucrose:

Sucrose is very sweet, but contains many calories.

To reduce caloric intake, many artificial sweeteners have been developed.

Aspartame, Saccharin, Sucralose

These artificial sweeteners were discovered accidentally.

 Artificial sweeteners

Aspartame:

It (sold as Equal) is hydrolyzed into

phenylalanine, which cannot be processed by
those individuals with the condition phenylketonuria.
 Artificial sweeteners

Saccharine:

It (sold at Sweet’n Low) was used extensively during World War I.

There were concerns in the 1970s that saccharin causes cancer.

 Artificial sweeteners

Sucralose:

It (sold as Splenda) has a very similar structure to sucrose.

 Polysaccharides

• Polymers of many monosaccharides units.

Amylose (20%) (starch that stores glucose in plants such

as rice, potatoes, beans, and wheat - energy storage).
• Starch
Amylopectin (80%)

• Glycogen (an energy storage in animals & humans)

• Cellulose (plant and wood structures).

 Polysaccharides

Amylose:

• Is a polysaccharide of α-glucose in a
continuous (unbranched) chain (helical or coil
form).

• Has α-1,4-glycosidic bonds between the

α-glucose units (250 to 4000 units).

α-1,4-glycosidic bond
 Polysaccharides
Amylopectin:

• Is a polysaccharide of glucose units in branched chains.

• Has α-1,4-glycosidic bonds between the α-glucose units.
• Has α-1,6 bonds to branches of glucose units.
(at about every 25 glucose units, there is a branch).
• Both forms of starch are water soluble.
 Polysaccharides
Glycogen:

- It is similar to amylopectin (more highly branched-every 10-15 units).

- It is an energy storage molecule found in animals/humans.

- It is stored mainly in the liver and in muscle cells.

- When glucose is needed for energy, glucose units are hydrolyzed

from the ends of the glycogen polymer.

- Because glycogen is highly branched, there are many ends available

for hydrolysis.
 Polysaccharides

Amylose, Amylopectin (starch)

H+ or α-amylase (enzyme in saliva)

Dextrins (6-8 glucose units) Digestion process

H+ or α-amylase (enzyme in pancreas)

Maltose (2 glucose units)

H+ or α-maltase (enzyme)

Many α-D-glucose units

 Respiration

C6H12O6 + 6O2 6CO2 + 6H2O + energy

glucose

Fermentation

Yeast
C6H12O6 2C2H5OH + CO2 + energy
Ethanol
 Polysaccharides
Cellulose:
• Is a polysaccharide of glucose units in unbranched chains with
-1,4-glycosidic bonds (2200 glucose units).
• Has rigid structure (H-bond) and insoluble in water.
• Is the major structural material of wood & plants (cotton: 100%).
• Cannot be digested by humans because of the
-1,4-glycosidic bonds (needs an enzyme: -glycosidase).
 Polysaccharides

Cellulose:

- Cellulose makes up the insoluble fiber in our diets.

- It passes through the digestive system without being metabolized.

- Fiber is important in adding bulk to waste to help eliminate it more

easily (even though it gives us no nutrition).
 Useful Carbohydrates

Amino Sugars
They contain an -NH2 group in place of an -OH group.

- The most abundant amino sugar in nature is D-glucosamine.

- Glucosamine helps keep the cartilage in joints healthy. But natural

glucosamine levels drop as people age.

- As a supplement, glucosamine is most often used to try to

ease the joint pain caused by arthritis.

CHO CHO CHO CHO O

H N H2 H 2N 2 H H N H2 H N HCCH 3
HO H HO H HO H HO H
H OH H OH HO 4 H H OH
H OH H OH H OH H OH
CH2 OH CH2 OH CH2 OH CH2 OH
D-Glucosamine D-Mannosamine D-Galactosamine N-Acetyl-D-
(C-2 stereoisomer (C-4 stereoisomer glucosamine
of D-glucosamine of D-glucosamine)
 Useful Carbohydrates

Amino Sugars
- The second most abundant amino sugar in nature is Chitin.

- It is a polysaccharide formed from N-acetyl-D-glucosamine units

joined together by 1,4--glycosidic bonds.
- Its structure is similar to cellulose (insoluble in water).
 Useful Carbohydrates

Glycosaminoglycans (GAGs)

They are a group of unbranched carbohydrates derived from alternating

amino sugar and glucuronate units.

Hyaluronate: extracellular fluids that lubricate joints and in the

vitreous humor of the eye.

β-glycosidic bond
 Useful Carbohydrates

Glycosaminoglycans (GAGs)

Chondroitin: a component of cartilage and tendons.

β-glycosidic bond

Heparin: stored in the mast cells of the liver, helps prevent blood
clotting.

α-glycosidic bond
 Useful Carbohydrates

Blood Type

- There are four blood types—A, B, AB, and O.

- Blood type is based on 3 or 4 monosaccharides attached to a

membrane protein of red blood cells.

- Each blood type has the monosaccharides below:

 Useful Carbohydrates

Blood Type

Type A blood contains a fourth monosaccharide:

Type B contains an additional D-galactose unit.

Type AB has both type A and type B carbohydrates.

 Useful Carbohydrates

Blood Type
 Useful Carbohydrates

Blood Type
 Useful Carbohydrates

Blood Type

- The short polysaccharide chains distinguish one type of the red blood
cell from another, and signal the cells about the foreign viruses, bacteria,
and other agents.

- The blood of one individual may contain antibodies to another type.

- Those with type O blood are called universal donors, because

people with any other blood type have no antibodies to type O.

- Those with type AB blood are universal recipients because their

blood contains no antibodies to A, B, or O.
 Useful Carbohydrates

Blood Type