Carbohydrates
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Learning Objectives
o Definition
o Classification
o Biochemical Functions & Significance of Carbohydrates
o Isomers of monosaccharides
o Structure & properties of Monosaccharides & Oligosaccharides
o Structure & properties of Polysaccharides
Carbohydrates
• Carbohydrates are chemically characterized as:
Poly hydroxy aldehydes or
Poly hydroxy ketones.
• Molecules with a 1:2:1 ratio of carbon,
hydrogen, oxygen
• Empirical formula (CH2O)n
• C-H covalent bonds hold much energy
– Carbohydrates are good energy storage
molecules
– Examples: Sugars, Starch, Glucose
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Functions
Variety of important functions in living systems:
◦ nutritional (energy storage, fuels, metabolic intermediates)
◦ structural (components of nucleotides, plant and bacterial cell walls, arthropod
exoskeletons, animal connective tissue)
◦ informational (cell surface of eukaryotes -- molecular recognition, cell-cell
communication)
◦ osmotic pressure regulation (bacteria)
Carbohydrates
Three Major Groups:
1) Monosaccharaides
2) Disaccharides
3) Polysaccharides
Know definition, example, functions and how they form
for each!
Sugars that contain an aldehyde group are called Aldoses.
Sugars that contain a keto group are called Ketoses
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How Are Carbohydrates
Named?
The name carbohydrate arises from the basic molecular formula
(CH2O)n, where
n =3 or more. (CH2O)n can be rewritten (CH2O)n to show that these
substances
are hydrates of carbon.
3 main classes of
carbohydrates
Monosaccharides- one unit of carbohydrate
The monosaccharides are also called simple sugars and have the
formula (CH2O)n.
Disaccharides- Two units of carbohydrates.
Oligosaccharide: two to ten monosaccharide units, make up an
oligosaccharides
they have general formula C n H2(n-1)On -1
Polysaccharides are made of > 10 monosaccharides / much
larger, containing hundreds of monosaccharide units.
Polysaccharides formed from union of pentoses are called
pentosans and by hexoses are called hexosans
Monosaccharides
Monosaccharides are those carbohydrates that cannot be
hydrolyzed into simpler carbohydrates: They may be
classified as trioses, tetroses, pentoses, hexoses,
or heptoses, depending upon the number of carbon atoms;
and as aldoses or ketoses depending upon whether
they have an aldehyde or ketone group.
Glucose C6H12O6
Glucose (C6H12O6)
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http://www.nutritionalhq.com/wp-content/uploads/2011/08/Glucose-molecule-model.jpg
What Is the Structure and Chemistry of
Monsaccharides?
Structure of a simple
aldose and a simple
ketose.
Monosaccharides Are Classified as
Aldoses and Ketoses
Monosaccharides consist typically of three to seven carbon
atoms and are described either as aldoses or ketoses,
depending on whether the molecule contains an aldehyde
function or a ketone group.
The simplest aldose is glyceraldehyde, and the simplest
ketose is dihydroxyacetone (Figure 7.1). These two simple
sugars are termed trioses because they each contain three
carbon atoms.
The structure and
stereochemical The Aldoses
relationships of
D-aldoses with three
to six carbons. Know
the ones in the boxes
The structure and
The Ketoses
stereochemical
relationships of D-ketoses
with three to six carbons.
Know the ones in the
boxes.
Aldoses with at least three carbons and ketoses with at
least four carbons contain
chiral centers.
The nomenclature for such molecules must specify the
configuration about each asymmetric center, and
drawings of these molecules must be based on a system
that clearly specifies these configurations. the Fischer
projection system is used almost universally for this
purpose today. The structures shown in Figures 7.2 and
7.3 are Fischer projections.
Isomers
Isomers are molecules that have the same
molecular formula, but have a different
arrangement of the atoms in space. (different
structures).
For example, a molecule with the formula AB2C2,
has two ways it can be drawn:
Isomer 1
Isomer 2
Examples of isomers:
1. Glucose
2. Fructose
3. Galactose
4. Mannose
Same chemical formula C6 H12 O6
ENANTIOMERS
Non-Superimposable COMPLETE mirror image (differ in configuration at
EVERY CHIRAL CENTER.
Asymmetric carbon
A carbon linked to four different atoms or groups
farthest from the carbonyl carbon
Also called Chiral carbon
The two members of the pair are designated as D and
L forms.
In D form the OH group on the asymmetric carbon is
on the right.
In L form the OH group is on the left side.
D-glucose and L-glucose are enantiomers:
EPIMERS
EPIMERS are sugars that differ in configuration at ONLY 1 POSITION.
