Carbohydrates
Introduction
Classification of Carbohydrates
Carbohydrates have the general formula Cx(H2O)y
Carbohydrates are defined as polyhydroxy aldehydes or ketones
or substances that hydrolyze to yield polyhydroxy aldehydes and
ketones
Monosaccharides are carbohydrates that cannot be hydrolyzed to
simpler carbohydrates
Disaccharides can be hydrolyzed to two monosaccharides
Oligosaccharides yield 2 to 10 monosaccharides
Polysacccharides yield >10 monosaccharides
Chapter22
Photosynthesis and Carbohydrate Metabolism
Carbohydrates are synthesized in plants by photosynthesis
Light from the sun is absorbed by chlorophyll and this is converted to the energy
necessary to biosynthesize carbohydrates
Carbohydrates act as a repository of solar energy
The energy is released when animals or plants metabolize carbohydrates
Much of the energy released by oxidation of glucose is trapped in
the molecule adenosine triphosphate (ATP)
The phosphoric anhydride bond formed when adenosine triphosphate (ADP) is
phosphorylated to make ATP is the repository of this energy
This chemical energy is released when ATP is hydrolyzed or a new anhydride
linkage is created
Chapter22
Chapter22
Monosaccharides
Classification of Monosaccharides
Monosaccharides are classified according to:
(1) The number of carbon atoms present in the molecule and
(2) whether they contain an aldehyde or ketone group
D and L Designations of Monosaccharides
The simplest carbohydrates are glyceraldehyde, which is chiral,
and dihydroxyacetone, which is achiral
Glyceraldehyde exists as two enantiomers
Chapter22
In the early 20th century (+)-glyceraldehyde was given the
stereochemical designation (D) and (-)-glyceraldehyde was given
the designation (L)
A monosaccharide whose highest numbered stereogenic center
has the same configuration as D-(+)-glyceraldehyde is a D sugar
A monosaccharide whose highest numbered stereogenic center
has the same configuration as L-(-)-glyceraldehyde is an L sugar
Chapter22
Structural Formulas for Monosaccharides
Fischer projections are used to represent stereochemistry in
carbohydrates
In Fischer projections horizontal lines are understood to project
out of the plane toward the reader and vertical lines are
understood to project behind the plane
A Fischer projection cannot be removed from the plane of the paper or turned 90 o
and still represent the molecule accurately
Glucose exists primarily in two cyclic hemiacetal forms that are
diastereomers of each other
The cyclic hemiacetal forms interconvert via the open-chain form
The cyclic hemiacetals differ only in configuration at C1 and are called anomers
The carbon at which their configurations differ is called the anomeric carbon
The -anomer has the C1 hydroxyl trans to the -CH2OH group
The -anomer has the C1 hydroxyl cis to the -CH2OH group
The flat cyclic representation of carbohydrates is called a Haworth
formula
Cyclic glucose actually exists in the chair form
Chapter22
Chapter22
In the -anomer of glucose all groups around the ring are
equatorial
The configuration at the anomeric carbon of a cyclic carbohydrate
can be left unspecified using a wavy bond
Fischer projections and Haworth formulas can easily be
interconverted (next slide)
A six-membered ring monosaccharide is designated a pyranose,
e.g., glucose in this form is glucopyranose
A five-membered ring monosaccharide is designated a furanose,
Chapter22
Chapter22
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Mutarotation
The - and -forms of glucose can be isolated separately
Pure -glucose has a specific rotation of +112o
Pure -glucose has a specific rotation of +18.7o
When either form of glucose is allowed to stand in aqueous solution,
the specific rotation of the solution slowly changes to +52.7 o
It does not matter whether one starts with pure - or-glucose
Mutarotation is the change in optical rotation as an equilibrium
mixture of anomers forms
Mutarotation of glucose results in an equilibrium mixture of 36% glucose and 64% -glucose
The more stable -glucose form predominates
A very small amount of the open-chain form exists in this equilibrium
Chapter22
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Chapter22
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Glycoside Formation
Glycosides are acetals at the anomeric carbon of carbohydrates
When glucose reacts with methanol in the presence of catalytic acid, the methyl
glycoside is obtained
A glycoside made from glucose is called a glucoside
Chapter22
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Chapter22
14
Glycosides can be hydrolyzed in aqueous acid
The alcohol obtained after hydrolysis of a glycoside is called an aglycone
Chapter22
15
Other Reactions of Monosaccharides
Enolization, Tautomerization and Isomerization
Monosaccharides dissolved in aqueous base will isomerize by a
series of keto-enol tautomerizations
A solution of D-glucose containing calcium hydroxide will form several products,
including D-fructose and D-mannose
A monosaccharide can be protected from keto-enol
tautomerization by conversion to a glycoside
Chapter22
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Formation of Ethers
The hydroxyl groups of carbohydrates can be converted to ethers
by the Williamson ether synthesis
Benzyl ethers are commonly used to protect or block carbohydrate
hydroxyl groups
Benzyl ethers can be easily removed by hydrogenolysis
Exhaustive methylation of methyl glucoside can be carried out
using dimethylsulfate
Chapter22
17
Exhaustive methylation can be used to prove that glucose exists in
the pyranose (6-membered ring) form
Hydrolysis of the pentamethyl derivative results in a free C5 hydroxyl
Silyl ethers are also used as protecting groups for the hydroxyls of
carbohydrates
Sterically bulky tert-butyldiphenylsilyl chloride (TBDPSCl) reacts selectively at the
C6 primary hydroxyl of glucose
Chapter22
18
Conversion to Esters
Carbohydrates react with acetic anhydride in the presence of weak
base to convert all hydroxyl groups to acetate esters
Conversion to Cyclic Acetals
Carbohydrates form cyclic acetals with acetone selectively
between cis-vicinal hydroxyl groups
Cyclic acetals from reaction with acetone are called acetonides
Chapter22
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Oxidation Reactions of Monosaccharides
Benedicts or Tollens Reagents: Reducing Sugars
Aldoses and ketoses give positive tests when treated with Tollens
solution or Benedicts reagent
Tollens reagent [Ag(NH3)2OH] gives a silver mirror when Ag+ is reduced to Ag0
Benedicts reagent (an alkaline solution of cupric citrate complex) gives a brick
red precipitate of Cu2O
In basic solution a ketose can be converted to an aldose that can then react with
Tollens or Benedictss reagent
Chapter22
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Carbohydrates with hemiacetal linkages are reducing sugars
because they react with Tollens and Benedicts reagents
The hemiacetal form is in equilibrium with a small amount of the aldehyde or
ketone form, which can react with Tollens and Benedicts reagents
Carbohydrates with only acetal groups (glycosidic linkages) do not
react with these reagents and are called non-reducing sugars
Acetals are not in equilibrium with the aldehyde or ketone and so cannot react
with these reagents
Chapter22
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Bromine Water: The Synthesis of Aldonic Acids
Bromine in water selectively oxidizes the aldehyde group of an
aldose to the corresponding carboxylic acid
An aldose becomes an aldonic acid
Nitric Acid Oxidation: Aldaric Acids
Dilute nitric acid oxidizes both the aldehyde and primary hydroxyl
groups of an aldose to an aldaric acid
Chapter22
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Periodate Oxidations: Oxidative Cleavage of Polyhydroxy
Compounds
Compounds with hydroxyl groups on adjacent carbons undergo
cleavage of carbon-carbon bonds between the hydroxyl groups
The products are aldehydes, ketones or carboxylic acids
With three or more contiguous hydroxyl groups, the internal carbons
become formic acid
Cleavage also takes place when a hydroxyl group is adjacent to an
aldehyde or ketone group
An aldehyde is oxidized to formic acid; a ketone is oxidized to carbon dioxide
Chapter22
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No cleavage results if there are intervening carbons that do not
bear hydroxyl or carbonyl groups
Chapter22
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Reduction of Monosaccharides: Alditols
Aldoses and ketoses can be reduced to alditols
Chapter22
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Reactions of Monosaccharides with
Phenylhydrazine: Osazones
An aldose or ketose will react with three equivalents of
phenylhydrazine to yield a phenylosazone
The mechanism for phenylosazone formation involves the
following steps:
Chapter22
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Reaction of D-Glucose or D-Mannose with excess phenylhydrazine
yields the same phenylosazone