Two sugars that differ in configuration at only one chiral center are
described as epimers
Examples of epimers :
◦ D-glucose & D-galactose (epimeric at C4)
◦ D-glucose & D-mannose (epimeric at C2)
◦ D-idose & L-glucose (epimeric at C5)
Diastereomers
Pairs of isomers that have opposite configurations
at one or more of the chiral centers but that are
not mirror images of each other are called or
diastereomeric pairs. Any two structures in a given
row in Figures 7.2 and 7.3 are diastereomeric pairs.
For example, D-mannose and D-talose are epimers
and D-glucose and D-mannose are epimers,
whereas D-glucose and D-talose are not epimers
but merely diastereomers.
Optical Activity
When a plane polarized light is passed through a solution containing
monosaccharides the light will either be rotated towards right or left.
This rotation is because of the presence of asymmetric carbon atom.
If it is rotated towards left- levorotatory (-)
If it is rotated towards right- dextrorotatory(+)
Thus, D-glucose (Figure 7.2) may also be called D(+)-glucose because it
is dextrorotatory, whereas D-fructose (Figure 7.3), which is
levorotatory, can also be named D(-)-fructose.
Cyclization
Less then 1%of CHO exist in an open chain form.
Predominantly found in ring form.
involving reaction of C-5 OH group with the C-1
aldehyde group or C-2 of keto group.
Cyclic monsaccharide structures and anomeric forms
Glucose (an aldose) can cyclize to form a cyclic
hemiacetal
Fructose (a ketose) can cyclize to form a cyclic
hemiketal
When hemiacetals and hemiketals are formed, the
carbonyl carbon atom becomes an asymmetric center
Isomers of monosaccharides that differ only in their
configuration about that asymmetric carbon are called
anomers
Cyclic form of glucose is a pyranose
Cyclic form of fructose is a furanose
Six membered ring structures are called Pyranoses
.
five membered ring structures are called
Furanoses .
Anomeric carbon
The carbonyl carbon after cyclization becomes the anomeric carbon
New asymmetric carbon is called anomeric C carbon.
This creates α and β configuration/ isomers are called anomers
Monosaccharides Exist in Cyclic, Anomeric Forms
7.2 What Is the Structure and Chemistry of
Monsaccharides?
MUTAROTATION
Unlike the other stereoisomeric forms, α and β
anomers spontaneously interconvert in solution.
This is called mutarotation.
Monosaccharides Can Be Converted to Several Derivative
Forms
A variety of chemical and enzymatic reactions produce derivatives of the simple
sugars
Some of the most common are:
◦ Sugar acids
◦ Sugar alcohols
◦ Deoxy sugars
◦ Sugar esters
◦ Amino sugars
◦ Acetals, ketals, and glycosides
Monosaccharide Derivatives
Reducing sugars are sugars with free anomeric
carbons - they will reduce oxidizing agents, such
as peroxide, ferricyanide and some metals (Cu2+
and Ag+).
These redox reactions oxidize the sugar to a
sugar acid.
Glucose is a reducing sugar - so these reactions
are the basis for diagnostic tests for blood sugar
Monosaccharides Can Be Converted to Several
Derivative Forms
More Monosaccharide Derivatives
Sugar Alcohols Sugar alcohols, another class of sugar derivative, can be prepared by
the mild reduction (with NaBH4 or similar agents) of the carbonyl groups of aldoses
and ketoses. Sugar alcohols, or alditols, are designated by the addition of –itol to the
name of the parent sugar (Figure 7.10). The alditols are linear molecules that cannot
cyclize in the manner of aldoses. Nonetheless, alditols are characteristically sweet
tasting, and sorbitol, mannitol, and xylitol are widely used to sweeten sugarless
gum and mints (Figure 7.11).
Sugar Alcohols
Deoxy Sugars
• Deoxy sugars are monosaccharides with one or more
hydroxyl groups replaced by hydrogens
• 2-Deoxy-D-ribose is a constituent of DNA
• Rhamnose is a component of ouabain, a toxic “cardiac
glycoside”
• Fucose is a component of some cell walls
Phosphate esters of glucose, fructose, and other monosaccharides are
important metabolic intermediates, and the ribose moiety of
nucleotides such as ATP and GTP is phosphorylated at the 5-position
Amino Sugars
• Sugars with an amino group at C-2 are amino sugars.
• They are found in many oligosaccharides and polysaccharides.
Acetals and Ketals
Acetals and ketals can be formed from hemiacetals and
hemiketals, respectively.
Glycosides
The pyranose and furanose forms
of monosaccharides react with
alcohols in dehydration synthesis
reactions to form glycosides, with
retention of the α- or β-
configuration at the C-1 carbon.
The new bond formed is called a
glycosidic bond.