Therefore, D-glucose and D-mannose differ in configuration only at C2
Compounds that differ in configuration at only one stereogenic center are called
epimers
Chapter22
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Synthesis and Degradation of Monosaccharides
Kiliani-Fischer Synthesis
The carbon chain of an aldose can be extended by:
Addition of cyanide to epimeric cyanohydrins
Hydrolysis to a mixture of epimeric aldonic acids or aldonolactones
Reduction of the epimeric aldonic acids or aldonolactones to the corresponding
aldoses
For example, D-glyceraldehyde can be converted to D-erythrose
and D-threose by the Kiliani-Fischer synthesis
Chapter22
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Chapter22
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The Ruff Degradation
An aldose can be shortened by one carbon via:
Oxidation with bromine water to the aldonic acid
Oxidative decarboxylation with hydrogen peroxide and ferric sulfate
Chapter22
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The D Family of Aldoses
Most biologically important aldoses are of the D family
Chapter22
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Disaccharides
Sucrose (Table sugar)
Sucrose is a disaccharide formed from D-glucose and D-fructose
The glycosidic linkage is between C1 of glucose and C2 of fructose
Sucrose is a nonreducing sugar because of its acetal linkage
Chapter22
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Maltose
Maltose is the disaccharide of D- glucose having an -linkage
Maltose results from hydrolysis of starch by the enzyme diastase
Maltose has a hemiacetal group in one glucose moiety; it is a reducing sugar
The two glucose units of maltose are joined by an -glucosidic linkage
Cellobiose
Cellobiose is the disaccharide of D-glucose having a -linkage
Cellobiose results from partial hydrolysis of cellulose
Cellobiose has a hemiacetal group in one glucose moiety; it is a reducing sugar
The two glucose units are connected by a -glucosidic linkage
Chapter22
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Polysaccharides
Homopolysaccharides are polymers of a single monosaccharide
whereas heteropolysaccharides contain more than one type of
monosaccharide
A polysaccharide made up of only glucose units is called a glucan
Three important glucans are starch, glycogen and cellulose
Starch
The storage form of glucose in plants is called starch
The two forms of starch are amylose and amylopectin
Amylose consists typically of more than 1000 D-glucopyranoside
units connected by linkages between C1 of one unit and C4 of
the next
Chapter22
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Amylose adopts a very compact helical arrangement
Amylopectin is similar to amylose but has branching points every
20-25 glucose units
Branches occur between C1 of one glucose unit and C6 of another
Chapter22
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Glycogen
Glycogen is the major carbohydrate storage molecule in animals
Glycogen is similar to amylopectin except that glycogen has far
more branching
Branching occurs ever 10-12 glucose units in glycogen
Glycogen is a very large polysaccharide
The large size of glycogen prevents if from leaving the storage cell
The storage of tens of thousands of glucose molecules into one molecule greatly
relieves the osmotic problem for the storage cell (this would be caused by the
attempted storage of many individual glucose molecules)
The highly branched nature of glycogen allows hydrolytic enzymes to have many
chain ends from which glucose molecules can be hydrolyzed
Glucose is the source of ready energy for the body
Long chain fatty acids of triacylglycerols are used for long term energy storage
Chapter22
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Cellulose
In cellulose, glucose units are joined by -glycosidic linkages
Cellulose chains are relatively straight
The linear chains of cellulose hydrogen bond with each other to
give the rigid, insoluble fibers found in plant cell walls
The resulting sheets then stack on top of each other
Humans lack enzymes to cleave the linkages in cellulose and so
cannot use cellulose as a source of glucose
Chapter22
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Glycolipids and Glycoproteins of the Cell Surface
Glycolipids and Glycoproteins are important for cell signaling and
recognition
A, B, and O human blood groups are determined by glycoprotein
antigens designated A, B, and H
Chapter22
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